JP5016828B2 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP5016828B2 JP5016828B2 JP2006051781A JP2006051781A JP5016828B2 JP 5016828 B2 JP5016828 B2 JP 5016828B2 JP 2006051781 A JP2006051781 A JP 2006051781A JP 2006051781 A JP2006051781 A JP 2006051781A JP 5016828 B2 JP5016828 B2 JP 5016828B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- photosensitive resin
- weight
- methacrylate
- acrylate
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 53
- -1 2-methyl Cyclohexyl Chemical group 0.000 claims description 61
- 229920006243 acrylic copolymer Polymers 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 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
- 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
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical compound COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 230000007261 regionalization Effects 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
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-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
- 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
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 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
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims 1
- 230000036211 photosensitivity Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 description 29
- 239000011229 interlayer Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- CPEXFJVZFNYXGU-UHFFFAOYSA-N 2,4,6-trihydroxybenzophenone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=CC=C1 CPEXFJVZFNYXGU-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SSLASPHAKUVIRG-UHFFFAOYSA-N (2-methylcyclohexyl) prop-2-enoate Chemical compound CC1CCCCC1OC(=O)C=C SSLASPHAKUVIRG-UHFFFAOYSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- HWZREQONUGCFIT-UHFFFAOYSA-N (3-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC=CC(C(=O)C=2C(=C(O)C(O)=CC=2)O)=C1 HWZREQONUGCFIT-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ODDDCGGSPAPBOS-UHFFFAOYSA-N 1-ethoxypropan-2-yl propanoate Chemical compound CCOCC(C)OC(=O)CC ODDDCGGSPAPBOS-UHFFFAOYSA-N 0.000 description 1
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VAHNPAMCADTGIO-UHFFFAOYSA-N 2-methoxyethyl propanoate Chemical compound CCC(=O)OCCOC VAHNPAMCADTGIO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NBLFJUWXERDUEN-UHFFFAOYSA-N 4-[(2,3,4-trihydroxyphenyl)methyl]benzene-1,2,3-triol Chemical compound OC1=C(O)C(O)=CC=C1CC1=CC=C(O)C(O)=C1O NBLFJUWXERDUEN-UHFFFAOYSA-N 0.000 description 1
- FNFYXIMJKWENNK-UHFFFAOYSA-N 4-[(2,4-dihydroxyphenyl)methyl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1CC1=CC=C(O)C=C1O FNFYXIMJKWENNK-UHFFFAOYSA-N 0.000 description 1
- YNICUQBUXHBYCH-UHFFFAOYSA-N 4-[(4-hydroxy-2,5-dimethylphenyl)-(2-hydroxyphenyl)methyl]-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(C(C=2C(=CC=CC=2)O)C=2C(=CC(O)=C(C)C=2)C)=C1C YNICUQBUXHBYCH-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- NYIWTDSCYULDTJ-UHFFFAOYSA-N 4-[2-(2,3,4-trihydroxyphenyl)propan-2-yl]benzene-1,2,3-triol Chemical compound C=1C=C(O)C(O)=C(O)C=1C(C)(C)C1=CC=C(O)C(O)=C1O NYIWTDSCYULDTJ-UHFFFAOYSA-N 0.000 description 1
- CJBUQOXMWGPKGP-UHFFFAOYSA-N 4-[3,3-bis(4-hydroxy-2,5-dimethylphenyl)-1-phenylpropyl]-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(C(CC(C=2C(=CC(O)=C(C)C=2)C)C=2C(=CC(O)=C(C)C=2)C)C=2C=CC=CC=2)=C1C CJBUQOXMWGPKGP-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- QRUOTIJTSNETKW-UHFFFAOYSA-N 4-ethoxybutan-1-ol Chemical compound CCOCCCCO QRUOTIJTSNETKW-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical group O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ZAUPOHZNANGEHI-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)C(C)(C1=CC=C(C=C1)O)C1(CC=CC=C1)O Chemical compound OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)C(C)(C1=CC=C(C=C1)O)C1(CC=CC=C1)O ZAUPOHZNANGEHI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000003519 bicyclobutyls Chemical group 0.000 description 1
- 150000005350 bicyclononyls Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical group C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- CAKADOHUDJINFO-UHFFFAOYSA-N cyclopenten-1-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CCCC1 CAKADOHUDJINFO-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 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 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
- 125000001624 naphthyl group Chemical group 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
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- JGUCHBHVJZMDEK-UHFFFAOYSA-N propanoic acid;1-propoxypropane Chemical compound CCC(O)=O.CCCOCCC JGUCHBHVJZMDEK-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-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
- 238000007348 radical reaction Methods 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C11/00—Details of pavings
- E01C11/22—Gutters; Kerbs ; Surface drainage of streets, roads or like traffic areas
- E01C11/221—Kerbs or like edging members, e.g. flush kerbs, shoulder retaining means ; Joint members, connecting or load-transfer means specially for kerbs
- E01C11/222—Raised kerbs, e.g. for sidewalks ; Integrated or portable means for facilitating ascent or descent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
- E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
- E01F9/535—Kerbs or road edgings specially adapted for alerting road users
- E01F9/541—Kerbs
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Liquid Crystal (AREA)
Description
本発明は感光性樹脂組成物に関する。 The present invention relates to a 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を使用している。
このような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、透過度が優れた感光性材料が使用されている。
最近、液晶ディスプレイ（ＬＣＤ）製造工程に適用される層間絶縁膜は、透過度を高めることによってバックライト効率を高めることができ、消費電力を低めることができるフォトレジストが要求されている。
In the TFT type liquid crystal display element and the integrated circuit element, an interlayer insulating film is used to insulate between wirings arranged between the layers.
When such an interlayer insulating film is formed, a photosensitive material having a low transmittance and an excellent transmittance is used to obtain an interlayer insulating film having a required pattern shape.
Recently, an interlayer insulating film applied to a liquid crystal display (LCD) manufacturing process is required to have a photoresist that can increase backlight efficiency by increasing transmittance and reduce power consumption.
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、前記バインダーの硬化用モノマーとしてはエポキシ系アクリレートが主に使用されてきた。しかし、従来のエポキシ系アクリレートの場合、層間絶縁膜の透過率、貯蔵安定性などの問題があり、これによってＬＣＤ製造工程上で不良を招くという問題点があった。
したがって、ＬＣＤ製造工程に適用される層間絶縁膜の透過率および貯蔵安定性を向上させるための研究がさらに必要であるのが実情である。
A conventional interlayer insulating film is composed of components such as PAC, a binder, and a solvent, and an epoxy acrylate has been mainly used as a curing monomer for the binder. However, the conventional epoxy acrylate has problems such as the transmittance of the interlayer insulating film and storage stability, which causes defects in the LCD manufacturing process.
Therefore, the actual situation is that further research is required to improve the transmittance and storage stability of the interlayer insulating film applied to the LCD manufacturing process.
このような従来の技術の問題点を解決するために、本発明は感度、絶縁性、耐化学性などの色々な性能に優れているだけでなく、特に透過度および貯蔵安定性を顕著に向上させてＬＣＤ製造工程の層間絶縁膜を形成するのに適し、膜の厚さが厚いＬＣＤ製造工程の層間絶縁膜に使用するのに適した感光性樹脂組成物、前記感光性樹脂の硬化体を含むＬＣＤ基板、および前記感光性樹脂組成物を利用したＬＣＤ基板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、現像後優れた平坦性を有し、フォト工程後ＬＣＤ製造工程に適用される層間絶縁膜にパターンの不良を招かない感光性樹脂組成物を提供することにある。
In order to solve such problems of the prior art, the present invention not only excels in various performances such as sensitivity, insulation and chemical resistance, but also significantly improves the permeability and storage stability. A photosensitive resin composition suitable for forming an interlayer insulating film in an LCD manufacturing process and suitable for use in an interlayer insulating film in an LCD manufacturing process having a thick film, and a cured body of the photosensitive resin. It is an object of the present invention to provide an LCD substrate including the same, and a method for forming a pattern of the LCD substrate using the photosensitive resin composition.
Another object of the present invention is to provide a photosensitive resin composition which has excellent flatness after development and does not cause a pattern defect in an interlayer insulating film applied to an LCD manufacturing process after a photo process.
前記目的を達成するために、本発明の感光性樹脂組成物は、
ａ）ｉ）不飽和カルボン酸、不飽和カルボン酸無水物又はこれらの混合物５〜５０重量％、
ｉｉ）下記の式（４）、（６）及び（７）からなる群から選択される少なくとも１種のエポキシ基含有不飽和化合物５〜７０重量％、及び
ｉｉｉ）オレフィン系不飽和化合物１０〜７０重量％を共重合させた後、未反応単量体を除去して得られたアクリル系共重合体１００重量部；
ｂ）１，２−キノンジアジド化合物５〜５０重量部；及び
ｃ）溶媒を感光性樹脂組成物内の固形分の含量が１０〜５０重量％になるように含むことを特徴とする。
In order to achieve the object, the photosensitive resin composition of the present invention comprises:
a) i) 5-50% by weight of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixtures thereof,
ii) at least one epoxy group-containing unsaturated compound selected from the group consisting of the following formulas (4), (6) and (7) : 5 to 70% by weight, and iii) olefinically unsaturated compounds 10 to 70 100% by weight of an acrylic copolymer obtained by removing unreacted monomers after copolymerization by weight%;
b) 1,2-quinonediazide compound 5-50 parts by weight; and c) a solvent is contained so that the solid content in the photosensitive resin composition is 10-50% by weight.
（式中、Ｒ1は水素原子またはメチル基であり、
Ｒ2は結合手又は炭素数１〜１０の炭化水素基、
Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7は、それぞれ同一又は異なって、炭素数１〜１０の炭化水素基を示す）。
(Wherein R 1 is a hydrogen atom or a methyl group,
R 2 is a bond or a hydrocarbon group having 1 to 10 carbon atoms,
R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms).
また、本発明は前記感光性樹脂組成物の硬化体を含むＬＣＤを提供する。
さらに、本発明は前記感光性樹脂組成物を利用したＬＣＤ基板のパターン形成方法を提供する。
The present invention also provides an LCD comprising a cured product of the photosensitive resin composition.
Furthermore, the present invention provides a method for forming a pattern on an LCD substrate using the photosensitive resin composition.
本発明による感光性樹脂組成物は、感度、絶縁性、耐化学性などの色々な性能が優れると共に、現像後の平坦性が優れており、特に透過度および貯蔵安定性を顕著に向上させてＬＣＤ製造工程の層間絶縁膜として使用することにおいて信頼度を得ることができる。
また、この感光性樹脂組成物を利用した本発明のＬＣＤ基板のパターン形成方法は、フォト工程後ＬＣＤ製造工程に適用される層間絶縁膜の優れたパターンを形成することができる。
The photosensitive resin composition according to the present invention is excellent in various performances such as sensitivity, insulation, chemical resistance and the like, and is excellent in flatness after development, and particularly significantly improves the transmittance and storage stability. Reliability can be obtained by using as an interlayer insulating film in the LCD manufacturing process.
Moreover, the pattern formation method of the LCD substrate of this invention using this photosensitive resin composition can form the outstanding pattern of the interlayer insulation film applied to the LCD manufacturing process after a photo process.
以下、本発明を詳細に説明する。
本発明の感光性樹脂組成物は、ａ）ｉ）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、ｉｉ）前記化学式（１）〜（８）からなる群から選択される１種以上のエポキシ基含有不飽和化合物、およびｉｉｉ）オレフィン系不飽和化合物を共重合させた後、未反応単量体を除去して得られたアクリル系共重合体、ｂ）１，２−キノンジアジド化合物、およびｃ）溶媒を含むことを特徴とする。
Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention is a) i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof; ii) 1 selected from the group consisting of the chemical formulas (1) to (8) One or more epoxy group-containing unsaturated compounds, and iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound and then removing unreacted monomers, b) 1,2-quinonediazide A compound, and c) 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、現像する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果たす。
前記ａ）のアクリル系共重合体は、ｉ）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、ｉｉ）前記化学式（１）〜（８）からなる群から選択される１種以上のエポキシ基含有不飽和化合物、およびｉｉｉ）オレフィン系不飽和化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合成した後、沈澱および濾過、真空乾燥工程によって未反応単量体を除去して得ることができる。
The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which no scum is generated during development.
The acrylic copolymer of a) is i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof; ii) one selected from the group consisting of the chemical formulas (1) to (8) The above epoxy group-containing unsaturated compound and iii) an olefinic unsaturated compound as a monomer, synthesized by radical reaction in the presence of a solvent and a polymerization initiator, and then unreacted by precipitation, filtration, and vacuum drying steps It can be obtained by removing the monomer.
本発明に使用される前記ａ）ｉ）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である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。
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、アルカリ水溶液に対する溶解性を適当に調整することができるという観点から、全体総単量体に対して５〜５０重量％で含まれるのが好ましく、さらに好ましくは１０〜４０重量％で含まれる。
The a) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or a mixture thereof used in the present invention is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citraconic acid, Unsaturated dicarboxylic acids such as methaconic acid and itaconic acid; or anhydrides of these unsaturated dicarboxylic acids can be used singly or in combination of two or more. Particularly, acrylic acid, methacrylic acid, or maleic anhydride can be used. It is more preferable to use copolymerization reactivity and solubility in an alkaline aqueous solution as a developer.
The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof is contained in an amount of 5 to 50% by weight based on the total total monomers from the viewpoint that the solubility in an alkaline aqueous solution can be appropriately adjusted. Preferably, it is contained at 10 to 40% by weight.
本発明に使用される前記ａ）ｉｉ）の前記化学式（１）〜（８）からなる群から選択される１種以上のエポキシ基含有不飽和化合物は、パターンの耐熱性、後工程での信頼性、共重合体の保存安定性などを向上させる作用を果たす。
式（１）〜（８）における、炭化水素基としては、炭素数が１〜１０が挙げられ、好ましくは１〜８、さらに１〜６、１〜４が好ましい。炭化水素基として、例えば、直鎖又は分岐の非環式炭化水素、単環式炭化水素、縮合多環式炭化水素、架橋環式炭化水素等が挙げられる。なかでも、直鎖又は分岐の非環式炭化水素、単環式炭化水素が好ましい。直鎖又は分岐の非環式炭化水素としては、アルキル、アルキレン等、つまり、メチル、エチル、プロピル、イソプロピル、n、sec、tert-ブチル、イソ、ネオ、tert-ペンチル、イソヘキシル等、ビニル、２−プロペニル、１−メチルルビニル、エチニル、２−プロピニル、２−ブテニル等が挙げられる。特に、メチル、エチル、プロピル、イソプロピル、n、sec、tert-ブチルが好ましい。単環式炭化水素及び縮合多環式炭化水素としては、シクロプロピル、シクロヘキシル、アリール、つまり、フェニル、トリル、キシル、ナフチル、ベンジル、トシル、インデニル等が挙げられる。架橋環式炭化水素としては、ビシクロブチル、ビシクロオクチル、ビシクロノニル等が挙げられる。
The one or more epoxy group-containing unsaturated compounds selected from the group consisting of the chemical formulas (1) to (8) of the a) ii) used in the present invention are the heat resistance of the pattern and the reliability in the subsequent process. And improves the storage stability of the copolymer.
As a hydrocarbon group in Formula (1)-(8), C1-C10 is mentioned, Preferably it is 1-8, Furthermore, 1-6, 1-4 are preferable. Examples of the hydrocarbon group include linear or branched acyclic hydrocarbons, monocyclic hydrocarbons, condensed polycyclic hydrocarbons, bridged cyclic hydrocarbons, and the like. Of these, linear or branched acyclic hydrocarbons and monocyclic hydrocarbons are preferred. Examples of linear or branched acyclic hydrocarbon include alkyl, alkylene and the like, that is, methyl, ethyl, propyl, isopropyl, n, sec, tert-butyl, iso, neo, tert-pentyl, isohexyl, vinyl, 2 -Propenyl, 1-methyllvinyl, ethynyl, 2-propynyl, 2-butenyl and the like. In particular, methyl, ethyl, propyl, isopropyl, n, sec, and tert-butyl are preferable. Monocyclic hydrocarbons and fused polycyclic hydrocarbons include cyclopropyl, cyclohexyl, aryl, ie, phenyl, tolyl, xyl, naphthyl, benzyl, tosyl, indenyl and the like. Examples of the bridged cyclic hydrocarbon include bicyclobutyl, bicyclooctyl, bicyclononyl and the like.
特に、Ｒ2における炭化水素基は、上述した炭化水素基の２価のものが挙げられ、なかでも、２価の直鎖又は分岐の非環式炭化水素が好ましく、具体的には、メチレン、エチレン、プロピレン等が好ましい。
化学式（１）〜（８）の化合物においては、特に、Ｒ2が結合手のものが好ましい。また、Ｒ3〜Ｒ7が、水素原子又は１〜４のアルキル基であることが好ましく、Ｒ2及びＲ3〜Ｒ7がこれらを組み合わせた化合物が好ましい。
In particular, the hydrocarbon group in R 2 includes the above-described divalent hydrocarbon groups, and among them, a divalent linear or branched acyclic hydrocarbon is preferable, specifically methylene, Ethylene, propylene and the like are preferable.
In the compounds of the chemical formulas (1) to (8), those in which R 2 is a bond are particularly preferable. Further, R 3 to R 7 is preferably a hydrogen atom or 1 to 4 of alkyl groups, compound R 2 and R 3 to R 7 is a combination of these are preferred.
前記化学式（１）〜（８）からなる群から選択される１種以上のエポキシ基含有不飽和化合物は単独または２種以上混合して使用することができる。その含量は、得られるパターンの耐熱性および後工程での信頼性を向上させ、共重合体の保存安定性を向上させるという観点から、全体総単量体に対して５〜７０重量％で含まれるのが好ましく、さらに好ましくは１０〜６０重量％で含まれる。 One or more epoxy group-containing unsaturated compounds selected from the group consisting of the chemical formulas (1) to (8) can be used alone or in combination. The content is 5 to 70% by weight based on the total amount of total monomers from the viewpoint of improving the heat resistance of the resulting pattern and reliability in the subsequent process and improving the storage stability of the copolymer. Preferably, it is contained at 10 to 60% by weight.
本発明に使用される前記ａ）ｉｉｉ）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σ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。 The a) iii) olefinically unsaturated compounds used in the present invention are 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, di-σ cyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate , Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Xylethyl acrylate, isobornyl 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, and the like, 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、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であるアルカリ水溶液に対する溶解性の面でさらに好ましい。
前記オレフィン系不飽和化合物は、アクリル系共重合体の耐熱性を向上させ、アクリル系共重合体が現像液であるアルカリ水溶液に対する適当な溶解性を確保するという観点から、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％で含まれる。このような単量体を溶液重合するために使用される溶媒は、メタノール、テトラヒドロキシフラン、トルエン、またはジオキサンなどを使用することができる。
In particular, the olefinically unsaturated compound is more preferably styrene, methyl methacrylate, or p-methoxystyrene in terms of copolymerization reactivity and solubility in an aqueous alkali solution that is a developer.
The olefinically unsaturated compound improves the heat resistance of the acrylic copolymer, and from the viewpoint of ensuring appropriate solubility in an alkaline aqueous solution that is the acrylic copolymer, The content is preferably 10 to 70% by weight, more preferably 20 to 50% by weight. As a solvent used for solution polymerization of such a monomer, methanol, tetrahydroxyfuran, toluene, dioxane or the like can be used.
このような単量体を溶液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使用することができる。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が挙げられる。 As the polymerization initiator used for solution polymerization of such a monomer, a radical polymerization initiator can be used. Specifically, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1, Examples thereof include 1-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2′-azobisisobutyrate, and the like.
こ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、沈澱および濾過、真空乾燥工程によって未反応単量体を除去して得られた前記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、現像性、残膜率などを向上させ、パターン現像、耐熱性などを確保するとともに、感度を維持してパターン現像を向上させるという観点から、５，０００〜３０，０００であるのが好ましく、さらに好ましくは５，０００〜２０，０００である。 The acrylic copolymer of a) obtained by radically reacting such a monomer in the presence of a solvent and a polymerization initiator, and removing unreacted monomer by precipitation, filtration, and vacuum drying, From the viewpoint of improving the developability, residual film ratio, etc., ensuring pattern development, heat resistance, etc., while maintaining the sensitivity and improving the pattern development, the polystyrene-reduced weight average molecular weight (Mw) is 5,000- It is preferably 30,000, more preferably 5,000 to 20,000.
本発明に使用される前記ｂ）の１，２−キノンジアジド化合物は感光性化合物として使用される。
前記１，２−キノンジアジド化合物は、１，２−キノンジアジド４−スルホン酸エステル、１，２−キノンジアジド５−スルホン酸エステル、または１，２−キノンジアジド６−スルホン酸エステルなどを使用することができる。
The 1,2-quinonediazide compound b) used in the present invention is used as a photosensitive compound.
As the 1,2-quinonediazide compound, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, or the like can be used.
このようなキノンジアジド化合物は、ナフトキノンジアジドスルホン酸ハロゲン化合物とフェノール化合物を弱塩基下で反応させて製造することができる。
前記フェノール化合物としては、２，３，４−トリヒドロキシベンゾフェノン、２，４，６−トリヒドロキシベンゾフェノン、２，２'−テトラヒドロキシベンゾフェノン、４，４'−テトラヒドロキシベンゾフェノン、２，３，４，３'−テトラヒドロキシベンゾフェノン、２，３，４，４'−テトラヒドロキシベンゾフェノン、２，３，４，２'−テトラヒドロキシ４'−メチルベンゾフェノン、２，３，４，４'−テトラヒドロキシ３'−メトキシベンゾフェノン、２，３，４，２'−ペンタヒドロキシベンゾフェノン、２，３，４，６'−ペンタヒドロキシベンゾフェノン、２，４，６、３'−ヘキサヒドロキシベンゾフェノン、２，４，６、４'−ヘキサヒドロキシベンゾフェノン、２，４，６、５'−ヘキサヒドロキシベンゾフェノン、３，４，５，３'−ヘキサヒドロキシベンゾフェノン、３，４，５，４'−ヘキサヒドロキシベンゾフェノン、３，４，５，５'−ヘキサヒドロキシベンゾフェノン、ビス（２，４−ジヒドロキシフェニル）メタン、ビス（ｐ−ヒドロキシフェニル）メタン、トリ（ｐ−ヒドロキシフェニル）メタン、１，１，１−トリ（ｐ−ヒドロキシフェニル）エタン、ビス（２，３，４−トリヒドロキシフェニル）メタン、２，２−ビス（２，３，４−トリヒドロキシフェニル）プロパン、１，１，３−トリス（２，５−ジメチル４−ヒドロキシフェニル）−３−フェニルプロパン、４，４'−［１−［４−［１−［４−ヒドロキシフェニル］−１−メチルエチル］フェニル］エチリデン］ビスフェノール、またはビス（２，５−ジメチル４−ヒドロキシフェニル）−２−ヒドロキシフェニルメタ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。
Such a quinonediazide compound can be produced by reacting a naphthoquinonediazidesulfonic acid halogen compound and a phenol compound under a weak base.
Examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2′-tetrahydroxybenzophenone, 4,4′-tetrahydroxybenzophenone, 2,3,4, 3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy3 ′ -Methoxybenzophenone, 2,3,4,2'-pentahydroxybenzophenone, 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4 '-Hexahydroxybenzophenone, 2,4,6,5'-Hexahydroxybenzophenone, 3,4,5 , 3′-hexahydroxybenzophenone, 3,4,5,4′-hexahydroxybenzophenone, 3,4,5,5′-hexahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxy) Phenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2, 3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4 -Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, or bis (2,5-dimethyl-4-hydroxyphenyl) -2 -Hydroxyphenylmethane etc. can be used and the said compound can be used individually or in mixture of 2 or more types.
このようなフェノール化合物とナフトキノンジアジドスルホン酸ハロゲン化合物でキノンジアジド化合物を合成する時、エステル化度は、残膜率を確保し、パターン上に発生するスカムを防止するという観点から、
５０〜９０％が好ましい。前記１，２−キノンジアジド化合物は、露光部と非露光部の溶解度差を確保してパターン形成を向上させるとともに、短時間の間に光を照射する時、未反応１，２−キノンジアジド化合物の残存を低下させ、現像液であるアルカリ水溶液に対する溶解度を適当に調整して現像を容易にするという観点から、ａ）のアクリル系共重合体１００重量部に対して５〜５０重量部で含まれるのが好ましく、さらに好ましくは１０〜４０重量部で含まれる。本発明に使用される前記ｃ）の溶媒は、層間絶縁膜の平坦性とコーティング斑が発生しないようにして、均一なパターンプロファイルを形成するようにする。
When synthesizing a quinonediazide compound with such a phenolic compound and a naphthoquinonediazide sulfonic acid halogen compound, the degree of esterification ensures a residual film ratio and prevents scum generated on the pattern,
50 to 90% is preferable. The 1,2-quinonediazide compound improves the pattern formation by ensuring the solubility difference between the exposed part and the non-exposed part, and the remaining unreacted 1,2-quinonediazide compound when irradiated with light for a short time. From the viewpoint of facilitating development by appropriately adjusting the solubility in an alkaline aqueous solution that is a developer, 5 to 50 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a) And more preferably 10 to 40 parts by weight. The solvent of c) used in the present invention forms a uniform pattern profile by preventing the flatness of the interlayer insulating film and coating unevenness.
前記溶媒は、メタノール、エタノール、ベンジルアルコール、ヘキシルアルコールなどのアルコール類；エチレングリコールメチルエーテルアセテート、エチレングリコールエチルエーテル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；エチレングリコールメチルエーテルプロピオネート、エチレングリコールエチルエーテルプロピオネートなどのエチレングリコールアルキルエーテルプロピオネート類；エチレングリコールメチルエーテル、エチレングリコールエチルエーテルなどのエチレングリコールモノアルキルエーテル類；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、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコール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などのプロピレングリコールアルキルエーテルプロピオネート類；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；ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテルなどのジプロピレングリコールアルキルエーテル類；ブチレングリコールモノメチルエーテル、ブチレングリコールモノエチルエーテルなどのブチレングリコールモノメチルエーテル類；またはジブチレングリコールジメチルエーテル、ジブチレングリコールジエチルエーテルなどのジブチレングリコールアルキルエー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, ethanol, benzyl alcohol and hexyl alcohol; ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; ethylene glycol methyl ether propionate and ethylene glycol ethyl ether. Ethylene glycol alkyl ether propionates such as propionate; ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. The Tylene glycol alkyl ethers; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol Propylene glycol alkyl ether propionates such as propyl ether propionate; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; dipropylene glycol dimethyl Dipropylene glycol alkyl ethers such as ether and dipropylene glycol diethyl ether; butylene glycol monomethyl ethers such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; or dibutylene glycol such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether Alkyl ethers and the like can be used.
前記溶媒は、コーティング厚さを適当な薄さにし、コーティング平坦性を確保するとともに、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を防止するという観点から、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、さらに好ましくは１５〜４０重量％になるように含ませる。 From the viewpoints of reducing the coating thickness to an appropriate thickness, ensuring the coating flatness, and preventing the coating equipment from being unduly applied during coating, the solvent has a solid content of 10%. It is preferably contained so as to be ˜50% by weight, and more preferably contained so as to be 15˜40% by weight.
このような成分からなる本発明の感光性樹脂組成物は、必要によって、ｄ）エポキシ樹脂、ｅ）接着剤、ｆ）アクリル化合物、またはｇ）界面活性剤などをさらに含むことができる。 The photosensitive resin composition of the present invention comprising such components can further contain d) an epoxy resin, e) an adhesive, f) an acrylic compound, or g) a surfactant, if necessary.
前記ｄ）のエポキシ樹脂は、感光性樹脂組成物から得られるパターンの耐熱性、感度などを向上させる作用を果たす。
前記エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、環状脂肪族エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、複素環式エポキシ樹脂、またはａ）のアクリル系共重合体とは異なるグリシジルメタクリレートを（共）重合した樹脂などを使用することができ、特にビスフェノールＡ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、またはグリシジルエステル型エポキシ樹脂を使用するのが好ましい。
The epoxy resin d) functions to improve the heat resistance and sensitivity of the pattern obtained from the photosensitive resin composition.
The epoxy resin may be a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic epoxy resin, or a) A resin obtained by (co) polymerizing glycidyl methacrylate, which is different from the acrylic copolymer, can be used, and in particular, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a glycidyl ester type epoxy resin is used. preferable.
前記エポキシ樹脂は、アクリル系共重合体に対する相溶性を確保して十分な塗布性能を得るという観点から、前記ａ）のアクリル系共重合体１００重量部に対して０．１〜３０重量部で含まれるのが好ましい。
また、前記ｅ）の接着剤は基板との接着性を向上させる作用を果たし、前記ａ）のアクリル系共重合体１００重量部に対して０．１〜２０重量部で含まれるのが好ましい。
The epoxy resin is used in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a) from the viewpoint of ensuring compatibility with the acrylic copolymer and obtaining sufficient coating performance. Preferably included.
The adhesive e) functions to improve adhesion to the substrate, and is preferably contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a).
前記接着剤は、カルボキシル基、メタクリル基、イソシアネート基、またはエポキシ基などのような反応性置換基を有するシランカップリング剤などを使用することができる。具体的に、γ−メタアクリルオキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ−イソシアネートプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、またはβ−（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などを使用することができる。 As the adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group can be used. Specifically, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane and the like can be used.
また、前記ｆ）のアクリル化合物は、感光性樹脂組成物から得られるパターンの透過率、耐熱性、感度などを向上させる作用を果たす。
前記アクリル化合物は下記の化学式（９）で示される化合物であるのが好ましい。
In addition, the acrylic compound of f) functions to improve the transmittance, heat resistance, sensitivity, and the like of the pattern obtained from the photosensitive resin composition.
The acrylic compound is preferably a compound represented by the following chemical formula (9).
（式中、Ｒは水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、または炭素数１〜５のアルカノイル基であり、
１＜ａ＜６であり、ａ＋ｂ＝６である。）
アルキル基としては、メチル、エチル、プロピル、ｎ−ブチル、ｔ−ブチル、ペンチル等が挙げられる。アルコキシ基としては、メトキシ、エトキシ、プロポキシ、ｎ−ブトキシ、ｔ−ブトキシ、ペントキシ等が挙げられる。アルカノイル基としては、ホルミル、アセチル、プロピオニル、ブチリル、イソブチリル、バレリル、イソバレリル、ピバロイル等が挙げられる。
(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkanoyl group having 1 to 5 carbon atoms,
1 <a <6 and a + b = 6. )
Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl, pentyl and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, t-butoxy, pentoxy and the like. Examples of the alkanoyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl and the like.
前記アクリル化合物は、前記アクリル系共重合体１００重量部に対して０．１〜３０重量部で含まれるのが好ましく、さらに好ましくは０．１〜１５重量部で含まれる。その含量が前記範囲内である場合にはパターンの透過率、耐熱性、感度などの向上においてさらに良い。
また、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。
The acrylic compound is preferably contained in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight, with respect to 100 parts by weight of the acrylic copolymer. When the content is within the above range, the pattern transmittance, heat resistance, sensitivity and the like are further improved.
In addition, the surfactant of g) functions to improve the applicability and developability of the photosensitive composition.
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）などを使用することができる。 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。 The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight with respect to 100 parts by weight of the acrylic polymer of a), and when the content is within the above range, It is even better in improving coatability and developability.
このような成分からなる本発明の感光性樹脂組成物の固形分濃度は１０〜５０重量％であるのが好ましく、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濾過した後に使用するのが良い。 The solid content concentration of the photosensitive resin composition of the present invention comprising such components is preferably 10 to 50% by weight, and the composition having a solid content in the above range is a 0.1 to 0.2 μm Millipore filter. It is good to use it after filtering with etc.
また、本発明は前記感光性樹脂組成物の硬化体を含むＬＣＤ基板および前記感光性樹脂組成物を利用したＬＣＤ基板のパターン形成方法を提供する。
本発明のＬＣＤ基板のパターン形成方法は、感光性樹脂組成物を有機絶縁膜で形成してＬＣＤ基板のパターンを形成する方法において、前記感光性樹脂組成物を使用することを特徴とする。
The present invention also provides an LCD substrate comprising a cured product of the photosensitive resin composition and a method for forming a pattern on the LCD substrate using the photosensitive resin composition.
The LCD substrate pattern forming method of the present invention is characterized in that the photosensitive resin composition is used in a method for forming a pattern of an LCD substrate by forming a photosensitive resin composition with an organic insulating film.
具体的な例として、前記感光性樹脂組成物を用いてＬＣＤ基板のパターンを形成する方法は次の通りである。
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。
As a specific example, a method for forming an LCD substrate pattern using the photosensitive resin composition is as follows.
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.
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。 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ことが良く、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；エチルアミン、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％の濃度で溶解して使用され、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 ethylamine and n-propylamine; diethylamine, n- Secondary amines such as propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; or tetramethylammonium hydroxide, tetraethylammonium An aqueous solution of a quaternary ammonium salt such as hydroxide can be used. At this time, the developer is used by dissolving an alkaline compound at a concentration of 0.1 to 10% by weight, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added. .
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、前記形成されたパターンに紫外線などの光を照射した後、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。 In addition, after developing with such a developer, the substrate is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions, dried, and a pattern is formed. Then, the pattern can be heat-treated at a temperature of 150 to 250 ° C. for 30 to 90 minutes with a heating device such as an oven to obtain a final pattern.
本発明による感光性樹脂組成物は感度、絶縁性、耐化学性などのいろいろな性能が優れると共に、現像後平坦性が優れており、特に透過度及び貯蔵安定性を顕著に向上させてＬＣＤ製造工程の層間絶縁膜に使用することにおいて信頼度を得ることができるだけでなく、同時に、前記感光性樹脂組成物を利用した本発明のＬＣＤ基板のパターン形成方法はフォト工程後ＬＣＤ製造工程に適用される層間絶縁膜の優れたパターンを形成することができるという長所がある。 The photosensitive resin composition according to the present invention has various performances such as sensitivity, insulation, and chemical resistance, and also has excellent post-development flatness, particularly LCD production with significantly improved transparency and storage stability. In addition to being able to obtain reliability in the use of an interlayer insulating film in the process, the pattern forming method of the LCD substrate of the present invention using the photosensitive resin composition is applied to the LCD manufacturing process after the photo process. There is an advantage that an excellent pattern of the interlayer insulating film can be formed.
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。 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.
参考例１
（アクリル系共重合体製造）
冷却管と撹拌機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、テトラヒドロキシフラン５００重量部、メタクリル酸２５重量部、下記の化学式（１ａ）
Reference 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), 500 parts by weight of tetrahydroxyfuran, 25 parts by weight of methacrylic acid, the following chemical formula (1a)
のメチルグリシジルメタクリレート２５重量部、スチレン１５重量部、ブチルメタクリレート１５重量部、およびジシクロペンテニルメタクリレート２０重量部を入れ、窒素置換した後、緩慢に攪拌した。前記反応溶液を６２℃まで昇温させて、５時間の間に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。 25 parts by weight of methyl glycidyl methacrylate, 15 parts by weight of styrene, 15 parts by weight of butyl methacrylate, and 20 parts by weight of dicyclopentenyl methacrylate were substituted with nitrogen, and then gently stirred. The reaction solution was heated to 62 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 5 hours.
前記アクリル系共重合体を含む重合体溶液の未反応単量体を除去するために、エーテルを貧溶媒１，０００重量部に前記重合体溶液１００重量部を沈殿させた。その後、メッシュを利用したフィルタリング工程によって未反応物が溶解された貧溶媒を除去した。その後、３０℃以下で真空乾燥して、フィルタリング工程後にも残っている未反応単量体が含まれている溶媒を完全に除去して、重量平均分子量が１０，０００であるアクリル系共重合体を製造した。この時、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。 In order to remove the unreacted monomer in the polymer solution containing the acrylic copolymer, 100 parts by weight of the polymer solution was precipitated in 1,000 parts by weight of ether as a poor solvent. Then, the poor solvent in which the unreacted substance was dissolved was removed by a filtering process using a mesh. Thereafter, the acrylic copolymer having a weight average molecular weight of 10,000 is vacuum-dried at 30 ° C. or lower to completely remove the solvent containing unreacted monomers remaining after the filtering step. Manufactured. At this time, the weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC.
（１，２−キノンジアジド化合物製造）
４，４'−［１−［４−［１−［４−ヒドロキシフェニル］−１−メチルエチル］フェニル］エチリデン］ビスフェノール１モルと、１，２−ナフトキノンジアジド−５−スルホン酸［クロライド］２モルとを縮合反応させて、４，４'−［１−［４−［１−［４−ヒドロキシフェニル］−１−メチルエチル］フェニル］エチリデン］ビスフェノール１，２−ナフトキノンジアジド−５−スルホン酸エステルを製造した。
(Production of 1,2-quinonediazide compound)
1,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1 mole and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] 2 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid Esters were prepared.
（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１００重量部と前記製造した４，４'−［１−［４−［１−［４−ヒドロキシフェニル］−１−メチルエチル］フェニル］エチリデン］ビスフェノール１，２−ナフトキノンジアジド−５−スルホン酸エステル２５重量部とを混合した。その後、前記混合物の固形分含量が２０重量部になるようにジプロピレングリコールジメチルエーテルで溶解させた後、０．２μｍのミリポアピルトで濾過して感光性樹脂組成物を製造した。
(Photosensitive resin composition production)
100 parts by weight of the prepared acrylic copolymer and the prepared 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2- 25 parts by weight of naphthoquinonediazide-5-sulfonic acid ester was mixed. Thereafter, the mixture was dissolved in dipropylene glycol dimethyl ether so that the solid content of the mixture was 20 parts by weight, and then filtered through a 0.2 μm Millipore pill to produce a photosensitive resin composition.
参考例２
参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（２ａ）
Reference example 2
In Reference Example 1 , instead of the methyl glycidyl methacrylate represented by the chemical formula 1a as a monomer during the polymerization of the acrylic copolymer, the following chemical formula (2a)
のエポキシ系メタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
参考例３
参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（３ａ）
Reference example 3
In Reference Example 1, instead of methyl glycidyl methacrylate represented by the chemical formula 1a as a monomer at the time of polymerization of the acrylic copolymer, the following chemical formula (3a)
のエポキシ系メタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
実施例４
参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（４ａ）
Example 4
In Reference Example 1, instead of the methyl glycidyl methacrylate represented by the chemical formula 1a as a monomer during the polymerization of the acrylic copolymer, the following chemical formula (4a)
のエポキシ系メタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
参考例５
参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（５ａ）
Reference Example 5
In Reference Example 1, instead of methyl glycidyl methacrylate represented by the chemical formula 1a as a monomer at the time of polymerization of the acrylic copolymer, the following chemical formula (5a)
のエポキシ系メタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
実施例６
前記参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（６ａ）
Example 6
In Reference Example 1, instead of methyl glycidyl methacrylate represented by Chemical Formula 1a as a monomer during polymerization of the acrylic copolymer, the following chemical formula (6a)
のエポキシ系メタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
実施例７
前記参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（７ａ）
Example 7
In Reference Example 1, instead of methyl glycidyl methacrylate represented by Chemical Formula 1a as a monomer during the polymerization of the acrylic copolymer, the following chemical formula (7a)
のエポキシ系メタクリレートを使用したことを除いては前記参考例１と同様な方法で実施して感光性樹脂組成物を製造した。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy-based methacrylate was used.
参考例８
前記参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（８ａ）
のエポキシ系ビニル化合物を使用したことを除いては前記参考例１と同様な方法で実施して感光性樹脂組成物を製造した。
比較例１
参考例１において、アクリル系共重合体重合時に単量体として前記化学式（１ａ）のメチルグリシジルメタクリレートの代わりに、グリシジルメタクリレートを使用したことを除いては参考例１と同様な方法で実施して感光性樹脂組成物を製造した。
Reference Example 8
In Reference Example 1, instead of methyl glycidyl methacrylate represented by Chemical Formula 1a as a monomer during polymerization of the acrylic copolymer, the following chemical formula (8a)
A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy vinyl compound was used.
Comparative Example 1
In Reference Example 1, the same procedure as in Reference Example 1 was carried out except that glycidyl methacrylate was used in place of methyl glycidyl methacrylate represented by the chemical formula (1a) as a monomer during the polymerization of the acrylic copolymer. A photosensitive resin composition was produced.
比較例２
前記参考例１において、アクリル系共重合体重合時に単量体として前記化学式１ａのメチルグリシジルメタクリレートの代わりに、下記の化学式（１０）
Comparative Example 2
In Reference Example 1, instead of methyl glycidyl methacrylate represented by the chemical formula 1a as a monomer during the polymerization of the acrylic copolymer, the following chemical formula (10)
のエポキシ系ビニル化合物を使用したことを除いては前記参考例１と同様な方法で実施して感光性樹脂組成物を製造した。前記各例で製造された感光性樹脂組成物を利用して下記のような方法で物性を評価した後、その結果を下記表１に示す。 A photosensitive resin composition was produced in the same manner as in Reference Example 1 except that the epoxy vinyl compound was used. The physical properties were evaluated by the following methods using the photosensitive resin compositions produced in the above examples , and the results are shown in Table 1 below.
イ）現像後平坦度−ガラス（ｇｌａｓｓ）基板上にスピンコーターを用いて前記実施例１〜８および比較例１〜２で製造した感光性樹脂組成物をそれぞれ塗布した後、９０℃で２分間ホットプレート上でプリペークして、厚さが３．０μｍである膜を形成した。その後、前記形成された膜の現像後の平坦度（ｕｎｉｆｏｒｍｉｔｙ）を測定するためにエリプソメータ（Ｅｌｉｐｓｏｍｅｔｅｒ）を利用した。この時、全体基板基準に平坦度が９５％を越える場合を○、９０〜９５％である場合を△、９０％未満である場合を×で示した。 B) Flatness after development-After applying the photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2 on a glass substrate using a spin coater, respectively, at 90 ° C. for 2 minutes. A film having a thickness of 3.0 μm was formed by pre-pacing on a hot plate. Thereafter, an ellipsometer was used to measure the uniformity of the formed film after development. At this time, the case where the flatness exceeds 95% with respect to the entire substrate is indicated by ◯, the case where it is 90 to 95% is indicated by Δ, and the case where it is less than 90% is indicated by ×.
ロ）感度−前記イ）で形成した膜に所定のパターンマスク（ｐａｔｔｅｒｎ ｍａｓｋ）を用いて、４３５ｎｍでの強度が２０ｍＷ／ｃｍ2である紫外線を１０μｍラインアンドスペース（Ｌｉｎｅ ＆ Ｓｐａｃｅ）１：１ＣＤ基準ドース（Ｄｏｓｅ）量を照射した後、テトラメチルアンモニウムヒドロキシド２．３８重量％の水溶液で２３℃で１分間現像した後、超純水で１分間洗浄した。その後、前記現像されたパターンに４３５ｎｍでの強度が２０ｍＷ／ｃｍ2である紫外線を５００ｍＪ／ｃｍ2で照射し、オーブンの中で２３０℃で６０分間加熱して硬化してパターン膜を得た。 B) Sensitivity-Using a predetermined pattern mask on the film formed in the above a), ultraviolet light having an intensity at 435 nm of 20 mW / cm 2 is 10 μm line and space (Line & Space) 1: 1 CD standard. After irradiating a dose amount, it was developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 23 ° C. for 1 minute, and then washed with ultrapure water for 1 minute. Thereafter, the developed pattern was irradiated with 500 mJ / cm 2 of ultraviolet light having an intensity at 435 nm of 20 mW / cm 2 and heated in an oven at 230 ° C. for 60 minutes to obtain a pattern film.
ハ）解像度−前記ロ）の感度測定時に形成されたパターン膜の最小大きさで測定した。
ニ）耐熱性−前記ロ）の感度測定時に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×で示した。
C) Resolution—Measured with the minimum size of the pattern film formed during the sensitivity measurement in b).
D) Heat resistance—The widths of the upper, lower, left and right sides of the pattern film formed during the sensitivity measurement in the above b) were measured. At this time, the case where the change rate of the angle is 0 to 20% based on the pre-bake basis is indicated by ○, the case where it is 20 to 40% is indicated by Δ, and the case where it exceeds 40% is indicated by ×.
ホ）透過度−分光光度計を用いて前記ロ）の感度測定時に形成されたパターン膜の４００ｎｍの透過率を測定した。
へ）常温貯蔵安定性−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×で示した。
E) Transmittance—The transmittance at 400 nm of the pattern film formed at the time of measuring the sensitivity in b) was measured using a spectrophotometer.
F) Storage stability at normal temperature After leaving in a clean room maintaining 40% humidity at 23 ° C. for 1 day to 2 weeks, the sensitivity (mJ / sqcm) change was checked. At this time, the case where the rate of change for two weeks was less than 10% was indicated by ◯, the case where it was 10-20% was indicated by Δ, and the case where it exceeded 20% was indicated by ×.
上記表１から、本発明によって実施例４、６及び７で製造した感光性樹脂組成物は現像後平坦度が優れており、特に感光性樹脂組成物を製造することにより透過度と貯蔵安定性が全て比較例１〜２と比較して非常に優れていて、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の場合には透過度が不良であり、貯蔵安定性が良くなくて層間絶縁膜に適用することに困難がある。 From Table 1 above, the photosensitive resin compositions produced in Examples 4, 6 and 7 according to the present invention have excellent post-development flatness, and in particular, by producing the photosensitive resin composition, permeability and storage stability. All were very superior to those of Comparative Examples 1 and 2, and superior reliability could be obtained when applied to the interlayer insulating film in the LCD process. On the other hand, in the case of Comparative Examples 1 and 2, the transmittance is poor, the storage stability is not good, and it is difficult to apply to the interlayer insulating film.
Claims (9)
ｉｉ）下記の式（４）、（６）及び（７）からなる群から選択される少なくとも１種のエポキシ基含有不飽和化合物５〜７０重量％、及び
ｉｉｉ）オレフィン系不飽和化合物１０〜７０重量％を共重合させた後、未反応単量体を除去して得られたアクリル系共重合体１００重量部；
ｂ）１，２−キノンジアジド化合物５〜５０重量部；及び
ｃ）溶媒を感光性樹脂組成物内の固形分の含量が１０〜５０重量％になるように含むことを特徴とする感光性樹脂組成物。
（式中、Ｒ1は水素原子またはメチル基であり、
Ｒ2は結合手又は２価の炭素数１〜１０の炭化水素基、
Ｒ3、Ｒ4、Ｒ5、Ｒ6およびＲ7は、それぞれ同一又は異なって、水素原子、炭素数１〜１０の炭化水素基を示す） a) i) 5-50% by weight of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixtures thereof,
ii) at least one epoxy group-containing unsaturated compound selected from the group consisting of the following formulas (4), (6) and (7) : 5 to 70% by weight, and iii) olefinically unsaturated compounds 10 to 70 100% by weight of an acrylic copolymer obtained by removing unreacted monomers after copolymerization by weight%;
a photosensitive resin composition comprising 5 to 50 parts by weight of a 1,2-quinonediazide compound; and c) a solvent so that the solid content in the photosensitive resin composition is 10 to 50% by weight. object.
(Wherein R 1 is a hydrogen atom or a methyl group,
R 2 is a bond or a divalent hydrocarbon group having 1 to 10 carbon atoms,
R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)
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| JP5014873B2 (en) * | 2007-05-11 | 2012-08-29 | 群栄化学工業株式会社 | Polymer resin and radiation-sensitive resin composition using the same |
| KR101373541B1 (en) * | 2007-06-01 | 2014-03-12 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
| JP4935565B2 (en) * | 2007-08-01 | 2012-05-23 | 住友化学株式会社 | Photosensitive resin composition |
| JP5075691B2 (en) * | 2008-03-14 | 2012-11-21 | 株式会社ダイセル | Light and / or thermosetting copolymer, curable resin composition, and cured product |
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| JP5774054B2 (en) * | 2012-05-31 | 2015-09-02 | エルジー・ケム・リミテッド | Novel polymer and coloring composition containing the same |
| JP6218393B2 (en) * | 2013-02-28 | 2017-10-25 | 東京応化工業株式会社 | Photosensitive resin composition for interlayer insulation film |
| KR102235159B1 (en) * | 2014-04-15 | 2021-04-05 | 롬엔드하스전자재료코리아유한회사 | Photosensitive resin composition, and insulating film and electric device using same |
| KR102380577B1 (en) * | 2016-05-27 | 2022-03-29 | 스미또모 가가꾸 가부시끼가이샤 | Resin composition and cured film |
| JP7190294B2 (en) * | 2018-09-10 | 2022-12-15 | 株式会社ダイセル | Copolymer, curable resin composition containing the copolymer, and cured product thereof |
| KR102655952B1 (en) * | 2018-10-31 | 2024-04-09 | 주식회사 동진쎄미켐 | Positive photosensitive resin composition |
| JP7483417B2 (en) * | 2020-03-09 | 2024-05-15 | 株式会社ダイセル | Photosensitive resin composition and cured product thereof |
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