JP3812654B2 - Positive photosensitive insulating resin composition and cured product thereof - Google Patents
Positive photosensitive insulating resin composition and cured product thereof Download PDFInfo
- Publication number
- JP3812654B2 JP3812654B2 JP2002014307A JP2002014307A JP3812654B2 JP 3812654 B2 JP3812654 B2 JP 3812654B2 JP 2002014307 A JP2002014307 A JP 2002014307A JP 2002014307 A JP2002014307 A JP 2002014307A JP 3812654 B2 JP3812654 B2 JP 3812654B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- compound
- insulating resin
- photosensitive insulating
- meth
- 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.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000035939 shock Effects 0.000 abstract description 11
- 125000005011 alkyl ether group Chemical group 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- -1 phenol compound Chemical class 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000000758 substrate Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000005011 phenolic resin Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 238000010292 electrical insulation Methods 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GBQZZLQKUYLGFT-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O GBQZZLQKUYLGFT-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NQQRXZOPZBKCNF-NSCUHMNNSA-N (e)-but-2-enamide Chemical compound C\C=C\C(N)=O NQQRXZOPZBKCNF-NSCUHMNNSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- PVMMVWNXKOSPRB-UHFFFAOYSA-N 1,2-dipropoxypropane Chemical compound CCCOCC(C)OCCC PVMMVWNXKOSPRB-UHFFFAOYSA-N 0.000 description 1
- XGQJGMGAMHFMAO-UHFFFAOYSA-N 1,3,4,6-tetrakis(methoxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound COCN1C(=O)N(COC)C2C1N(COC)C(=O)N2COC XGQJGMGAMHFMAO-UHFFFAOYSA-N 0.000 description 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- QIBPJPNDSZRXRO-UHFFFAOYSA-N 2-(chloromethyl)prop-2-enenitrile Chemical compound ClCC(=C)C#N QIBPJPNDSZRXRO-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、半導体素子の層間絶縁膜（パッシベーション膜）、表面保護膜（オーバーコート膜）、高密度実装基板用絶縁膜などに用いられるポジ型感光性絶縁樹脂組成物およびそれを硬化してなる硬化物に関する。より詳細には、永久膜レジストとして解像性に優れているとともに電気絶縁性、熱衝撃性、密着性、硬化収縮率等の特性に優れた硬化物、およびそのような硬化物が得られるポジ型感光性絶縁樹脂組成物に関する。
【０００２】
【発明の技術的背景】
従来、電子機器の半導体素子に用いられる層間絶縁膜、表面保護膜などには耐熱性、機械的特性などに優れているポリイミド系樹脂が広く使用されている。また、生産性の向上、膜形成精度の向上などのために感光性を付与した感光性ポリイミド系樹脂の検討が種々なされている。たとえば、ポリイミド前駆体にエステル結合あるいはイオン結合により光架橋基を導入したネガ型が実用化されている。さらに、ポジ型としては特開平5-5996号公報や特開2000-98601号公報などにはポリイミド前駆体とオルソキノンジアジド化合物からなる組成物が記載されている。しかしながら、ネガ型では解像性や膜形成に問題があり、ポジ型では耐熱性や電気絶縁性、基板への密着性などに問題がある。その他にも多数の特許が出願されているが、半導体素子の高集積化、薄型化などによる要求特性を十分に満足することが困難になっている。さらに、硬化後の膜減り（体積収縮率）や硬化時の多段階ベーク、雰囲気制御などの問題点を抱えており、工業的に実施する場合には使用しにくいという問題が指摘されている。
【０００３】
【発明の目的】
本発明は、上記のような従来技術に伴う問題点を解決し、解像性、電気絶縁性、熱衝撃性、密着性、硬化収縮率等の諸特性に優れた硬化物を得ることができる半導体素子用の層間絶縁膜、表面保護膜などの用途に適したポジ型感光性絶縁樹脂組成物を提供することを目的としている。
【０００４】
さらに、本発明は、このようなポジ型感光性絶縁樹脂組成物を硬化させた硬化物を提供することを目的とする。
【０００５】
【発明の概要】
本発明者らは、前記問題点を解決すべく鋭意研究した結果、優れた特性を有するポジ型感光性絶縁樹脂組成物を見出すに至った。すなわち、本発明のポジ型感光性絶縁樹脂組成物は、（Ａ）フェノール性水酸基を有するアルカリ可溶性樹脂、（Ｂ）キノンジアジド基を有する化合物、（Ｃ）架橋微粒子、（Ｄ）分子中に少なくとも２つ以上のアルキルエーテル化されたアミノ基を有する化合物および（Ｅ）溶剤から構成されることを特徴とする。
【０００６】
【発明の具体的説明】
以下、本発明にかかるポジ型感光性絶縁樹脂組成物、およびその硬化物について具体的に説明する。
[ 感光性絶縁樹脂組成物 ]
本発明のポジ型感光性絶縁樹脂組成物は、（Ａ）フェノール性水酸基を有するアルカリ可溶性樹脂、（Ｂ）キノンジアジド基を有する化合物、（Ｃ）架橋微粒子、（Ｄ）分子中に少なくとも２つ以上のアルキルエーテル化されたアミノ基を含有する化合物、および（Ｅ）溶剤とから構成される。また、本発明の感光性絶縁樹脂組成物は、必要に応じ、熱感応性酸発生剤やエポキシ化合物、密着助剤、レベリング剤などのその他添加剤などを含有することもできる。
【０００７】
（Ａ）フェノール性水酸基を有するアルカリ可溶性樹脂；
本発明において用いられるフェノール性水酸基を有するアルカリ可溶性樹脂（以下、「フェノール樹脂（Ａ）」という。）としては、特に限定されないが、ノボラック樹脂が好ましい。このようなノボラック樹脂はフェノール類とアルデヒド類とを触媒の存在下で、縮合させることにより得られる。
この際使用されるフェノール類としては、たとえばフェノール、ｏ-クレゾール、ｍ-クレゾール、ｐ-クレゾール、ｏ-エチルフェノール、ｍ-エチルフェノール、ｐ-エチルフェノール、ｏ-ブチルフェノール、ｍ-ブチルフェノール、ｐ-ブチルフェノール、2,3-キシレノール、2,4-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール、2,3,5-トリメチルフェノール、3,4,5-トリメチルフェノール、カテコール、レゾルシノール、ピロガロール、α-ナフトール、β-ナフトールなどが挙げられる。
【０００８】
また、アルデヒド類としてはホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒドなどが挙げられる。このようなノボラック樹脂としては、具体的には、フェノール／ホルムアルデヒド縮合ノボラック樹脂、クレゾール／ホルムアルデヒド縮合ノボラック樹脂、フェノール-ナフトール／ホルムアルデヒド縮合ノボラック樹脂などが挙げられる。
【０００９】
また、ノボラック樹脂以外のフェノール性水酸基を有するアルカリ可溶性樹脂としては、ポリヒドロキシスチレンおよびその共重合体、フェノール-キシリレングリコール縮合樹脂、クレゾール-キシリレングリコール縮合樹脂、フェノール-ジシクロペンタジエン縮合樹脂などを挙げることができる。
本発明ではまた、上記フェノール性水酸基を有するアルカリ可溶性樹脂とフェノール性低分子化合物（以下、「フェノール化合物（ａ）」という。）とを併用することができる。たとえば、4,4'-ジヒドロキシジフェニルメタン、4,4'-ジヒドロキシジフェニルエーテル、トリス（4-ヒドロキシフェニル）メタン、1,1-ビス（4-ヒドロキシフェニル）-1-フェニルエタン、トリス（4-ヒドロキシフェニル）エタン、1,3-ビス[1-（4-ヒドロキシフェニル）-1-メチルエチル]ベンゼン、1,4-ビス[1-（4-ヒドロキシフェニル）-1-メチルエチル]ベンゼン、4,6-ビス[1-（4-ヒドロキシフェニル）-1-メチルエチル]-1,3-ジヒドロキシベンゼン、1,1-ビス（4-ヒドロキシフェニル）-1-[4-｛1-（4-ヒドロキシフェニル）-1-メチルエチル｝フェニル]エタン、1,1,2,2-テトラ（4-ヒドロキシフェニル）エタンなどが挙げられる。これらのフェノール化合物（ａ）は、フェノール性水酸基を有するアルカリ可溶性樹脂（Ａ）中に（Ａ）成分の一部として、０〜40重量％、特に０〜30重量％の範囲で含有することができる。
【００１０】
フェノール樹脂（Ａ）は、得られる絶縁膜の解像性、熱衝撃性、耐熱性などの観点から、重量平均分子量が2,000以上であることが必要であり、特に2,000〜20,000程度の範囲が好ましい。
本発明の組成物において、フェノール樹脂（Ａ）の含有量（フェノール化合物（ａ）を併用する場合は合計量）は、組成物全体の30〜80重量部、好ましくは40〜70重量部である。フェノール樹脂（Ａ）の割合がこの範囲であると、得られる組成物を用いて形成された膜がアルカリ水溶液による十分な現像性を有している。
【００１１】
（Ｂ）キノンジアジド基を有する化合物
本発明におけるキノンジアジド基を有する化合物（以下、「キノンジアジド化合物（Ｂ）」という。）は、フェノール性水酸基を１つ以上有する化合物と1,2-ナフトキノンジアジド-4-スルホン酸または1,2-ナフトキノンジアジド-5-スルホン酸とのエステル化合物である。前記フェノール性水酸基を１つ以上有する化合物としては特に、限定されないが具体的には下記に示す構造の化合物が好ましい。
【００１２】
【化１】
（式１において、X1〜X10は、それぞれ相互に同一または異なってもよく、水素原子、炭素数1〜4のアルキル基、炭素数1〜4のアルコキシ基または水酸基である。X1〜X5の少なくとも１つは水酸基である。また、Aは単結合、O、S、CH2、C(CH3)2、C(CF3)2、C=O、またはSO2である。）
【００１４】
【化２】
（式2において、X11〜X24は、それぞれ相互に同一または異なってもよく、前記X1〜X10の場合と同様である。X11〜X15の少なくとも１つは水酸基である。また、R1〜R4は、水素原子または炭素数1〜4のアルキル基である。）
【００１６】
【化３】
（式3において、X25〜X39は、それぞれ相互に同一または異なってもよく、前記X1〜X10の場合と同様である。但し、X25〜X29およびX30〜X34のそれぞれの組み合わせにおいて少なくとも１つは水酸基である。また、R5は、水素原子または炭素数1〜4のアルキル基である。）
【００１８】
【化４】
（式4において、X40〜X58は、それぞれ相互に同一または異なってもよく、前記X1〜X10の場合と同様である。X40〜X44、X45〜X49およびX50〜X54のそれぞれの組み合わせにおいて少なくとも１つは水酸基である。また、R6〜R8は、水素原子または炭素数1〜4のアルキル基である。）
【００２０】
【化５】
（式5において、X59〜X72は、それぞれ相互に同一または異なってもよく、前記X1〜X10の場合と同様である。但し、X59〜X62およびX63〜X67のそれぞれの組み合わせにおいて少なくとも１つは水酸基である。）
このようなキノンジアジド基を有する化合物の具体例としては、以下のものが挙げられる。4,4'-ジヒドロキシジフェニルメタン、4,4'-ジヒドロキシジフェニルエーテル、2,3,4-トリヒドロキシベンゾフェノン、2,3,4,4'-テトラヒドロキシベンゾフェノン、2,3,4,2',4'-ペンタヒドロキシベンゾフェノン、トリス（4-ヒドロキシフェニル）メタン、トリス（4-ヒドロキシフェニル）エタン、1,1-ビス（4-ヒドロキシフェニル）-1-フェニルエタン、1,3-ビス［1-（4-ヒドロキシフェニル）-1-メチルエチル］ベンゼン、1,4-ビス［1-（4-ヒドロキシフェニル）-1-メチルエチル］ベンゼン、4,6-ビス［1-（4-ヒドロキシフェニル）-1-メチルエチル］-1,3-ジヒドロキシベンゼン、1,1-ビス（4-ヒドロキシフェニル）-1-［4-｛1-（4-ヒドロキシフェニル）-1-メチルエチル｝フェニル］エタンなどの1,2-ナフトキノンジアジド-4-スルホン酸または1,2-ナフトキノンジアジド-5-スルホン酸エステル化合物。
【００２２】
本発明の組成物においては、キノンジアジド化合物（Ｂ）は、フェノール樹脂（Ａ）100重量部に対して10〜50重量部、好ましくは15〜30重量部である。配合量が10重量部未満では未露光部の残膜率が低下したり、マスクパターンに忠実な像が得られない場合がある。また、配合量が50重量部を超えるとパターン形状が劣化したり、硬化時に発泡することがある。
【００２３】
（Ｃ）架橋微粒子
本発明における架橋微粒子（以下、「架橋微粒子（Ｃ）」という。）は、架橋微粒子を構成する重合体のＴｇが0℃以下であれば特に限定されるものではないが、不飽和重合性基を２個以上有する架橋性モノマー（以下、「架橋性モノマー」と称す。）と、架橋微粒子（Ｃ）のＴｇが0℃以下となるように選択される１種以上のその他モノマー（以下、「その他モノマー」と称す。）を共重合したものが好ましく、さらに、その他モノマーとして架橋微粒子（Ｃ）のＴｇが０℃以下となるようなものであって、重合性基以外の官能基、たとえば、カルボキシル基、エポキシ基、アミノ基、イソシアネート基、水酸基等の官能基を有するモノマーを共重合したものが用いられる。
【００２４】
架橋性モノマーの例としては、ジビニルベンゼン、ジアリルフタレート、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレートなどの重合性不飽和基を複数有する化合物を挙げることができる。なかでも、ジビニルベンゼンが好ましい。
【００２５】
本発明における架橋微粒子（Ｃ）を製造する際に用いられる架橋性モノマーは、共重合に用いる全モノマーに対して1〜20重量％の範囲、より好ましくは2〜10重量％の範囲の量で用いられる。
その他モノマーの例としては、ブタジエン、イソプレン、ジメチルブタジエン、クロロプレン、1,3-ペンタジエンなどのジエン化合物、（メタ）アクリロニトリル、α-クロロアクリロニトリル、α-クロロメチルアクリロニトリル、α-メトキシアクリロニトリル、α-エトキシアクリロニトリル、クロトン酸ニトリル、ケイ皮酸ニトリル、イタコン酸ジニトリル、マレイン酸ジニトリル、フマル酸ジニトリルなどの不飽和ニトリル化合物類、（メタ）アクリルアミド、N,N'-メチレンビス（メタ）アクリルアミド、N,N'-エチレンビス（メタ）アクリルアミド、Ｎ,Ｎ’-ヘキサメチレンビス（メタ）アクリルアミド、N-ヒドロキシメチル（メタ）アクリルアミド、N-（2-ヒドロキシエチル）（メタ）アクリルアミド、Ｎ,Ｎ-ビス（2-ヒドロキシエチル）（メタ）アクリルアミド、クロトン酸アミド、ケイ皮酸アミド等の不飽和アミド類、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ラウリル、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレートなどの（メタ）アクリル酸エステル類、スチレン、α-メチルスチレン、ｏ-メトキシスチレン、ｐ-ヒドロキシスチレン、ｐ-イソプロペニルフェノールなどの芳香族ビニル化合物、ビスフェノールＡのジグリシジルエーテル、グリコールのジグリシジルエーテルなどと（メタ）アクリル酸、ヒドロキシアルキル（メタ）アクリレートなどとの反応によって得られるエポキシ（メタ）アクリレートおよび、ヒドロキシアルキル（メタ）アクリレートとポリイソシアナートとの反応によって得られるウレタン（メタ）アクリレート類、グリシジル（メタ）アクリレート、（メタ）アリルグリシジルエーテルなどのエポキシ基含有不飽和化合物、（メタ）アクリル酸、イタコン酸、コハク酸-β-（メタ）アクリロキシエチル、マレイン酸-β-（メタ）アクリロキシエチル、フタル酸-β-（メタ）アクリロキシエチル、ヘキサヒドロフタル酸-β-（メタ）アクリロキシエチルなどの不飽和酸化合物、ジメチルアミノ（メタ）アクリレート、ジエチルアミノ（メタ）アクリレート等のアミノ基含有不飽和化合物、（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド等のアミド基含有不飽和化合物、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等の水酸基含有不飽和化合物などを例示することができる。これらのその他モノマーとしては、ブタジエン、イソプレン、（メタ）アクリロニトリル、（メタ）アクリル酸アルキルエステル類、スチレン、ｐ-ヒドロキシスチレン、ｐ-イソプロペニルフェノール、グリシジル（メタ）アクリレート、（メタ）アクリル酸、ヒドロキシアルキル（メタ）アクリレート類などが好ましく用いられる。
【００２６】
このような他のモノマーとしては、少なくとも１種のジエン化合物、具体的にはブタジエンを用いることが好ましい。このようなジエン化合物は、共重合に用いる全モノマーに対して２０〜８０重量％、好ましくは３０〜７０重量％の量で用いられることが望ましい。
本発明で用いられる架橋微粒子（Ｃ）は、他のモノマーとしてブタジエンなどのジエン化合物が全モノマーに対して上記のような量で共重合されていると、ゴム状の軟らかい微粒子となり、特に得られる硬化膜にクラック（割れ）が生ずるのを防止でき、耐久性に優れた硬化膜を得ることができる。
【００２７】
本発明において架橋微粒子（Ｃ）の平均粒子径は、通常30〜500nm、好ましくは40〜200nm、さらに好ましくは５０〜１２０ｎｍであることが好ましい。架橋微粒子（Ｃ）の粒径コントロール方法は、特に限定されるものではないが、乳化重合により架橋微粒子（Ｃ）を合成する場合、使用する乳化剤の量により、乳化重合中のミセルの数を制御し、粒径をコントロールする方法が例示できる。
【００２８】
また、架橋微粒子（Ｃ）の配合量は前記フェノール樹脂（Ａ）100重量部に対して、1〜50重量部、好ましくは5〜30重量部である。配合量が1重量部未満では、得られる硬化膜の熱衝撃性が低下し、50重量部を越えると解像性や得られる硬化膜の耐熱性が低下したり、他成分との相溶性分散性が低下することがある。
（Ｄ）分子中に少なくとも２つ以上のアルキルエーテル化されたアミノ基を有する化合物（硬化剤）
分子中に少なくとも2つ以上のアルキルエーテル化されたアミノ基を有する化合物（以下、「硬化剤（Ｄ）」という。）は、前記フェノール樹脂（Ａ）と反応する架橋剤（硬化剤）として作用するものである。硬化剤（Ｄ）としては（ポリ）メチロール化メラミン、（ポリ）メチロール化グリコールウリル、（ポリ）メチロール化ベンゾグアナミン、（ポリ）メチロール化ウレアなどの活性メチロール基の全部または一部をアルキルエーテル化した含窒素化合物を挙げることができる。ここで、アルキル基としてはメチル基、エチル基、ブチル基、またはこれらを混合したものを挙げることができ、一部自己縮合してなるオリゴマー成分を含有していてもよい。具体的にはヘキサメトキシメチル化メラミン、ヘキサブトキシメチル化メラミン、テトラメトキシメチル化グリコールウリル、テトラブトキシメチル化グリコールウリルなどを用いることができ、これらの硬化剤（Ｄ）は１種単独または２種以上を併用しても構わない。
【００２９】
本発明における硬化剤（Ｄ）の配合量は前記フェノール樹脂（Ａ）100重量部に対して、1〜100重量部、好ましくは5〜50重量部である。配合量が１重量部未満では硬化が不十分になり、得られる硬化物の電気絶縁性が低下したりすることがあり、100重量部を越えるとパターニング特性が低下したり、耐熱性が低下することがある。
【００３０】
（Ｅ）溶剤
溶媒（Ｅ）は、樹脂組成物の取り扱い性を向上させたり、粘度や保存安定性を調節するために添加される。このような有機溶媒の種類は、特に制限されるものではないが、たとえば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；エチルセロソルブ、ブチルセロソルブ等のセロソルブ類、ブチルカルビトール等のカルビトール類；乳酸メチル、乳酸エチル、乳酸n-プロピル、乳酸イソプロピル等の乳酸エステル類；酢酸エチル、酢酸n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸イソブチル、酢酸n-アミル、酢酸イソアミル、プロピオン酸イソプロピル、プロピオン酸n-ブチル、プロピオン酸イソブチル等の脂肪族カルボン酸エステル類；3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類；トルエン、キシレン等の芳香族炭化水素類；2-ヘプタノン、3-ヘプタノン、4-ヘプタノン、シクロヘキサノン等のケトン類；N-ジメチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類；γ-ブチロラクン等のラクトン類を挙げることができる。これらの有機溶媒は、１種単独あるいは２種以上を混合して使用することもできる。
【００３１】
本発明のポジ型感光性絶縁樹脂組成物中には、その他添加剤として熱感応性酸発生剤、エポキシ化合物、密着助剤およびレベリング剤などを含有することができる。熱感応性酸発生剤としては、加熱処理により酸を発生する化合物であれば特に限定されず、この発生した酸の触媒作用により硬化剤（Ｄ）中のアルキルエーテル基とフェノール樹脂（Ａ）との反応が促進される。熱感応性酸発生剤としてはオニウム塩化合物などを挙げることができる。また、エポキシ化合物としてはたとえば、ノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族エポキシ樹脂などが挙げられる。これらのその他添加剤は得られる感光性絶縁樹脂組成物の特性を損なわない程度に含有することができる。
【００３２】
[ 硬化物 ]
本発明にかかる感光性絶縁樹脂組成物は、フェノール樹脂（Ａ）、キノンジアジド化合物（Ｂ）、架橋微粒子（Ｃ）、硬化剤（Ｄ）、溶剤（Ｅ）、および必要に応じ、その他添加剤を含有し、解像性に優れているとともに、その硬化物は電気絶縁性、熱衝撃性、密着性、硬化収縮率などに優れている。従って、本発明のポジ型感光性絶縁樹脂組成物は、特に、半導体素子の層間絶縁膜用や表面保護膜用材料などとして好適に使用することができる。
【００３３】
本発明にかかるポジ型感光性絶縁樹脂組成物を配線パターンが施されたシリコンウエハーなどの基板に塗工し、乾燥して溶剤などを揮発させて塗膜を形成する。その後所望のマスクパターンを介して露光し、次いで、アルカリ性現像液により現像して、露光部を溶解、除去することにより所望のパターンを得ることができる。さらに、絶縁膜特性を発現させるために現像後に加熱処理を行うことにより、硬化膜を得ることができる。
【００３４】
樹脂組成物を支持体に塗工する方法としては、たとえば、ディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法、カーテンコート法などの塗布方法を用いることができ、塗布の厚さは、塗布手段、組成物溶液の固形分濃度や粘度を調節することにより、適宜制御することができる。
露光に用いられる放射線としては、たとえば、低圧水銀灯、高圧水銀灯、メタルハライドランプ、ｇ線ステッパー、ｉ線ステッパーなどの紫外線、電子線、レーザー光線などが挙げられ、露光量としては使用する光源や樹脂膜厚などによって適宜選定されるが、たとえば高圧水銀灯からの紫外線照射の場合、樹脂膜厚5〜50μｍでは、1,000〜20,000Ｊ／ｍ2程度である。
【００３５】
その後、アルカリ性現像液により現像して、露光部を溶解、除去することによって所望のパターンを形成する。この場合の現像方法としては、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法などを挙げることができ、現像条件としては通常、20〜40℃で１〜10分程度である。
前記アルカリ性現像液としては、たとえば、水酸化ナトリウム、水酸化カリウム、アンモニア水、テトラメチルアンモニウムヒドロキシド、コリンなどのアルカリ性化合物を濃度が１〜10重量％程度になるように水に溶解したアルカリ性水溶液を挙げることができる。前記アルカリ性水溶液には、たとえば、メタノール、エタノールなどの水溶性の有機溶剤や界面活性剤などを適量添加することもできる。なお、アルカリ性現像液で現像した後は、水で洗浄し、乾燥する。
【００３６】
さらに、現像後に絶縁膜としての特性を十分に発現させるために加熱処理を行うことによって硬化させることができる。このような硬化条件は特に制限されるものではないが、硬化物の用途に応じて、100〜250℃の温度で、30分〜10時間程度加熱し、組成物を硬化させることができる。また、硬化を十分に進行させたり、得られたパターン形状の変形を防止するために二段階で加熱することもでき、たとえば、第一段階では、50〜100℃の温度で10分〜2時間程度加熱し、さらに100〜250℃の温度で20分〜8時間程度加熱して硬化させることもできる。このような硬化条件であれば、加熱設備として一般的なオーブンや、赤外線炉などを使用することができる。
【００３７】
【発明の効果】
本発明によれば、解像性、電気絶縁性、熱衡塑性、密着性、硬化収縮率などに優れた硬化物、特に絶縁性および熱衡撃性に優れた硬化物を有するポジ型感光性絶縁樹脂組成物を得ることができる。
【００３８】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明はこれら実施例により何ら限定されるものではない。なお、以下の実施例、比較例における部は特に断らない限り重量部の意味で用いる。
また、硬化物の各特性については、下記の要領で実施した。
解像性：
6インチのシリコンエウハーに感光性絶縁樹脂組成物をスピンコートし、ホットプレートで100℃、5分間加熱し、10μｍ厚の均一な塗膜を作製した。その後、アライナー（Karl Suss社製 MA-100）を用い、パターンマスクを介して高圧水銀灯からの紫外線を波長350nmにおける露光量が3,000〜5,000Ｊ／ｍ2となるように露光し、2.38重量％テトラメチルアンモニウムハイドロキサイド水溶液を用いて23℃で2分間、浸漬現像し、超純水で１分間洗浄してパターンを得た。得られたパターンの最小寸法を解像度とした。
電気絶縁性（体積抵抗率）：
樹脂組成物をSUS基板に塗布し、ホットプレートで100℃、5分間加熱し、10μm厚の均一な樹脂塗膜を作製した。その後、対流式オーブンで170℃、2時間加熱して硬化膜を得た。この得られた硬化膜をプレッシャークッカー試験装置（タバイエスペック（株）社製）で、温度；121℃、湿度；100％、圧力：２.１気圧の条件下で168時間処理した。試験前後での層間の体積抵抗率を測定し、耐性を確認した。
熱衝撃性：
基板１上にパターン状の銅箔２を有している熱衝撃用の評価基板に光性絶縁樹脂組成物を塗布し、ホットプレートで100℃、5分間加熱し、基板上に10μm厚の樹脂塗膜を有する基材を作製した。その後、対流式オーブンで170℃、2時間加熱して樹脂塗膜を硬化させて硬化膜を得た。この基材を冷熱衝撃試験器（タバイエスペック（株）社製）で-55℃／30分〜150℃／30分を1サイクルとして耐性試験を行った。硬化膜にクラックなどの欠陥が発生するまでのサイクル数を確認した。
密着性：
SiO2をスパッタしたシリコンウエハーに樹脂組成物を塗布し、ホットプレートで100℃、5分間加熱し、10μｍ厚の均一な樹脂塗膜を有する基材を作製した。その後、対流式オーブンで170℃、2時間加熱して硬化膜を得た。この得られた硬化膜をプレッシャークッカー試験装置（タバイエスペック（株）社製）で、温度；121℃、湿度；100％、圧力：２.１気圧の条件下で168時間処理した。試験前後での密着性をJIS K 5400に準拠してクロスカット試験（碁盤目テープ法）を行い、確認した。
硬化収縮率：
6インチのシリコンエウハーに樹脂組成物を基板上にスピンコートし、ホットプレートで100℃、5分間加熱し、均一な塗膜を有する基材を作製した。その際の樹脂膜厚を（Ａ）とし、その後、対流式オーブンで170℃、2時間加熱して硬化膜を得た。この時の樹脂膜厚を（Ｂ）とし、以下の式により算出した値を硬化収縮率とした。
【００３９】
硬化収縮率= ｛1-（Ｂ）／（Ａ）｝×100
【００４０】
【実施例１】
表１に示すとおり、フェノール樹脂（A-1）100重量部、キノンジアジド化合物（B-1）20重量部、架橋微粒子（C-1）10重量部、硬化剤（D-1）15重量部を乳酸エチル（「Ｅ-１」と略記する。）145重量部に溶解した。この組成物の特性を前記評価方法にしたがって測定した。得られた結果を表２に示す。
【００４１】
【実施例２〜５】
実施例１と同様にして、表１に示した組成のポジ型感光性絶縁樹脂組成物を調製し、これらの特性を実施例１と同様に測定した。得られた結果を表２に示す。
【００４２】
【比較例１〜４】
表１に示す各組成物を調製し、実施例１と同様に物性を測定した。結果を表２に示す。
【００４３】
【表１】
注）表１に記載の組成は、以下のとおりである。
フェノール樹脂；
A-1：m-クレゾール／p-クレゾール=60／40（モル比）からなるクレゾールノボラック樹脂（ポリスチレン換算重量平均分子量=8,700）
A-2：m-クレゾール／p-クレゾール=50/50（モル比）からなるクレゾールノボラック樹脂（ポリスチレン換算重量平均分子量=7,500）
A-3：ポリヒドロキシスチレン（丸善石油化学（株）製、商品名；マルカリンカー S-2P）
フェノール化合物；
a-1：1,1-ビス（4-ヒドロキシフェニル）-1-[4-｛1-（4-ヒドロキシフェニル）-1-メチルエチル｝フェニル]エタン
キノンジアジド化合物；
B-1：1,1-ビス（4-ヒドロキシフェニル）-1-[4-｛1-（4-ヒドロキシフェニル）-1-メチルエチル｝フェニル]エタンと1,2-ナフトキノンジアジド-5-スルホン酸との平均2.0モル縮合物
B-2：1,1-ビス（4-ヒドロキシフェニル）-1-フェニルエタンと1,2-ナフトキノンジアジド-5-スルホン酸との平均1.5モル縮合物
架橋微粒子；
C-1：ブタジエン／ヒドロキシブチルメタクリレート／メタクリル酸／ジビニルベンゼン
＝60／32／6／2（重量％）、平均粒径=65ｎｍ
架橋剤；
D-1：ヘキサメトキシメチル化メラミン（三井サイテック（株）製、商品名；サイメル300）
D-2：テトラメトキシメチルグルコールウリル（三井サイテック（株）製、商品名；サイメル1174）
溶剤；
E-1：乳酸エチル
E-2：2-ヘプタノン
その他添加剤；
F-1：ジエチレングリコールジグリシジルエーテル
F-2：サンエイドSI-150（三新化学工業（株）製）
【００４５】
【表２】
【図面の簡単な説明】
【図１】 図１は、熱衝撃性の評価用基板の断面図である。
【図２】 図２は、評価基板の模式図である。
【符号の説明】
１ … 基板
２ … 銅箔[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive photosensitive insulating resin composition used for an interlayer insulating film (passivation film), a surface protective film (overcoat film), an insulating film for a high-density mounting substrate, etc. of a semiconductor element, and a cured product thereof. It relates to a cured product. More specifically, a cured product having excellent resolution as a permanent film resist and excellent properties such as electrical insulation, thermal shock, adhesion, and curing shrinkage, and a positive for obtaining such a cured product. Type photosensitive insulating resin composition.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, polyimide resins having excellent heat resistance, mechanical properties, and the like have been widely used for interlayer insulating films, surface protective films, and the like used in semiconductor devices of electronic devices. In addition, various studies have been made on photosensitive polyimide resins imparted with photosensitivity in order to improve productivity and film formation accuracy. For example, a negative type in which a photocrosslinking group is introduced into a polyimide precursor by an ester bond or an ionic bond has been put into practical use. Furthermore, as a positive type, JP-A-5-5996, JP-A-2000-98601 and the like describe a composition comprising a polyimide precursor and an orthoquinonediazide compound. However, the negative type has problems in resolution and film formation, and the positive type has problems in heat resistance, electrical insulation, adhesion to a substrate, and the like. Many other patents have been filed, but it is difficult to sufficiently satisfy the required characteristics due to high integration and thinning of semiconductor elements. Furthermore, there are problems such as film reduction after curing (volume shrinkage), multi-stage baking during curing, atmosphere control, and the like, which are difficult to use when industrially implemented.
[0003]
OBJECT OF THE INVENTION
The present invention solves the problems associated with the prior art as described above, and can provide a cured product excellent in various properties such as resolution, electrical insulation, thermal shock, adhesion, and curing shrinkage. An object of the present invention is to provide a positive photosensitive insulating resin composition suitable for applications such as an interlayer insulating film and a surface protective film for semiconductor elements.
[0004]
Furthermore, an object of the present invention is to provide a cured product obtained by curing such a positive photosensitive insulating resin composition.
[0005]
SUMMARY OF THE INVENTION
As a result of diligent research to solve the above problems, the present inventors have found a positive photosensitive insulating resin composition having excellent characteristics. That is, the positive photosensitive insulating resin composition of the present invention comprises (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound having a quinonediazide group, (C) crosslinked fine particles, and (D) at least 2 in the molecule. It is composed of a compound having one or more alkyl etherified amino groups and (E) a solvent.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the positive photosensitive insulating resin composition and the cured product thereof according to the present invention will be specifically described.
[ Photosensitive insulating resin composition ]
The positive photosensitive insulating resin composition of the present invention comprises (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound having a quinonediazide group, (C) crosslinked fine particles, and (D) at least two in the molecule. A compound containing an alkyl etherified amino group, and (E) a solvent. Moreover, the photosensitive insulating resin composition of this invention can also contain other additives, such as a heat-sensitive acid generator, an epoxy compound, a close_contact | adherence adjuvant, a leveling agent, etc. as needed.
[0007]
(A) an alkali-soluble resin having a phenolic hydroxyl group;
The alkali-soluble resin having a phenolic hydroxyl group (hereinafter referred to as “phenol resin (A)”) used in the present invention is not particularly limited, but a novolac resin is preferable. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.
Examples of phenols used at this time include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.
[0008]
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Specific examples of such novolak resins include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.
[0009]
Examples of alkali-soluble resins having phenolic hydroxyl groups other than novolak resins include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensed resins, cresol-xylylene glycol condensed resins, phenol-dicyclopentadiene condensed resins, etc. Can be mentioned.
In the present invention, the alkali-soluble resin having a phenolic hydroxyl group and a phenolic low molecular compound (hereinafter referred to as “phenol compound (a)”) can be used in combination. For example, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ) Ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) ) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like. These phenol compounds (a) may be contained in the alkali-soluble resin (A) having a phenolic hydroxyl group as a part of the component (A) in the range of 0 to 40% by weight, particularly 0 to 30% by weight. it can.
[0010]
The phenol resin (A) needs to have a weight average molecular weight of 2,000 or more, particularly in the range of about 2,000 to 20,000, from the viewpoint of the resolution, thermal shock resistance, heat resistance, and the like of the obtained insulating film. .
In the composition of the present invention, the content of the phenol resin (A) (the total amount when the phenol compound (a) is used in combination) is 30 to 80 parts by weight, preferably 40 to 70 parts by weight of the entire composition. . When the proportion of the phenol resin (A) is within this range, a film formed using the resulting composition has sufficient developability with an alkaline aqueous solution.
[0011]
(B) Compound having a quinonediazide group
The compound having a quinonediazide group in the present invention (hereinafter referred to as “quinonediazide compound (B)”) is a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphtho It is an ester compound with quinonediazide-5-sulfonic acid. The compound having one or more phenolic hydroxyl groups is not particularly limited, but specifically, a compound having the structure shown below is preferable.
[0012]
[Chemical 1]
(In Equation 1, X1~ XTenMay be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. X1~ XFiveAt least one of these is a hydroxyl group. A is a single bond, O, S, CH2, C (CHThree)2, C (CFThree)2, C = O, or SO2It is. )
[0014]
[Chemical 2]
(In Equation 2, X11~ Xtwenty fourMay be the same or different from each other, and the X1~ XTenIt is the same as the case of. X11~ X15At least one of these is a hydroxyl group. R1~ RFourIs a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
[0016]
[Chemical Formula 3]
(In Equation 3, Xtwenty five~ X39May be the same or different from each other, and the X1~ XTenIt is the same as the case of. However, Xtwenty five~ X29And X30~ X34In each of the combinations, at least one is a hydroxyl group. RFiveIs a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
[0018]
[Formula 4]
(In Equation 4, X40~ X58May be the same or different from each other, and the X1~ XTenIt is the same as the case of. X40~ X44, X45~ X49And X50~ X54In each of the combinations, at least one is a hydroxyl group. R6~ R8Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
[0020]
[Chemical formula 5]
(In Equation 5, X59~ X72May be the same or different from each other, and the X1~ XTenIt is the same as the case of. However, X59~ X62And X63~ X67In each of the combinations, at least one is a hydroxyl group. )
Specific examples of such a compound having a quinonediazide group include the following. 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4' -Pentahydroxybenzophenone, Tris (4-hydroxyphenyl) methane, Tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4 -Hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1 1 such as -methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfuric acid Phosphate ester compound.
[0022]
In the composition of this invention, a quinonediazide compound (B) is 10-50 weight part with respect to 100 weight part of phenol resin (A), Preferably it is 15-30 weight part. If the blending amount is less than 10 parts by weight, the remaining film ratio in the unexposed part may decrease or an image faithful to the mask pattern may not be obtained. On the other hand, if the blending amount exceeds 50 parts by weight, the pattern shape may be deteriorated or foaming may occur during curing.
[0023]
(C) Cross-linked fine particles
The crosslinked fine particles (hereinafter referred to as “crosslinked fine particles (C)”) in the present invention are not particularly limited as long as the Tg of the polymer constituting the crosslinked fine particles is 0 ° C. or lower. And a crosslinkable monomer (hereinafter referred to as “crosslinkable monomer”), and one or more other monomers (hereinafter referred to as “crosslinkable fine particles”) selected so that the Tg of the crosslinked fine particles (C) is 0 ° C. or less. The other copolymer is preferably a copolymerized copolymer fine particle (C) having a Tg of 0 ° C. or lower, and a functional group other than a polymerizable group, for example, What copolymerized the monomer which has functional groups, such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, and a hydroxyl group, is used.
[0024]
Examples of cross-linkable monomers include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferable.
[0025]
The crosslinkable monomer used in producing the crosslinked fine particles (C) in the present invention is in the range of 1 to 20% by weight, more preferably in the range of 2 to 10% by weight, based on the total monomers used for copolymerization. Used.
Examples of other monomers include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxy. Unsaturated nitrile compounds such as acrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumarate dinitrile, (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N ' -Ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2 -Hydroxyethyl) (Me ) Unsaturated amides such as acrylamide, crotonic acid amide, cinnamic acid amide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic (Meth) acrylates such as hexyl acid, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, Epoxy (meth) acrylates obtained by the reaction of aromatic vinyl compounds such as p-isopropenylphenol, diglycidyl ether of bisphenol A, diglycidyl ether of glycol, etc. with (meth) acrylic acid, hydroxyalkyl (meth) acrylate, etc. And epoxy group-containing unsaturated compounds such as urethane (meth) acrylates, glycidyl (meth) acrylates, (meth) allyl glycidyl ethers obtained by reaction of hydroxyalkyl (meth) acrylates with polyisocyanates, (meth) Acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acryloxyethyl, hexahydrophthalic acid-β- ( Unsaturated acid compounds such as (meth) acryloxyethyl, amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate, and amide group-containing unsaturated compounds such as (meth) acrylamide and dimethyl (meth) acrylamide Compound, hydroxyethyl (meth) acrylate And hydroxyl-containing unsaturated compounds such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. These other monomers include butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic acid, Hydroxyalkyl (meth) acrylates and the like are preferably used.
[0026]
As such another monomer, it is preferable to use at least one diene compound, specifically, butadiene. Such a diene compound is desirably used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, based on all monomers used for copolymerization.
The crosslinked fine particles (C) used in the present invention are particularly obtained as rubber-like soft fine particles when a diene compound such as butadiene is copolymerized in the above amount with respect to all monomers as other monomers. Cracks can be prevented from occurring in the cured film, and a cured film having excellent durability can be obtained.
[0027]
In the present invention, the average particle size of the crosslinked fine particles (C) is usually 30 to 500 nm, preferably 40 to 200 nm, more preferably 50 to 120 nm. The method for controlling the particle size of the crosslinked fine particles (C) is not particularly limited, but when the crosslinked fine particles (C) are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of emulsifier used. In addition, a method for controlling the particle size can be exemplified.
[0028]
Moreover, the compounding quantity of crosslinked fine particle (C) is 1-50 weight part with respect to 100 weight part of said phenol resin (A), Preferably it is 5-30 weight part. If the blending amount is less than 1 part by weight, the thermal shock resistance of the resulting cured film will decrease, and if it exceeds 50 parts by weight, the resolution and the heat resistance of the resulting cured film will decrease, or will be compatible with other components. May decrease.
(D) Compound (curing agent) having at least two alkyl etherified amino groups in the molecule
A compound having at least two alkyl etherified amino groups in the molecule (hereinafter referred to as “curing agent (D)”) acts as a crosslinking agent (curing agent) that reacts with the phenol resin (A). To do. As the curing agent (D), all or part of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea are alkyletherified. A nitrogen-containing compound can be mentioned. Here, examples of the alkyl group include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like can be used, and these curing agents (D) can be used alone or in combination. You may use the above together.
[0029]
The compounding quantity of the hardening | curing agent (D) in this invention is 1-100 weight part with respect to 100 weight part of said phenol resins (A), Preferably it is 5-50 weight part. If the blending amount is less than 1 part by weight, curing may be insufficient, and the electrical insulation of the resulting cured product may decrease, and if it exceeds 100 parts by weight, patterning characteristics may decrease or heat resistance may decrease. Sometimes.
[0030]
(E) Solvent
A solvent (E) is added in order to improve the handleability of a resin composition, or to adjust a viscosity or storage stability. The type of the organic solvent is not particularly limited, but examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol mono Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene Glycol monomethyl ether ace Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, Aliphatic carboxylic acid esters such as n-butyl propionate and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Other esters such as chill, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun. These organic solvents can be used alone or in combination of two or more.
[0031]
The positive photosensitive insulating resin composition of the present invention may contain a heat-sensitive acid generator, an epoxy compound, an adhesion aid, a leveling agent, and the like as other additives. The heat-sensitive acid generator is not particularly limited as long as it is a compound that generates an acid by heat treatment, and the alkyl ether group and the phenol resin (A) in the curing agent (D) by the catalytic action of the generated acid. The reaction of is promoted. Examples of the heat-sensitive acid generator include onium salt compounds. Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. These other additives can be contained to such an extent that the characteristics of the resulting photosensitive insulating resin composition are not impaired.
[0032]
[ Hardened material ]
The photosensitive insulating resin composition according to the present invention comprises a phenol resin (A), a quinonediazide compound (B), a crosslinked fine particle (C), a curing agent (D), a solvent (E), and other additives as necessary. In addition to being excellent in resolution, the cured product is excellent in electrical insulation, thermal shock, adhesion, cure shrinkage, and the like. Therefore, the positive photosensitive insulating resin composition of the present invention can be suitably used particularly as a material for an interlayer insulating film or a surface protective film of a semiconductor element.
[0033]
The positive photosensitive insulating resin composition according to the present invention is applied to a substrate such as a silicon wafer on which a wiring pattern has been applied, and dried to evaporate the solvent and form a coating film. Thereafter, exposure is performed through a desired mask pattern, followed by development with an alkaline developer, and a desired pattern can be obtained by dissolving and removing the exposed portion. Furthermore, a cured film can be obtained by performing a heat treatment after development in order to develop the insulating film characteristics.
[0034]
As a method of coating the resin composition on the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, and the like can be used. The thickness can be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the composition solution.
Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet rays such as g-line steppers and i-line steppers, electron beams, and laser beams. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, 1,000 to 20,000 J / m for a resin film thickness of 5 to 50 μm2Degree.
[0035]
Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing the exposed portion. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The developing conditions are usually 20 to 40 ° C. and about 1 to 10 minutes.
Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by weight. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.
[0036]
Furthermore, it can be cured by performing a heat treatment in order to sufficiently develop the characteristics as an insulating film after development. Such curing conditions are not particularly limited, but the composition can be cured by heating at a temperature of 100 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. In addition, curing can be sufficiently advanced, or heating can be performed in two stages in order to prevent deformation of the obtained pattern shape. For example, in the first stage, the temperature is 50 to 100 ° C. for 10 minutes to 2 hours. It can also be cured by heating to a certain degree and further heating at a temperature of 100 to 250 ° C. for about 20 minutes to 8 hours. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as heating equipment.
[0037]
【The invention's effect】
According to the present invention, a positive photosensitive material having a cured product excellent in resolution, electrical insulation, thermostrength plasticity, adhesion, cure shrinkage, etc., in particular, a cured product excellent in insulation and thermal shock resistance. An insulating resin composition can be obtained.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, parts are used in terms of parts by weight unless otherwise specified.
Moreover, about each characteristic of hardened | cured material, it implemented in the following way.
Resolution:
A 6-inch silicon wafer was spin-coated with the photosensitive insulating resin composition and heated on a hot plate at 100 ° C. for 5 minutes to prepare a uniform coating film having a thickness of 10 μm. After that, using an aligner (MA-100 manufactured by Karl Suss), UV light from a high-pressure mercury lamp through a pattern mask has an exposure dose of 3,000 to 5,000 J / m at a wavelength of 350 nm.2Then, it was immersed and developed at 23 ° C. for 2 minutes using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and washed with ultrapure water for 1 minute to obtain a pattern. The minimum dimension of the obtained pattern was taken as the resolution.
Electrical insulation (volume resistivity):
The resin composition was applied to a SUS substrate and heated on a hot plate at 100 ° C. for 5 minutes to produce a 10 μm thick uniform resin coating film. Thereafter, the film was heated in a convection oven at 170 ° C. for 2 hours to obtain a cured film. The obtained cured film was treated with a pressure cooker test apparatus (manufactured by Tabai Espec Co., Ltd.) for 168 hours under conditions of temperature: 121 ° C., humidity: 100%, pressure: 2.1 atm. The volume resistivity between the layers before and after the test was measured to confirm the resistance.
Thermal shock resistance:
A photo-insulating resin composition is applied to a thermal shock evaluation substrate having a patterned copper foil 2 on a substrate 1, heated at 100 ° C. for 5 minutes on a hot plate, and a 10 μm thick resin on the substrate. A substrate having a coating film was prepared. Thereafter, the resin coating film was cured by heating at 170 ° C. for 2 hours in a convection oven to obtain a cured film. The substrate was subjected to a resistance test using a thermal shock tester (manufactured by Tabai Espec Co., Ltd.) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. The number of cycles until a defect such as a crack occurred in the cured film was confirmed.
Adhesion:
SiO2The resin composition was applied to a silicon wafer sputtered with and heated on a hot plate at 100 ° C. for 5 minutes to prepare a substrate having a uniform resin coating film having a thickness of 10 μm. Thereafter, the film was heated in a convection oven at 170 ° C. for 2 hours to obtain a cured film. The obtained cured film was treated with a pressure cooker test apparatus (manufactured by Tabai Espec Co., Ltd.) for 168 hours under conditions of temperature: 121 ° C., humidity: 100%, pressure: 2.1 atm. The adhesion before and after the test was confirmed by performing a cross-cut test (cross cut tape method) in accordance with JIS K 5400.
Curing shrinkage:
A resin composition was spin-coated on a 6-inch silicon wafer on a substrate and heated on a hot plate at 100 ° C. for 5 minutes to prepare a substrate having a uniform coating film. The resin film thickness at that time was set to (A), and then heated at 170 ° C. for 2 hours in a convection oven to obtain a cured film. The resin film thickness at this time was defined as (B), and the value calculated by the following equation was defined as the curing shrinkage rate.
[0039]
Curing shrinkage = {1- (B) / (A)} × 100
[0040]
[Example 1]
As shown in Table 1, 100 parts by weight of phenol resin (A-1), 20 parts by weight of quinonediazide compound (B-1), 10 parts by weight of crosslinked fine particles (C-1), and 15 parts by weight of curing agent (D-1) Dissolved in 145 parts by weight of ethyl lactate (abbreviated as “E-1”). The properties of this composition were measured according to the evaluation method. The obtained results are shown in Table 2.
[0041]
[Examples 2 to 5]
In the same manner as in Example 1, positive photosensitive insulating resin compositions having the compositions shown in Table 1 were prepared, and these characteristics were measured in the same manner as in Example 1. The obtained results are shown in Table 2.
[0042]
[Comparative Examples 1-4]
Each composition shown in Table 1 was prepared, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.
[0043]
[Table 1]
Note) The composition described in Table 1 is as follows.
Phenolic resin;
A-1: Cresol novolak resin consisting of m-cresol / p-cresol = 60/40 (molar ratio) (polystyrene equivalent weight average molecular weight = 8,700)
A-2: Cresol novolak resin consisting of m-cresol / p-cresol = 50/50 (molar ratio) (polystyrene equivalent weight average molecular weight = 7,500)
A-3: Polyhydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd., trade name: Marcalinker S-2P)
Phenolic compounds;
a-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane
Quinonediazide compounds;
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfone Average 2.0 molar condensate with acid
B-2: Average 1.5 molar condensate of 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1,2-naphthoquinonediazide-5-sulfonic acid
Crosslinked fine particles;
C-1: Butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene
= 60/32/6/2 (% by weight), average particle size = 65 nm
Cross-linking agent;
D-1: Hexamethoxymethylated melamine (Mitsui Cytec Co., Ltd., trade name: Cymel 300)
D-2: Tetramethoxymethyl glycoluril (Mitsui Cytec Co., Ltd., trade name: Cymel 1174)
solvent;
E-1: Ethyl lactate
E-2: 2-Heptanone
Other additives;
F-1: Diethylene glycol diglycidyl ether
F-2: Sun-Aid SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.)
[0045]
[Table 2]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a thermal shock resistance evaluation substrate.
FIG. 2 is a schematic diagram of an evaluation board.
[Explanation of symbols]
1 ... Substrate
2 ... Copper foil
Claims (4)
前記（Ｂ）キノンジアジド基を有する化合物の量が１０〜５０重量部であり、
前記（Ｃ）架橋微粒子の量が１〜５０重量部であり、
前記（Ｄ）分子中に少なくとも２つ以上のアルキルエーテル化されたアミノ基を有する化合物の量が１〜１００重量部である、請求項１に記載のポジ型感光性絶縁樹脂組成物。For 100 parts by weight of the alkali-soluble resin (A) having a phenolic hydroxyl group,
The amount of the compound (B) having a quinonediazide group is 10 to 50 parts by weight,
The amount of the (C) crosslinked fine particles is 1 to 50 parts by weight,
The positive photosensitive insulating resin composition according to claim 1, wherein the amount of the compound (D) having at least two alkyl etherified amino groups in the molecule is 1 to 100 parts by weight.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002014307A JP3812654B2 (en) | 2002-01-23 | 2002-01-23 | Positive photosensitive insulating resin composition and cured product thereof |
| CN2009101659142A CN101644891B (en) | 2002-01-23 | 2003-01-15 | Positively photosensitive insulating resin composition and cured object obtained therefrom |
| US10/475,084 US7214454B2 (en) | 2002-01-23 | 2003-01-15 | Positively photosensitive insulating resin composition and cured object obtained therefrom |
| KR1020037013775A KR100895364B1 (en) | 2002-01-23 | 2003-01-15 | Positive photosensitive insulating resin composition and its hardened | cured material |
| CN038002817A CN1864099B (en) | 2002-01-23 | 2003-01-15 | Positively photosensitive insulating resin composition and cured object obtained therefrom |
| EP03700565.9A EP1469346B1 (en) | 2002-01-23 | 2003-01-15 | Positive photosensitive insulating resin composition and cured object obtained therefrom |
| PCT/JP2003/000260 WO2003062925A1 (en) | 2002-01-23 | 2003-01-15 | Positively photosensitive insulating resin composition and cured object obtained therefrom |
| TW092101127A TWI266953B (en) | 2002-01-23 | 2003-01-20 | Positively photosensitive insulating resin composition and cured object obtained therefrom |
| US11/692,486 US7371500B2 (en) | 2002-01-23 | 2007-03-28 | Positive photosensitive insulating resin composition and cured product thereof |
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| JP2002014307A JP3812654B2 (en) | 2002-01-23 | 2002-01-23 | Positive photosensitive insulating resin composition and cured product thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009063808A1 (en) | 2007-11-12 | 2009-05-22 | Hitachi Chemical Company, Ltd. | Positive-type photosensitive resin composition, method for production of resist pattern, semiconductor device, and electronic device |
| WO2010026988A1 (en) | 2008-09-04 | 2010-03-11 | 日立化成工業株式会社 | Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component |
| US8461699B2 (en) | 2008-12-26 | 2013-06-11 | Hitachi Chemical Company, Ltd. | Positive-type photosensitive resin composition, method for producing resist pattern, semiconductor device, and electronic device |
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| JP4655882B2 (en) * | 2004-10-29 | 2011-03-23 | Ｊｓｒ株式会社 | Positive photosensitive insulating resin composition and cured product thereof |
| JP4692219B2 (en) * | 2004-10-29 | 2011-06-01 | Ｊｓｒ株式会社 | Positive photosensitive insulating resin composition and cured product thereof |
| JP2007052359A (en) * | 2005-08-19 | 2007-03-01 | Jsr Corp | Pattern forming method, its cured material, and circuit board |
| JP4640037B2 (en) * | 2005-08-22 | 2011-03-02 | Ｊｓｒ株式会社 | Positive photosensitive insulating resin composition and cured product thereof |
| WO2007119949A1 (en) * | 2006-04-13 | 2007-10-25 | Kolon Industries, Inc | Composition for positive type photoresist and positive type photoresist film manufactured thereby |
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| JP4765951B2 (en) * | 2007-02-08 | 2011-09-07 | Ｊｓｒ株式会社 | Large silicon wafer having insulating film and method for manufacturing the same |
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| JP5067028B2 (en) * | 2007-06-12 | 2012-11-07 | 日立化成工業株式会社 | Positive photosensitive resin composition, method for producing resist pattern, and electronic device |
| JP5498874B2 (en) | 2010-06-28 | 2014-05-21 | 東京応化工業株式会社 | Positive photosensitive resin composition |
| TWI481657B (en) | 2010-09-15 | 2015-04-21 | Asahi Kasei E Materials Corp | A phenol resin composition and a hardened embossed pattern, and a method for manufacturing the semiconductor |
| JP5968227B2 (en) | 2010-12-27 | 2016-08-10 | 旭化成株式会社 | Photosensitive resin composition for alkali development, cured relief pattern, and semiconductor device |
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| JP2013134346A (en) * | 2011-12-26 | 2013-07-08 | Hitachi Chemical Co Ltd | Photosensitive resin composition, manufacturing method of patterned cured film, semiconductor device, and electronic component |
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| JP6513596B2 (en) * | 2016-04-04 | 2019-05-15 | 日立化成株式会社 | PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR MANUFACTURING PATTERN CURED FILM, SEMICONDUCTOR DEVICE AND ELECTRONIC COMPONENT |
| JP2018028690A (en) * | 2017-10-31 | 2018-02-22 | 日立化成株式会社 | Photosensitive resin composition, method for producing patterned cured film, semiconductor device and electronic component |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07228611A (en) * | 1994-02-15 | 1995-08-29 | Japan Synthetic Rubber Co Ltd | Polymer emulsion |
| CA2228654A1 (en) * | 1997-02-18 | 1998-08-18 | James J. Briguglio | Positive-tone photoimageable crosslinkable coating |
| US6190833B1 (en) * | 1997-03-30 | 2001-02-20 | Jsr Corporation | Radiation-sensitive resin composition |
| CN1224858A (en) * | 1998-01-30 | 1999-08-04 | 莫顿国际股份有限公司 | Positive-tone photoimageable crosslinkable coating |
| JP2001005175A (en) * | 1999-06-23 | 2001-01-12 | Victor Co Of Japan Ltd | Photoresist for information recoding medium |
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| WO2009063808A1 (en) | 2007-11-12 | 2009-05-22 | Hitachi Chemical Company, Ltd. | Positive-type photosensitive resin composition, method for production of resist pattern, semiconductor device, and electronic device |
| US9786576B2 (en) | 2007-11-12 | 2017-10-10 | Hitachi Chemical Company, Ltd | Positive-type photosensitive resin composition, method for production of resist pattern, semiconductor device, and electronic device |
| WO2010026988A1 (en) | 2008-09-04 | 2010-03-11 | 日立化成工業株式会社 | Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component |
| US8426985B2 (en) | 2008-09-04 | 2013-04-23 | Hitachi Chemical Company, Ltd. | Positive-type photosensitive resin composition, method for producing resist pattern, and electronic component |
| US8461699B2 (en) | 2008-12-26 | 2013-06-11 | Hitachi Chemical Company, Ltd. | Positive-type photosensitive resin composition, method for producing resist pattern, semiconductor device, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1864099B (en) | 2010-06-16 |
| CN1864099A (en) | 2006-11-15 |
| JP2003215789A (en) | 2003-07-30 |
| CN101644891A (en) | 2010-02-10 |
| CN101644891B (en) | 2012-06-06 |
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