JP2007279728A - Negative photosensitive resin composition - Google Patents
Negative photosensitive resin composition Download PDFInfo
- Publication number
- JP2007279728A JP2007279728A JP2007097084A JP2007097084A JP2007279728A JP 2007279728 A JP2007279728 A JP 2007279728A JP 2007097084 A JP2007097084 A JP 2007097084A JP 2007097084 A JP2007097084 A JP 2007097084A JP 2007279728 A JP2007279728 A JP 2007279728A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin composition
- photosensitive resin
- negative photosensitive
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 57
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 43
- -1 phenylmaleimide compound Chemical class 0.000 claims abstract description 39
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- MCNPOZMLKGDJGP-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-UHFFFAOYSA-N 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- MJEKXIMDWJVYTC-UHFFFAOYSA-N 1-butyl-10H-acridin-9-one Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC MJEKXIMDWJVYTC-UHFFFAOYSA-N 0.000 claims description 3
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- KIJJAQMJSXOBIE-UHFFFAOYSA-N (2-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC1CCCCC1OC(=O)C(C)=C KIJJAQMJSXOBIE-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OJSJBCPURCWPEU-UHFFFAOYSA-N 2-(dimethylamino)-3-(2-ethylhexyl)benzoic acid Chemical compound CCCCC(CC)CC1=CC=CC(C(O)=O)=C1N(C)C OJSJBCPURCWPEU-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- JSLWEMZSKIWXQB-UHFFFAOYSA-N 2-dodecylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CCCCCCCCCCCC)=CC=C3SC2=C1 JSLWEMZSKIWXQB-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- DCTLJGWMHPGCOS-UHFFFAOYSA-N Osajin Chemical compound C1=2C=CC(C)(C)OC=2C(CC=C(C)C)=C(O)C(C2=O)=C1OC=C2C1=CC=C(O)C=C1 DCTLJGWMHPGCOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- IDLJKTNBZKSHIY-UHFFFAOYSA-N [4-(diethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=CC=C1 IDLJKTNBZKSHIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- AQNSVANSEBPSMK-UHFFFAOYSA-N dicyclopentenyl methacrylate Chemical compound C12CC=CC2C2CC(OC(=O)C(=C)C)C1C2.C12C=CCC2C2CC(OC(=O)C(=C)C)C1C2 AQNSVANSEBPSMK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002114 octoxynol-9 Polymers 0.000 claims description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- SSLASPHAKUVIRG-UHFFFAOYSA-N (2-methylcyclohexyl) prop-2-enoate Chemical compound CC1CCCCC1OC(=O)C=C SSLASPHAKUVIRG-UHFFFAOYSA-N 0.000 claims 1
- AHRCXHWJTKJMDX-UHFFFAOYSA-N 2-pentoxyethyl prop-2-enoate Chemical compound CCCCCOCCOC(=O)C=C AHRCXHWJTKJMDX-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class 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 1
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 28
- 229920005989 resin Polymers 0.000 abstract description 28
- 239000011229 interlayer Substances 0.000 abstract description 16
- 230000035945 sensitivity Effects 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 10
- 125000006850 spacer group Chemical group 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- SXPVZPQNFIDDPP-UHFFFAOYSA-N 3-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1C1=CC(=O)NC1=O SXPVZPQNFIDDPP-UHFFFAOYSA-N 0.000 description 5
- WIDLYFZFVAGYAJ-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-3-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(=O)NC1=O WIDLYFZFVAGYAJ-UHFFFAOYSA-N 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SVBSJWKYFYUHTF-UHFFFAOYSA-N ethyl 2-butoxyacetate Chemical compound CCCCOCC(=O)OCC SVBSJWKYFYUHTF-UHFFFAOYSA-N 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BKFQHFFZHGUTEZ-UHFFFAOYSA-N methyl 2-butoxyacetate Chemical compound CCCCOCC(=O)OC BKFQHFFZHGUTEZ-UHFFFAOYSA-N 0.000 description 1
- YVWPDYFVVMNWDT-UHFFFAOYSA-N methyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OC YVWPDYFVVMNWDT-UHFFFAOYSA-N 0.000 description 1
- VBCSBEIIIFLVQV-UHFFFAOYSA-N methyl 3-butoxypropanoate Chemical compound CCCCOCCC(=O)OC VBCSBEIIIFLVQV-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- LVDAGIFABMFXSJ-UHFFFAOYSA-N propyl 2-butoxyacetate Chemical compound CCCCOCC(=O)OCCC LVDAGIFABMFXSJ-UHFFFAOYSA-N 0.000 description 1
- ADOFEJQZDCWAIL-UHFFFAOYSA-N propyl 2-ethoxyacetate Chemical compound CCCOC(=O)COCC ADOFEJQZDCWAIL-UHFFFAOYSA-N 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- HJIYVZIALQOKQI-UHFFFAOYSA-N propyl 3-butoxypropanoate Chemical compound CCCCOCCC(=O)OCCC HJIYVZIALQOKQI-UHFFFAOYSA-N 0.000 description 1
- IYVPXMGWHZBPIR-UHFFFAOYSA-N propyl 3-ethoxypropanoate Chemical compound CCCOC(=O)CCOCC IYVPXMGWHZBPIR-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 231100000628 reference dose Toxicity 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
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26B—HAND-HELD CUTTING TOOLS NOT OTHERWISE PROVIDED FOR
- B26B3/00—Hand knives with fixed blades
- B26B3/08—Hand knives with fixed blades specially adapted for cutting cardboard, or wall, floor, or like covering materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26B—HAND-HELD CUTTING TOOLS NOT OTHERWISE PROVIDED FOR
- B26B9/00—Blades for hand knives
- B26B9/02—Blades for hand knives characterised by the shape of the cutting edge, e.g. wavy
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Forests & Forestry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、ネガティブ感光性樹脂組成物に関する。 The present invention relates to a negative photosensitive resin composition.
ＴＦＴ型液晶表示素子や集積回路素子には層間に配置される配線の間を絶縁するために層間絶縁膜が使用され、液晶カラーディスプレイの大面積化、高画質、高対比表示のためにオーバーコート用レジスト、ブラックマトリックス用レジスト、コラムスペーサ用レジスト、カラーフィルター用レジストなど画像形成用液晶表示素子の材料として使用されている。
層間絶縁膜を形成する場合には必要とするパターン形状の層間絶縁膜を得るための工程数が少なく平坦性に優れた感光性材料が使用されている。
In TFT type liquid crystal display elements and integrated circuit elements, an interlayer insulating film is used to insulate between the wirings arranged between the layers, and an overcoat for large area, high image quality and high contrast display of the liquid crystal color display. It is used as a material for liquid crystal display elements for image formation, such as resist for black matrix, resist for black matrix, resist for column spacer, resist for color filter.
When forming an interlayer insulating film, a photosensitive material having a small number of steps for obtaining an interlayer insulating film having a required pattern shape and excellent in flatness is used.
また、液晶ディスプレイ（ＬＣＤ）の表示品位向上によりＴＦＴ型液晶表示素子の構造も変化しており、層間絶縁膜の膜の厚さを厚くして平坦性を高めて使用する場合が増加している。さらに、ＬＣＤ製造工程に適用される層間絶縁膜は優れた透過率が要求される。
従来の層間絶縁膜は、ＰＡＣ、バインダー、溶媒などの成分からなり、前記バインダーとしてはアクリル樹脂が主に使用されてきた。しかし、前記アクリル樹脂の場合、層間絶縁膜で要求される高耐熱性を得ることが難しいため、脱ガス（Outgassing）によるフォト装備の損傷と残像の問題を引き起こす。また、各層を構成しているＩＴＯ、ＳｉＮｘなどとの接着力を得ることが難しく、熱硬化後有色化して、層間絶縁膜で要求される高透過率を達成しにくく、常温保管時に分子量の上昇の問題を引き起こして、感度およびパターン形状変化などの保存安定性に問題点があった。
In addition, the structure of the TFT type liquid crystal display element is changing due to the improvement of the display quality of the liquid crystal display (LCD), and the number of cases in which the flatness is increased by increasing the thickness of the interlayer insulating film is increasing. . Furthermore, the interlayer insulating film applied to the LCD manufacturing process is required to have excellent transmittance.
Conventional interlayer insulating films are composed of components such as PAC, binder and solvent, and acrylic resin has been mainly used as the binder. However, in the case of the acrylic resin, since it is difficult to obtain the high heat resistance required for the interlayer insulating film, the photo equipment is damaged due to outgassing and the problem of afterimage occurs. In addition, it is difficult to obtain adhesive strength with ITO, SiNx, etc. that make up each layer, it is colored after thermosetting, it is difficult to achieve the high transmittance required for interlayer insulation films, and the molecular weight increases during storage at room temperature This causes the problem of storage stability such as sensitivity and pattern shape change.
従来の画像形成用液晶素子の材料として使用されるオーバーコート用レジスト樹脂、ブラックマトリックス用レジスト樹脂、コラムスペーサ用レジスト樹脂、カラーフィルター用レジスト樹脂の場合、アクリル樹脂が主に使用されており、これらアクリル樹脂は光開始剤とエチレン性不飽和結合を有する多官能モノマーによる硬化速度が遅く、硬化後に体積の収縮が発生するという問題点があった。 In the case of the resist resin for overcoat, the resist resin for black matrix, the resist resin for column spacer, and the resist resin for color filter that are used as materials for conventional liquid crystal elements for image formation, acrylic resin is mainly used. The acrylic resin has a problem that the curing rate by the polyfunctional monomer having a photoinitiator and an ethylenically unsaturated bond is slow, and volume shrinkage occurs after curing.
このような従来の技術の問題点を解決するために、本発明は、接着力、耐熱性、絶縁性、平坦性、耐化学性、常温保存安定性などの性能に優れて液晶表示素子の画像形成用材料に適し、特に液晶表示素子の有機絶縁膜形成時に感度、残膜率、ＵＶ透過率が優れているため層間有機絶縁膜として使用することに適したネガティブ感光性樹脂組成物、前記感光性樹脂の硬化体を含むＴＦＴ型液晶表示素子および前記ネガティブ感光性樹脂組成物を利用したＴＦＴ型液晶表示素子のパターン形成方法を提供することを目的とする。
本発明の他の目的は、オーバーコート用レジスト樹脂、ブラックマトリックス用レジスト樹脂、コラムスペーサ用レジスト樹脂、またはカラーフィルター用レジスト樹脂として使用して、感度および残膜率を向上させることができるネガティブ感光性樹脂組成物、前記感光性樹脂の硬化体を含むＴＦＴ型液晶表示素子および前記ネガティブ感光性樹脂組成物を利用したＴＦＴ型液晶表示素子のパターン形成方法を提供することにある。
In order to solve such problems of the prior art, the present invention is superior in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, room temperature storage stability, etc. A negative photosensitive resin composition suitable for use as an interlayer organic insulating film because of its excellent sensitivity, residual film rate, and UV transmittance, particularly when forming an organic insulating film of a liquid crystal display device, It aims at providing the pattern formation method of the TFT type liquid crystal display element containing the hardened | cured material of photosensitive resin, and the TFT type liquid crystal display element using the said negative photosensitive resin composition.
Another object of the present invention is to provide a negative photosensitive resin which can be used as an overcoat resist resin, a black matrix resist resin, a column spacer resist resin, or a color filter resist resin to improve sensitivity and residual film ratio. It is providing the pattern formation method of the TFT type liquid crystal display element using the photosensitive resin composition, the TFT type liquid crystal display element containing the hardening body of the said photosensitive resin, and the said negative photosensitive resin composition.
前記目的を達成するために、本発明は、ネガティブ感光性樹脂組成物において、
ａ）ｉ）下記の式（１）
（式中、Ｒはヒドロキシ（ＯＨ−）またはカルボキシ（ＣＨ３ＣＯＯ−）基である。）
で表示されるフェニルマレイミド系化合物；
ｉｉ）アリルアクリル系化合物；および
ｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物；
を共重合させて得られたアクリル系共重合体；
ｂ）光開始剤；
ｃ）エチレン性不飽和結合を有する多官能性モノマー；
ｄ）エポキシ基またはアミン基を含むシリコン系化合物；および
ｅ）溶媒
を含むことを特徴とするネガティブ感光性樹脂組成物を提供する。
In order to achieve the above object, the present invention provides a negative photosensitive resin composition,
a) i) the following formula (1)
(In the formula, R is a hydroxy (OH − ) or carboxy (CH 3 COO − ) group.)
A phenylmaleimide compound represented by:
ii) allyl acrylic compounds; and iii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof;
An acrylic copolymer obtained by copolymerization of
b) a photoinitiator;
c) a polyfunctional monomer having an ethylenically unsaturated bond;
A negative photosensitive resin composition comprising: d) a silicon-based compound containing an epoxy group or an amine group; and e) a solvent.
好ましくは、本発明は
ａ）ｉ）式（１）で表示されるフェニルマレイミド系化合物５〜８０重量％；
ｉｉ）アリルアクリル系化合物５〜８０重量％；および
ｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物５〜４０重量％；
を共重合させて得られたアクリル系共重合体１００重量部；
ｂ）光開始剤０．００１〜３０重量部；
ｃ）エチレン性不飽和結合を有する多官能性モノマー１０〜１００重量部；
ｄ）エポキシ基またはアミン基を含むシリコン系化合物０．０００１〜５重量部；および
ｅ）溶媒を感光性樹脂組成物内の固形分の含量が１０〜５０重量％になるように含む。
Preferably, the present invention provides: a) i) 5 to 80% by weight of a phenylmaleimide compound represented by the formula (1);
ii) 5 to 80% by weight of an allyl acrylic compound; and iii) 5 to 40% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof;
100 parts by weight of an acrylic copolymer obtained by copolymerizing
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) 0.0001 to 5 parts by weight of a silicon-based compound containing an epoxy group or an amine group; and e) a solvent so that the solid content in the photosensitive resin composition is 10 to 50% by weight.
また、本発明は前記ネガティブ感光性樹脂組成物の硬化体を含むことを特徴とするＴＦＴ型液晶表示素子を提供する。
さらに、本発明は前記ネガティブ感光性樹脂組成物を利用することを特徴とするＴＦＴ型液晶表示素子のパターン形成方法を提供する。
The present invention also provides a TFT-type liquid crystal display device comprising a cured product of the negative photosensitive resin composition.
Furthermore, the present invention provides a method for forming a pattern of a TFT-type liquid crystal display element, wherein the negative photosensitive resin composition is used.
本発明によるネガティブ感光性樹脂組成物は、接着力、耐熱性、絶縁性、平坦性、耐化学性、常温保存安定性などの性能に優れ、液晶表示素子の画像形成用材料に好適に用いることができる。特に液晶表示素子の有機絶縁膜形成時に、感度、残膜率、ＵＶ透過率が優れているため、層間有機絶縁膜として好適に使用することができる。
また、オーバーコート用レジスト樹脂、ブラックマトリックス用レジスト樹脂、コラムスペーサ用レジスト樹脂、またはカラーフィルター用レジスト樹脂として好適に使用することができ、感度および耐熱性、接着力、常温保存安定性を向上させることができるという効果がある。
The negative photosensitive resin composition according to the present invention is excellent in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, and room temperature storage stability, and should be suitably used as an image forming material for liquid crystal display elements. Can do. In particular, when forming an organic insulating film of a liquid crystal display element, it is excellent in sensitivity, remaining film ratio, and UV transmittance, and therefore can be suitably used as an interlayer organic insulating film.
In addition, it can be suitably used as resist resin for overcoat, resist resin for black matrix, resist resin for column spacer, or resist resin for color filter, improving sensitivity and heat resistance, adhesive strength, and room temperature storage stability. There is an effect that can be.
以下、本発明を詳細に説明する。
本発明のネガティブ感光性樹脂組成物は、ａ）ｉ）前記式（１）で表示されるフェニルマレイミド系化合物、ｉｉ）アリルアクリル系化合物、およびｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物を共重合させて得られたアクリル系共重合体、ｂ）光開始剤、ｃ）エチレン性不飽和結合を有する多官能性モノマー、ｄ）エポキシ基またはアミン基を含むシリコン系化合物、およびｅ）溶媒を含む。
Hereinafter, the present invention will be described in detail.
The negative photosensitive resin composition of the present invention comprises: a) i) a phenylmaleimide compound represented by the formula (1), ii) an allylacrylic compound, and iii) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Or an acrylic copolymer obtained by copolymerizing a mixture thereof, b) a photoinitiator, c) a polyfunctional monomer having an ethylenically unsaturated bond, d) a silicon system containing an epoxy group or an amine group A compound, and e) a solvent.
本発明に使用される前記ａ）のアクリル系共重合体は、現像時にスカムが発生しない所定のパターンを容易に形成することができるようにする作用をする。
前記ａ）のアクリル系共重合体は、ａ）ｉ）前記式（１）で表示されるフェニルマレイミド系化合物、ｉｉ）アリルアクリル系化合物、およびｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物を単量体として溶媒および重合開始剤の存在下でラジカル反応して製造することができる。
The acrylic copolymer of a) used in the present invention acts to easily form a predetermined pattern in which no scum is generated during development.
The acrylic copolymer of a) includes a) i) a phenylmaleimide compound represented by the formula (1), ii) an allylacrylic compound, and iii) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Or a mixture thereof as a monomer can be produced by radical reaction in the presence of a solvent and a polymerization initiator.
前記ａ）ｉ）の式（１）で表示されるフェニルマレイミド系化合物は、耐熱性および接着力、常温保存安定性を向上させる作用を果たす。
前記フェニルマレイミド系化合物は、４−ヒドロキシフェニルマレイミドまたは４−カルボキシフェニルマレイミドなどを使用することができる。
前記フェニルマレイミド系化合物は、その含量が少なすぎると、耐熱性および接着力が低下し、多すぎるとアルカリ水溶性に対する溶解性が低下するという観点から、全単量体に対して５〜８０重量％に含まれるのが好ましく、さらに好ましくは５〜４０重量％である。
The phenylmaleimide compound represented by formula (1) in a) i) functions to improve heat resistance, adhesive strength, and storage stability at room temperature.
As the phenylmaleimide compound, 4-hydroxyphenylmaleimide or 4-carboxyphenylmaleimide can be used.
When the content of the phenylmaleimide-based compound is too small, the heat resistance and the adhesive strength are lowered, and when the content is too large, the solubility in alkaline water solubility is lowered to 5 to 80 wt. %, Preferably 5 to 40% by weight.
本発明に使用される前記ａ）ｉｉ）のアリルアクリル系化合物は、光開始剤によるエチレン性不飽和結合を有する多官能モノマーとの硬化速度を増加させ、現像液内で溶解性を低下させて残膜率を向上させる作用を果たす。
前記アリルアクリル系化合物は、下記式（２）で表示される化合物であるのが好ましく、具体的にアリルアクリレートまたはアリルメタクリレートなどを使用することができる。
（式中、Ｘは水素またはメチル基である。）
前記アリルアクリル系化合物は、その含量が少なすぎると光硬化速度が遅くなり、多すぎるとコンタクトホール生成およびパターン形成で解像力低下が発生するという観点から、全単量体に対して５〜８０重量％で含まれるのが好ましく、さらに好ましくは２０〜７０重量％である。
The allyl acrylic compound of a) ii) used in the present invention increases the curing rate with a polyfunctional monomer having an ethylenically unsaturated bond by a photoinitiator and decreases the solubility in a developer. It works to improve the remaining film rate.
The allyl acrylic compound is preferably a compound represented by the following formula (2), and specifically, allyl acrylate or allyl methacrylate can be used.
(In the formula, X is hydrogen or a methyl group.)
The allylacrylic compound is 5 to 80% by weight based on the total monomer from the viewpoint that if the content is too small, the photocuring rate is slow, and if the content is too large, the resolution decreases due to contact hole generation and pattern formation. %, Preferably 20 to 70% by weight.
前記ａ）ｉｉｉ）の不飽和カルボン酸、不飽和カルボン酸無水物またはこれらの混合物はアクリル酸、メタクリル酸などの不飽和モノカルボン酸；マレイン酸、フマル酸、シトラコン酸、メタコン酸、イタコン酸などの不飽和ジカルボン酸；またはこれらの不飽和ジカルボン酸の無水物などを単独または２種以上混合して使用することができ、特にアクリル酸、メタクリル酸、または無水マレイン酸を使用するのが、共重合反応性と現像液のアルカリ水溶液に対する溶解性において、さらに好ましい。 The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixture thereof of a) iii) is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, etc. These unsaturated dicarboxylic acids; or anhydrides of these unsaturated dicarboxylic acids can be used alone or in admixture of two or more, and in particular, acrylic acid, methacrylic acid, or maleic anhydride is used. It is further preferable in terms of polymerization reactivity and solubility of the developer in an alkaline aqueous solution.
前記不飽和カルボン酸、不飽和カルボン酸無水物またはこれらの混合物は、その含量が少なすぎるとアルカリ水溶液に溶解しにくく、多すぎるとアルカリ水溶液に対する溶解性が過度に大きくなるという観点から、全単量体に対して５〜４０重量％で含まれるのが好ましく、さらに好ましくは１０〜３０重量％である。 From the viewpoint that the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride, or a mixture thereof is difficult to dissolve in the alkaline aqueous solution if the content is too small, and that the solubility in the alkaline aqueous solution is excessively large if the content is too large, It is preferably contained at 5 to 40% by weight, more preferably 10 to 30% by weight with respect to the monomer.
前記のような単量体をアクリル系共重合体に重合するために使用される溶媒は、メタノール、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールメチルエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールブチルエーテルアセテート、プロピレングリコールメチルエチルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネート、プロピレングリコールブチルエーテルプロピオネート、トルエン、キシレン、メチルエチルケトン、シクロヘキサノン、４−ヒドロキシ４−メチル２−ペンタノン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ２−メチルプロピオン酸メチル、２−ヒドロキシ２−メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、３−ヒドロキシプロピオン酸メチル、３−ヒドロキシプロピオン酸エチル、３−ヒドロキシプロピオン酸プロピル、３−ヒドロキシプロピオン酸ブチル、２−ヒドロキシ３−メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸プロピル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸プロピル、エトキシ酢酸ブチル、プロポキシ酢酸メチル、プロポキシ酢酸エチル、プロポキシ酢酸プロピル、プロポキシ酢酸ブチル、ブトキシ酢酸メチル、ブトキシ酢酸エチル、ブトキシ酢酸プロピル、ブトキシ酢酸ブチル、２−メトキシプロピオン酸メチル、２−メトキシプロピオン酸エチル、２−メトキシプロピオン酸プロピル、２−メトキシプロピオン酸ブチル、２−エトキシプロピオン酸メチル、２−エトキシプロピオン酸エチル、２−エトキシプロピオン酸プロピル、２−エトキシプロピオン酸ブチル、２−ブトキシプロピオン酸メチル、２−ブトキシプロピオン酸エチル、２−ブトキシプロピオン酸プロピル、２−ブトキシプロピオン酸ブチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−メトキシプロピオン酸プロピル、３−メトキシプロピオン酸ブチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸プロピル、３−エトキシプロピオン酸ブチル、３−プロポキシプロピオン酸メチル、３−プロポキシプロピオン酸エチル、３−プロポキシプロピオン酸プロピル、３−プロポキシプロピオン酸ブチル、３−ブトキシプロピオン酸メチル、３−ブトキシプロピオン酸エチル、３−ブトキシプロピオン酸プロピル、または３−ブトキシプロピオン酸ブチルなどのようなエーテル類などを使用することができ、前記化合物を単独または２種以上混合して使用することができる。 Solvents used to polymerize the above monomers into acrylic copolymers are methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether ace , Propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone , Cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, lactic acid Lopyr, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, methylbutoxyacetate, ethylbutoxyacetate Propyl, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2- Butyl propoxyate butyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propyl propionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxy Ethers such as methyl propionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate can be used, and the above compounds can be used alone or in combination of two or more. Can be used.
このような単量体をアクリル系共重合体に重合するために使用される重合開始剤はラジカル重合開始剤を用いることができ、具体的に２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２，４−ジメチルバレロニトリル）、２，２−アゾビス（４−メトキシ２，４−ジメチルバレロニトリル）、１，１−アゾビス（シクロヘキサン−１−カルボニトリル）、またはジメチル２，２−アゾビスイソブチレートなどを使用することができる。 The polymerization initiator used to polymerize such a monomer into an acrylic copolymer can be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2 -Azobisisobutyrate or the like can be used.
また、前記共重合体は、本発明のアクリル系共重合体製造時にｉｖ）のオレフィン系不飽和化合物をさらに含ませてアクリル系共重合体を製造することができる。前記ｉｖ）のオレフィン系不飽和化合物は、メチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、ｓｅｃ−ブチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、メチルアクリレート、イソプロピルアクリレート、シクロヘキシルメタクリレート、２−メチルシクロヘキシルメタクリレート、ジシクロペンテニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルメタクリレート、ジシクロペンタニルメタクリレート、１−アダマンチルアクリレート、１−アダマンチルメタクリレート、ジシクロペンタニルオキシエチルメタクリレート、イソボロニルメタクリレート、シクロヘキシルアクリレート、２−メチルシクロヘキシルアクリレート、ジシクロペンタニルオキシエチルアクリレート、イソボロニルアクリレート、フェニルメタクリレート、フェニルアクリレート、ベンジルアクリレート、２−ヒドロキシエチルメタクリレート、スチレン、σ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ビニルトルエン、ｐ−メトキシスチレン、１，３−ブタジエン、イソプレン、または２，３−ジメチル１，３−ブタジエンなどを使用することができ、前記化合物を単独または２種以上混合して使用することができる。 In addition, the copolymer may further include an olefin unsaturated compound of iv) at the time of manufacturing the acrylic copolymer of the present invention to manufacture an acrylic copolymer. The olefinic unsaturated compound of iv) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl. Acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate Dicyclopentanyloxyethyl acrylate, Soboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, or the like can be used, and the above compounds can be used alone or in admixture of two or more.
特に、前記オレフィン系不飽和化合物は、スチレン、ジシクロペンタニルメチルメタクリレート、またはｐ−メトキシスチレンを使用するのが、共重合反応性および現像液のアルカリ水溶液に対する溶解性側面でさらに好ましい。
前記オレフィン系不飽和化合物は全体総単量体に対して１０〜７０重量％で含まれるのが好ましく、さらに好ましくは２０〜５０重量％である。その含量が前記範囲内である場合にはアクリル系共重合体の保存安全性の低下、アクリル系共重合体が現像液のアルカリ水溶液に溶解しにくいという問題点などを同時に解決することができる。
前記のような単量体を溶媒と重合開始剤存在下でラジカル反応させて製造されるａ）のアクリル系共重合体は、ポリスチレン換算重量平均分子量（Ｍｗ）が６，０００〜９０，０００であるのが好ましく、さらに好ましくは６，０００〜４０、０００である。前記ポリスチレン換算重量平均分子量が小さすぎるネガティブ感光性樹脂組成物の場合、現像性、残膜率などが低下したり、パターン形状、耐熱性などが劣ることがあり、大きすぎるとコンタクトホールおよびパターン現像が劣るという問題点がある。
In particular, it is more preferable to use styrene, dicyclopentanylmethyl methacrylate, or p-methoxystyrene as the olefinically unsaturated compound in terms of copolymerization reactivity and solubility in an aqueous alkali solution.
The olefinically unsaturated compound is preferably contained in an amount of 10 to 70% by weight, more preferably 20 to 50% by weight, based on the total total monomers. When the content is within the above range, it is possible to solve simultaneously the problems such as a decrease in the storage safety of the acrylic copolymer and the difficulty in dissolving the acrylic copolymer in the alkaline aqueous solution of the developer.
The acrylic copolymer of a) produced by radical reaction of the above monomers in the presence of a solvent and a polymerization initiator has a polystyrene equivalent weight average molecular weight (Mw) of 6,000 to 90,000. It is preferable that it is 6,000 to 40,000. In the case of the negative photosensitive resin composition having a polystyrene-reduced weight average molecular weight that is too small, the developability, the remaining film ratio, etc. may decrease, or the pattern shape, heat resistance, etc. may be inferior. Is inferior.
本発明に使用される前記ｂ）の光開始剤は、Ｉｒｇａｃｕｒｅ ３６９、Ｉｒｇａｃｕｒ ６５１、Ｉｒｇａｃｕｒｅ ９０７、Ｄａｒｏｃｕｒ ＴＰＯ、Ｉｒｇａｃｕｒｅ ８１９、トリアジン系、ベンゾイン、アセトフェノン系、イミダゾール系、またはキサントン系などの化合物を使用することができる。
具体的に、前記光開始剤は、２，４−ビストリクロロメチル−６−ｐ−メトキシスチリル−ｓ−トリアジン、２−ｐ−メトキシスチリル−４，６−ビストリクロロメチル−ｓ−トリアジン、２，４−トリクロロメチル−６−トリアジン、２，４−トリクロロメチル−４−メチルナフチル−６−トリアジン、ベンゾフェノン、ｐ−（ジエチルアミノ）ベンゾフェノン、２，２−ジクロロ−４−フェノキシアセトフェノン、２，２−ジエトキシアセトフェノン、２−ドデシルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、または２，２−ビス−２−クロロフェニル−４，５，４，５−テトラフェニル−２−１，２−ビイミダゾールなどの化合物を単独または２種以上混合して使用することができる。
The photoinitiator of b) used in the present invention is a compound such as Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, triazine, benzoin, acetophenone, imidazole, or xanthone. be able to.
Specifically, the photoinitiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2, 4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-di Ethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-1,2- Compounds such as biimidazole can be used alone or in admixture of two or more.
前記光開始剤は、その含量が少なすぎると低い感度によって残膜率が悪くなり、多すぎると保存安定性に問題が発生することがあり、高い硬化度によって現像時にパターンの接着力が低下することがあるという観点から、前記ａ）のアクリル系共重合体１００重量部に対して０．００１〜３０重量部で含むのが好ましく、さらに好ましくは０．０１〜２０重量部である。 If the content of the photoinitiator is too low, the remaining film rate may be deteriorated due to low sensitivity, and if it is too high, a problem may occur in storage stability, and a high degree of curing reduces the adhesion of the pattern during development. From the standpoint of the possibility, it is preferably contained in an amount of 0.001 to 30 parts by weight, more preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a).
本発明に使用される前記ｃ）のエチレン性不飽和結合を有する多官能性モノマーは一般に少なくとも２つ以上のエチレン系二重結合を有する架橋性モノマーであって、１，４−ブタンジオールジアクリレート、１，３−ブチレングリコールジアクリレート、エチレングリコールジアクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ジペンタエリスリトールヘキサジアクリレート、ジペンタエリスリトールトリジアクリレート、ジペンタエリスリトールジアクリレート、ソルビトールトリアクリレート、ビスフェノールＡジアクリレート誘導体、ジペンタエリスリトールポリアクリレート、またはこれらのメタクリレート類などを使用することができる。 The polyfunctional monomer having an ethylenically unsaturated bond of c) used in the present invention is generally a crosslinkable monomer having at least two ethylenic double bonds, and is 1,4-butanediol diacrylate. 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipenta Erythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A Acrylate derivatives, dipentaerythritol polyacrylate or the like of these methacrylates can be used.
前記エチレン性不飽和結合を有する多官能性モノマーは、その含量が少なすぎると感光性樹脂との低い硬化度によってコンタクトホールおよびパターンの実現が難しく、多すぎると高い硬化度によって現像時にコンタクトホールおよびパターンの解像力が低下することがあるという観点から、前記ａ）のアクリル系共重合体１００重量部に対して１０〜１００重量部で含まれるのが好ましく、さらに好ましくは１０〜６０重量部である。 If the content of the polyfunctional monomer having an ethylenically unsaturated bond is too small, it is difficult to realize a contact hole and a pattern due to a low degree of curing with the photosensitive resin. From the viewpoint that the resolving power of the pattern may be lowered, it is preferably contained in 10 to 100 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). .
本発明に使用される前記ｄ）のエポキシ基またはアミン基を含むシリコン系化合物は、（３−グリシドオキシプロピル）トリメトキシシラン、（３−グリシドオキシプロピル）トリエトキシシラン、（３−グリシドオキシプロピル）メチルジメトキシシラン、（３−グリシドオキシプロピル）トリメトキシシラン、（３−グリシドオキシプロピル）ジメチルエトキシシラン、（３−グリシドオキシプロピル）ジメチルエトキシシラン、３，４−エポキシブチルトリメトキシシラン、３，４−エポキシブチルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシランまたはアミノプロピルトリメトキシシランなどを単独または２種以上混合して使用することができる。 The silicon compound containing an epoxy group or an amine group of d) used in the present invention is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidyl). Sidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, etc. Singly or in combination of two or more It is possible to use Te.
前記エポキシ基またはアミン基を含むシリコン系化合物は、その含量が少なすぎる場合にはＩＴＯ電極と感光性樹脂との接着力が劣り、硬化後の耐熱特性が劣ることがあり、多すぎる現像液内で非露光部の白化現象および現像後にコンタクトホールやパターンのスカムが発生することがあるという観点から、前記ａ）のアクリル系共重合体１００重量部に対して０．０００１〜５重量部で含まれるのが好ましく、さらに好ましくは０．００５〜２重量部である。
本発明に使用される前記ｅ）の溶媒は、層間絶縁膜の平坦性とコーティング染みを発生させず、均一なパターンプロファイルを形成するようにする。
When the content of the silicon-based compound containing an epoxy group or an amine group is too small, the adhesive force between the ITO electrode and the photosensitive resin is inferior, the heat resistance after curing may be inferior, and the developer is too much in the developer. In view of the whitening phenomenon of the non-exposed area and the occurrence of contact hole and pattern scum after development, the content is 0.0001 to 5 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). The amount is preferably 0.005 to 2 parts by weight.
The solvent e) used in the present invention does not cause flatness of the interlayer insulating film and coating stain, and forms a uniform pattern profile.
前記溶媒はメタノール、エタノールなどのアルコール類；テトラヒドロフランなどのエーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどのグリコールエーテル類；メチルセロソルブアセテート、エチルセロソルブアセテートなどのエチレングリコールアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテルなどのジエチレングリコール類；プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテルなどのプロピレングリコールモノアルキルエーテル類；プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのプロピレングリコールアルキルエーテルアセテート類；プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネート、プロピレングリコールブチルエーテルプロピオネートなどのプロピレングリコールアルキルエーテルアセテート類；トルエン、キシレンなどの芳香族炭化水素類；メチルエチルケトン、シクロヘキサノン、４−ヒドロキシ４−メチル２−ペンタノンなどのケトン類；または酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ２−メチルプロピオン酸メチル、２−ヒドロキシ２−メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、３−ヒドロキシプロピオン酸メチル、３−ヒドロキシプロピオン酸エチル、３−ヒドロキシプロピオン酸プロピル、３−ヒドロキシプロピオン酸ブチル、２−ヒドロキシ３−メチルブタン酸メチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸プロピル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、エトキシ酢酸プロピル、エトキシ酢酸ブチル、プロポキシ酢酸メチル、プロポキシ酢酸エチル、プロポキシ酢酸プロピル、プロポキシ酢酸ブチル、ブトキシ酢酸メチル、ブトキシ酢酸エチル、ブトキシ酢酸プロピル、ブトキシ酢酸ブチル、２−メトキシプロピオン酸メチル、２−メトキシプロピオン酸エチル、２−メトキシプロピオン酸プロピル、２−メトキシプロピオン酸ブチル、２−エトキシプロピオン酸メチル、２−エトキシプロピオン酸エチル、２−エトキシプロピオン酸プロピル、２−エトキシプロピオン酸ブチル、２−ブトキシプロピオン酸メチル、２−ブトキシプロピオン酸エチル、２−ブトキシプロピオ酸プロピル、２−ブトキシプロピオン酸ブチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−メトキシプロピオン酸プロピル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸プロピル、３−エトキシプロピオン酸ブチル、３−プロポキシプロピオン酸メチル、３−プロポキシプロピオン酸エチル、３−プロポキシプロピオン酸プロピル、３−プロポキシプロピオン酸ブチル、３−ブトキシプロピオン酸メチル、３−ブトキシプロピオン酸エチル、３−ブトキシプロピオン酸プロピル、３−ブトキシプロピオン酸ブチルなどのエステル類などを使用することができる。 Examples of the solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol methyl ether Propylene glycol alkyl ether acetates such as teracetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propio , Propylene glycol alkyl ether acetates such as propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, Ethyl acetate, propyl acetate, butyl acetate, 2-hydride Ethyl xylpropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 -Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetic acid Butyl, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxy Methyl diacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl xypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxy Esters such as propyl propionate and butyl 3-butoxypropionate can be used.
特に、前記溶媒は溶解性、各成分との反応性、および塗布膜の形成が容易なグリコールエーテル類、エチレンアルキルエーテルアセテート類、およびジエチレングリコール類からなる群より１種以上選択して使用するのが好ましい。
前記溶媒は全体感光性樹脂組成物の固形分含量が１０〜５０重量％になるように含まれるのが好ましく、前記範囲の固形分を有する組成物は０．１〜０．２μｍのミリポアフィルターなどでろ過した後に使用するのが良い。さらに好ましくは１５〜４０重量％である。前記全体組成物の固形分含量が少なすぎるとコーティング厚さが薄くなり、コーティング平坦性が低下するという問題点があり、５０重量％を超過する場合にはコーティング厚さが厚くなり、コーティング時にコーティング装備に無理を与えることがあるからである。
In particular, the solvent may be used by selecting one or more from the group consisting of glycol ethers, ethylene alkyl ether acetates, and diethylene glycols that are soluble, reactive with each component, and easy to form a coating film. preferable.
The solvent is preferably included so that the total photosensitive resin composition has a solid content of 10 to 50% by weight, and the composition having the solid content in the above range is a 0.1 to 0.2 μm Millipore filter or the like. It is good to use after filtering with. More preferably, it is 15 to 40% by weight. If the solid content of the whole composition is too small, the coating thickness becomes thin and the coating flatness is deteriorated. If it exceeds 50% by weight, the coating thickness becomes thick and the coating is coated at the time of coating. This is because it may impair the equipment.
前記のような成分からなる本発明のネガティブ感光性樹脂組成物は、必要によって、ｆ）光増感剤およびｇ）界面活性剤を追加的に含むことができる。
前記ｆ）の光増感剤は、使用する紫外線波長に適切な感度を有し光開始剤より速い光開始反応によって光開始剤にエネルギーを移転させて光開始剤の光開始反応速度を助ける。
前記光増感剤は、ＤＥＴＸ、ＩＴＸ、ｎ−ブチルアクリドン、または２−エチルヘキシル−ジメチルアミノベンゾエートなどを単独または２種以上混合して使用することができる。
前記光増感剤は、前記ｂ）の光開始剤１００重量部に対して０．００１〜７０重量部で含まれるのが好ましく、その含量が前記範囲内である場合にはネガティブ感光性樹脂組成物の光硬化速度の向上においてさらに良い。
The negative photosensitive resin composition of the present invention comprising the above components can additionally contain f) a photosensitizer and g) a surfactant, if necessary.
The photosensitizer of f) has an appropriate sensitivity to the ultraviolet wavelength to be used, and transfers the energy to the photoinitiator by a photoinitiation reaction faster than the photoinitiator, thereby assisting the photoinitiator reaction rate of the photoinitiator.
As the photosensitizer, DETX, ITX, n-butylacridone, 2-ethylhexyl-dimethylaminobenzoate, or the like can be used alone or in admixture of two or more.
The photosensitizer is preferably contained in an amount of 0.001 to 70 parts by weight with respect to 100 parts by weight of the photoinitiator of b), and when the content is within the above range, the negative photosensitive resin composition. It is even better in improving the photocuring speed of the product.
前記ｇ）の界面活性剤は感光性組成物の塗布性や現像性を向上させる作用を果たす。
前記界面活性剤は、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、Ｆ１７１、Ｆ１７２、Ｆ１７３（商品名：大日本インキ化学工業株式会社）、ＦＣ４３０、ＦＣ４３１（商品名：住友スリーエム株式会社）、またはＫＰ３４１（商品名：信越化学工業株式会社）等を使用することができる。
The surfactant of g) functions to improve the coating property and developability of the photosensitive composition.
The surfactant is polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173 (trade name: Dainippon Ink & Chemicals, Inc.), FC430, FC431 (trade name: Sumitomo 3M Limited). Alternatively, KP341 (trade name: Shin-Etsu Chemical Co., Ltd.) or the like can be used.
前記界面活性剤は、前記ａ）のアクリル系重合体１００重量部に対して０．０００１〜２重量部で含まれるのが好ましく、その含量が前記範囲内である場合にはネガティブ感光性組成物の塗布性や現像性の向上においてさらに良い。
また、本発明のネガティブ感光性樹脂組成物は、必要によって、前記の組成物に熱重合禁止剤、消泡剤などの相溶性のある添加剤を添加することができ、用途によって顔料を添加することができる。例えば、ＴＦＴ型液晶表示素子の画像形成用材料の一つのブラックマトリックス用レジストおよびカラーフィルター用レジストは、前記の組成物に顔料を配合したものであって、この時、顔料はブラックマトリックス用レジストおよびカラーフィルター用レジストの用途によって適切に選択することができ、無機および有機顔料の両方とも使用可能である。
The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a), and when the content is within the above range, the negative photosensitive composition. It is even better in improving the coating property and developing property.
Moreover, the negative photosensitive resin composition of this invention can add compatible additives, such as a thermal-polymerization inhibitor and an antifoamer, to the said composition as needed, and a pigment is added according to a use. be able to. For example, a black matrix resist and a color filter resist, which are image forming materials for TFT-type liquid crystal display elements, are obtained by blending a pigment with the above-described composition. It can be appropriately selected depending on the application of the color filter resist, and both inorganic and organic pigments can be used.
また、本発明は前記のようなネガティブ感光性樹脂の硬化体を含むＴＦＴ型液晶表示素子および前記ネガティブ感光性樹脂組成物を利用したＴＦＴ型液晶表示素子のパターン形成方法を提供する。
本発明のＴＦＴ型液晶表示素子のパターン形成方法はネガティブ感光性樹脂組成物を有機絶縁膜、オーバーコート用レジスト、ブラックマトリックス用レジスト、コラムスペーサ用レジスト、またはカラーフィルター用レジストとして形成してＴＦＴ型液晶表示素子を形成する方法において、前記ネガティブ感光性樹脂組成物を使用することを特徴とする。
具体的に、前記ネガティブ感光性樹脂組成物を利用してＴＦＴ型液晶表示素子のパターンを形成する方法の一例は次の通りである。
In addition, the present invention provides a TFT type liquid crystal display element comprising the cured product of the negative photosensitive resin as described above and a method for forming a pattern of the TFT type liquid crystal display element using the negative photosensitive resin composition.
The pattern forming method of the TFT type liquid crystal display element of the present invention comprises forming a negative photosensitive resin composition as an organic insulating film, an overcoat resist, a black matrix resist, a column spacer resist, or a color filter resist. In the method of forming a liquid crystal display element, the negative photosensitive resin composition is used.
Specifically, an example of a method for forming a pattern of a TFT type liquid crystal display element using the negative photosensitive resin composition is as follows.
まず、本発明の感光性樹脂組成物を、スプレー法、ロールコーター法、回転塗布法などで基板表面に塗布し、プリベークによって溶媒を除去して、塗布膜を形成する。この時、前記プリベークは７０〜１１０℃の温度で１〜１５分間実施するのが好ましい。
その後、予め準備されたパターンによって可視光線、紫外線、遠紫外線、電子線、Ｘ線などを前記形成された塗布膜に照射し、現像液で現像して不必要な部分を除去することによって所定のパターンを形成する。
First, the photosensitive resin composition of the present invention is applied to the substrate surface by a spray method, a roll coater method, a spin coating method, or the like, and the solvent is removed by pre-baking to form a coating film. At this time, the pre-bake is preferably performed at a temperature of 70 to 110 ° C. for 1 to 15 minutes.
Thereafter, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary portions. Form a pattern.
前記現像液は、アルカリ水溶液を使用するのが好ましく、具体的に水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどの無機アルカリ類；ｎ−プロピルアミンなどの１級アミン類；ジエチルアミン、ｎ−プロピルアミンなどの２級アミン類；トリメチルアミン、メチルジエチルアミン、ジメチルエチルアミン、トリエチルアミンなどの３級アミン類；ジメチルエタノールアミン、メチルジエタノールアミン、トリエタノールアミンなどのアルコールアミン類；またはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシドなどの４級アンモニウム塩の水溶液などを使用することができる。この時、前記現像液はアルカリ性化合物を０．１〜１０重量％の濃度に溶解して使用され、メタノール、エタノールなどのような水溶性有機溶媒および界面活性剤を適正量で添加することもできる。 The developer is preferably an alkaline aqueous solution, specifically inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; diethylamine and n-propylamine. Secondary amines such as: trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine and other tertiary amines; dimethylethanolamine, methyldiethanolamine, triethanolamine and other alcohol amines; or tetramethylammonium hydroxide, tetraethylammonium hydroxide An aqueous solution of a quaternary ammonium salt such as can be used. At this time, the developer is used by dissolving an alkaline compound in a concentration of 0.1 to 10% by weight, and a water-soluble organic solvent such as methanol and ethanol and a surfactant can be added in appropriate amounts. .
また、このような現像液で現像した後、超純水で３０〜９０秒間洗浄して不必要な部分を除去し、乾燥してパターンを形成し、パターンをオーブンなどの加熱装置によって１５０〜２５０℃の温度で３０〜９０分間加熱処理して最終パターンを得ることができる。
前記のような本発明によるネガティブ感光性樹脂組成物は、接着力、耐熱性、絶縁性、平坦性、耐化学性、常温保存安定性などの性能に優れ、液晶表示素子の画像形成用材料に好適に使用することができる。特に液晶表示素子の有機絶縁膜形成時の感度、残膜率、ＵＶ透過率が優れているため、層間有機絶縁膜として好適に使用することができる。また、オーバーコート用レジスト樹脂、ブラックマトリックス用レジスト樹脂、コラムスペーサ用レジスト樹脂、またはカラーフィルター用レジスト樹脂として使用することにより、感度および耐熱性、接着力、常温保存安定性を向上させることに適した材料である。
以下、本発明の理解のために好ましい実施例を提示するが、下記の実施例は本発明を例示するものに過ぎず、本発明の範囲が下記の実施例に限定されるわけではない。
Moreover, after developing with such a developing solution, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions, dried to form a pattern, and the pattern is 150 to 250 by a heating device such as an oven. The final pattern can be obtained by heat treatment at a temperature of 30 ° C. for 30 to 90 minutes.
The negative photosensitive resin composition according to the present invention as described above is excellent in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, and room temperature storage stability, and is used as an image forming material for liquid crystal display elements. It can be preferably used. In particular, since the sensitivity, residual film ratio, and UV transmittance at the time of forming an organic insulating film of a liquid crystal display element are excellent, it can be suitably used as an interlayer organic insulating film. Also suitable for improving sensitivity and heat resistance, adhesive strength, and room temperature storage stability by using as overcoat resist resin, black matrix resist resin, column spacer resist resin, or color filter resist resin. Material.
Hereinafter, preferred examples will be presented for the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
実施例１
（アクリル系共重合体製造）
冷却管と攪拌器を備えたフラスコに２，２'−アゾビス（２，４−ジメチルバレロニトリル）１０重量部、プロピレングリコールモノメチルエーテルアセテート４００重量部、メタクリル酸３０重量部、アリルメタクリレート３０重量部、前記式（１）の４−ヒドロキシフェニルマレイミド１０重量部、およびスチレン３０重量部を入れて、窒素置換した後、緩慢に攪拌した。前記反応溶液を５５℃まで昇温させて、２４時間この温度を維持しながらアクリル系共重合体を含む重合体溶液を製造した。
前記のように製造したアクリル系共重合体をヘキサン５，０００重量部に滴下させて析出し、ろ過分離した後、ここにプロピオネート２００重量部を入れ、３０℃まで加熱して、固形分濃度が４５重量％であり、重合体の重量平均分子量は１８，０００である重合体溶液を製造した。この時の重量平均分子量はＧＰＣを用いて測定したポリスチレン換算平均分子量である。
Example 1
(Acrylic copolymer production)
In a flask equipped with a condenser and a stirrer, 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 400 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, 10 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) and 30 parts by weight of styrene were added, and after nitrogen substitution, the mixture was gently stirred. The reaction solution was heated to 55 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 24 hours.
The acrylic copolymer produced as described above was dropped into 5,000 parts by weight of hexane, precipitated, and filtered and separated, and then 200 parts by weight of propionate was added and heated to 30 ° C. A polymer solution having a weight average molecular weight of 18,000 and a polymer weight of 45% was produced. The weight average molecular weight at this time is an average molecular weight in terms of polystyrene measured using GPC.
（ネガティブ感光性樹脂組成物製造）
前記製造したアクリル系共重合体を含む重合体溶液１００重量部、光開始剤としてＩｒｇａｃｕｒｅ ８１９ １５重量部、光増感剤として２−エチルヘキシル−４−ジメチルアミノベンゾエート５重量部およびｎ−ブチルアクリドン５重量部、エチレン性不飽和結合を有する多官能性モノマーとしてジペンタエリスリトールヘキサアクリレート４０重量部およびトリメチロールプロパントリアクリレート１０重量部、シリコン系化合物として２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン１重量部、およびシリコン系界面活性剤としてＦ１７１ ２重量部を混合した。前記混合物に固形分濃度が３５重量％になるようにジエチレングリコールジメチルエーテルを加えて溶解した後、０．２μｍのミリポアフィルターでろ過してネガティブ感光性樹脂組成物コーティング溶液を製造した。
(Manufacture of negative photosensitive resin composition)
100 parts by weight of the polymer solution containing the acrylic copolymer prepared, 15 parts by weight of Irgacure 819 as a photoinitiator, 5 parts by weight of 2-ethylhexyl-4-dimethylaminobenzoate as a photosensitizer, and n-butylacridone 5 parts by weight, 40 parts by weight of dipentaerythritol hexaacrylate and 10 parts by weight of trimethylolpropane triacrylate as a polyfunctional monomer having an ethylenically unsaturated bond, and 2- (3,4-epoxycyclohexyl) ethyltri as a silicon compound 1 part by weight of methoxysilane and 2 parts by weight of F171 as a silicon-based surfactant were mixed. Diethylene glycol dimethyl ether was added to the mixture so as to have a solid concentration of 35% by weight and dissolved, and then filtered through a 0.2 μm Millipore filter to prepare a negative photosensitive resin composition coating solution.
実施例２
前記実施例１のアクリル系共重合体製造において前記式（１）の４−ヒドロキシフェニルマレイミドを２０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン２０重量部を使用し、固形分の濃度が４５重量％であり、重量平均分子量が１７，８００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 2
In production of the acrylic copolymer of Example 1, 20 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene are used. The negative photosensitive resin was prepared in the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,800 was produced. A composition coating solution was prepared.
実施例３
前記実施例１のアクリル系共重合体製造において前記式（１）の４−ヒドロキシフェニルマレイミドを３０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン１０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１８，１００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 3
In the production of the acrylic copolymer of Example 1, 30 parts by weight of 4-hydroxyphenylmaleimide of formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 10 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 18,100 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.
実施例４
前記実施例１のアクリル系共重合体製造において前記式（１）の４−ヒドロキシフェニルマレイミドを４０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１８，２１０であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 4
In production of the acrylic copolymer of Example 1, 40 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) was used, and 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used. The negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that an acrylic copolymer having a concentration of 45% by weight and a weight average molecular weight of 18,210 was produced. Manufactured.
実施例５
前記実施例１のアクリル系共重合体製造において前記式（１）の４−カルボキシフェニルマレイミドを１０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン３０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１７，７００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 5
In production of the acrylic copolymer of Example 1, 10 parts by weight of 4-carboxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 30 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,700 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.
実施例６
前記実施例１のアクリル系共重合体製造において前記式（１）の４−カルボキシフェニルマレイミドを２０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン２０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１７，５００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 6
In production of the acrylic copolymer of Example 1, 20 parts by weight of 4-carboxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,500 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.
実施例７
前記実施例１のアクリル系共重合体製造において前記式（１）の４−カルボキシフェニルマレイミドを３０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン１０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１７，３００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 7
In the production of the acrylic copolymer of Example 1, 30 parts by weight of 4-carboxyphenylmaleimide of formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 10 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,300 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.
実施例８
前記実施例１のアクリル系共重合体製造において前記式（１）の４−カルボキシフェニルマレイミドを４０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１８，１００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Example 8
In the production of the acrylic copolymer of Example 1, 40 parts by weight of 4-carboxyphenylmaleimide of the formula (1) was used, and 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used. The negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that an acrylic copolymer having a concentration of 45% by weight and a weight average molecular weight of 18,100 was produced. Manufactured.
比較例１
前記実施例１のアクリル系共重合体製造においてメタアクリル酸グリシジルを２０重量部で使用し、メタクリル酸３０重量部、アリルメタアクリレート３０重量部、スチレン２０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１７，４００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Comparative Example 1
In the preparation of the acrylic copolymer of Example 1, 20 parts by weight of glycidyl methacrylate was used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene were used. A negative photosensitive resin composition coating solution was produced in the same manner as in Example 1 except that an acrylic copolymer having a weight average molecular weight of 17,400 was produced. did.
比較例２
前記実施例１のアクリル系共重合体製造においてメタアクリル酸グリシジルを４０重量部で使用し、メタクリル酸３０重量部、アリルメタクリレート３０重量部を使用して、固形分の濃度が４５重量％であり、重量平均分子量が１８，１００であるアクリル系共重合体を製造したことを除いては、前記実施例１と同様の方法で、ネガティブ感光性樹脂組成物コーティング溶液を製造した。
Comparative Example 2
In the acrylic copolymer production of Example 1, 40 parts by weight of glycidyl methacrylate was used, 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used, and the solid content was 45% by weight. A negative photosensitive resin composition coating solution was produced in the same manner as in Example 1 except that an acrylic copolymer having a weight average molecular weight of 18,100 was produced.
前記実施例１〜８および比較例１または２で製造されたネガティブ感光性樹脂組成物コーティング溶液を利用して、下記のような方法で物性を評価した。その結果を下記表１に示した。
イ）感度−ガラス基板上にスピンコーターを使用して前記実施例１〜８および比較例１〜２で製造された感光性樹脂組成物溶液を塗布した後、９０℃で２分間ホットプレート上でプリベークして膜を形成した。
前記で得られた膜に所定のパターンマスクを使用して、３６５ｎｍでの強度が１５ｍＷ／ｃｍ２の紫外線を、感度が１０μｍラインアンドスペース１：１ＣＤ基準ドーズ量を１５秒間照射した。この後、テトラメチルアンモニウムヒドロキシド０．３８重量％の水溶液で２３℃で２分間現像し、超純水で１分間洗浄した。
続いて、前記で現像されたパターンに３６５ｎｍでの強度が１５ｍＷ／ｃｍ２の紫外線を３４秒間照射し、オーブンの中で２２０℃で６０分間加熱、硬化してパターン膜を得た。
Using the negative photosensitive resin composition coating solutions prepared in Examples 1 to 8 and Comparative Example 1 or 2, the physical properties were evaluated by the following methods. The results are shown in Table 1 below.
A) Sensitivity—After applying the photosensitive resin composition solutions prepared in Examples 1 to 8 and Comparative Examples 1 and 2 on a glass substrate using a spin coater, the mixture was heated on a hot plate at 90 ° C. for 2 minutes. Pre-baked to form a film.
The film obtained above was irradiated with ultraviolet rays having an intensity of 15 mW / cm 2 at 365 nm and a 10 μm line and space 1: 1 CD reference dose for 15 seconds using a predetermined pattern mask. Thereafter, development was carried out with an aqueous solution of 0.38% by weight of tetramethylammonium hydroxide at 23 ° C. for 2 minutes and washed with ultrapure water for 1 minute.
Subsequently, the pattern developed above was irradiated with ultraviolet rays having an intensity at 365 nm of 15 mW / cm 2 for 34 seconds, and heated and cured in an oven at 220 ° C. for 60 minutes to obtain a pattern film.
ロ）耐熱性−前記イ）の感度測定時形成されたパターン膜の上、下および左、右の幅を測定した。この時、角の変化率がミッドベーク前基準、０〜２０％である場合を○、２０〜４０％である場合を△、４０％を越える場合を×で表示した。 B) Heat resistance—The widths of the upper, lower, left and right sides of the pattern film formed during the sensitivity measurement in the above a) were measured. At this time, the case where the angle change rate was 0 to 20% based on the pre-mid-bake basis was indicated as ◯, the case where it was 20 to 40% as Δ, and the case where it exceeded 40% as ×.
ハ）接着性−前記イ）の感度測定時形成されたパターン膜に手動式ローラーの圧着装置を利用して同一の速度で一回往復させた後、基板の全体面積を１００等分した時の剥離される面積を測定して百分率で表示した。 C) Adhesiveness--When the pattern film formed at the time of sensitivity measurement in the above a) is reciprocated once at the same speed by using a manual roller crimping device, the entire area of the substrate is divided into 100 equal parts. The area to be peeled was measured and displayed as a percentage.
ニ）常温保存安定性−２３℃の４０％湿度を維持するクリーンルームに１日から２週まで１日単位で放置した後、感度（ｍＪ／ｓｑｃｍ）変化をチェックした。この時、２週間の変化率が１０％未満である場合を○、１０〜２０％である場合を△、２０％を越える場合を×で表示した。
表１に示したように、本発明によってフェニルマレイミド系化合物を含んで製造したアクリル系共重合体を使用した実施例１〜８では、感度が１００〜１６０ｍＪ／ｃｍ２と優れており、耐熱性と接着性において非常に良好であり、液晶の残像形成影響が少なく、特に接着性と常温保存安定性とも比較例１〜２と比較して非常に優れていた。従って、ＬＣＤ工程の層間絶縁膜に適用することにおいて、より優れた信頼度を得ることができた。これに反し、比較例１〜２の場合、耐熱性および接着力、常温保存安定性が劣り、層間絶縁膜に適用することが困難である。 As shown in Table 1, in Examples 1 to 8 using an acrylic copolymer produced by including a phenylmaleimide compound according to the present invention, the sensitivity is excellent at 100 to 160 mJ / cm 2, and heat resistance In addition, the adhesiveness was very good, and there was little influence on the afterimage formation of the liquid crystal. In particular, both the adhesiveness and the room temperature storage stability were very excellent as compared with Comparative Examples 1 and 2. Therefore, when applied to the interlayer insulating film in the LCD process, higher reliability can be obtained. On the other hand, in the case of Comparative Examples 1 and 2, heat resistance, adhesive strength, and room temperature storage stability are inferior, and it is difficult to apply to the interlayer insulating film.
以上より、本発明によるネガティブ感光性樹脂組成物を、画像形成用材料の層間絶縁膜として使用する場合、非常に優れた感度、耐熱性、接着性および常温保存安定性を得ることができ、オーバーコート用レジスト樹脂、ブラックマトリックス用レジスト樹脂、コラムスペーサ用レジスト樹脂、カラーフィルター用レジスト樹脂として使用する場合、耐熱性、接着性および常温保存安定性の向上に寄与することを予測することができた。
本発明の記載された具体的な例についてのみ詳しく説明したが、本発明の技術思想範囲内で多様な変形および修正が可能であることは当業者において明白であり、このような変形および修正が添付された特許請求の範囲に属することは当然である。
From the above, when the negative photosensitive resin composition according to the present invention is used as an interlayer insulating film of an image forming material, it is possible to obtain very excellent sensitivity, heat resistance, adhesiveness, and storage stability at room temperature. When used as a resist resin for coating, a resist resin for black matrix, a resist resin for column spacers, or a resist resin for color filters, it could be predicted that it will contribute to the improvement of heat resistance, adhesiveness, and room temperature storage stability. .
Although only specific examples of the present invention have been described in detail, it is obvious to those skilled in the art that various modifications and alterations are possible within the scope of the technical idea of the present invention. Of course, it is within the scope of the appended claims.
Claims (15)
ａ）ｉ）下記の式（１）
（式中、Ｒはヒドロキシ（ＯＨ−）またはカルボキシ（ＣＨ３ＣＯＯ−）基である。）
で表示されるフェニルマレイミド系化合物；
ｉｉ）アリルアクリル系化合物；および
ｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物；
を共重合させて得られたアクリル系共重合体；
ｂ）光開始剤；
ｃ）エチレン性不飽和結合を有する多官能性モノマー；
ｄ）エポキシ基またはアミン基を含むシリコン系化合物；および
ｅ）溶媒
を含むことを特徴とするネガティブ感光性樹脂組成物。 A negative photosensitive resin composition comprising:
a) i) the following formula (1)
(In the formula, R is a hydroxy (OH − ) or carboxy (CH 3 COO − ) group.)
A phenylmaleimide compound represented by:
ii) allyl acrylic compounds; and iii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof;
An acrylic copolymer obtained by copolymerization of
b) a photoinitiator;
c) a polyfunctional monomer having an ethylenically unsaturated bond;
d) a silicon-based compound containing an epoxy group or an amine group; and e) a solvent.
ｉｉ）アリルアクリル系化合物５〜８０重量％；および
ｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物５〜４０重量％；
を共重合させて得られたアクリル系共重合体１００重量部；
ｂ）光開始剤０．００１〜３０重量部；
ｃ）エチレン性不飽和結合を有する多官能性モノマー１０〜１００重量部；
ｄ）エポキシ基またはアミン基を含むシリコン系化合物０．０００１〜５重量部；および
ｅ）溶媒を感光性樹脂組成物内の固形分の含量が１０〜５０重量％になるように含む請求項１に記載のネガティブ感光性樹脂組成物。 a) i) 5 to 80% by weight of a phenylmaleimide compound represented by the formula (1);
ii) 5 to 80% by weight of an allyl acrylic compound; and iii) 5 to 40% by weight of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof;
100 parts by weight of an acrylic copolymer obtained by copolymerizing
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) a silicon compound containing an epoxy group or an amine group in an amount of 0.0001 to 5 parts by weight; and e) a solvent so that the solid content in the photosensitive resin composition is 10 to 50% by weight. The negative photosensitive resin composition as described in 2.
（式中、Ｘは水素またはメチル基である。）
で表示されるアリルメタアクリレートまたはアリルアクリレートである請求項１に記載のネガティブ感光性樹脂組成物： The allyl acrylic compound of a) ii) is represented by the following formula (2):
(In the formula, X is hydrogen or a methyl group.)
The negative photosensitive resin composition according to claim 1, which is allyl methacrylate or allyl acrylate represented by:
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| JP2008020566A (en) * | 2006-07-12 | 2008-01-31 | Jsr Corp | Radiation-sensitive composition for colored layer formation, color filter and color liquid crystal display element |
| WO2010136385A1 (en) * | 2009-05-25 | 2010-12-02 | Basf Se | Crosslinkable dielectrics and methods of preparation and use thereof |
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| US8853820B2 (en) | 2009-05-25 | 2014-10-07 | Basf Se | Crosslinkable dielectrics and methods of preparation and use thereof |
| CN102713754A (en) * | 2009-11-20 | 2012-10-03 | 可隆工业株式会社 | Photosensitive resin composition |
| JP2013534326A (en) * | 2010-08-03 | 2013-09-02 | 東進セミケム株式会社 | Negative photosensitive resin composition |
| CN103052916A (en) * | 2010-08-03 | 2013-04-17 | 株式会社东进世美肯 | Negative photosensitive resin composition |
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| JP2012063626A (en) * | 2010-09-16 | 2012-03-29 | Jsr Corp | Radiation-sensitive resin composition, interlayer insulating film, formation method of interlayer insulating film, and display element |
| EP2689381A1 (en) * | 2011-03-24 | 2014-01-29 | Bilcare Technologies Singapore Pte. Ltd. | Inherent disorder reader adapted to be connected to a mobile device |
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| JP2013105136A (en) * | 2011-11-16 | 2013-05-30 | Jsr Corp | Array substrate, liquid crystal display and manufacturing method of array substrate |
| CN113448164A (en) * | 2020-03-26 | 2021-09-28 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200745753A (en) | 2007-12-16 |
| TWI422971B (en) | 2014-01-11 |
| KR20070100042A (en) | 2007-10-10 |
| KR101313538B1 (en) | 2013-10-01 |
| CN101051186A (en) | 2007-10-10 |
| JP5194225B2 (en) | 2013-05-08 |
| CN101051186B (en) | 2012-06-27 |
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