JP2009175651A - Positive photosensitive resin composition, cured layer, protecting layer, insulating layer and semiconductor device and display therewith - Google Patents
Positive photosensitive resin composition, cured layer, protecting layer, insulating layer and semiconductor device and display therewith Download PDFInfo
- Publication number
- JP2009175651A JP2009175651A JP2008094632A JP2008094632A JP2009175651A JP 2009175651 A JP2009175651 A JP 2009175651A JP 2008094632 A JP2008094632 A JP 2008094632A JP 2008094632 A JP2008094632 A JP 2008094632A JP 2009175651 A JP2009175651 A JP 2009175651A
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- Prior art keywords
- group
- positive photosensitive
- general formula
- resin composition
- photosensitive resin
- 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 abstract description 50
- 239000004065 semiconductor Substances 0.000 title claims description 20
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000000962 organic group Chemical group 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 9
- 125000004423 acyloxy group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000005011 alkyl ether group Chemical group 0.000 claims description 5
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- -1 diazonaphthoquinone compound Chemical class 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 43
- 150000003961 organosilicon compounds Chemical class 0.000 description 14
- 235000012431 wafers Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- 0 Cc1cc(C)c(C(c2ccc(*)cc2)c2c(C)cc(C)cc2*)c(*)c1 Chemical compound Cc1cc(C)c(C(c2ccc(*)cc2)c2c(C)cc(C)cc2*)c(*)c1 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BMVJLODMRABQES-UHFFFAOYSA-N 2-(aminomethyl)-3-trimethoxysilylpropan-1-ol Chemical compound OCC(C[Si](OC)(OC)OC)CN BMVJLODMRABQES-UHFFFAOYSA-N 0.000 description 2
- PMJIKKNFJBDSHO-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxy-3-methylpentane-1,5-diol Chemical compound NCCC[Si](OCC)(OCC)OC(C)(CCO)CCO PMJIKKNFJBDSHO-UHFFFAOYSA-N 0.000 description 2
- LPDSHSYDVSVSDV-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypentane-1,5-diol Chemical compound NCCC[Si](OC)(OC)OC(CCO)CCO LPDSHSYDVSVSDV-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- UBGIFSWRDUBQIC-UHFFFAOYSA-N perylene-2,3,8,9-tetracarboxylic acid Chemical compound C1=CC2=C(C(O)=O)C(C(=O)O)=CC(C=3C4=C5C=C(C(C(O)=O)=C4C=CC=3)C(O)=O)=C2C5=C1 UBGIFSWRDUBQIC-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 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
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- XZGAWWYLROUDTH-UHFFFAOYSA-N 1,1,1-triethoxy-3-(3,3,3-triethoxypropyltetrasulfanyl)propane Chemical compound CCOC(OCC)(OCC)CCSSSSCCC(OCC)(OCC)OCC XZGAWWYLROUDTH-UHFFFAOYSA-N 0.000 description 1
- RILDMGJCBFBPGH-UHFFFAOYSA-N 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(Cl)=C2C(Cl)=C(C(O)=O)C(C(=O)O)=C(Cl)C2=C1Cl RILDMGJCBFBPGH-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- AZJINWLRLJLXND-UHFFFAOYSA-N 2,5-dioxofuran-3-carbonitrile Chemical compound O=C1OC(=O)C(C#N)=C1 AZJINWLRLJLXND-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- BZTWCPPIAGYIHH-UHFFFAOYSA-N 2-(aminomethyl)-3-triethoxysilylpropan-1-ol Chemical compound OCC(C[Si](OCC)(OCC)OCC)CN BZTWCPPIAGYIHH-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- TUXAJHDLJHMOQB-UHFFFAOYSA-N 2-diazonio-4-sulfonaphthalen-1-olate Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC([N+]#N)=C([O-])C2=C1 TUXAJHDLJHMOQB-UHFFFAOYSA-N 0.000 description 1
- VJKZIQFVKMUTID-UHFFFAOYSA-N 2-diazonio-5-sulfonaphthalen-1-olate Chemical compound N#[N+]C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1[O-] VJKZIQFVKMUTID-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- SMDGQEQWSSYZKX-UHFFFAOYSA-N 3-(2,3-dicarboxyphenoxy)phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O SMDGQEQWSSYZKX-UHFFFAOYSA-N 0.000 description 1
- FMXFZZAJHRLHGP-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)sulfonylphthalic acid Chemical compound OC(=O)C1=CC=CC(S(=O)(=O)C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O FMXFZZAJHRLHGP-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- VMYGHBXIDJKWOX-UHFFFAOYSA-N 3-[(3-aminophenyl)-dimethoxysilyl]oxypentane-1,5-diol Chemical compound OCCC(CCO)O[Si](OC)(OC)C1=CC=CC(N)=C1 VMYGHBXIDJKWOX-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- VGQSAGBJSFBWQU-UHFFFAOYSA-N 3-[[(3-aminophenyl)-diethoxysilyl]oxymethyl]pentane-1,5-diol Chemical compound OCCC(CCO)CO[Si](OCC)(OCC)C1=CC=CC(N)=C1 VGQSAGBJSFBWQU-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Polyamides (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
本発明は、ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜およびそれを用いた半導体装置、表示体装置に関する。 The present invention relates to a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device using the same, and a display device.
従来、半導体装置である表面保護膜、層間絶縁膜には、耐熱性に優れ、かつ卓越した電気特性及び機械特性等を有したポリイミド樹脂が用いられてきた。しかし、最近では高極性のイミド環由来のカルボニル基が無いことから耐湿信頼性が良いとされるポリベンゾオキサゾール樹脂が使われ始めており、樹脂自身に感光性を付与することにより、レリーフパターン形成工程の一部の簡略化を可能とする感光性樹脂組成物が開発されている。
現在では、安全性の面からの更なる改良によりアルカリ水溶液で現像が可能であるポリベンゾオキサゾール前駆体と感光剤であるジアゾキノン化合物により構成されるポジ型感光性樹脂組成物が開発されている（特許文献１参照）。ここで、ポジ型感光性樹脂組成物のレリーフパターンの作製を現像メカニズムより説明する。ウェハ上の塗膜に、ステッパー等の露光装置でマスクの上から化学線を照射（露光）することにより、露光された部分（以下露光部）と露光されていない部分（以下未露光部）が出来る。この未露光部中に存在するジアゾキノン化合物はアルカリ水溶液に不溶であり、また樹脂と相互作用することで更にアルカリ水溶液に対し耐性を持つようになる。一方、露光部に存在していたジアゾキノン化合物は化学線の作用によって化学変化を起こし、アルカリ水溶液に可溶となり、樹脂の溶解を促進させる。この露光部と未露光部との溶解性の差を利用し、露光部を溶解除去することにより未露光部のみのレリーフパターンの作製が可能となる。
Conventionally, a polyimide resin having excellent heat resistance and excellent electrical characteristics and mechanical characteristics has been used for a surface protective film and an interlayer insulating film which are semiconductor devices. Recently, however, polybenzoxazole resin, which is considered to have good moisture resistance reliability since there is no carbonyl group derived from a highly polar imide ring, has begun to be used. By providing photosensitivity to the resin itself, a relief pattern forming process A photosensitive resin composition that can simplify a part of the above has been developed.
At present, a positive photosensitive resin composition composed of a polybenzoxazole precursor that can be developed with an alkaline aqueous solution and a diazoquinone compound that is a photosensitizer has been developed by further improvement in terms of safety ( Patent Document 1). Here, the production of the relief pattern of the positive photosensitive resin composition will be described from the development mechanism. By exposing (exposing) actinic radiation to the coating film on the wafer from above the mask with an exposure device such as a stepper, there are exposed portions (hereinafter exposed portions) and unexposed portions (hereinafter unexposed portions). I can do it. The diazoquinone compound present in the unexposed area is insoluble in the alkaline aqueous solution, and further has resistance to the alkaline aqueous solution by interacting with the resin. On the other hand, the diazoquinone compound present in the exposed area undergoes a chemical change by the action of actinic radiation, becomes soluble in an alkaline aqueous solution, and promotes dissolution of the resin. By utilizing this difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a relief pattern of only the unexposed portion can be produced.
ところが、特許文献１で開示されている感光性樹脂組成物の硬化膜は、シリコンウエハー等の基板との密着性が悪く、温湿度処理後に剥離したりする問題がある場合があった。 However, the cured film of the photosensitive resin composition disclosed in Patent Document 1 has a problem of poor adhesion to a substrate such as a silicon wafer and may be peeled off after the temperature and humidity treatment.
本発明は上記事情にかんがみてなされたものであり、その目的とするところは温湿度処理後のシリコンウエハー等の基板との密着性に優れたポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜およびそれを用いた半導体装置、表示体装置を提供するものである。 The present invention has been made in view of the above circumstances, and the object thereof is a positive photosensitive resin composition, a cured film, and a protective film excellent in adhesion to a substrate such as a silicon wafer after temperature and humidity treatment. An insulating film, a semiconductor device using the insulating film, and a display device are provided.
その目的とするところは、引っ張り伸度に優れたポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜およびそれを用いた半導体装置、表示体装置を提供するものである。 The object is to provide a positive photosensitive resin composition excellent in tensile elongation, a cured film, a protective film, an insulating film, a semiconductor device using the same, and a display device.
このような目的は、下記［１］〜［１１］に記載の本発明により達成される。
［１］アルカリ可溶性樹脂（Ａ）と、感光性ジアゾキノン化合物（Ｂ）と、一般式（１）で示されるケイ素化合物（Ｃ−１）を含むことを特徴とするポジ型感光性樹脂組成物。
［２］前記アルカリ可溶性樹脂（Ａ）が一般式（２）で示される繰り返し単位を有するポリアミド系樹脂を含むものである、［１］に記載のポジ型感光性樹脂組成物。
−Ｏ−Ｒ7、−ＣＯＯ−Ｒ7のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ7は炭素数１〜１５の有機基である。ここで、Ｒ5が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ5として水酸基がない場合は、Ｒ6は少なくとも１つはカルボキシル基でなければならない。また、Ｒ6としてカルボキシル
基がない場合、Ｒ5は少なくとも１つは水酸基でなければならない。）
［３］前記一般式（２）で示される繰り返し単位を有するポリアミド系樹脂のＸが、下記式（３）からなる群より選択される１種以上を含み、かつ、Ｙが下記式（４）からなる群より選択される1種以上を含む、［２］に記載のポジ型感光性樹脂組成物。
（ＣＨ3）−、−Ｃ（ＣＨ3）2−、−Ｏ−、−Ｓ−、−ＳＯ2−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ3）2−、又は単結合である。Ｒ8は、アルキル基、アルコキシ基、アシルオ
キシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｓ＝１〜３の整数である。）
、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｖ＝０〜４の整数である。）
［４］前記一般式（２）で示されるケイ素化合物（Ｃ−１）のｉが０である、［１］ないし［３］のいずれかに記載のポジ型感光性組成物。
［５］前記一般式（２）で示されるケイ素化合物（Ｃ−１）のＲ1がメチル基またはエチ
ル基である、［１］ないし［４］のいずれかに記載のポジ型感光性組成物。
［６］前記一般式（２）で示されるケイ素化合物（Ｃ−１）のＲ4がメチレン基またはエ
チレン基である、［１］ないし［５］のいずれかに記載のポジ型感光性組成物。
［７］前記アルカリ可溶性樹脂（Ａ）１００重量部に対して、一般式（１）で示されるケイ素化合物（Ｃ−１）を０．１〜２０重量部含むものである、［１］ないし［６］のいずれかに記載のポジ型感光性樹脂組成物。
［８］［１］ないし［７］のいずれかに記載のポジ型感光性樹脂組成物の硬化物で構成されていることを特徴とする硬化膜。
［９］［８］に記載の硬化膜で構成されていることを特徴とする保護膜。
［１０］［８］に記載の硬化膜で構成されていることを特徴とする絶縁膜。
［１１］［８］に記載の硬化膜を有していることを特徴とする半導体装置。
［１２］［８］に記載の硬化膜を有していることを特徴とする表示体装置。
Such an object is achieved by the present invention described in the following [1] to [11].
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive diazoquinone compound (B), and a silicon compound (C-1) represented by the general formula (1).
[2] The positive photosensitive resin composition according to [1], wherein the alkali-soluble resin (A) includes a polyamide-based resin having a repeating unit represented by the general formula (2).
It is either —O—R 7 or —COO—R 7 , which may be the same or different. m is an integer of 0 to 8, and n is an integer of 0 to 8. R 7 is an organic group having 1 to 15 carbon atoms. Here, when there are a plurality of R 5 s , they may be different or the same. When R 5 has no hydroxyl group, at least one R 6 must be a carboxyl group. In addition, when there is no carboxyl group as R 6 , at least one R 5 must be a hydroxyl group. )
[3] X of the polyamide-based resin having the repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (3), and Y represents the following formula (4) The positive photosensitive resin composition according to [2], comprising one or more selected from the group consisting of:
(CH 3 ) —, —C (CH 3 ) 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, or a single bond. . R 8 is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer of s = 1-3. )
[4] The positive photosensitive composition according to any one of [1] to [3], wherein i of the silicon compound (C-1) represented by the general formula (2) is 0.
[5] The positive photosensitive composition according to any one of [1] to [4], wherein R 1 of the silicon compound (C-1) represented by the general formula (2) is a methyl group or an ethyl group. .
[6] The positive photosensitive composition according to any one of [1] to [5], wherein R 4 of the silicon compound (C-1) represented by the general formula (2) is a methylene group or an ethylene group. .
[7] From [1] to [6], comprising 0.1 to 20 parts by weight of the silicon compound (C-1) represented by the general formula (1) with respect to 100 parts by weight of the alkali-soluble resin (A). The positive photosensitive resin composition according to any one of the above.
[8] A cured film comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [7].
[9] A protective film comprising the cured film according to [8].
[10] An insulating film comprising the cured film according to [8].
[11] A semiconductor device comprising the cured film according to [8].
[12] A display device having the cured film according to [8].
本発明によれば、温湿度処理後のシリコンウエハー等の基板との密着性に優れたポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜およびそれを用いた半導体装置、表示体装置を提供することができる。 According to the present invention, a positive photosensitive resin composition, a cured film, a protective film, an insulating film excellent in adhesion to a substrate such as a silicon wafer after temperature and humidity treatment, and a semiconductor device and a display device using the same Can be provided.
本発明によれば、引っ張り伸度に優れたポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜およびそれを用いた半導体装置、表示体装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition excellent in tensile elongation, a cured film, a protective film, an insulating film, a semiconductor device using the same, and a display body apparatus can be provided.
以下、本発明のポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、表示体装置の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the positive photosensitive resin composition, cured film, protective film, insulating film, semiconductor device, and display device of the present invention will be described in detail.
本発明は、アルカリ可溶樹脂（Ａ）と、感光性ジアゾキノン化合物（Ｂ）と、下記一般式（１）で示されるケイ素化合物（Ｃ−１）を含むことを特徴とするポジ型感光性樹脂組成物に関するものである。 The present invention includes a positive photosensitive resin comprising an alkali-soluble resin (A), a photosensitive diazoquinone compound (B), and a silicon compound (C-1) represented by the following general formula (1): It relates to a composition.
本発明は、一般式（２）で示されるアルカリ可溶性樹脂（Ａ）を含むことを特徴とするポジ型感光性樹脂組成物であって、Ｘが、下記式（３）からなる群より選択される１種以上を含み、かつ、Ｙが下記式（４）からなる群より選択される1種以上を含むことを特徴
とするものである。
（ＣＨ3）−、−Ｃ（ＣＨ3）2−、−Ｏ−、−Ｓ−、−ＳＯ2−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ3）2−、又は単結合である。Ｒ8は、アルキル基、アルコキシ基、アシルオ
キシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｓ＝１〜３の整数である。）
(CH 3 ) —, —C (CH 3 ) 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, or a single bond. . R 8 is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer of s = 1-3. )
本発明は、前記アルカリ可溶性樹脂（Ａ）１００重量部に対して、ケイ素化合物（Ｃ−１）を０．１〜２０重量部含むことを特徴とするポジ型感光性樹脂組成物に関するものである。 The present invention relates to a positive photosensitive resin composition comprising 0.1 to 20 parts by weight of a silicon compound (C-1) with respect to 100 parts by weight of the alkali-soluble resin (A). .
また、本発明の硬化膜は、上記記載の感光性樹脂組成物の硬化物で構成されていることを特徴とする。また、本発明の保護膜、絶縁膜は、上記記載の硬化膜で構成されていることを特徴とする。更に半導体装置、表示体装置は、上記記載の硬化膜を有していることを特徴とする。
以下に本発明のポジ型感光性樹脂組成物の各成分について詳細に説明する。なお下記は例示であり、本発明は何ら下記に限定されるものではない。
Moreover, the cured film of this invention is comprised with the hardened | cured material of the said photosensitive resin composition, It is characterized by the above-mentioned. In addition, the protective film and the insulating film of the present invention are formed of the cured film described above. Further, the semiconductor device and the display device have the cured film described above.
Hereinafter, each component of the positive photosensitive resin composition of the present invention will be described in detail. The following is an example, and the present invention is not limited to the following.
本発明に係るアルカリ可溶性樹脂（Ａ）としては、特に制限されるものではないが、例えば、クレゾール型ノボラック樹脂、ヒドロキシスチレン樹脂、メタクリル酸樹脂、メタクリル酸エステル樹脂等のアクリル系樹脂、水酸基、カルボキシル基等を含む環状オレフィン系樹脂、ポリアミド系樹脂等が挙げられる。これらの中でも耐熱性に優れ、機械特性が良いという点からポリアミド系樹脂が好ましく、具体的にはポリベンゾオキサゾール構造およびポリイミド構造の少なくとも一方を有し、かつ主鎖または側鎖に水酸基、カルボキシル基、エーテル基またはエステル基を有する樹脂、ポリベンゾオキサゾール前駆体構造を有する樹脂、ポリイミド前駆体構造を有する樹脂、ポリアミド酸エステル構造を有する樹脂等が挙げられる。このようなポリアミド系樹脂としては、例えば下記一般式（２）で示されるポリアミド系樹脂を挙げることができる。 The alkali-soluble resin (A) according to the present invention is not particularly limited, and examples thereof include acrylic resins such as cresol type novolac resin, hydroxystyrene resin, methacrylic acid resin, and methacrylic ester resin, hydroxyl group, and carboxyl. Examples thereof include cyclic olefin resins containing a group and polyamide resins. Among these, polyamide resins are preferred from the viewpoint of excellent heat resistance and good mechanical properties. Specifically, they have at least one of a polybenzoxazole structure and a polyimide structure, and have hydroxyl groups or carboxyl groups in the main chain or side chain. , A resin having an ether group or an ester group, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, a resin having a polyamic acid ester structure, and the like. As such a polyamide-type resin, the polyamide-type resin shown, for example by following General formula (2) can be mentioned.
−Ｏ−Ｒ7、−ＣＯＯ−Ｒ7のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ7は炭素数１〜１５の有機基である。ここで、Ｒ5が複数
ある場合は、それぞれ異なっていても同じでもよい。Ｒ5として水酸基がない場合は、Ｒ6は少なくとも１つはカルボキシル基でなければならない。また、Ｒ6としてカルボキシル
基がない場合、Ｒ5は少なくとも１つは水酸基でなければならない。）
It is either —O—R 7 or —COO—R 7 , which may be the same or different. m is an integer of 0 to 8, and n is an integer of 0 to 8. R 7 is an organic group having 1 to 15 carbon atoms. Here, when there are a plurality of R 5 s , they may be different or the same. When R 5 has no hydroxyl group, at least one R 6 must be a carboxyl group. In addition, when there is no carboxyl group as R 6 , at least one R 5 must be a hydroxyl group. )
一般式（２）で示されるポリアミド系樹脂において、Ｘの置換基としてのＯ−Ｒ7、Ｙ
の置換基としてのＯ−Ｒ7、ＣＯＯ−Ｒ7は、水酸基、カルボキシル基のアルカリ水溶液に対する溶解性を調節する目的で、炭素数１〜１５の有機基であるＲ7で保護された基であ
り、必要により水酸基、カルボキシル基を保護しても良い。Ｒ7の例としては、ホルミル
基、メチル基、エチル基、プロピル基、イソプロピル基、ターシャリーブチル基、ターシャリーブトキシカルボニル基、フェニル基、ベンジル基、テトラヒドロフラニル基、テトラヒドロピラニル基等が挙げられる。
In the polyamide resin represented by the general formula (2), O—R 7 and Y as substituents for X
O—R 7 and COO—R 7 as substituents in the above are groups protected by R 7 , which is an organic group having 1 to 15 carbon atoms, for the purpose of adjusting the solubility of hydroxyl groups and carboxyl groups in an aqueous alkaline solution. Yes, the hydroxyl group and carboxyl group may be protected if necessary. Examples of R 7 include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.
一般式（２）で示される構造を含むポリアミド系樹脂は、例えば、Ｘを含むジアミン或いはビス（アミノフェノール）、２，４−ジアミノフェノール等から選ばれる化合物と、Ｙを含むテトラカルボン酸二無水物、トリメリット酸無水物、ジカルボン酸或いはジカルボン酸ジクロライド、ジカルボン酸誘導体等から選ばれる化合物とを反応して得られるものである。なお、ジカルボン酸の場合には反応収率等を高めるため、１−ヒドロキシ−１，２，３−ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。 The polyamide resin containing the structure represented by the general formula (2) is, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol and the like, and tetracarboxylic dianhydride containing Y Product, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, a dicarboxylic acid derivative and the like. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
一般式（２）で示されるポリアミド系樹脂のＸとしては、例えばベンゼン環、ナフタレン環等の芳香族化合物、ビスフェノール類、ピロール類、フラン類等の複素環式化合物、シロキサン化合物等が挙げられ、より具体的には下記式（５）で示されるものを好ましく挙げることができる。これらは、必要により１種類又は２種類以上組み合わせて用いてもよい。 Examples of X of the polyamide-based resin represented by the general formula (2) include aromatic compounds such as a benzene ring and a naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles and furans, and siloxane compounds. More specifically, what is shown by following formula (5) can be mentioned preferably. These may be used alone or in combination of two or more.
一般式（２）で示すように、ＸにはＲ5が０〜８個結合される（式（５）において、Ｒ5は省略）。 As shown in the general formula (2), 0 to 8 R 5 are bonded to X (in the formula (5), R 5 is omitted).
式（５）中で好ましいものとしては、耐熱性、機械特性が特に優れる下記式（６）で表されるものが挙げられる。 Preferred examples of the formula (5) include those represented by the following formula (6), which are particularly excellent in heat resistance and mechanical properties.
アルキル基のいずれかであり、同一でも異なっても良い。Ｒ16は、アルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｓ＝１〜３、ｔ＝０〜４の整数である。）
さらに、式（６）の中でも、下記式（３）で示されるものが特に好ましい。一般式（２）で示されるポリアミド系樹脂のＸが下記式（３）である場合、一般式（１）で示されるケイ素化合物（Ｃ−１）との組合せにより、温湿度処理後の基板との密着性がより優れる。 Further, among the formulas (6), those represented by the following formula (3) are particularly preferable. When X of the polyamide-based resin represented by the general formula (2) is the following formula (3), a combination with the silicon compound (C-1) represented by the general formula (1) Better adhesion.
（ＣＨ3）−、−Ｃ（ＣＨ3）2−、−Ｏ−、−Ｓ−、−ＳＯ2−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ3）2−、又は単結合である。Ｒ8は、アルキル基、アルコキシ基、アシルオ
キシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｓ＝１〜３の整数である。）
(CH 3 ) —, —C (CH 3 ) 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, or a single bond. . R 8 is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer of s = 1-3. )
又、一般式（２）で示されるポリアミド系樹脂のＹは有機基であり、前記Ｘと同様のものが挙げられ、例えば、ベンゼン環、ナフタレン環等の芳香族化合物、ビスフェノール類、ピロール類、ピリジン類、フラン類等の複素環式化合物、シロキサン化合物等が挙げられ、より具体的には下記式（７）で示されるものを好ましく挙げることができる。これらは１種類又は２種類以上組み合わせて用いてもよい。 In addition, Y of the polyamide-based resin represented by the general formula (2) is an organic group, and examples thereof include those similar to X. For example, aromatic compounds such as benzene ring and naphthalene ring, bisphenols, pyrroles, Examples thereof include heterocyclic compounds such as pyridines and furans, siloxane compounds, and the like, and more specifically, those represented by the following formula (7) can be preferably exemplified. These may be used alone or in combination of two or more.
一般式（２）で示すように、Ｙには、Ｒ6が０〜８個結合される（式（７）において、
Ｒ6は省略）。
As shown in the general formula (2), 0 to 8 R 6 are bonded to Y (in the formula (7),
R 6 is omitted).
式（７）の中で好ましいものとしては、耐熱性、機械特性が特に優れる下記式（８）、式（９）で示されるものが挙げられる。
下記式（８）中のテトラカルボン酸二無水物由来の構造については、Ｃ＝Ｏ基に結合する位置が両方メタ位であるもの、両方パラ位であるものを挙げているが、メタ位とパラ位をそれぞれ含む構造でもよい。
Preferred examples of the formula (7) include those represented by the following formulas (8) and (9), which are particularly excellent in heat resistance and mechanical properties.
As for the structure derived from tetracarboxylic dianhydride in the following formula (8), the position where both C═O groups are bonded to the meta position, and both the para positions are listed. A structure including each of the para positions may be used.
、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。Ｒ23は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｖ＝０〜４の整数である。）
さらに、式（８）、（９）の中でも、下記式（４）で示されるものが特に好ましい。一般式（２）で示されるポリアミド系樹脂のＹが下記式（４）である場合、一般式（１）で示されるケイ素化合物（Ｃ−１）との組合せにより、温湿度処理後の基板との密着性がより優れる。
また、上述の一般式（２）で示されるポリアミド系樹脂は、該ポリアミド系樹脂の末端
をアミノ基とし、該アミノ基をアルケニル基またはアルキニル基を少なくとも１個有する脂肪族基、または環式化合物基を含む酸無水物を用いてアミドとしてキャップすることが好ましい。これにより、保存性を向上することができる。
このような、アミノ基と反応した後のアルケニル基またはアルキニル基を少なくとも１個有する脂肪族基または環式化合物基を含む酸無水物に起因する基としては、例えば式（１０）、式（１１）で示される基等を挙げることができる。これらは単独で用いてもよいし、２種類以上組み合わせて用いても良い。
The polyamide resin represented by the general formula (2) is an aliphatic group having a terminal amino group and at least one alkenyl group or alkynyl group, or a cyclic compound. It is preferred to cap as an amide with an acid anhydride containing a group. Thereby, preservability can be improved.
Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (10) and formula (11). ) And the like. These may be used alone or in combination of two or more.
またこの方法に限定される事はなく、該ポリアミド系樹脂中に含まれる末端の酸をアルケニル基又はアルキニル基を少なくとも１個有する脂肪族基又は環式化合物基を含むアミ
ン誘導体を用いてアミドとしてキャップすることもできる。
The method is not limited to this method, and the terminal acid contained in the polyamide-based resin is converted into an amide by using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. It can also be capped.
本発明に係る感光性ジアゾキノン化合物（Ｂ）は、例えば、フェノール化合物と１，２−ナフトキノン−２−ジアジド−５−スルホン酸または１，２−ナフトキノン−２−ジアジド−４−スルホン酸とのエステルが挙げられる。具体的には、式（１３）〜式（１６）に示すエステル化合物を挙げることができる。これらは単独で用いてもよいし、２種以上組み合わせて用いても良い。 The photosensitive diazoquinone compound (B) according to the present invention is, for example, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Is mentioned. Specific examples include ester compounds represented by formula (13) to formula (16). These may be used alone or in combination of two or more.
本発明に係る感光性ジアゾキノン化合物（Ｂ）の添加量は、アルカリ可溶性樹脂（Ａ）１００重量部に対して１〜５０重量部が好ましい。より好ましくは１０〜４０重量部である。添加量が上記範囲内であるとすると、特に感度が優れる。 As for the addition amount of the photosensitive diazoquinone compound (B) based on this invention, 1-50 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A). More preferably, it is 10 to 40 parts by weight. When the addition amount is within the above range, the sensitivity is particularly excellent.
本発明に係るケイ素化合物（Ｃ−１）は、下記一般式（１）で示される構造である。 The silicon compound (C-1) according to the present invention has a structure represented by the following general formula (1).
前記ケイ素化合物を適用することにより、塗膜と基板との密着性が向上する為、温湿度処理後のＪＩＳ Ｄ０２０２に準拠した密着性試験においてもパターンの剥離等は見られ
ない。
前記ケイ素化合物（Ｃ−１）のアルコキシシラン基が、基板と相互作用するのに対し、アルキロールアミノ基が、アルカリ可溶性樹脂（Ａ）と相互作用するため、温湿度処理後においても基板との密着性が良好であると考えられる。
Since the adhesion between the coating film and the substrate is improved by applying the silicon compound, pattern peeling or the like is not observed in the adhesion test in accordance with JIS D0202 after the temperature and humidity treatment.
While the alkoxysilane group of the silicon compound (C-1) interacts with the substrate, the alkylolamino group interacts with the alkali-soluble resin (A). It is considered that the adhesion is good.
前記ケイ素化合物を適用することにより、硬化膜の引っ張り伸度が向上する。また、添加量を増加させる事により、伸度はさらに向上する。
前期ケイ素化合物（Ｃ−１）のアルキロールアミノ基がアルカリ可溶性樹脂（Ａ）に架橋するため、硬化膜の引っ張り伸度が向上すると考えられる。
By applying the silicon compound, the tensile elongation of the cured film is improved. Further, the elongation is further improved by increasing the amount added.
It is considered that the tensile elongation of the cured film is improved because the alkylolamino group of the silicon compound (C-1) is crosslinked to the alkali-soluble resin (A).
一般式（１）中のＲ1、Ｒ2は炭素数１〜１０のアルキル基であり、特に限定されるものではないが、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、セカンダリーブチル基、ターシャリーブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基等が挙げられ、その中でも、加水分解性に優れるメチル基、エチル基が好ましい。 R 1 and R 2 in the general formula (1) are alkyl groups having 1 to 10 carbon atoms and are not particularly limited, but are methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl. Group, tertiary butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, etc. A methyl group and an ethyl group which are excellent in hydrolyzability are preferred.
一般式（１）中のＲ3は有機基であり、特に限定されるものではないが、例えばメチレ
ン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、ターシャリブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、フェニレン基、ベンジレン基、フェネチレン基、ナフチレン基、ビフェニレン基等が挙げられ、その中でも、溶媒溶解性に優れるエチレン基、プロピレン基が好ましい。
R 3 in the general formula (1) is an organic group and is not particularly limited. For example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, tertiary ribylene group, pentylene group, hexylene Group, heptylene group, octylene group, phenylene group, benzylene group, phenethylene group, naphthylene group, biphenylene group and the like. Among them, ethylene group and propylene group excellent in solvent solubility are preferable.
一般式（１）中のＲ4は炭素数１〜１０のアルキレン基であり、特に限定されるもので
はないが、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、セカンダリーブチレン基、ターシャリーブチレン基、ペンチレン基、へキシレン基、ヘプチレン基、オクチレン基、２−エチルヘキシレン基、ノニレン基、デシレン基等が挙げられ、その中でも、アルカリ可溶性樹脂との相互作用に優れるメチレン基、エチレン基が好ましい。
R 4 in the general formula (1) is an alkylene group having 1 to 10 carbon atoms, and is not particularly limited, but includes a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a secondary butylene group, A tertiary butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, and the like. Among them, a methylene group excellent in interaction with an alkali-soluble resin, An ethylene group is preferred.
一般式（１）中のｉは０〜２の整数であるが、ｉ＝０の場合、基板との密着性がより優れるため好ましい。 I in the general formula (1) is an integer of 0 to 2, but i = 0 is preferable because adhesion to the substrate is more excellent.
前記有機ケイ素化合物（Ｃ−１）の添加量は、特に限定されるものではないが、アルカリ可溶性樹脂（Ａ）１００重量部に対して、０．０５〜５０重量部であることが好ましく、０．１〜２０重量部が特に好ましい。添加量が上記範囲内であると、基板との密着性とポジ型感光性樹脂組成物の保存性が両立する。 The amount of the organosilicon compound (C-1) added is not particularly limited, but is preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). .1 to 20 parts by weight is particularly preferable. When the addition amount is within the above range, adhesion to the substrate and storage stability of the positive photosensitive resin composition are compatible.
一般式（１）で示されるケイ素化合物は、特に限定されるものではないが、例えば、ビ
ス（２−ヒドロキシメチル）−３−アミノメチルトリメトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノエチルトリメトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノプロピルトリメトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノフェニルトリメトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノメチルトリエトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノエチルトリエトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノプロピルトリエトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノフェニルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノメチルトリメトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノメチルトリメトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノエチルトリメトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノプロピルトリメトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノフェニルトリメトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノメチルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノエチルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノプロピルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノフェニルトリエトキシシラン等が挙げられ、その中でも、基板との密着性や保存安定性に優れるビス（２−ヒドロキシメチル）−３−アミノプロピルトリエトキシシラン、ビス（２−ヒドロキシエチル）−３−アミノプロピルトリエトキシシラン、ビス（２−ヒドロキシメチル）−３−アミノプロピルトリメトキシしラン、ビス（２−ヒドロキシエチル）−３−アミノプロピルトリメトキシシランが好ましい。これらは単独でも２種以上混合して用いても良い。
The silicon compound represented by the general formula (1) is not particularly limited, and examples thereof include bis (2-hydroxymethyl) -3-aminomethyltrimethoxysilane and bis (2-hydroxymethyl) -3-amino. Ethyltrimethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-hydroxymethyl) -3-aminophenyltrimethoxysilane, bis (2-hydroxymethyl) -3-aminomethyltri Ethoxysilane, bis (2-hydroxymethyl) -3-aminoethyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminophenyltriethoxysilane Bis (2-hydroxyethyl) -3-aminomethyltrimeth Silane, bis (2-hydroxyethyl) -3-aminomethyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminoethyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltrimethoxysilane, Bis (2-hydroxyethyl) -3-aminophenyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminomethyltriethoxysilane, bis (2-hydroxyethyl) -3-aminoethyltriethoxysilane, bis ( 2-hydroxyethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminophenyltriethoxysilane, and the like. Among them, bis ( 2-hydroxymethyl) -3-aminopropyltriethoxy Lan, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltrimethoxysilane Is preferred. These may be used alone or in combination of two or more.
さらに本発明のポジ型感光性樹脂組成物は、高感度で更にパターニング時のスカムを改善する目的で、フェノール性水酸基を有する化合物を併用することができる。 Furthermore, the positive photosensitive resin composition of the present invention can be used in combination with a compound having a phenolic hydroxyl group for the purpose of improving the scum at the time of patterning with high sensitivity.
具体的な構造としては、式（１９）で表されるものが挙げられる。これらは１種類又は２種類以上組み合わせて用いてもよい。 As a specific structure, one represented by the formula (19) can be given. These may be used alone or in combination of two or more.
前記フェノール性水酸基を有する化合物の含有量は、特に限定されないが、アルカリ可溶性樹脂（Ａ）１００重量部に対して、１〜３０重量部が好ましく、より好ましくは１〜２０重量部である。添加量が、上記範囲内であると現像時において更にスカムの発生が抑制され、また露光部の溶解性が促進されることにより感度が向上する。 Although content of the compound which has the said phenolic hydroxyl group is not specifically limited, 1-30 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A), More preferably, it is 1-20 weight part. When the addition amount is in the above range, the occurrence of scum is further suppressed during development, and the sensitivity is improved by promoting the solubility of the exposed area.
本発明における樹脂組成物およびポジ型感光性樹脂組成物には、必要によりアクリル系、シリコーン系、フッ素系、ビニル系等のレベリング剤、あるいは一般式（１）で示される化合物以外のシランカップリング剤等の添加剤等を含んでも良い。 In the resin composition and the positive photosensitive resin composition in the present invention, a silane coupling other than the leveling agent such as acrylic, silicone, fluorine, and vinyl, or the compound represented by the general formula (1), if necessary. An additive such as an agent may be included.
前記シランカップリング剤としては、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシプロピル）テトラスルフィド、３−イソシアネートプロピルトリエトキシシラン、さらに、アミノ基を有するケイ素化合物と酸二無水物又は酸無水物とを反応することにより得られるシランカップリング剤等が挙げられるが、これらに限定されない。 Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and 3-methacryloxy. Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples thereof include, but are not limited to, propyltriethoxysilane, and a silane coupling agent obtained by reacting a silicon compound having an amino group with an acid dianhydride or acid anhydride.
前記アミノ基を有するケイ素化合物としては、特に制限されるわけではないが、例えば、３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）―３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリエトキシシラン等が挙げられる。 The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.
前記酸無水物としては、特に制限されるわけではないが、例えば、無水マレイン酸、クロロ無水マレイン酸、シアノ無水マレイン酸、シトコン酸、無水フタル酸等などが挙げられる。また、使用にあたっては単独、又は２種類以上を併用して使用することができる。 The acid anhydride is not particularly limited, and examples thereof include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, and phthalic anhydride. Moreover, in using, it can be used individually or in combination of 2 or more types.
前記酸二無水物としては、特に制限されるわけではないが、例えば、ピロメリット酸二無水物、ベンゼン−１，２，３,４−テトラカルボン酸二無水物、３，３'，４，４'−ベ
ンゾフェノンテトラカルボン酸二無水物、２，３，３'，４'−ベンゾフェノンテトラカルボン酸二無水物、ナフタレン−２，３，６，７−テトラカルボン酸二無水物、ナフタレン−１，２，５，６−テトラカルボン酸二無水物、ナフタレン−１，２，４，５−テトラカルボン酸二無水物、ナフタレン−１，４，５，８−テトラカルボン酸二無水物、ナフタレン−１，２，６，７−テトラカルボン酸二無水物、４，８−ジメチル−１，２，３，５，６，７−ヘキサヒドロナフタレン−１，２，５，６−テトラカルボン酸二無水物、４，８−ジメチル−１，２，３，５，６，７−ヘキサヒドロナフタレン−２，３，６，７−テトラカルボン酸二無水物、２，６−ジクロロナフタレン−１，４，５，８−テトラカルボン酸二無水物、２，７−ジクロロナフタレン−１，４，５，８−テトラカルボン酸二無水物、２，３，６，７−テトラクロロナフタレン−１，４，５，８−テトラカルボン酸二無水物、１，４，５，８−テトラクロロナフタレン−２，３，６，７−テトラカルボン酸二無水物、３,３',４，４'−ジフェニルテトラカルボン酸二無水物、２,２',３，３'−ジフェニルテトラカルボン酸二無水物、２,３，３',４'−ジフェニルテトラカルボン酸二無水物、３，３", ４，４"−ｐ−テルフェニルテトラカルボン酸二無水物, ２，２", ３，３"−ｐ−テルフェニルテトラカルボン酸二無水物, ２，３，３",４"−ｐ−テルフェニルテト
ラカルボン酸二無水物、２，２−ビス（２，３−ジカルボキシフェニル）−プロパン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）−プロパン二無水物、ビス（２，３−ジカルボキシフェニル）エーテル二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（２，３−ジカルボキシフェニル）スルホン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、１，１−ビス（３，４−ジカルボ
キシフェニル）エタン二無水物、ペリレン−２，３，８，９−テトラカルボン酸二無水物、ペリレン−３，４，９，１０−テトラカルボン酸二無水物、ペリレン−４，５，１０，１１−テトラカルボン酸二無水物、ペリレン−５，６，１１，１２−テトラカルボン酸二無水物、フェナンスレン−１，２，７，８−テトラカルボン酸二無水物、フェナンスレン−１，２，６，７,８−テトラカルボン酸二無水物、フェナンスレン−１，２，９，１０
−テトラカルボン酸二無水物、ピラジン−２，３，５，６−テトラカルボン酸二無水物、ピロリジン−２，３，４，５−テトラカルボン酸二無水物、チオフェン−２，３，４，５，−テトラカルボン酸二無水物、４，４'−ヘキサフルオロイソプロピリデンジフタル酸
二無水物等などが挙げられる。また、使用にあたっては単独、又は２種類以上を併用して使用することができる。
The acid dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4, 4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1, 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1 , 2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride 4,8-dimethyl-1,2,3,5,6 7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8- Tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic Acid dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3 , 3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-ter Phenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis ( 2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-di Carboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxy) Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3 4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1 , 2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10
-Tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4, Examples include 5, -tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidenediphthalic dianhydride, and the like. Moreover, in using, it can be used individually or in combination of 2 or more types.
前記アミノ基を有するケイ素化合物と酸二無水物又は酸無水物とを反応することにより得られるシランカップリング剤としては、ポジ型感光性樹脂組成物の保存性と現像時、あるいは加熱処理後のシリコンウエハー等の基板に対する密着性が両立する、ビス（３，４−ジカルボキシフェニル）エーテル二無水物と３−アミノプロピルトリエトキシシラン、３，３', ４，４'−ベンゾフェノンテトラカルボン酸二無水物と３−アミノプロピルトリエトキシシラン、ビス（３，４−ジカルボキシフェニル）スルホン二無水物と３−アミノプロピルトリエトキシシラン、無水マレイン酸と３−アミノプロピルトリエトキシシランの組合せが好ましい。 As a silane coupling agent obtained by reacting the silicon compound having an amino group with an acid dianhydride or an acid anhydride, the storability and development of the positive photosensitive resin composition, or after the heat treatment Bis (3,4-dicarboxyphenyl) ether dianhydride and 3-aminopropyltriethoxysilane, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, which have good adhesion to substrates such as silicon wafers Combinations of anhydride and 3-aminopropyltriethoxysilane, bis (3,4-dicarboxyphenyl) sulfone dianhydride and 3-aminopropyltriethoxysilane, maleic anhydride and 3-aminopropyltriethoxysilane are preferred.
本発明においては、これらの成分を溶剤に溶解し、ワニス状にして使用する。溶剤としては、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、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ジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジ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メチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル−１，３−ブチレングリコールアセテート、１，３−ブチレングリコール−３−モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチル−３−メトキシプロピオネート等が挙げられ、単独でも混合して用いても良い。 In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.
本発明のポジ型感光性樹脂組成物の使用方法は、まず該組成物を適当な支持体（基板）、例えば、シリコンウエハー、セラミック基板、アルミ基板等に塗布する。塗布量は、半導体素子上に塗布する場合、硬化後の最終膜厚が０．１〜３０μｍになるよう塗布する。膜厚が下限値を下回ると、半導体素子の保護表面膜としての機能を十分に発揮することが困難となり、上限値を越えると、微細な加工パターンを得ることが困難となるばかりでなく、加工に時間がかかりスループットが低下する。塗布方法としては、スピンナーを用いた回転塗布、スプレーコーターを用いた噴霧塗布、浸漬、印刷、ロールコーティング等がある。次に、６０〜１３０℃でプリベークして塗膜を乾燥後、所望のパターン形状に化学線を照射する。化学線としては、Ｘ線、電子線、紫外線、可視光線等が使用できるが、２００〜５００ｎｍの波長のものが好ましい。 In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support (substrate) such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. When applied on a semiconductor element, the applied amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.
次に照射部を現像液で溶解除去することによりレリーフパターンを得る。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の第１アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の第２アミン類、トリエチルアミン、メチルジエチルアミン等の第３アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、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等の第４級アンモニウム塩等のアルカリ類の水溶液、及びこれにメタノール、エタノールのごときアルコール類等の水溶性有機溶媒や界面活性剤を適当量添加した水溶液を好適に使用することができる。現像方法としては、スプレー
、パドル、浸漬、超音波等の方式が可能である。
Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.
次に、現像によって形成したレリーフパターンをリンスする。リンス液としては、蒸留水を使用する。次に加熱処理を行い、オキサゾール環、イミド環、又はオキサゾール環及びイミド環を形成し、耐熱性に富む最終パターンを得る。
加熱処理温度は、１８０℃〜３８０℃が好ましく、より好ましくは２００℃〜３５０℃である。ここで行う加熱処理が前述した熱処理工程のことである。
Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring, an imide ring, or an oxazole ring and an imide ring, thereby obtaining a final pattern rich in heat resistance.
The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C. The heat treatment performed here is the heat treatment step described above.
次に、本発明によるポジ型感光性樹脂組成物の硬化膜について説明する。ポジ型感光性樹脂組成物の硬化物である硬化膜は、半導体素子等の半導体装置用途のみならず、ＴＦＴ型液晶や有機ＥＬ等の表示体装置用途、多層回路の層間絶縁膜やフレキシブル銅張板のカバーコート、ソルダーレジスト膜や液晶配向膜としても有用である。 Next, the cured film of the positive photosensitive resin composition according to the present invention will be described. The cured film, which is a cured product of the positive photosensitive resin composition, is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT liquid crystal and organic EL, interlayer insulating films for multilayer circuits, and flexible copper-clad It is also useful as a plate cover coat, solder resist film or liquid crystal alignment film.
半導体装置用途の例としては、半導体素子上に上述のポジ型感光性樹脂組成物の硬化膜を形成してなるパッシベーション膜、パッシベーション膜上に上述のポジ型感光性樹脂組成物の硬化膜を形成してなるバッファーコート膜等の保護膜、また、半導体素子上に形成された回路上に上述のポジ型感光性樹脂組成物の硬化膜を形成してなる層間絶縁膜等の絶縁膜、また、α線遮断膜、平坦化膜、突起（樹脂ポスト）、隔壁等を挙げることができる。 Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described positive photosensitive resin composition formed on the passivation film. A protective film such as a buffer coating film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned positive photosensitive resin composition on a circuit formed on a semiconductor element, Examples include an α-ray blocking film, a planarizing film, a protrusion (resin post), and a partition wall.
表示体装置用途の例としては、表示体素子上に上述のポジ型感光性樹脂組成物の硬化膜を形成してなる保護膜、ＴＦＴ素子やカラーフィルター用等の絶縁膜または平坦化膜、ＭＶＡ型液晶表示装置用等の突起、有機ＥＬ素子陰極用等の隔壁等を挙げることができる。その使用方法は、半導体装置用途に準じ、表示体素子やカラーフィルターを形成した基板上にパターン化されたポジ型感光性樹脂組成物層を、上記の方法で形成することによるものである。表示体装置用途の、特に絶縁膜や平坦化膜用途では、高い透明性が要求されるが、このポジ型感光性樹脂組成物層の硬化前に、後露光工程を導入することにより、透明性に優れた樹脂層が得られることもでき、実用上更に好ましい。 Examples of display device applications include a protective film formed by forming a cured film of the above-described positive photosensitive resin composition on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA, and the like. Protrusions for a liquid crystal display device, partition walls for an organic EL element cathode, and the like. The usage method is based on forming the positive photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. High transparency is required for display device applications, especially for insulating films and flattening films. Transparency can be achieved by introducing a post-exposure step before curing the positive photosensitive resin composition layer. It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practice.
以下、実施例により本発明を具体的に説明する。
≪実施例１≫
［アルカリ可溶性樹脂（Ａ−１）の合成］
ジフェニルエーテル−４，４’−ジカルボン酸０．９００モルと１−ヒドロキシ−１，２，３−ベンゾトリアゾール１．８００モルとを反応させて得られたジカルボン酸誘導体（活性エステル）４４３．２１ｇ（０．９００モル）とヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン３６６．２６ｇ（１．０００モル）とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、Ｎ−メチル−２−ピロリドン３２００ｇを加えて溶解させた。その後オイルバスを用いて７５℃にて１２時間反応させた。
次にＮ−メチル−２−ピロリドン１００ｇに溶解させた５−ノルボルネン−２、３−ジカルボン酸無水物３２．８ｇ（０．２００モル）を加え、更に１２時間攪拌して反応を終了した。反応混合物を濾過した後、反応混合物を水／イソプロパノール＝３／１（体積比）の溶液に投入、沈殿物を濾集し水で充分洗浄した後、真空下で乾燥し、目的の式（Ａ−１）で示されるアルカリ可溶性樹脂を得た。
Hereinafter, the present invention will be described specifically by way of examples.
Example 1
[Synthesis of Alkali-soluble Resin (A-1)]
443.21 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.900 mol of diphenyl ether-4,4′-dicarboxylic acid with 1.800 mol of 1-hydroxy-1,2,3-benzotriazole .900 mol) and 366.26 g (1.000 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. The flask was placed in a four-necked separable flask, and 3200 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 32.8 g (0.200 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the target formula (A An alkali-soluble resin represented by -1) was obtained.
［感光性ジアゾキノン化合物の合成］
式（Ｑ−１）で示されるフェノール１５．８２ｇ（０．０２５モル）と、トリエチルアミン８．４０ｇ（０．０８３モル）とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた４つ口のセパラブルフラスコに入れ、テトラヒドロフラン１３５ｇを加えて溶
解させた。この反応溶液を１０℃以下に冷却した後に、１，２−ナフトキノン−２−ジアジド−４−スルホニルクロライド２２．３０ｇ（０．０８３モル）をテトラヒドロフラン１００ｇと共に１０℃以上にならないように徐々に滴下した。その後１０℃以下で５分攪拌した後、室温で５時間攪拌して反応を終了させた。反応混合物を濾過した後、反応混合物を水／メタノール＝３／１（体積比）の溶液に投入、沈殿物を濾集し水で充分洗浄した後、真空下で乾燥し、式（Ｂ−１）で示される感光性ジアゾキノン化合物を得た。
[Synthesis of photosensitive diazoquinone compound]
15.82 g (0.025 mol) of phenol represented by the formula (Q-1) and 8.40 g (0.083 mol) of triethylamine were equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Into a four-necked separable flask, 135 g of tetrahydrofuran was added and dissolved. After cooling the reaction solution to 10 ° C. or lower, 22.30 g (0.083 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was gradually added dropwise with 100 g of tetrahydrofuran so as not to exceed 10 ° C. . Thereafter, the mixture was stirred at 10 ° C. or lower for 5 minutes and then stirred at room temperature for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the formula (B-1 The photosensitive diazoquinone compound shown by this was obtained.
［ポジ型感光性樹脂組成物の作製］
合成した式（Ａ−１）で示されるアルカリ可溶性樹脂１００ｇ、式（Ｂ−１）の構造を有する感光性ジアゾキノン化合物１５ｇ、下記式（Ｃ−１）の構造を有するケイ素化合物１０ｇを、γ―ブチロラクトン１５０ｇに溶解した後、孔径０．２μｍのテフロン（登録商標）製フィルターで濾過しポジ型感光性樹脂組成物を得た。
[Preparation of positive photosensitive resin composition]
100 g of the alkali-soluble resin represented by the formula (A-1) synthesized, 15 g of the photosensitive diazoquinone compound having the structure of the formula (B-1), and 10 g of the silicon compound having the structure of the following formula (C-1) After dissolving in 150 g of butyrolactone, it was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a positive photosensitive resin composition.
［温湿度処理後の密着性評価］
上記ポジ型感光性樹脂組成物をシリコンウエハー上にスピンコーターを用いて塗布した後、ホットプレートにて１２０℃で４分プリベークし、膜厚約８．０μｍの塗膜を得た。
次にクリーンオーブンを用いて酸素濃度１，０００ｐｐｍ以下で、１５０℃／３０分＋３２０℃／３０分で加熱硬化を行い、硬化膜を得た。この硬化膜に、ＪＩＳ Ｋ５４００
に準拠してカッターナイフにて１×１（ｍｍ）サイズの正方形が縦横１０列づつ計１００個の碁盤目を作製した。このサンプルをプレッシャークッカー（温湿度処理）試験；１２５℃、１００％、０．２ＭＰａの条件下２４時間連続処理した後、ＪＩＳ Ｄ０２０２に
準拠して評価した。その結果、剥れた碁盤目の数は０個であった。碁盤目１００個のうち１個でも剥れると実用上問題であることを考えると、温湿度処理後も良好な密着性を示すことが確認された。
[Adhesion evaluation after temperature and humidity treatment]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 8.0 μm.
Next, heat curing was performed at 150 ° C./30 minutes + 320 ° C./30 minutes using a clean oven at an oxygen concentration of 1,000 ppm or less to obtain a cured film. To this cured film, JIS K5400
In accordance with the above, 100 squares in total of 10 rows of 1 × 1 (mm) size squares were prepared with a cutter knife. This sample was subjected to a pressure cooker (temperature / humidity treatment) test; continuously treated for 24 hours under conditions of 125 ° C., 100%, and 0.2 MPa, and then evaluated according to JIS D0202. As a result, the number of peeled grids was zero. Considering that even one of the 100 grids is peeled off, it is confirmed that it exhibits a good adhesion even after the temperature and humidity treatment.
[硬化膜の引っ張り伸度の測定]
上記ポジ型感光性樹脂組成物を６インチのシリコンウェハー上に硬化膜の膜厚が約１０．０μｍとなるように塗布し、１２０℃／４分でプリベークを行った。
次にクリーンオーブンで酸素濃度を１，０００ｐｐｍ以下で、１５０℃／３０分＋３２０℃／３０分で加熱硬化を行い、硬化膜を得た。この硬化膜の付いたウェハーをダイシングソーを用いて、１０ｍｍの短冊状にカットした後、２％のＨＦ水溶液（フッ酸）に浸漬させることによって、ウェハーから硬化膜を剥離し、乾燥機にて６０℃／８時間で剥離し硬化膜を乾燥させ、引張り伸度測定用フィルムを得た。
次に、フィルムを引っ張り試験器にて引っ張り伸度を測定（引張り速度：０．５ｍｍ／ｍｉｎ）したところ、４５％と良好であった。また、引っ張り伸度は下記式より求めた。
引っ張り伸度（％）＝｛（破断時のフィルムの長さ−測定開始前のフィルムの長さ）／（測定開始前のフィルムの長さ）｝×１００
[Measurement of tensile elongation of cured film]
The positive photosensitive resin composition was applied onto a 6-inch silicon wafer so that the thickness of the cured film was about 10.0 μm, and prebaked at 120 ° C./4 minutes.
Next, heat curing was performed in a clean oven at an oxygen concentration of 1,000 ppm or less at 150 ° C./30 minutes + 320 ° C./30 minutes to obtain a cured film. The wafer with this cured film is cut into a 10 mm strip using a dicing saw, and then immersed in a 2% HF aqueous solution (hydrofluoric acid) to peel the cured film from the wafer and with a dryer. Peeling was performed at 60 ° C. for 8 hours, and the cured film was dried to obtain a film for measuring tensile elongation.
Next, when the tensile elongation of the film was measured with a tensile tester (tensile speed: 0.5 mm / min), it was as good as 45%. The tensile elongation was determined from the following formula.
Tensile elongation (%) = {(film length at break−film length before starting measurement) / (film length before starting measurement)} × 100
≪実施例２≫
下記式（Ｃ−１）の構造を有するケイ素化合物１０ｇ添加する代わりに１ｇ添加した以外は実施例１と同様にポジ型感光性樹脂組成物を作製し、評価を行った。
<< Example 2 >>
A positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that 1 g was added instead of adding 10 g of the silicon compound having the structure of the following formula (C-1).
≪比較例１≫
下記式（Ｃ−１）の構造を有するケイ素化合物の代わりに、下記式（Ｃ−２）の構造を有するケイ素化合物を１０ｇ添加した以外は実施例１と同様にポジ型感光性樹脂組成物を作製し、評価を行った。
≪Comparative example 1≫
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 10 g of a silicon compound having the structure of the following formula (C-2) was added instead of the silicon compound having the structure of the following formula (C-1). Fabricated and evaluated.
≪比較例２≫
下記式（Ｃ−１）の構造を有するケイ素化合物の代わりに、下記式（Ｃ−３）の構造を有するケイ素化合物を１０ｇ添加した以外は実施例１と同様にポジ型感光性樹脂組成物を
作製し、評価を行った。
≪Comparative example 2≫
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that 10 g of a silicon compound having the structure of the following formula (C-3) was added instead of the silicon compound having the structure of the following formula (C-1). Fabricated and evaluated.
≪比較例３≫
下記式（Ｃ−１）の構造を有するケイ素化合物を添加しない以外は実施例１と同様にポジ型感光性樹脂組成物を作製し、評価を行った。
以下に、実施例及び比較例の（Ｑ−１）、（Ｂ−１）、（Ｃ−１）、（Ｃ−２）、（Ｃ−３）の構造、及び表１を示す。ここで、表１中のアルカリ可溶性樹脂、及びケイ素化合物の数字は添加重量部を示す。
«Comparative Example 3»
A positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that a silicon compound having the structure of the following formula (C-1) was not added.
The structures of (Q-1), (B-1), (C-1), (C-2), and (C-3) of Examples and Comparative Examples and Table 1 are shown below. Here, the numbers of the alkali-soluble resin and the silicon compound in Table 1 represent parts by weight.
表１に示すように、実施例１、及び２は，温湿度処理後の密着評価において剥れは見られず、密着性が良好であり、引っ張り伸度も良好であることが分かる。 As shown in Table 1, in Examples 1 and 2, no peeling was observed in the adhesion evaluation after the temperature and humidity treatment, it was found that the adhesion was good and the tensile elongation was also good.
本発明のポジ型感光性樹脂組成物の硬化膜は、温湿度処理後の基板との密着性に優れるため、半導体素子、表示素子の表面保護膜、層間絶縁膜等に好適に用いられる。 Since the cured film of the positive photosensitive resin composition of the present invention is excellent in adhesion to the substrate after the temperature and humidity treatment, it is suitably used for a surface protective film, an interlayer insulating film, etc. for semiconductor elements and display elements.
Claims (12)
感光性ジアゾキノン化合物（Ｂ）と、
一般式（１）で示されるケイ素化合物（Ｃ−１）と、
を含むことを特徴とするポジ型感光性樹脂組成物。
A photosensitive diazoquinone compound (B);
A silicon compound (C-1) represented by the general formula (1);
A positive photosensitive resin composition comprising:
−Ｏ−Ｒ7、−ＣＯＯ−Ｒ7のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ7は炭素数１〜１５の有機基である。ここで、Ｒ5が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ5として水酸基がない場合は、Ｒ6は少なくとも１つはカルボキシル基でなければならない。また、Ｒ6としてカルボキシル
基がない場合、Ｒ5は少なくとも１つは水酸基でなければならない。） The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) includes a polyamide-based resin having a repeating unit represented by the general formula (2).
It is either —O—R 7 or —COO—R 7 , which may be the same or different. m is an integer of 0 to 8, and n is an integer of 0 to 8. R 7 is an organic group having 1 to 15 carbon atoms. Here, when there are a plurality of R 5 s , they may be different or the same. When R 5 has no hydroxyl group, at least one R 6 must be a carboxyl group. In addition, when there is no carboxyl group as R 6 , at least one R 5 must be a hydroxyl group. )
（ＣＨ3）−、−Ｃ（ＣＨ3）2−、−Ｏ−、−Ｓ−、−ＳＯ2−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ3）2−、又は単結合である。Ｒ8は、アルキル基、アルコキシ基、アシルオ
キシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｓ＝１〜３の整数である。）
(CH 3 ) —, —C (CH 3 ) 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, or a single bond. . R 8 is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer of s = 1-3. )
ある、請求項１ないし４のいずれかに記載のポジ型感光性組成物。 The positive photosensitive composition according to claim 1 , wherein R 1 of the silicon compound (C-1) represented by the general formula (2) is a methyl group or an ethyl group.
基である、請求項１ないし５のいずれかに記載のポジ型感光性組成物。 The positive photosensitive composition according to claim 1, wherein R 4 of the silicon compound (C-1) represented by the general formula (2) is a methylene group or an ethylene group.
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| WO2011083872A1 (en) * | 2010-01-08 | 2011-07-14 | Fujifilm Corporation | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition and resist film |
| JP2011141494A (en) * | 2010-01-08 | 2011-07-21 | Fujifilm Corp | Pattern forming method, chemically amplified resist composition and resist film |
| JP2012128383A (en) * | 2010-03-30 | 2012-07-05 | Fujifilm Corp | Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same |
| KR20190035603A (en) * | 2016-07-27 | 2019-04-03 | 도레이 카부시키가이샤 | Resin composition |
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| JPH11312675A (en) * | 1998-04-27 | 1999-11-09 | Sumitomo Bakelite Co Ltd | Semiconductor device and manufacture thereof |
| JP2004170611A (en) * | 2002-11-19 | 2004-06-17 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method of manufacturing relief pattern and electronic parts |
| JP2008046258A (en) * | 2006-08-11 | 2008-02-28 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for producing pattern and electronic component |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11312675A (en) * | 1998-04-27 | 1999-11-09 | Sumitomo Bakelite Co Ltd | Semiconductor device and manufacture thereof |
| JP2004170611A (en) * | 2002-11-19 | 2004-06-17 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method of manufacturing relief pattern and electronic parts |
| JP2008046258A (en) * | 2006-08-11 | 2008-02-28 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for producing pattern and electronic component |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011083872A1 (en) * | 2010-01-08 | 2011-07-14 | Fujifilm Corporation | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition and resist film |
| JP2011141494A (en) * | 2010-01-08 | 2011-07-21 | Fujifilm Corp | Pattern forming method, chemically amplified resist composition and resist film |
| US9223219B2 (en) | 2010-01-08 | 2015-12-29 | Fujifilm Corporation | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition and resist film |
| JP2012128383A (en) * | 2010-03-30 | 2012-07-05 | Fujifilm Corp | Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same |
| KR20190035603A (en) * | 2016-07-27 | 2019-04-03 | 도레이 카부시키가이샤 | Resin composition |
| KR102367407B1 (en) | 2016-07-27 | 2022-02-25 | 도레이 카부시키가이샤 | resin composition |
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