JP2009057458A - Heat-resistant resin composition - Google Patents
Heat-resistant resin composition Download PDFInfo
- Publication number
- JP2009057458A JP2009057458A JP2007225670A JP2007225670A JP2009057458A JP 2009057458 A JP2009057458 A JP 2009057458A JP 2007225670 A JP2007225670 A JP 2007225670A JP 2007225670 A JP2007225670 A JP 2007225670A JP 2009057458 A JP2009057458 A JP 2009057458A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- heat
- resistant resin
- relief pattern
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- -1 fatty acid esters Chemical class 0.000 claims description 30
- 239000004065 semiconductor Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000004420 diamide group Chemical group 0.000 claims description 5
- 229940124530 sulfonamide Drugs 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000010884 ion-beam technique Methods 0.000 claims description 3
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 7
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000007363 ring formation reaction Methods 0.000 description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 125000002971 oxazolyl group Chemical group 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HDDLVZWGOPWKFW-UHFFFAOYSA-N trimethyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound COC(=O)CC(O)(C(=O)OC)CC(=O)OC HDDLVZWGOPWKFW-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RGCVYEOTYJCNOS-UHFFFAOYSA-N (4-cyano-2-methylphenyl)boronic acid Chemical compound CC1=CC(C#N)=CC=C1B(O)O RGCVYEOTYJCNOS-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- KILURZWTCGSYRE-MUCWUPSWSA-K (e)-4-bis[[(e)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(/C)O[Al](O\C(C)=C\C(C)=O)O\C(C)=C\C(C)=O KILURZWTCGSYRE-MUCWUPSWSA-K 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-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
- YOJKKXRJMXIKSR-UHFFFAOYSA-N 1-nitro-2-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1 YOJKKXRJMXIKSR-UHFFFAOYSA-N 0.000 description 1
- DLZBUNUDESZERL-UHFFFAOYSA-N 1-o-heptyl 6-o-nonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCC DLZBUNUDESZERL-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- RWAOPZVGICHCOI-UHFFFAOYSA-N 2,4-diaminobenzene-1,3-diol Chemical compound NC1=CC=C(O)C(N)=C1O RWAOPZVGICHCOI-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- PTUUTGJMRQWABQ-UHFFFAOYSA-N triphenyl(phenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[SiH2]C1=CC=CC=C1 PTUUTGJMRQWABQ-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- ODHUFJLMXDXVRC-UHFFFAOYSA-N tripropyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCOC(=O)CC(O)(C(=O)OCCC)CC(=O)OCCC ODHUFJLMXDXVRC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Abstract
Description
本発明は、半導体装置の表面保護膜、または層間絶縁膜として使用されるポリベンズオキサゾール樹脂の前駆体となる樹脂組成物、該樹脂組成物を用いた耐熱性を有する硬化レリーフパターンの製造方法、並びに該硬化レリーフパターンを有してなる半導体装置に関する。 The present invention relates to a resin composition serving as a precursor of a polybenzoxazole resin used as a surface protective film or an interlayer insulating film of a semiconductor device, a method for producing a cured relief pattern having heat resistance using the resin composition, The present invention also relates to a semiconductor device having the cured relief pattern.
従来から、半導体装置の表面保護膜、層間絶縁膜には、優れた耐熱性と電気特性、機械特性などを併せ持つポリベンズオキサゾール(以下、PBOともいう)樹脂が用いられている。このPBO樹脂は、各種溶剤への溶解性が低いため一般的に前駆体のヒドロキシポリアミドの状態で溶剤に溶解された組成物として使用されている。従って、使用の際には前駆体を閉環(オキサゾール環への閉環)させてPBO樹脂へ変換する硬化工程が必要となる。この閉環工程は通常300℃以上に加熱する熱硬化により行われている。 Conventionally, polybenzoxazole (hereinafter also referred to as PBO) resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor device. Since this PBO resin has low solubility in various solvents, it is generally used as a composition dissolved in a solvent in the form of a precursor hydroxypolyamide. Therefore, in use, a curing step is required in which the precursor is closed (closed to an oxazole ring) and converted into a PBO resin. This ring closing step is usually performed by thermosetting which is heated to 300 ° C. or higher.
しかしながら、近年では、従来品に比べて耐熱性に劣る半導体装置が開発され、表面保護膜、または層間絶縁膜としての熱硬化温度の低下が求められ、特に280℃以下での熱硬化性を求められることも多くなっている。しかしながら、従来のPBO前駆体樹脂組成物は、280℃以下の領域ではPBO前駆体からPBOへの閉環反応が充分に進行しないものであったため、280℃以下の温度で硬化させて得られた膜はPBOに期待される、優れた耐熱性と電気特性、機械特性などを有するものではなかった。
低温でオキサゾール環への閉環反応を進行させるためには、濃硫酸、オキシ塩化リン、ポリリン酸などの脱水剤の使用が有効なことが従来から知られている(例えば、非特許文献1参照)。しかしながら、これらの脱水剤をPBO前駆体樹脂組成物に添加することは、組成物の安定性を考慮すると適切でなく、未だに満足なものが提案されていない。
However, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and a reduction in the thermosetting temperature as a surface protective film or an interlayer insulating film is required, and in particular, thermosetting at 280 ° C. or lower is required. There are many things that can be done. However, in the conventional PBO precursor resin composition, the ring closure reaction from the PBO precursor to PBO does not proceed sufficiently in the region of 280 ° C. or lower, and thus the film obtained by curing at a temperature of 280 ° C. or lower. Did not have the excellent heat resistance, electrical properties, mechanical properties, etc. expected of PBO.
Conventionally, it has been known that the use of a dehydrating agent such as concentrated sulfuric acid, phosphorus oxychloride, polyphosphoric acid or the like is effective for proceeding the ring-closing reaction to the oxazole ring at a low temperature (for example, see Non-Patent Document 1). . However, it is not appropriate to add these dehydrating agents to the PBO precursor resin composition in view of the stability of the composition, and no satisfactory one has been proposed yet.
さらには、このPBO前駆体樹脂組成物は、アルカリ性水溶液で現像可能なポジ型感光性樹脂組成物として用いられることが多い(例えば、特許文献1など参照)。このポジ型感光性樹脂の現像メカニズムは、未露光部の感光性ジアゾキノン化合物がアルカリ性水溶液に不溶であるのに対し、露光することにより該感光性ジアゾキノン化合物が化学変化を起こしインデンカルボン酸化合物となってアルカリ性水溶液に可溶となることを利用したものである。この露光部と未露光部の間の現像液に対する溶解速度の差を利用し、未露光部のみのレリーフパターンの作製が可能となる。 Furthermore, this PBO precursor resin composition is often used as a positive photosensitive resin composition that can be developed with an alkaline aqueous solution (see, for example, Patent Document 1). The development mechanism of this positive photosensitive resin is that the photosensitive diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but when exposed, the photosensitive diazoquinone compound undergoes a chemical change to become an indenecarboxylic acid compound. It makes use of being soluble in an alkaline aqueous solution. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, it becomes possible to produce a relief pattern of only the unexposed portion.
PBO前駆体樹脂組成物を、感光性ジアゾキノン化合物を含むポジ型感光性樹脂組成物に用いた場合に、オキサゾール環への閉環を促進させる手法の選択は安定性、リソグラフィー性能の観点から、さらに困難である。これに対して特許文献2ではポリオキサゾール前駆体、活性光線照射により酸を発生する化合物に加え、加熱により塩基を発生するアミンイミド化合物を含有してなる感光性樹脂組成物が提案されている。さらに特許文献3では、低温硬化性に優れるポジ型感光性樹脂組成物として、アルカリ可溶性樹脂、ジアゾキノン化合物、及び脂肪族スルホン酸化合物を含むことを特徴とするポジ型感光性樹脂組成物が提案されており、また特許文献4では、低い熱硬化温度で使用してもPBOの閉環反応が十分進行するポジ型感光性樹脂組成物として、ヒドロキシポリアミド、エステル化合物、及び感光性ジアゾキノン化合物を含むことを特徴とするポジ型感光性樹脂組成物が提案されている。
これらの技術に比して本発明の耐熱性樹脂組成物は280℃以下でのオキサゾール環への閉環反応、組成物の安定性、リソグラフィー特性を、より高い次元で満たすものである。
When the PBO precursor resin composition is used for a positive photosensitive resin composition containing a photosensitive diazoquinone compound, it is more difficult to select a method for promoting the ring closure to the oxazole ring from the viewpoint of stability and lithography performance. It is. On the other hand, Patent Document 2 proposes a photosensitive resin composition containing an amine imide compound that generates a base by heating in addition to a polyoxazole precursor and a compound that generates an acid upon irradiation with actinic rays. Further, Patent Document 3 proposes a positive photosensitive resin composition comprising an alkali-soluble resin, a diazoquinone compound, and an aliphatic sulfonic acid compound as a positive photosensitive resin composition having excellent low-temperature curability. Patent Document 4 includes a hydroxypolyamide, an ester compound, and a photosensitive diazoquinone compound as a positive photosensitive resin composition in which the ring closure reaction of PBO proceeds sufficiently even when used at a low thermosetting temperature. A characteristic positive photosensitive resin composition has been proposed.
Compared with these techniques, the heat-resistant resin composition of the present invention satisfies the cyclization reaction to the oxazole ring at 280 ° C. or lower, the stability of the composition, and the lithography properties at a higher level.
本発明は、低い熱硬化温度で使用してもPBOの閉環反応が充分進行する耐熱性樹脂組成物、該組成物を用いた硬化レリーフパターンの製造方法、並びに該硬化レリーフパターンを有してなる半導体装置を提供することを目的とする。さらに、感光性ジアゾキノン化合物を含有する場合には、低い熱硬化温度で使用してもPBOの閉環反応が充分進行することに加えて、高感度な耐熱性樹脂組成物、該組成物を用いた硬化レリーフパターンの製造方法、並びに該硬化レリーフパターンを有してなる半導体装置を提供することを目的とする。 The present invention comprises a heat-resistant resin composition in which the ring closing reaction of PBO proceeds sufficiently even when used at a low thermosetting temperature, a method for producing a cured relief pattern using the composition, and the cured relief pattern. An object is to provide a semiconductor device. Furthermore, in the case of containing a photosensitive diazoquinone compound, the PBO ring-closing reaction sufficiently proceeds even when used at a low thermosetting temperature, and a highly sensitive heat-resistant resin composition and the composition were used. It is an object of the present invention to provide a method for producing a cured relief pattern and a semiconductor device having the cured relief pattern.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、特定の構造を有するヒドロキシポリアミドに可塑剤を組み合わせることで、上記の課題を解決する耐熱性樹脂組成物が得られることを見出し、本発明をなすに至った。
すなわち、本発明の第一は、下記の一般式(1)で表わされる繰り返し単位を有するヒドロキシポリアミド100質量部に対し、可塑剤1〜50質量部を含有することを特徴とする耐熱性樹脂組成物である。
As a result of intensive studies to solve the above problems, the inventor has obtained a heat-resistant resin composition that solves the above problems by combining a plasticizer with a hydroxy polyamide having a specific structure. The headline and the present invention were made.
That is, the first of the present invention is a heat-resistant resin composition comprising 1 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of a hydroxypolyamide having a repeating unit represented by the following general formula (1). It is a thing.
また本発明の耐熱性樹脂組成物においては、さらに感光性ジアゾキノン化合物1〜50質量部を含有することが好ましい。
さらに本発明の耐熱性樹脂組成物においては可塑剤が、フタル酸エステル類、二塩基脂肪酸エステル類、スルホンアミド類から選択される少なくとも1つの化合物であることがより好ましく、さらに好ましくは可塑剤が、フタル酸エステル類であることが最も好ましい。
Moreover, in the heat resistant resin composition of this invention, it is preferable to contain 1-50 mass parts of photosensitive diazoquinone compounds further.
Furthermore, in the heat resistant resin composition of the present invention, the plasticizer is more preferably at least one compound selected from phthalic acid esters, dibasic fatty acid esters, and sulfonamides, and more preferably the plasticizer is Most preferred are phthalates.
また本発明の第二は、(1)上述の耐熱性樹脂組成物を層またはフィルムの形で基板上に形成し、(2)マスクを介して化学線で露光するか、光線、電子線またはイオン線を直接照射し、(3)露光部または照射部を溶出除去し、(4)得られたレリーフパターンを加熱処理することを特徴とする硬化レリーフパターンの製造方法である。
さらに本発明の第三は、上述硬化レリーフパターンの製造方法で得られた硬化レリーフパターン層を有してなる半導体装置である。
In the second aspect of the present invention, (1) the above-mentioned heat-resistant resin composition is formed on a substrate in the form of a layer or a film, and (2) it is exposed with actinic radiation through a mask, or a light beam, an electron beam or It is a method for producing a cured relief pattern, characterized by directly irradiating an ion beam, (3) eluting and removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern.
Furthermore, a third aspect of the present invention is a semiconductor device having a cured relief pattern layer obtained by the above-described method for producing a cured relief pattern.
本発明によれば、低い熱硬化温度で使用してもPBOの閉環反応が充分進行する新規な耐熱性樹脂組成物、該組成物を用いた硬化レリーフパターンの製造方法、並びに該硬化レリーフパターンを有してなる半導体装置が提供される。さらに、感光性ジアゾキノン化合物を含有する場合には、低い熱硬化温度で使用してもPBOの閉環反応が充分進行することに加えて、高感度である新規な耐熱性樹脂組成物、該組成物を用いた硬化レリーフパターンの製造方法、並びに該硬化レリーフパターンを有してなる半導体装置を提供することを目的とする。 According to the present invention, a novel heat-resistant resin composition in which the ring closure reaction of PBO proceeds sufficiently even when used at a low thermosetting temperature, a method for producing a cured relief pattern using the composition, and the cured relief pattern A semiconductor device is provided. Further, when a photosensitive diazoquinone compound is contained, a novel heat-resistant resin composition having high sensitivity, in addition to sufficiently progressing the ring-closing reaction of PBO even when used at a low thermosetting temperature, the composition An object of the present invention is to provide a method for producing a cured relief pattern using, and a semiconductor device having the cured relief pattern.
<耐熱性樹脂組成物>
本発明の耐熱性樹脂組成物を構成する各成分について、以下具体的に説明する。
(A)ヒドロキシポリアミド
本発明の耐熱性樹脂組成物のベースポリマーであるヒドロキシポリアミドは、下記一般式(1)のジヒドロキシジアミド単位m個を含むポリマーである。該ジヒドロキシジアミド単位は、X1(NH2)2(OH)2の構造を有するビスアミノフェノールおよびY1(COOH)2の構造を有するジカルボン酸からなる。ここで、該ビスアミノフェノールの2組のアミノ基とヒドロキシ基はそれぞれ互いにオルト位にあるものであり、該ヒドロキシポリアミドを閉環して、耐熱性樹脂であるポリベンズオキサゾールに変化する。mは2〜1000の範囲が好ましく、3〜50の範囲がより好ましく、3〜20の範囲であることが最も好ましい。該ヒドロキシポリアミドには、必要に応じて、下記一般式(1)のジアミド単位n個を縮合させてもよい。該ジアミド単位は、X2(NH2)2の構造を有するジアミンおよびY2(COOH)2の構造を有するジカルボン酸からなる。nは0〜500の範囲が好ましく、0〜10の範囲がより好ましい。ヒドロキシポリアミド中における該ジアミド単位の割合が高すぎると現像液として使用するアルカリ性水溶液への溶解性が低下するので、m/(m+n)の値は0.5以上であることが好ましく、0.7以上であることがより好ましく、0.8以上であることが最も好ましい。
<Heat resistant resin composition>
Each component which comprises the heat resistant resin composition of this invention is demonstrated concretely below.
(A) Hydroxypolyamide The hydroxypolyamide, which is the base polymer of the heat-resistant resin composition of the present invention, is a polymer containing m dihydroxydiamide units of the following general formula (1). The dihydroxydiamide unit consists of a bisaminophenol having a structure of X 1 (NH 2 ) 2 (OH) 2 and a dicarboxylic acid having a structure of Y 1 (COOH) 2 . Here, the two groups of amino group and hydroxy group of the bisaminophenol are each in the ortho position, and the hydroxypolyamide is closed to change into polybenzoxazole which is a heat resistant resin. m is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20. If necessary, the hydroxypolyamide may be condensed with n diamide units of the following general formula (1). The diamide unit is composed of a diamine having a structure of X 2 (NH 2 ) 2 and a dicarboxylic acid having a structure of Y 2 (COOH) 2 . n is preferably in the range of 0 to 500, and more preferably in the range of 0 to 10. If the ratio of the diamide unit in the hydroxy polyamide is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of m / (m + n) is preferably 0.5 or more, 0.7 More preferably, it is more preferably 0.8 or more.
X1(NH2)2(OH)2の構造を有するビスアミノフェノールとしては、例えば、3,3’−ジヒドロキシベンジジン、3,3’−ジアミノ−4,4’−ジヒドロキシビフェニル、4,4’−ジアミノ−3,3’−ジヒドロキシビフェニル、3,3’−ジアミノ−4,4’−ジヒドロキシジフェニルスルホン、4,4’−ジアミノ−3,3’−ジヒドロキシジフェニルスルホン、ビス−(3−アミノ−4−ヒドロキシフェニル)メタン、2,2−ビス−(3−アミノ−4−ヒドロキシフェニル)プロパン、2,2−ビス−(3−アミノ−4−ヒドロキシフェニル)ヘキサフルオロプロパン、2,2−ビス−(4−アミノ−3−ヒドロキシフェニル)ヘキサフルオロプロパン、ビス−(4−アミノ−3−ヒドロキシフェニル)メタン、2,2−ビス−(4−アミノ−3−ヒドロキシフェニル)プロパン、4,4’−ジアミノ−3,3’−ジヒドロキシベンゾフェノン、3,3’−ジアミノ−4,4’−ジヒドロキシベンゾフェノン、4,4’−ジアミノ−3,3’−ジヒドロ
キシジフェニルエーテル、3,3’−ジアミノ−4,4’−ジヒドロキシジフェニルエーテル、1,4−ジアミノ−2,5−ジヒドロキシベンゼン、1,3−ジアミノ−2,4−ジヒドロキシベンゼン、1,3−ジアミノ−4,6−ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは単独あるいは混合して使用してもよい。
Examples of the bisaminophenol having the structure of X 1 (NH 2 ) 2 (OH) 2 include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-diamino-4,6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.
これらのビスアミノフェノールのうち特に好ましいものは、X1が下記から選ばれる芳香族基の場合である。
また、X2(NH2)2の構造を有するジアミンとしては、芳香族ジアミン、シリコンジアミンなどが挙げられる。
このうち芳香族ジアミンとしては、例えば、m−フェニレンジアミン、p−フェニレンジアミン、2,4−トリレンジアミン、3,3’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルスルホン、3,3’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルスルフィド、3,3’−ジアミノジフェニルケトン、4,4’−ジアミノジフェニルケトン、3,4’−ジアミノジフェニルケトン、2,2’−ビス(4−アミノフェニル)プロパン、2,2’−ビス(4−アミノフェニル)ヘキサフルオロプロパン、1,3−ビス(3−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,4−ビス(4−アミノフェノキシ)ベンゼン、4−メチル−2,4−ビス(4−アミノフェニル)−1−ペンテン、4−メチル−2,4−ビス(4−アミノフェニル)−2−ペンテン、1,4−ビス(α,α−ジメチル−4−アミノベンジル)ベンゼン、イミノ−ジ−p−フェニレンジアミン、1,5−ジアミノナフタレン、2,6−ジアミノナフタレン、4−メチル−2,4−ビス(4−アミノフェニル)ペンタン、5(または6)−アミノ−1−(4−アミノフェニル)−1,3,3−トリメチルインダン、ビス(p−アミノフェニル)ホスフィンオキシド、4,4’−ジアミノアゾベンゼン、4,4’−ジアミノジフェニル尿素、4,4’−ビス(4−アミノフェノキシ)ビフェニル、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス[4−(3−アミノフェノキシ)フェニル]ベンゾフェノン、4,4’−ビス(4−アミノフェノキシ)ジフェニルスルホン、4,4’−ビス[4−(α,α−ジメチル−4−アミノベンジル)フェノキシ]ベンゾフェノン、4,4’−ビス[4−(α,α−ジメチル−4−アミノベンジル)フェノキシ]ジフェニルスルホン、4,4’−ジアミノビフェニル、4,4’−ジアミノベンゾフェノン、フェニルインダンジアミン、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、3,3’−ジメチル−4,4’−ジアミノビフェニル、o−トルイジンスルホン、2,2−ビス(4−アミノフェノキシフェニル)プロパン、ビス(4−アミノフェノキシフェニル)スルホン、ビス(4−アミノフェノキシフェニル)スルフィド、1,4−(4−アミノフェノキシフェニル)ベンゼン、1,3−(4−アミノフェノキシフェニル
)ベンゼン、9,9’−ビス(4−アミノフェニル)フルオレン、4,4’−ジ−(3−アミノフェノキシ)ジフェニルスルホン、4,4’−ジアミノベンズアニリドおよびこれら芳香族ジアミンの芳香核の水素原子が、塩素原子、フッ素原子、臭素原子、メチル基、メトキシ基、シアノ基、フェニル基からなる群より選ばれた少なくとも一種の基または原子によって置換された化合物が挙げられる。
As the diamine having a structure of X 2 (NH 2) 2, an aromatic diamine, such as silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9′-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4, 4′-diaminobenzanilide and at least one group selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group, as the hydrogen atom of the aromatic nucleus of these aromatic diamines Or the compound substituted by the atom is mentioned.
また、基材との接着性を高めるためにシリコンジアミンを選択することができ、この例としては、ビス(4−アミノフェニル)ジメチルシラン、ビス(4−アミノフェニル)テトラメチルシロキサン、ビス(4−アミノフェニル)テトラメチルジシロキサン、ビス(γ−アミノプロピル)テトラメチルジシロキサン、1,4−ビス(γ−アミノプロピルジメチルシリル)ベンゼン、ビス(4−アミノブチル)テトラメチルジシロキサン、ビス(γ−アミノプロピル)テトラフェニルジシロキサン等が挙げられる。 Further, silicon diamine can be selected in order to enhance the adhesion to the substrate. Examples of this include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and bis (4 -Aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis ( γ-aminopropyl) tetraphenyldisiloxane and the like.
また、Y1(COOH)2またはY2(COOH)2の構造を有する好ましいジカルボン酸としては、Y1、Y2が下記から選ばれた芳香族基の場合が挙げられる。
これらのうちジカルボン酸の好ましい例としては、4,4’−ジフェニルエーテルジカルボン酸やイソフタル酸が挙げられ、該ジカルボン酸を塩素化した4,4’−ジフェニルエーテルジカルボニルクロライドやイソフタロイルクロリドがPBO前駆体のヒドロキシポリアミドの合成に用いられる。 Among these, preferred examples of dicarboxylic acids include 4,4′-diphenyl ether dicarboxylic acid and isophthalic acid, and 4,4′-diphenyl ether dicarbonyl chloride or isophthaloyl chloride obtained by chlorinating the dicarboxylic acid is a PBO precursor. Used in the synthesis of natural hydroxypolyamides.
上記一般式(1)で示される繰り返し単位を有するヒドロキシポリアミドにおいて、その末端基を特定の有機基で封止することも本発明の範囲に含まれる。
このような封止基としては、例えば、特開平05−197153号公報に記載されているような不飽和結合を有する基、または、4−メチルシクロヘキシル−1,2−ジカルボン酸無水物が挙げられ、これらで封止した場合、加熱硬化後の塗膜の機械物性(特に伸度)や、硬化レリーフパターン形状が良好となることが期待される。このような封止基のうちの好適例としては、下記基が挙げられる。
In the hydroxypolyamide having the repeating unit represented by the general formula (1), it is also included in the scope of the present invention to seal the terminal group with a specific organic group.
Examples of such a blocking group include a group having an unsaturated bond as described in JP-A No. 05-197153, or 4-methylcyclohexyl-1,2-dicarboxylic anhydride. When sealed with these, it is expected that the mechanical properties (particularly elongation) of the coating film after heat curing and the cured relief pattern shape will be good. Preferable examples of such a sealing group include the following groups.
(B)可塑剤
本発明の耐熱性樹脂組成物においては、可塑剤を含有させることが重要である。可塑剤としてはフタル酸ジメチル、フタル酸ジエチル、フタル酸ジプロピル、フタル酸ジイソプロピル、フタル酸ジブチル、フタル酸ジイソブチル、フタル酸ジアミル、フタル酸ジ−n−ヘキシル、フタル酸ジシクロヘキシル、フタル酸ジヘプチル、フタル酸ジ−n−オクチル、フタル酸ジノニル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジウンデシル、フタル酸ジトリデシル、フタル酸ジフェニル、フタル酸ジ(2−エチルヘキシル)、フタル酸ジ(2−ブトキシエチル)、フタル酸ベンジル2−エチルヘキシル、フタル酸ベンジルn−ブチル、フタル酸ベンジルイソノニル、イソフタル酸ジメチルなどのフタル酸エステル類、トリメリット酸トリス(2−エチルヘキシル)などのトリメリット酸エステル類、アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸ジ−n−プロピル、アジピン酸ジイソプロピル、アジピン酸ジイソブチル、アジピン酸ジイソノニル、アジピン酸ジイソデシル、アジピン酸ジ(2−ブトキシエチル)、アジピン酸ジ(2−エチルヘキシル)、アジピン酸ジ(ブチルジグリコール)、アジピン酸ヘプチルノニル、アゼライン酸ジメチル、アゼライン酸ジ(2−エチルヘキシル)、コハク酸ジエチル、セバシン酸ジメチル、セバシン酸ジエチル、セバシン酸ジブチル、セバシン酸ジ−n−オクチル、セバシン酸ジ(2−エチルヘキシル)、フマル酸ジブチル、フマル酸ジ(2−エチルヘキシル)、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジ−n−ブチル、マレイン酸ジ(2−エチルヘキシル)、などの二塩基脂肪酸エステル類、リン酸トリメチル、リン酸トリエチル、リン酸トリブチル、リン酸トリ−n−アミル、リン酸トリフェニル、リン酸トリ−o−クレシル、リン酸トリキシレニル、リン酸ジフェニル2−エチルヘキシル、リン酸ジフェニルクレシル、リン酸トリス(2−ブトキシエチル)、リン酸トリス(2−エチルヘキシル)などのリン酸エステル類、ジエチレングリコールジアセチレート、ジエチレングリコールジベンゾエート、グリセロールモノオレイエート、グリセロールトリブチレート、グリセロールトリアセテート、トリエチレングリコールジアセテートなどの多価アルコールのエステル、クエン酸トリメチル、クエン酸トリエチル、クエン酸トリ−n−プロピル、クエン酸トリブチル、クエン酸トリ−n−アミル、エチルフタリルエチルグリコラート、ブチルフタリルブチルグリコラート、O−アセチルクエン酸トリエチル、O−アセチルクエン酸トリブチル、o−アセチルリシノール酸メチルなどのヒドロキシカルボン酸エステル類、p−トルエンスルホンアミド、N−メチル−p−トルエンスルホンアミド、N−エチル−p−トルエンスルホンアミド、N−シクロヘキシル−p−トルエンスル
ホンアミド、N,N−ジエチル−p−トルエンスルホンアミド、N,N−ビス(2−ヒドロキシエチル)−p−トルエンスルホンアミド、o−トルエンスルホンアミド、N−エチル−o−トルエンスルホンアミド、ベンゼンスルホンアミド、N−n−ブチルベンゼンスルホンアミド、p−ヒドロキシベンゼンスルホンアミド、o−ニトロベンゼンスルホンアミド、p−ニトロベンゼンスルホンアミド、スルファニルアミドなどのスルホンアミド類、ポリ(1,3−ブタンジオールアジペート)等のポリエステル、サンソサイザーE−PS、サンソサイザーEP−O、サンソサイザーE−4030、サンソサイザーE−6000、サンソサイザーE−2000H、サンソサイザーE−9000H(商品名、新日本理化社製)などのエポキシ系、アルフォンUP−1000、アルフォンUP−1010、アルフォンUP−1021、アルフォンUP−1061、アルフォンUP−1080、アルフォンUP−1190、アルフォンUG−4000、アルフォンUG−4010(商品名、東亞合成社製)などのアクリル樹脂系、カンファー、ニトロビフェニル等が挙げられる。
(B) Plasticizer In the heat resistant resin composition of the present invention, it is important to contain a plasticizer. Plasticizers include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, di-n-hexyl phthalate, dicyclohexyl phthalate, diheptyl phthalate, phthalic acid Di-n-octyl, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, diphenyl phthalate, di (2-ethylhexyl) phthalate, di (2-butoxyethyl) phthalate, phthalate Phenylates such as benzyl 2-ethylhexyl acrylate, benzyl n-butyl phthalate, benzylisononyl phthalate, dimethyl isophthalate, trimellitic esters such as trimellitic acid tris (2-ethylhexyl), adipic acid Methyl, diethyl adipate, di-n-propyl adipate, diisopropyl adipate, diisobutyl adipate, diisononyl adipate, diisodecyl adipate, di (2-butoxyethyl) adipate, di (2-ethylhexyl) adipate, adipine Di (butyldiglycol) acid, heptylnonyl adipate, dimethyl azelate, di (2-ethylhexyl) azelate, diethyl succinate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, sebacin Dibasic acid di (2-ethylhexyl), dibutyl fumarate, di (2-ethylhexyl) fumarate, dimethyl maleate, diethyl maleate, di-n-butyl maleate, di (2-ethylhexyl) maleate, etc. Fatty acid Tellurium, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-n-amyl phosphate, triphenyl phosphate, tri-o-cresyl phosphate, trixylenyl phosphate, diphenyl 2-ethylhexyl phosphate, diphenyl phosphate Phosphoric esters such as cresyl, tris (2-butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, diethylene glycol diacetylate, diethylene glycol dibenzoate, glycerol monooleate, glycerol tributyrate, glycerol triacetate, Esters of polyhydric alcohols such as triethylene glycol diacetate, trimethyl citrate, triethyl citrate, tri-n-propyl citrate, tributyl citrate, tri-n-amyl citrate, ethyl phthalyl ethyl Hydroxyglycolates such as luglycolate, butylphthalylbutylglycolate, triethyl O-acetylcitrate, tributyl O-acetylcitrate, methyl o-acetylricinoleate, p-toluenesulfonamide, N-methyl-p- Toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, N, N-diethyl-p-toluenesulfonamide, N, N-bis (2-hydroxyethyl) -p- Toluenesulfonamide, o-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, p-hydroxybenzenesulfonamide, o-nitrobenzenesulfonamide, p-nitroben Sulfonamides such as polysulfonamide, sulfanilamide, polyesters such as poly (1,3-butanediol adipate), SUNSOSIZER E-PS, SUNSOSIZER EP-O, SUNSOSIZER E-4030, SUNSOSIZER E-6000, Epoxy systems such as SUNSOSIZER E-2000H and SUNSOSIZER E-9000H (trade name, manufactured by Shin Nippon Chemical Co., Ltd.), Alfon UP-1000, Alfon UP-1010, Alfon UP-1021, Alfon UP-1061, Alfon UP-1080 , Alfon UP-1190, Alfon UG-4000, Alfon UG-4010 (trade name, manufactured by Toagosei Co., Ltd.), camphor, nitrobiphenyl, and the like.
中でも、可塑剤としては、フタル酸エステル類、二塩基脂肪酸エステル類、スルホンアミド類から選択される化合物であることがより好ましい。
さらに、可塑剤は、フタル酸エステル類から選択される化合物であることが最も好ましい。
上述の可塑剤を、前述のヒドロキシポリアミドに加えると、280℃以下の低い温度での熱処理でもPBOの環化反応が充分に進行し、優れた耐熱性と電気特性、機械特性などを発現する。
可塑剤の添加量としては、ヒドロキシポリアミド100質量部に対して、1〜50質量部が好ましく、10〜50質量部がより好ましく、15〜50質量部がさらに好ましい。可塑剤の添加量は1質量部以上であれば280℃以下の低温での熱処理でPBOの環化促進効果が得られ、50質量部以下であれば得られた硬化膜の特性を損なうことがない。
Among these, the plasticizer is more preferably a compound selected from phthalic acid esters, dibasic fatty acid esters, and sulfonamides.
Furthermore, the plasticizer is most preferably a compound selected from phthalates.
When the above-mentioned plasticizer is added to the above-mentioned hydroxypolyamide, the cyclization reaction of PBO sufficiently proceeds even under heat treatment at a low temperature of 280 ° C. or less, and excellent heat resistance, electrical properties, mechanical properties, etc. are exhibited.
As addition amount of a plasticizer, 1-50 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide, 10-50 mass parts is more preferable, 15-50 mass parts is further more preferable. If the added amount of the plasticizer is 1 part by mass or more, the effect of promoting cyclization of PBO can be obtained by heat treatment at a low temperature of 280 ° C. or less, and if it is 50 parts by mass or less, the properties of the obtained cured film may be impaired. Absent.
(C)感光性ジアゾキノン化合物
本発明で用いる感光性ジアゾキノン化合物は、1,2−ナフトキノンジアジド構造を有する化合物であり、米国特許第2,772,972号明細書、第2,797,213号明細書、第3,669,658号明細書により公知の物質である。好ましいものの例としては、例えば、下記のものが挙げられる。
(C) Photosensitive diazoquinone compound The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-naphthoquinonediazide structure, and U.S. Pat. Nos. 2,772,972 and 2,797,213. No. 3,669,658, which is a known substance. As an example of a preferable thing, the following are mentioned, for example.
これらの中で特に好ましいものとしては下記のものがある。
感光性ジアゾキノン化合物のヒドロキシポリアミドへの配合量は、該ヒドロキシポリアミド100質量部に対し、1〜50質量部が好ましく、10〜30質量部がより好ましい。感光性ジアゾキノン化合物の配合量が1質量部以上だと樹脂のパターニング性が良好であり、逆に50質量部を以下であれば硬化後の膜の引張り伸び率が保たれ、露光部の現像残渣(スカム)の発生は抑制される。 1-50 mass parts is preferable with respect to 100 mass parts of said hydroxy polyamide, and, as for the compounding quantity to the hydroxy polyamide of the photosensitive diazoquinone compound, 10-30 mass parts is more preferable. If the blending amount of the photosensitive diazoquinone compound is 1 part by mass or more, the patterning property of the resin is good. Conversely, if it is 50 parts by mass or less, the tensile elongation rate of the cured film is maintained, and the development residue in the exposed part The occurrence of (scum) is suppressed.
(D)その他の成分
本発明の耐熱性樹脂組成物には、必要に応じて、染料、界面活性剤、基板との密着性を高めるための接着助剤、架橋剤を添加することも可能である。
上記添加剤について更に具体的に述べると、染料としては、例えば、メチルバイオレット、クリスタルバイオレット、マラカイトグリーン等が挙げられる。
染料の添加量としては、ヒドロキシポリアミド100質量部に対して、0.1〜30質量部が好ましい。
(D) Other components In the heat-resistant resin composition of the present invention, if necessary, a dye, a surfactant, an adhesion aid for enhancing adhesion to the substrate, and a crosslinking agent can be added. is there.
The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green.
As addition amount of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.
また、界面活性剤としては、例えば、ポリプロピレングリコールまたはポリオキシエチレンラウリルエーテル等のポリグリコール類あるいはその誘導体からなる非イオン系界面活性剤、例えばフロラード(商品名、住友3M社製)、メガファック(商品名、大日本インキ化学工業社製)あるいはスルフロン(商品名、旭硝子社製)等のフッ素系界面活性剤、例えばKP341(商品名、信越化学工業社製)、DBE(商品名、チッソ社製)、グラノール(商品名、共栄社化学社製)等の有機シロキサン界面活性剤が挙げられる。
界面活性剤の添加量としては、ヒドロキシポリアミド100質量部に対して、0.01〜10質量部が好ましい。
Examples of the surfactant include non-ionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether, or derivatives thereof, such as Fluorard (trade name, manufactured by Sumitomo 3M), Megafuck ( Fluorosurfactants such as trade name, Dainippon Ink and Chemicals) or Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso) ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
As addition amount of surfactant, 0.01-10 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.
また、接着助剤としては、例えば、アルキルイミダゾリン、酪酸、アルキル酸、ポリヒドロキシスチレン、ポリビニルメチルエーテル、t−ブチルノボラック、エポキシシラン、エポキシポリマー等、および各種シランカップリング剤が挙げられる。
シランカップリング剤の具体的な好ましい例としては、例えば、N−フェニル−3−アミノプロピルトリアルコキシシラン、3−メルカプトプロピルトリアルコキシシラン、2−(トリアルコキシシリルエチル)ピリジン、3−メタクリロキシプロピルトリアルコキシシラン、3−メタクリロキシプロピルジアルコキシアルキルシラン、3−グリシドキシ
プロピルトリアルコキシシラン、3−グリシドキシプロピルジアルコキシアルキルシラン、3−アミノプロピルトリアルコキシシランもしくは3−アミノプロピルジアルコキシアルキルシラン並びに酸無水物もしくは酸二無水物の反応物、3−アミノプロピルトリアルコキシシランまたは3−アミノプロピルジアルコキシアルキルシランのアミノ基をウレタン基またはウレア基に変換したものなどを挙げることができる。なお、この際のアルキル基としてはメチル基、エチル基、ブチル基などが、酸無水物としてはマレイン酸無水物、フタル酸無水物などが、酸二無水物としてはピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、4,4’−オキシジフタル酸二無水物などが、ウレタン基としてはt−ブトキシカルボニルアミノ基などが、ウレア基としてはフェニルアミノカルボニルアミノ基などが挙げられる。
接着助剤の添加量としては、ヒドロキシポリアミド100質量部に対して、0.1〜30質量部が好ましい。
Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.
Specific preferred examples of the silane coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, and 3-methacryloxypropyl. Trialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkyl Silane and acid anhydride or acid dianhydride reactant, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane amino group converted to urethane group or urea group And the like of. In this case, methyl group, ethyl group, butyl group, etc. as the alkyl group, maleic anhydride, phthalic anhydride, etc. as the acid anhydride, pyromellitic dianhydride as the acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc., t-butoxycarbonylamino group as a urethane group, phenylamino as a urea group Examples thereof include a carbonylamino group.
The addition amount of the adhesion assistant is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the hydroxy polyamide.
架橋剤としては、1,1,2,2−テトラ(p−ヒドロキシフェニル)エタン、テトラグリシジルエーテル、グリセロールトリグリシジルエーテル、オルソセカンダリーブチルフェニルグリシジルエーテル、1,6−ビス(2,3−エポキシプロポキシ)ナフタレン、ジグリセロールポリグリシジルエーテル、ポリエチレングリコールグリシジルエーテルなどのエポキシ化合物、アセチルアセトンアルミ(III)塩、アセチルアセトンチタン(IV)塩、アセチルアセトンクロム(III)塩、アセチルアセトンマグネシウム(II)塩、アセチルアセトンニッケル(II)塩、トリフルオロアセチルアセトンアルミ(III)塩、トリフルオロアセチルアセトンチタン(IV)塩、トリフルオロアセチルアセトンクロム(III)塩、トリフルオロアセチルアセトンマグネシウム(II)塩、トリフルオロアセチルアセトンニッケル(II)塩などの金属キレート剤、ニカラックMW−30MH、MW−100LH(商品名、三和ケミカル社製)、サイメル300、サイメル303(商品名、三井サイテック社製)などのアルキル化メラミン樹脂が挙げられる。
架橋剤の添加量としては、ヒドロキシポリアミド100質量部に対して、0.1〜30質量部が好ましい。
Examples of the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethane, tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy ) Epoxy compounds such as naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone magnesium (II) ) Salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, Metal chelating agents such as fluoroacetylacetone magnesium (II) salt and trifluoroacetylacetone nickel (II) salt, Nicalak MW-30MH, MW-100LH (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, Cymel 303 (trade name, And alkylated melamine resins such as Mitsui Cytec).
As addition amount of a crosslinking agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.
(E)溶剤
本発明においては、これらの成分を溶剤に溶解してワニス状にし、耐熱性樹脂組成物として使用しても良い。このような溶剤としては、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を単独または混合して使用できる。これらの溶媒のうち、非アミド系溶媒がフォトレジストなどへの影響が少ない点から好ましく、具体的なより好ましい例としてはγ−ブチロラクトン、シクロペンタノン、シクロヘキサノン、イソホロンなどを挙げることができる。
溶剤の添加量としては、ヒドロキシポリアミド100質量部に対して、50〜1000質量部が好ましい。
(E) Solvent In the present invention, these components may be dissolved in a solvent to form a varnish and used as a heat resistant resin composition. Examples of such a solvent 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- Methoxypropionate or the like can be used alone or in combination. Of these solvents, non-amide solvents are preferable from the viewpoint of little influence on photoresists, and specific more preferable examples include γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone and the like.
As addition amount of a solvent, 50-1000 mass parts is preferable with respect to 100 mass parts of hydroxy polyamide.
<硬化レリーフパターン、及び半導体装置の製造方法>
次に、本発明の耐熱性樹脂組成物を基板に塗布して硬化レリーフパターンを製造する方法について、以下具体的に説明する。
第一番目に、本発明の耐熱性樹脂組成物を、例えば、シリコンウエハー、セラミック基板、アルミ基板等の基板に、スピナーを用いた回転塗布やロールコーターにより塗布する。これをオーブンやホットプレートを用いて50〜140℃で乾燥して溶媒を除去する。
第二番目に、マスクを介して、コンタクトアライナーやステッパを用いて化学線による露光を行うか、光線、電子線またはイオン線を直接照射する。
第三番目に、照射部を現像液で溶解除去し、引き続きリンス液によるリンスを行うことで所望のレリーフパターンを得る。現像方法としてはスプレー、パドル、ディップ、超音波等の方式が可能である。リンス液は蒸留水、脱イオン水等が使用できる。
<Curing relief pattern and method for manufacturing semiconductor device>
Next, a method for producing a cured relief pattern by applying the heat resistant resin composition of the present invention to a substrate will be specifically described below.
First, the heat-resistant resin composition of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spinner or a roll coater. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent.
Second, exposure with actinic radiation is performed through a mask using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated.
Third, the irradiated portion is dissolved and removed with a developer, and then rinsed with a rinse solution to obtain a desired relief pattern. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.
本発明の耐熱性樹脂組成物により形成された樹脂膜を現像するために用いられる現像液は、アルカリ可溶性ポリマーを溶解除去するものであり、アルカリ化合物を溶解したアルカリ性水溶液であることが必要である。現像液中に溶解されるアルカリ化合物は、無機アルカリ化合物、有機アルカリ化合物のいずれであってもよい。
該無機アルカリ化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、リン酸水素二アンモニウム、リン酸水素二カリウム、リン酸水素二ナトリウム、ケイ酸リチウム、ケイ酸ナトリウム、ケイ酸カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、ホウ酸リチウム、ホウ酸ナトリウム、ホウ酸カリウム、アンモニア等が挙げられる。
The developer used for developing the resin film formed by the heat resistant resin composition of the present invention is for dissolving and removing the alkali-soluble polymer, and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. . The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.
また、該有機アルカリ化合物としては、例えば、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、トリメチルヒドロキシエチルアンモニウムヒドロキシド、メチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、n−プロピルアミン、ジ−n−プロピルアミン、イソプロピルアミン、ジイソプロピルアミン、メチルジエチルアミン、ジメチルエタノールアミン、エタノールアミン、トリエタノールアミン等が挙げられる。
さらに、必要に応じて、上記アルカリ性水溶液に、メタノール、エタノール、プロパノール、エチレングリコール等の水溶性有機溶媒、界面活性剤、保存安定剤、樹脂の溶解抑止剤等を適量添加することができる。
Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, or the like can be added to the alkaline aqueous solution.
最後に、得られたレリーフパターンを加熱処理して、ポリベンズオキサゾール構造を有する耐熱性硬化レリーフパターンを形成することができる。この加熱処理は、180℃以上の温度を5分間以上与えるものであり、ある一定温度を保っても良いし、連続的に昇温してもよい。好ましい加熱処理条件は最高温度が200℃以上で、200℃以上である時間が30分間以上のものである。
具体的には、MRAM、有機半導体、銅配線を有するCMOS等の300℃以上の加熱ができない耐熱性に劣る半導体装置の製造に本発明の組成物を使用する場合は、加熱処理温度を180〜290℃にすることが好ましく、220〜250℃にすることがより好ましい。一方、300℃以上に加熱することに問題のない半導体装置の製造に使用する場合は、300〜350℃にすることがより好ましい。
Finally, the obtained relief pattern can be heat-treated to form a heat-resistant cured relief pattern having a polybenzoxazole structure. In this heat treatment, a temperature of 180 ° C. or higher is applied for 5 minutes or more, and a certain constant temperature may be maintained, or the temperature may be continuously increased. Preferred heat treatment conditions are such that the maximum temperature is 200 ° C. or higher and the time of 200 ° C. or higher is 30 minutes or longer.
Specifically, when the composition of the present invention is used for the production of a semiconductor device having inferior heat resistance, such as MRAM, organic semiconductor, and CMOS having copper wiring, which cannot be heated at 300 ° C. or higher, the heat treatment temperature is set to 180 to It is preferable to set it as 290 degreeC, and it is more preferable to set it as 220-250 degreeC. On the other hand, when used for the manufacture of a semiconductor device which does not have a problem in heating to 300 ° C. or higher, it is more preferably 300 to 350 ° C.
上述の製造方法によって作成した硬化レリーフパターンは、表面保護膜、層間絶縁膜、再配線用絶縁膜、フリップチップ装置用保護膜、あるいはバンプ構造を有する装置の保護膜として、公知の半導体装置の製造方法と組み合わせることで、半導体装置を製造することができる。また、多層回路の層間絶縁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等としても有用である。 The cured relief pattern created by the above-described manufacturing method is used to manufacture a known semiconductor device as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. A semiconductor device can be manufactured by combining with the method. It is also useful as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.
本発明を参考例、実施例、比較例に基づいて更に具体的に説明するが、本発明はこれら実施例などにより何ら限定されるものではない。
<ヒドロキシポリアミドの合成>
〔参考例1〕
容量2Lのセパラブルフラスコ中で、2,2−ビス(3−アミノ−4−ヒドロキシフェニル)−ヘキサフルオロプロパン197.8g(0.54mol)、ピリジン75.9g
(0.96mol)、N,N−ジメチルアセトアミド(以下、「DMAc」という。)692gを室温(25℃)で混合攪拌し溶解させた。これに、別途ジエチレングリコールジメチルエーテル(以下、「DMDG」という。)88g中に5−ノルボルネン−2,3−ジカルボン酸無水物19.7g(0.12mol)を溶解させたものを、滴下ロートより滴下した。滴下に要した時間は40分、反応液温は最大で28℃であった。
滴下終了後、湯浴により50℃に加温し18時間撹拌したのち反応液のIRスペクトルの測定を行い1385cm−1および1772cm−1のイミド基の特性吸収が現れたことを確認した。
The present invention will be described more specifically based on reference examples, examples, and comparative examples, but the present invention is not limited to these examples.
<Synthesis of hydroxy polyamide>
[Reference Example 1]
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and 75.9 g of pyridine.
(0.96 mol) and 692 g of N, N-dimethylacetamide (hereinafter referred to as “DMAc”) were mixed and stirred at room temperature (25 ° C.) to dissolve. A solution obtained by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of diethylene glycol dimethyl ether (hereinafter referred to as “DMDG”) separately was added dropwise to the dropping funnel. . The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 cm −1 and 1772 cm −1 appeared.
次にこれを水浴により8℃に冷却し、これに別途DMDG398g中に4,4’−ジフェニルエーテルジカルボン酸ジクロライド142.3g(0.48mol)を溶解させたものを、滴下ロートより滴下した。滴下に要した時間は80分、反応液温は最大で12℃であった。滴下終了から3時間後、上記反応液を12lの水に高速攪拌下で滴下し重合体を分散析出させ、これを回収し、適宜水洗、脱水の後に真空乾燥を施し、ヒドロキシポリアミドP−1を得た。このようにして合成されたヒドロキシポリアミドのゲルパーミエーションクロマトグラフィー(以下、「GPC」ともいう。)による重量平均分子量は、ポリスチレン換算で14000であった。GPCの分析条件を以下に記す。
カラム:昭和電工社製、商標名;Shodex、KF−807/KF−806M/KF−806M/KF−802.5;直列
溶離液:テトラヒドロフラン、40℃
流速 :1.0ml/分
検出器:昭和電工製、商標名;Shodex RI−101
Next, this was cooled to 8 ° C. with a water bath, and a solution obtained by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of DMDG was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of the dropping, the above reaction solution was dropped into 12 liters of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water and dehydrated appropriately, followed by vacuum drying to obtain hydroxypolyamide P-1. Obtained. The weight average molecular weight of the hydroxypolyamide thus synthesized by gel permeation chromatography (hereinafter also referred to as “GPC”) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex, KF-807 / KF-806M / KF-806M / KF-802.5; serial eluent: tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI-101
また、更にヒドロキシポリアミドの精製が必要な場合は、以下の方法にて実施することが可能である。すなわち、上記で得られたヒドロキシポリアミドをDMDGに再溶解した後、これを陽イオン交換樹脂および陰イオン交換樹脂にて処理し、それにより得られた溶液をイオン交換水中に投入後、析出したヒドロキシポリアミドを濾別、水洗、真空乾燥することにより精製されたヒドロキシポリアミドを得ることができる。 Further, when further purification of hydroxypolyamide is required, it can be carried out by the following method. That is, after re-dissolving the hydroxypolyamide obtained above in DMDG, this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was poured into ion exchange water and then precipitated hydroxy By purifying the polyamide by filtration, washing with water and vacuum drying, a purified hydroxypolyamide can be obtained.
〔参考例2〕
容量2Lのセパラブルフラスコ中で、2,2−ビス(3−アミノ−4−ヒドロキシフェニル)−ヘキサフルオロプロパン171.4g(0.47mol)、ピリジン71.2g(0.90mol)、N,N−ジメチルアセトアミド(以下、「DMAc」という。)600gを室温(25℃)で混合攪拌し溶解させた。これに、別途γ−ブチロラクトン(以下、「GBL」という。)30g中に4−メチルシクロヘキシル−1,2−ジカルボン酸無水物6.1g(0.04mol)を溶解させたものを、滴下ロートより滴下した。滴下に要した時間は10分、反応液温は最大で27℃であった。
[Reference Example 2]
In a 2 L separable flask, 171.4 g (0.47 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 71.2 g (0.90 mol) of pyridine, N, N -600 g of dimethylacetamide (hereinafter referred to as “DMAc”) was mixed and stirred at room temperature (25 ° C.) for dissolution. Separately, 6.1 g (0.04 mol) of 4-methylcyclohexyl-1,2-dicarboxylic anhydride was dissolved in 30 g of γ-butyrolactone (hereinafter referred to as “GBL”) from a dropping funnel. It was dripped. The time required for the dropwise addition was 10 minutes, and the maximum reaction solution temperature was 27 ° C.
滴下終了後、5時間撹拌したのち反応液をGPC(低分子量測定用)にて分析を行い4−メチルシクロヘキシル−1,2−ジカルボン酸無水物が消失したことを確認した。GPC(低分子量測定用)の分析条件を以下に記す。
カラム:昭和電工社製、商標名;Shodex、KF−802/KF−801/KF−801;直列
溶離液:テトラヒドロフラン、40℃
流速 :1.0ml/分
検出器:昭和電工製、商標名;Shodex RI−930
After stirring for 5 hours, the reaction solution was analyzed by GPC (for low molecular weight measurement) and it was confirmed that 4-methylcyclohexyl-1,2-dicarboxylic anhydride had disappeared. The analysis conditions for GPC (for low molecular weight measurement) are described below.
Column: manufactured by Showa Denko KK, trade name: Shodex, KF-802 / KF-801 / KF-801; serial eluent: tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko, trade name: Shodex RI-930
次にこれをドライアイスバスにより−10℃に冷却し、これに別途GBL612g中に4,4’−ジフェニルエーテルジカルボン酸ジクロライド99.6g(0.34mol)とイソフタロイルクロリド22.8g(0.12mol)を溶解させたものを、滴下ロー
トより滴下した。滴下に要した時間は120分、反応液温は最大で2℃であった。滴下終了から3時間後、GPC法で測定した重量平均分子量25000(ポリスチレン換算)のヒドロキシポリアミドP−2を得た。
Next, this was cooled to −10 ° C. with a dry ice bath, and separately, 99.6 g (0.34 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride and 22.8 g (0.12 mol) of isophthaloyl chloride were added to 612 g of GBL. ) Was dissolved from the dropping funnel. The time required for the dropwise addition was 120 minutes, and the maximum reaction solution temperature was 2 ° C. Three hours after the completion of dropping, hydroxypolyamide P-2 having a weight average molecular weight of 25000 (polystyrene conversion) measured by GPC method was obtained.
<感光性ジアゾキノン化合物の合成>
〔参考例3〕
容量1Lのセパラブルフラスコに2,2−ビス(3−アミノ−4−ヒドロキシフェニル)−ヘキサフルオロプロパン109.9g(0.3mol)、テトラヒドロフラン(THF)330g、ピリジン47.5g(0.6mol)を入れ、これに室温下で5−ノルボルネン−2,3−ジカルボン酸無水物98.5g(0.6mol)を粉体のまま加えた。そのまま室温で3日間撹拌反応を行ったあと、HPLCにて反応を確認したところ、原料は全く検出されず、生成物が単一ピークとして純度99%で検出された。この反応液をそのまま1Lのイオン交換水中に撹拌下で滴下し、析出物を濾別した後、これにTHF500mLを加え撹拌溶解し、この均一溶液を陽イオン交換樹脂:アンバーリスト15(オルガノ社製)100gが充填されたガラスカラムを通し残存するピリジンを除去した。次にこの溶液を3Lのイオン交換水中に高速撹拌下で滴下することにより生成物を析出させ、これを濾別した後、真空乾燥した。
生成物がイミド化していることは、IRスペクトルで1394cm−1および1774cm−1のイミド基の特性吸収が現れ1540cm−1および1650cm−1付近のアミド基の特性吸収が存在しないこと、およびNMRスペクトルでアミドおよびカルボン酸のプロトンのピークが存在しないことにより確認した。
<Synthesis of photosensitive diazoquinone compound>
[Reference Example 3]
In a 1 L separable flask, 109.9 g (0.3 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 330 g of tetrahydrofuran (THF), 47.5 g (0.6 mol) of pyridine. Into this, 98.5 g (0.6 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added in powder form at room temperature. After stirring for 3 days at room temperature, the reaction was confirmed by HPLC. As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was dropped as it was into 1 L of ion-exchanged water with stirring, and the precipitate was filtered off. Then, 500 mL of THF was added and dissolved by stirring. This homogeneous solution was dissolved in cation exchange resin: Amberlyst 15 (manufactured by Organo). ) The remaining pyridine was removed through a glass column packed with 100 g. Next, this solution was dropped into 3 L of ion exchange water under high-speed stirring to precipitate a product, which was filtered off and then vacuum-dried.
The product is imidized, it is not characteristic absorption of amide groups in the vicinity of 1540 cm -1 and 1650 cm -1 appear characteristic absorption of an imide group 1394Cm -1 and 1774 cm -1 in the IR spectrum is present, and NMR spectrum This was confirmed by the absence of amide and carboxylic acid proton peaks.
次に、該生成物65.9g(0.1mol)、1,2−ナフトキノンジアジド−4−スルホニルクロライドを53.7g(0.2mol)、アセトン560g加え、20℃で撹拌溶解した。これに、トリエチルアミン21.2g(0.21mol)をアセトン106.2gで希釈したものを、30分かけて一定速度で滴下した。この際、反応液は氷水浴などを用いて20〜30℃の範囲で温度制御した。
滴下終了後、更に30分間、20℃で撹拌放置した後、36重量%濃度の塩酸水溶液5.6gを一気に投入し、次いで反応液を氷水浴で冷却し、析出した固形分を吸引濾別した。この際得られた濾液を、0.5重量%濃度の塩酸水溶液5Lに、その撹拌下で1時間かけて滴下し、目的物を析出させ、吸引濾別して回収した。得られたケーク状回収物を、再度イオン交換水5lに分散させ、撹拌、洗浄、濾別回収し、この水洗操作を3回繰り返した。最後に得られたケーク状物を、40℃で24時間真空乾燥し、感光性ジアゾキノン化合物Q−1を得た。
Next, 65.9 g (0.1 mol) of the product, 53.7 g (0.2 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride and 560 g of acetone were added and dissolved by stirring at 20 ° C. A solution prepared by diluting 21.2 g (0.21 mol) of triethylamine with 106.2 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 5.6 g of a 36 wt% hydrochloric acid aqueous solution was added at once. The reaction solution was then cooled in an ice water bath, and the precipitated solid was filtered off with suction. . The filtrate obtained at this time was dropped into 5 L of a 0.5% by weight aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 l of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the cake-like material obtained was vacuum-dried at 40 ° C. for 24 hours to obtain photosensitive diazoquinone compound Q-1.
<耐熱性樹脂組成物の調製>
[実施例1〜5、比較例1〜3]
上記参考例1、2で得られたヒドロキシポリアミド(P−1またはP−2)100質量部に対して、上記参考例3で得られた感光性ジアゾキノン化合物(Q−1)または以下に示す感光性ジアゾキノン化合物(Q−2、ダイトーケミックス社製)を表1中に記載の量加え、さらに下記で示す可塑剤、その他添加剤Zを表1中に記載の量添加してGBL170質量部に溶解した後、0.2μmのフィルターで濾過して、表1に記載した実施例1〜5、及び比較例1〜3のポジ型感光性耐熱性樹脂組成物を調製した。
<Preparation of heat resistant resin composition>
[Examples 1-5, Comparative Examples 1-3]
The photosensitive diazoquinone compound (Q-1) obtained in Reference Example 3 or the photosensitivity shown below with respect to 100 parts by mass of the hydroxypolyamide (P-1 or P-2) obtained in Reference Examples 1 and 2 above. The diazoquinone compound (Q-2, manufactured by Daitokemix Co., Ltd.) was added in the amount shown in Table 1, and the plasticizer shown below and other additives Z were added in the amounts shown in Table 1 and dissolved in 170 parts by mass of GBL. Then, it filtered with a 0.2 micrometer filter, and prepared the positive photosensitive heat-resistant resin composition of Examples 1-5 described in Table 1, and Comparative Examples 1-3.
<耐熱性樹脂組成物の評価>
(1)オキサゾール化率評価
上記耐熱性樹脂組成物を東京エレクトロン社製スピンコーター(クリーントラックMark−8)にて、6インチシリコンウエハーにスピン塗布し、ホットプレートにて120
℃、180秒間プリベークを行い、塗膜を形成した。縦型キュア炉(光陽リンドバーグ社製)にて、窒素雰囲気中、250℃あるいは350℃で1時間のキュア(加熱硬化処理)を施した。得られた硬化膜のIRスペクトルを顕微ATR法により測定し、1490cm−1のピークを基準として用いて各々のスペクトルの大きさを揃えた後、オキサゾール環の特性吸収である1050cm−1のピークの大きさを用いて、以下の式により350℃でのオキサゾール化率を100%とした時の250℃でのオキサゾール化率を算出し表2に示した。
オキサゾール化率(%)=(250℃加熱処理サンプルの1050cm−1のピークの高さ)÷(350℃加熱処理サンプルの1050cm−1のピークの高さ)×100
<Evaluation of heat resistant resin composition>
(1) Evaluation of Oxazolization Rate The above heat-resistant resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (Clean Track Mark-8) manufactured by Tokyo Electron Co., Ltd., and 120 on a hot plate.
Pre-baking was performed at 180 ° C. for 180 seconds to form a coating film. In a vertical curing furnace (manufactured by Koyo Lindberg), curing (heat curing treatment) was performed in a nitrogen atmosphere at 250 ° C. or 350 ° C. for 1 hour. The IR spectrum of the obtained cured film was measured by a microscopic ATR method, and after adjusting the size of each spectrum using the peak at 1490 cm −1 as a reference, the peak at 1050 cm −1 which is the characteristic absorption of the oxazole ring was measured. Using the size, the oxazolation rate at 250 ° C. when the oxazolation rate at 350 ° C. was taken as 100% was calculated according to the following formula and shown in Table 2.
Oxazole rate (%) = (250 ℃ heat treatment the peak height of the sample 1050cm -1) ÷ (350 ℃ heat treatment the peak height of 1050 cm -1 of sample) × 100
(2)粘度変化率評価
23℃にて1週間放置後の粘度の変化率を次のように測定し表2に示した。粘度の変化率が5%以内であれば安定性良好とした。
粘度変化率(%)=(1週間放置後の粘度−耐熱性樹脂組成物調製直後の粘度)÷耐熱性樹脂組成物調製直後の粘度×100
(2) Viscosity change rate evaluation The viscosity change rate after standing at 23 ° C. for 1 week was measured as follows and shown in Table 2. If the rate of change in viscosity was within 5%, the stability was considered good.
Viscosity change rate (%) = (viscosity after standing for 1 week−viscosity immediately after preparation of heat resistant resin composition) ÷ viscosity immediately after preparation of heat resistant resin composition × 100
(3)感度評価
上記実施例1〜5、及び比較例1〜3の耐熱性樹脂組成物を東京エレクトロン社製スピンコーター(クリーントラックMark−8)にて、6インチシリコンウエハーにスピン塗布し、ホットプレートにて120℃、180秒間プリベークを行い、膜厚10.7μmの塗膜を形成した。膜厚は大日本スクリーン製造社製膜厚測定装置(ラムダエース)にて測定した。
得られた塗膜に、テストパターン付きレチクルを通してi線(365nm)の露光波長を有するニコン社製ステッパ(NSR2005i8A)を用いて露光量を段階的に変化させて露光した。これをAZエレクトロニックマテリアルズ社製、アルカリ現像液(AZ300MIFデベロッパー、2.38質量%水酸化テトラメチルアンモニウム水溶液)を用い、23℃の条件下で現像後膜厚が9.1μmとなるように現像時間を調整して現像を行い、ポジ型のレリーフパターンを形成した。耐熱性樹脂組成物の感度を表2に示した。
なお、耐熱性樹脂組成物の感度は、次のようにして評価した。
[感度(mJ/cm2)]
上記現像時間において、塗膜の露光部を完全に溶解除去しうる最小露光量。
(3) Sensitivity evaluation The heat resistant resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were spin-coated on a 6-inch silicon wafer with a spin coater (clean track Mark-8) manufactured by Tokyo Electron, Pre-baking was performed at 120 ° C. for 180 seconds on a hot plate to form a coating film having a thickness of 10.7 μm. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.
The obtained coating film was exposed with a stepper (NSR2005i8A) manufactured by Nikon Corporation having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern while changing the exposure stepwise. This was developed using an alkali developer (AZ300MIF developer, 2.38 mass% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials, so that the film thickness after development was 9.1 μm at 23 ° C. Development was carried out by adjusting the time to form a positive relief pattern. The sensitivity of the heat resistant resin composition is shown in Table 2.
The sensitivity of the heat resistant resin composition was evaluated as follows.
[Sensitivity (mJ / cm 2 )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
実施例から、本発明の必須成分である可塑剤を添加した組成物は、最終膜として期待される諸性能を得るのに充分高いオキサゾール化率を示し、かつ、安定性(粘度変化率)、パターニング特性(感度)にも問題がなかった。これに対し、可塑剤を加えなかった組成物のオキサゾール化率は低く、可塑剤の代わりに熱により酸を発生する化合物を加えた組成は、オキサゾール化率は高いものの安定性、パターニング特性が悪化した。 From the examples, the composition to which the plasticizer which is an essential component of the present invention is added exhibits a sufficiently high oxazolation rate to obtain various properties expected as a final film, and is stable (viscosity change rate). There was no problem in patterning characteristics (sensitivity). On the other hand, the composition with no plasticizer added has a low oxazolation rate, and the composition with an acid-generating compound instead of a plasticizer adds heat, but the stability and patterning characteristics are poor. did.
本発明の耐熱性樹脂組成物は、半導体装置の表面保護膜、層間絶縁膜、再配線用絶縁膜、フリップチップ装置用保護膜、及びバンプ構造を有する装置の保護膜、多層回路の層間絶縁膜、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、並びに液晶配向膜等として好適に利用できる。 The heat resistant resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, and an interlayer insulating film for a multilayer circuit It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.
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JP2009275078A (en) * | 2008-05-13 | 2009-11-26 | Toyohashi Univ Of Technology | Heat-resistant resin composition |
US8785103B2 (en) | 2011-12-29 | 2014-07-22 | Cheil Industries Inc. | Photosensitive novolac resin, positive photosensitive resin composition including same, photosensitive resin film prepared by using the same, and semiconductor device including the photosensitive resin film |
US8815489B2 (en) | 2011-11-29 | 2014-08-26 | Cheil Industries Inc. | Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and semiconductor device including the photosensitive resin film |
US9268221B2 (en) | 2010-12-30 | 2016-02-23 | Cheil Industries Inc. | Positive photosensitive resin composition, photosensitive resin layer prepared by using the same, and semiconductor device including the photosensitive resin layer |
JP2017198977A (en) * | 2016-04-14 | 2017-11-02 | 旭化成株式会社 | Photosensitive resin composition and manufacturing method of cured relief pattern |
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JP2009275078A (en) * | 2008-05-13 | 2009-11-26 | Toyohashi Univ Of Technology | Heat-resistant resin composition |
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JP2017198977A (en) * | 2016-04-14 | 2017-11-02 | 旭化成株式会社 | Photosensitive resin composition and manufacturing method of cured relief pattern |
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