JP2020173431A - Negative type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern - Google Patents
Negative type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern Download PDFInfo
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- JP2020173431A JP2020173431A JP2020041280A JP2020041280A JP2020173431A JP 2020173431 A JP2020173431 A JP 2020173431A JP 2020041280 A JP2020041280 A JP 2020041280A JP 2020041280 A JP2020041280 A JP 2020041280A JP 2020173431 A JP2020173431 A JP 2020173431A
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- photosensitive resin
- resin composition
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 98
- 239000011342 resin composition Substances 0.000 title claims abstract description 98
- 239000004642 Polyimide Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000002243 precursor Substances 0.000 claims abstract description 79
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 10
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims abstract description 9
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims abstract description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 7
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims abstract description 6
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 22
- 238000012360 testing method Methods 0.000 abstract description 22
- 238000003860 storage Methods 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 57
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 description 56
- 239000010408 film Substances 0.000 description 38
- 229920000642 polymer Polymers 0.000 description 30
- 239000010949 copper Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007983 Tris buffer Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000008393 encapsulating agent Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000013007 heat curing Methods 0.000 description 7
- 150000002923 oximes Chemical class 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 206010034960 Photophobia Diseases 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 208000013469 light sensitivity Diseases 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 125000004386 diacrylate group Chemical group 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- DRAVOWXCEBXPTN-UHFFFAOYSA-N isoguanine Chemical compound NC1=NC(=O)NC2=C1NC=N2 DRAVOWXCEBXPTN-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003212 purines Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- DQOKNNHAZSNFOC-UHFFFAOYSA-N (3-butoxy-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CCCCOCC(O)COC(=O)C(C)=C DQOKNNHAZSNFOC-UHFFFAOYSA-N 0.000 description 2
- AZNUOOZUBQUQJV-UHFFFAOYSA-N (3-butoxy-2-hydroxypropyl) prop-2-enoate Chemical compound CCCCOCC(O)COC(=O)C=C AZNUOOZUBQUQJV-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LHBQGXZUVXFJRH-UHFFFAOYSA-N 1-hydroxybut-3-en-2-one Chemical compound OCC(=O)C=C LHBQGXZUVXFJRH-UHFFFAOYSA-N 0.000 description 2
- HPZMWTNATZPBIH-UHFFFAOYSA-N 1-methyladenine Chemical compound CN1C=NC2=NC=NC2=C1N HPZMWTNATZPBIH-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- LUEYUHCBBXWTQT-UHFFFAOYSA-N 4-phenyl-2h-triazole Chemical compound C1=NNN=C1C1=CC=CC=C1 LUEYUHCBBXWTQT-UHFFFAOYSA-N 0.000 description 2
- PZNXJCRPOUAPKN-UHFFFAOYSA-N 5-hydroxypent-1-en-3-one Chemical compound OCCC(=O)C=C PZNXJCRPOUAPKN-UHFFFAOYSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
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- BVIAOQMSVZHOJM-UHFFFAOYSA-N N(6),N(6)-dimethyladenine Chemical compound CN(C)C1=NC=NC2=C1N=CN2 BVIAOQMSVZHOJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WNQITGRHOWFLEA-LMWFVWJRSA-N [(1R,4S,5R,8S,9R,10S,12R,13R)-1,5,9-trimethyl-11,14,15,16-tetraoxatetracyclo[10.3.1.04,13.08,13]hexadecan-10-yl] acetate Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2O[C@@H](OC(C)=O)[C@@H]4C WNQITGRHOWFLEA-LMWFVWJRSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Abstract
Description
本発明は、ネガ型感光性樹脂組成物、ポリイミドの製造方法および硬化レリーフパターンの製造方法に関するものである。 The present invention relates to a negative photosensitive resin composition, a method for producing polyimide, and a method for producing a cured relief pattern.
従来、電子部品の絶縁材料、及び半導体装置のパッシベーション膜、表面保護膜、層間絶縁膜等には、優れた耐熱性、電気特性及び機械特性を併せ持つポリイミド樹脂、ポリベンゾオキサゾール樹脂、フェノール樹脂等が用いられている。これらの樹脂の中でも、感光性樹脂組成物の形態で提供されるものは、該組成物の塗布、露光、現像、及びキュアによる熱イミド化処理によって、耐熱性のレリーフパターン皮膜を容易に形成することができる。このような感光性樹脂組成物は、従来の非感光型材料に比べて、大幅な工程短縮を可能にするという特徴を有している。 Conventionally, polyimide resins, polybenzoxazole resins, phenol resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. It is used. Among these resins, those provided in the form of a photosensitive resin composition easily form a heat-resistant relief pattern film by applying, exposing, developing, and thermally imidizing the composition by curing. be able to. Such a photosensitive resin composition has a feature that a process can be significantly shortened as compared with a conventional non-photosensitive material.
ところで、半導体装置(以下、「素子」とも言う。)は、目的に合わせて、様々な方法でプリント基板に実装される。従来の素子は、素子の外部端子(パッド)からリードフレームまで細いワイヤで接続するワイヤボンディング法により作製されることが一般的であった。しかしながら、素子の高速化が進み、動作周波数がGHzまで到達した今日、実装における各端子の配線長さの違いが、素子の動作に影響を及ぼすまでに至った。そのため、ハイエンド用途の素子の実装では、実装配線の長さを正確に制御する必要が生じ、ワイヤボンディングではその要求を満たすことが困難となった。 By the way, a semiconductor device (hereinafter, also referred to as an "element") is mounted on a printed circuit board by various methods according to a purpose. Conventional elements have generally been manufactured by a wire bonding method in which a thin wire is used to connect an external terminal (pad) of the element to a lead frame. However, as the speed of the device has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting has come to affect the operation of the device. Therefore, in the mounting of elements for high-end applications, it becomes necessary to accurately control the length of the mounting wiring, and it is difficult to meet this requirement by wire bonding.
したがって、半導体チップの表面に再配線層を形成し、その上にバンプ(電極)を形成した後、該チップを裏返して、プリント基板に直接実装する、フリップチップ実装が提案されている(例えば特許文献1参照)。このフリップチップ実装では、配線距離を正確に制御できるため、高速な信号を取り扱うハイエンド用途の素子に、又は実装サイズの小ささから携帯電話等に、それぞれ採用され、需要が急拡大している。フリップチップ実装にポリイミド、ポリベンゾオキサゾール、フェノール樹脂等の材料を使用する場合、該樹脂層のパターンが形成された後に、金属配線層形成工程を経る。金属配線層は、通常、樹脂層表面をプラズマエッチングして表面を粗化した後、メッキのシード層となる金属層を、1μm以下の厚みでスパッタにより形成した後、その金属層を電極として、電解メッキにより形成される。このとき、一般に、シード層となる金属としてはチタン(Ti)が、電解メッキにより形成される再配線層の金属としては銅(Cu)が用いられる。 Therefore, a flip chip mounting method has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the bumps (electrodes), and then the chip is turned over and mounted directly on a printed circuit board (for example, a patent). Reference 1). Since this flip-chip mounting can accurately control the wiring distance, it is used for high-end applications that handle high-speed signals, or for mobile phones and the like due to its small mounting size, and demand is rapidly expanding. When a material such as polyimide, polybenzoxazole, or phenol resin is used for flip-chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. In the metal wiring layer, usually, the surface of the resin layer is plasma-etched to roughen the surface, and then a metal layer to be a seed layer for plating is formed by sputtering with a thickness of 1 μm or less, and then the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, generally, titanium (Ti) is used as the metal to be the seed layer, and copper (Cu) is used as the metal of the rewiring layer formed by electroplating.
また、近年、ファンアウト型半導体パッケージが注目されている。ファンナウト型の半導体パッケージでは、半導体チップを封止材(樹脂層)で覆うことにより半導体チップのチップサイズよりも大きいチップ封止体を形成する。更に、半導体チップ及び封止材の領域にまで及ぶ再配線層を形成する。再配線層は、薄い膜厚で形成される。また、再配線層は、封止材の領域まで形成できるため、外部接続端子の数を多くすることができる。 In recent years, fan-out type semiconductor packages have been attracting attention. In a funout type semiconductor package, a chip encapsulant larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with a sealing material (resin layer). Further, a rewiring layer extending to the area of the semiconductor chip and the encapsulant is formed. The rewiring layer is formed with a thin film thickness. Further, since the rewiring layer can be formed up to the area of the sealing material, the number of external connection terminals can be increased.
このような金属再配線層について、信頼性試験後に再配線された金属層と樹脂層との密着性が高いことが求められる。特に近年では、再配線層を加熱硬化させる温度がより低温であることが求められている。信頼性試験としては、例えば、空気中、125℃以上の高温で100時間以上保存する、高温保存試験;配線を組んで電圧を印加しながら、空気中で、125℃程度の温度で100時間以上に亘る保存下での動作を確認する、高温動作試験;空気中で、−65℃〜−40℃程度の低温状態と、125℃〜150℃程度の高温状態とをサイクルで行き来させる、温度サイクル試験;85℃以上の温度で湿度85%以上の水蒸気雰囲気下で保存する、高温高湿保存試験;高温高湿保存試験と同じ試験を、配線を組んで電圧を印加しながら行なう、高温高湿バイアス試験;並びに空気中又は窒素下で260℃のはんだリフロー炉を複数回通過させる、はんだリフロー試験等を挙げることができる。 Such a metal rewiring layer is required to have high adhesion between the metal layer rewired after the reliability test and the resin layer. Particularly in recent years, it has been required that the temperature at which the rewiring layer is heat-cured is lower. As a reliability test, for example, a high temperature storage test in which the product is stored in air at a high temperature of 125 ° C. or higher for 100 hours or longer; while wiring is assembled and a voltage is applied, the temperature in the air is about 125 ° C. for 100 hours or longer. High-temperature operation test to confirm the operation under storage; a temperature cycle in which a low-temperature state of about -65 ° C to -40 ° C and a high-temperature state of about 125 ° C to 150 ° C are cycled back and forth in air. Test; High temperature and high humidity storage test in which the product is stored at a temperature of 85 ° C or higher and in a water vapor atmosphere of 85% or more in humidity; Bias test; and a solder reflow test in which a solder reflow furnace at 260 ° C. is passed a plurality of times in air or in nitrogen can be mentioned.
しかしながら、従来、上記信頼性試験の中で、高温保存試験の場合、試験後、再配線されたCu層の、樹脂層に接する界面でボイドが発生する、という問題があった。特に、加熱硬化させる温度が低温の場合、より顕著となる傾向にある。Cu層と樹脂層との界面でボイドが発生すると、両者の密着性が低下してしまう。 However, conventionally, in the above reliability test, in the case of the high temperature storage test, there is a problem that voids are generated at the interface of the rewired Cu layer in contact with the resin layer after the test. In particular, when the temperature for heat curing is low, it tends to be more remarkable. If voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two is lowered.
また、ボイドの問題に加えて、金属再配線層には耐薬品性が求められ、また、微細化要求も大きくなっている。このため、特に半導体の再配線層の形成に用いられる感光性樹脂組成物には、ボイドの発生を抑制するとともに、高い耐薬品性と解像性を示すことが求められる。 Further, in addition to the problem of voids, the metal rewiring layer is required to have chemical resistance, and the demand for miniaturization is also increasing. Therefore, in particular, the photosensitive resin composition used for forming the rewiring layer of a semiconductor is required to suppress the generation of voids and to exhibit high chemical resistance and resolution.
本発明は、このような従来の実情に鑑みて考案されたものであり、高い耐薬品性および解像度が得られ、かつ、高温保存(high temperature storage)試験後、Cu層の、樹脂層に接する界面でボイドの発生を抑制することができるネガ型感光性樹脂組成物(以下、本明細書において単に「感光性樹脂組成物」ともいう。)を提供することを目的の一つとする。また、本発明のネガ型感光性樹脂組成物を用いた硬化レリーフパターンの形成方法を提供することも目的の一つである。 The present invention has been devised in view of such conventional circumstances, has high chemical resistance and resolution, and comes into contact with the resin layer of the Cu layer after a high temperature storage test. One of the objects is to provide a negative type photosensitive resin composition (hereinafter, also simply referred to as “photosensitive resin composition” in the present specification) capable of suppressing the generation of voids at an interface. Another object of the present invention is to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention.
本発明者らは、特定のポリイミド前駆体と、特定の構造を有するシランカップリング剤、および特定の有機溶媒を組み合わせることにより、上記課題を解決することができることを見出し、本発明を完成するに至った。すなわち、本発明は以下のとおりである。
[1]
以下の成分:
(A)ポリイミド前駆体;
(B)光重合開始剤;
(C)下記一般式(1):
で表されるシランカップリング剤;及び
(D)γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール, アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、及びε―カプロラクトンからなる群から選択される少なくとも1種を含有する、有機溶媒;
を含む、ネガ型感光性樹脂組成物。
[2]
前記一般式(1)において、R20がフェニルアミノ基、及びウレイド基を含む置換基からなる群から選択される少なくとも1種である、[1]に記載のネガ型感光性樹脂組成物。
[3]
前記一般式(1)において、R20がフェニルアミノ基を含む置換基である、[1]または[2]に記載のネガ型感光性樹脂組成物。
[4]
(E)熱塩基発生剤を更に含む、[1]〜[3]のいずれかに記載のネガ型感光性樹脂組成物。
[5]
前記(D)有機溶媒が、γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール, アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、及びε―カプロラクトンからなる群から選択される少なくとも2種を含有する、[1]〜[4]のいずれかに記載のネガ型感光性樹脂組成物。
[6]
前記(A)ポリイミド前駆体が、下記一般式(2):
で表される構造単位を有する、[1]〜[5]のいずれかに記載のネガ型感光性樹脂組成物。
[7]
前記一般式(2)において、R1及びR2の少なくとも一方は、下記一般式(3):
で表される1価の有機基である、[6]に記載のネガ型感光性樹脂組成物。
[8]
前記一般式(2)において、X1が、下記一般式(20a):
[9]
前記一般式(2)において、X1が、下記一般式(20b):
[10]
前記一般式(2)において、X1が、下記一般式(20c):
[11]
前記一般式(2)において、Y1が、下記一般式(21b):
[12]
前記一般式(2)において、Y1が、下記一般式(21c):
で表される構造を含む、[6]〜[10]のいずれかに記載のネガ型感光性樹脂組成物。
[13]
前記(A)ポリイミド前駆体が、下記一般式(4):
で表される構造単位を有する、[6]又は[7]に記載のネガ型感光性樹脂組成物。
[14]
前記(A)ポリイミド前駆体が、下記一般式(5):
で表される構造単位を有する、[6]又は[7]に記載のネガ型感光性樹脂組成物。
[15]
前記(A)ポリイミド前駆体が、下記一般式(4):
下記一般式(5):
で表される構造単位を同時に含む、[6]又は[7]に記載のネガ型感光性樹脂組成物。
[16]
前記(A)ポリイミド前駆体が、前記一般式(4)と(5)で表される構造単位の共重合体である、[15]に記載のネガ型感光性樹脂組成物。
[17]
前記(A)ポリイミド前駆体が、下記一般式(6):
で表される構造単位を有する、[6]又は[7]に記載のネガ型感光性樹脂組成物。
[18]
100質量部の前記(A)ポリイミド前駆体と、
前記(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の前記(B)光重合開始剤と、
前記(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の前記(C)シランカップリング剤と、
を含む、[1]〜[17]のいずれかに記載のネガ型感光性樹脂組成物。
[19]
[1]〜[18]のいずれかに記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
[20]
以下の工程:
(1)[1]〜[18]のいずれかに記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を前記基板上に形成する工程;
(2)前記感光性樹脂層を露光する工程;
(3)露光後の前記感光性樹脂層を現像して、レリーフパターンを形成する工程;及び、
(4)前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程;
を含む、硬化レリーフパターンの製造方法。
The present inventors have found that the above problems can be solved by combining a specific polyimide precursor, a silane coupling agent having a specific structure, and a specific organic solvent, and complete the present invention. I arrived. That is, the present invention is as follows.
[1]
The following ingredients:
(A) Polyimide precursor;
(B) Photopolymerization initiator;
(C) The following general formula (1):
Silane coupling agent represented by; and (D) at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. Seed-containing organic solvent;
Negative type photosensitive resin composition containing.
[2]
In the general formula (1) is at least one R 20 is selected from the group consisting of substituents containing a phenylamino group and a ureido group, a negative type photosensitive resin composition according to [1].
[3]
In Formula (1), R 20 is a substituent containing a phenylamino group, [1] or a negative photosensitive resin composition according to [2].
[4]
(E) The negative photosensitive resin composition according to any one of [1] to [3], further comprising a thermal base generator.
[5]
The organic solvent (D) contains at least two selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. The negative photosensitive resin composition according to any one of [1] to [4].
[6]
The polyimide precursor of (A) has the following general formula (2):
The negative type photosensitive resin composition according to any one of [1] to [5], which has a structural unit represented by.
[7]
In the general formula (2), at least one of R 1 and R 2 is the following general formula (3):
The negative photosensitive resin composition according to [6], which is a monovalent organic group represented by.
[8]
In the general formula (2), X 1 is the following general formula (20a):
[9]
In the general formula (2), X 1 is the following general formula (20b):
[10]
In the general formula (2), X 1 is the following general formula (20c):
[11]
In the general formula (2), Y 1 is the following general formula (21b):
[12]
In the general formula (2), Y 1 is the following general formula (21c):
The negative type photosensitive resin composition according to any one of [6] to [10], which comprises the structure represented by.
[13]
The polyimide precursor of (A) has the following general formula (4):
The negative type photosensitive resin composition according to [6] or [7], which has a structural unit represented by.
[14]
The polyimide precursor of (A) has the following general formula (5):
The negative type photosensitive resin composition according to [6] or [7], which has a structural unit represented by.
[15]
The polyimide precursor of (A) has the following general formula (4):
The following general formula (5):
The negative photosensitive resin composition according to [6] or [7], which simultaneously contains the structural unit represented by.
[16]
The negative photosensitive resin composition according to [15], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[17]
The polyimide precursor of (A) has the following general formula (6):
The negative type photosensitive resin composition according to [6] or [7], which has a structural unit represented by.
[18]
With 100 parts by mass of the polyimide precursor (A)
0.1 to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.
0.1 to 20 parts by mass of the (C) silane coupling agent based on 100 parts by mass of the (A) polyimide precursor.
The negative type photosensitive resin composition according to any one of [1] to [17].
[19]
A method for producing polyimide, which comprises a step of converting the negative photosensitive resin composition according to any one of [1] to [18] into polyimide.
[20]
The following steps:
(1) A step of applying the negative photosensitive resin composition according to any one of [1] to [18] onto a substrate to form a photosensitive resin layer on the substrate;
(2) A step of exposing the photosensitive resin layer;
(3) A step of developing the photosensitive resin layer after exposure to form a relief pattern;
(4) A step of heat-treating the relief pattern to form a cured relief pattern;
A method for manufacturing a cured relief pattern, including.
本発明によれば、高い耐薬品性と解像度が得られ、高温保存(high temperature storage)試験後、Cu層の、樹脂層に接する界面でボイドの発生を抑制するネガ型感光性樹脂組成物およびポリイミドの製造方法を提供することができ、また該ネガ型感光性樹脂組成物を用いた硬化レリーフパターンの形成方法を提供することができる。 According to the present invention, a negative photosensitive resin composition capable of obtaining high chemical resistance and resolution and suppressing the generation of voids at the interface of the Cu layer in contact with the resin layer after a high temperature storage test and A method for producing polyimide can be provided, and a method for forming a cured relief pattern using the negative photosensitive resin composition can be provided.
以下、本発明を実施するための形態(以下、「実施形態」と略記する。)について詳細に説明する。尚、本発明は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。
なお、本明細書を通じ、一般式において同一符号で表されている構造は、分子中に複数存在する場合に、互いに同一であるか、又は異なっていてもよい。
Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In addition, throughout the present specification, the structures represented by the same reference numerals in the general formula may be the same as or different from each other when a plurality of structures are present in the molecule.
<ネガ型感光性樹脂組成物>
本実施形態に係るネガ型感光性樹脂組成物は、以下の成分:
(A)ポリイミド前駆体;
(B)光重合開始剤;
(C)特定の構造を有するシランカップリング剤;および
(D)特定の有機溶媒;
を含む。
<Negative photosensitive resin composition>
The negative photosensitive resin composition according to this embodiment has the following components:
(A) Polyimide precursor;
(B) Photopolymerization initiator;
(C) Silane coupling agent having a specific structure; and (D) Specific organic solvent;
including.
ネガ型感光性樹脂組成物は、高い解像度を得るという観点から、100質量部の(A)ポリイミド前駆体と、(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の(B)光重合開始剤と、(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の(C)特定の構造を有するシランカップリング剤とを含むことが好ましい。 From the viewpoint of obtaining high resolution, the negative photosensitive resin composition has 100 parts by mass of the (A) polyimide precursor and 0.1 to 20 parts by mass of (A) polyimide precursor based on 100 parts by mass. It is preferable to contain (B) a photopolymerization initiator and (C) a silane coupling agent having a specific structure of 0.1 to 20 parts by mass based on 100 parts by mass of the polyimide precursor.
(A)ポリイミド前駆体
本実施形態における(A)ポリイミド前駆体は、ネガ型感光性樹脂組成物に含まれる樹脂成分であり、加熱環化処理を施すことによってポリイミドに変換される。
ポリイミド前駆体は、下記一般式(2):
で表される構造単位を有するポリアミドであることが好ましい。
(A) Polyimide precursor The (A) polyimide precursor in the present embodiment is a resin component contained in a negative photosensitive resin composition, and is converted into polyimide by subjecting it to a heat cyclization treatment.
The polyimide precursor has the following general formula (2):
It is preferable that the polyamide has a structural unit represented by.
R1及びR2の少なくとも一方は、好ましくは、下記一般式(3):
で表される1価の有機基である。
At least one of R 1 and R 2 is preferably the following general formula (3):
It is a monovalent organic group represented by.
一般式(2)におけるn1は、2〜150の整数であれば限定されないが、ネガ型感光性樹脂組成物の感光特性及び機械特性の観点から、3〜100の整数が好ましく、5〜70の整数がより好ましい。 N 1 in the general formula (2) is not limited as long as it is an integer of 2 to 150, but an integer of 3 to 100 is preferable from the viewpoint of the photosensitive characteristics and mechanical characteristics of the negative photosensitive resin composition, and 5 to 70 An integer of is more preferred.
一般式(2)中、X1で表される4価の有機基は、耐熱性と感光特性とを両立するという観点で、好ましくは炭素数6〜40の有機基であり、より好ましくは、−COOR1基及び−COOR2基と−CONH−基とが互いにオルト位置にある芳香族基、又は脂環式脂肪族基である。X1で表される4価の有機基として、具体的には、芳香族環を含有する炭素原子数6〜40の有機基、例えば、下記一般式(20):
X1基としては、上記式(20)で表される構造のなかでも、下記式(20A)、(20B)、または(20C):
上記一般式(2)中、Y1で表される2価の有機基は、耐熱性と感光特性とを両立するという観点で、好ましくは炭素数6〜40の芳香族基であり、例えば、下記式(21):
で表される構造が挙げられるが、これらに限定されるものではない。また、Y1の構造は1種でも2種以上の組み合わせでもよい。上記式(21)で表される構造を有するY1基は、耐熱性及び感光特性を両立するという観点で好ましい。
In formula (2), the divalent organic group represented by Y 1 is a perspective of achieving both the heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula (21):
The structure represented by is mentioned, but is not limited to these. Further, the structure of Y 1 may be one kind or a combination of two or more kinds. One Y group having a structure represented by the above formula (21) is preferable from the viewpoint of achieving both heat resistance and photosensitive characteristics.
Y1基としては、上記式(21)で表される構造のなかでも、下記式(21A)、(21B)または(21C):
上記一般式(3)中のL1は、水素原子又はメチル基であることが好ましく、L2及びL3は、感光特性の観点から水素原子であることが好ましい。また、m1は、感光特性の観点から2以上10以下の整数、好ましくは2以上4以下の整数である。 L 1 in the general formula (3) is preferably a hydrogen atom or a methyl group, and L 2 and L 3 are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Further, m 1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.
一実施形態において、(A)ポリイミド前駆体は、下記一般式(4):
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式(4)において、R1及びR2の少なくとも一方は、上記一般式(3)で表される1価の有機基であることがより好ましい。(A)ポリイミド前駆体が、一般式(4)で表されるポリイミド前駆体を含むことで、特に解像性の効果が高くなる。
In one embodiment, the (A) polyimide precursor is based on the following general formula (4):
It is preferably a polyimide precursor having a structural unit represented by.
In the general formula (4), at least one of R 1 and R 2 is more preferably a monovalent organic group represented by the general formula (3). When the polyimide precursor (A) contains the polyimide precursor represented by the general formula (4), the effect of resolution is particularly high.
一実施形態において、(A)ポリイミド前駆体は、下記一般式(5):
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式(5)において、R1及びR2の少なくとも一方は、上記一般式(3)で表される1価の有機基であることがより好ましい。(A)ポリイミド前駆体が、一般式(4)で表されるポリイミド前駆体に加えて、一般式(5)で表されるポリイミド前駆体を含むことにより、特に解像性の効果がさらに高くなる。
In one embodiment, the (A) polyimide precursor is based on the following general formula (5):
It is preferably a polyimide precursor having a structural unit represented by.
In the general formula (5), at least one of R 1 and R 2 is more preferably a monovalent organic group represented by the general formula (3). Since the polyimide precursor (A) contains the polyimide precursor represented by the general formula (5) in addition to the polyimide precursor represented by the general formula (4), the effect of resolution is particularly high. Become.
これらの中で、(A)ポリイミド前駆体は、上記一般式(4)と(5)で表される構造単位を同時に含むか、又は、上記一般式(4)と(5)で表される構造単位の共重合体であることが、耐薬品性、解像度、及び高温保存試験後のボイド抑制の観点から特に好ましい。(A)ポリイミド前駆体が一般式(4)と(5)で表される構造単位の共重合体である場合には、一方の式中のR1、R2、及びn1が、それぞれ、他方の式中のR1、R2、及びn1とは同じであるか、又は異なってよい。 Among these, the (A) polyimide precursor simultaneously contains the structural units represented by the above general formulas (4) and (5), or is represented by the above general formulas (4) and (5). A copolymer of structural units is particularly preferable from the viewpoint of chemical resistance, resolution, and void suppression after a high temperature storage test. (A) When the polyimide precursor is a copolymer of structural units represented by the general formulas (4) and (5), R 1 , R 2 , and n 1 in one of the formulas are respectively. R 1 , R 2 , and n 1 in the other equation may be the same or different.
一実施形態において、(A)ポリイミド前駆体は、下記一般式(6):
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式(6)において、R1及びR2の少なくとも一方は、上記一般式(3)で表される1価の有機基であることがより好ましい。(A)ポリイミド前駆体が、一般式(6)で表されるポリイミド前駆体を含むことで、特に耐薬品性の効果が高くなる。
In one embodiment, the (A) polyimide precursor is based on the following general formula (6):
It is preferably a polyimide precursor having a structural unit represented by.
In the general formula (6), it is more preferable that at least one of R 1 and R 2 is a monovalent organic group represented by the general formula (3). When the polyimide precursor (A) contains the polyimide precursor represented by the general formula (6), the effect of chemical resistance is particularly high.
(A)ポリイミド前駆体の調製方法
(A)ポリイミド前駆体は、まず前述の一般式(2)中の4価の有機基X1を含むテトラカルボン酸二無水物と、光重合性の不飽和二重結合を有するアルコール類及び任意に不飽和二重結合を有さないアルコール類とを反応させて、部分的にエステル化したテトラカルボン酸(以下、アシッド/エステル体ともいう)を調製した後、これと、前述の一般式(2)中の2価の有機基Y1を含むジアミン類とをアミド重縮合させることにより得られる。
Process for the preparation of (A) a polyimide precursor (A) the polyimide precursor, first a tetracarboxylic acid dianhydride containing tetravalent organic group X 1 in the aforementioned general formula (2), photopolymerizable unsaturated After reacting alcohols having a double bond and alcohols having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form). , this and can be obtained by engagement diamines and amides polycondensed containing divalent organic group Y 1 in the above general formula (2).
(アシッド/エステル体の調製)
本実施形態では、(A)ポリイミド前駆体を調製するために好適に用いられる、4価の有機基X1を含むテトラカルボン酸二無水物としては、上記一般式(20)に示される構造を有するテトラカルボン酸二無水物をはじめ、例えば、無水ピロメリット酸、ジフェニルエーテル−3,3’,4,4’−テトラカルボン酸二無水物、ベンゾフェノン−3,3’,4,4’−テトラカルボン酸二無水物、ビフェニル−3,3’,4,4’−テトラカルボン酸二無水物、ジフェニルスルホン−3,3’,4,4’−テトラカルボン酸二無水物、ジフェニルメタン−3,3’,4,4’−テトラカルボン酸二無水物、2,2−ビス(3,4−無水フタル酸)プロパン、2,2−ビス(3,4−無水フタル酸)−1,1,1,3,3,3−ヘキサフルオロプロパン等を、好ましくは無水ピロメリット酸、ジフェニルエーテル−3,3’,4,4’−テトラカルボン酸二無水物、ベンゾフェノン−3,3’,4,4’−テトラカルボン酸二無水物、ビフェニル−3,3’,4,4’−テトラカルボン酸二無水物を挙げることができるが、これらに限定されるものではない。また、これらは単独で用いることができるのは勿論のこと2種以上を混合して用いてもよい。
(Preparation of acid / ester)
In the present embodiment, the tetracarboxylic acid dianhydride containing the tetravalent organic group X 1 preferably used for preparing the (A) polyimide precursor has the structure represented by the above general formula (20). Including tetracarboxylic acid dianhydride having, for example, pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic Acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3' , 4,4'-Tetracarboxylic hydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1, 3,3,3-hexafluoropropane and the like, preferably pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-. Tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride can be mentioned, but is not limited thereto. In addition, these can be used alone or in combination of two or more.
本実施形態では、(A)ポリイミド前駆体を調製するために好適に用いられる、光重合性の不飽和二重結合を有するアルコール類としては、例えば、2−アクリロイルオキシエチルアルコール、1−アクリロイルオキシ−3−プロピルアルコール、2−アクリルアミドエチルアルコール、メチロールビニルケトン、2−ヒドロキシエチルビニルケトン、2−ヒドロキシ−3−メトキシプロピルアクリレート、2−ヒドロキシ−3−ブトキシプロピルアクリレート、2−ヒドロキシ−3−フェノキシプロピルアクリレート、2−ヒドロキシ−3−ブトキシプロピルアクリレート、2−ヒドロキシ−3−t−ブトキシプロピルアクリレート、2−ヒドロキシ−3−シクロヘキシルオキシプロピルアクリレート、2−メタクリロイルオキシエチルアルコール、1−メタクリロイルオキシ−3−プロピルアルコール、2−メタクリルアミドエチルアルコール、メチロールビニルケトン、2−ヒドロキシエチルビニルケトン、2−ヒドロキシ−3−メトキシプロピルメタクリレート、2−ヒドロキシ−3−ブトキシプロピルメタクリレート、2−ヒドロキシ−3−フェノキシプロピルメタクリレート、2−ヒドロキシ−3−ブトキシプロピルメタクリレート、2−ヒドロキシ−3−t−ブトキシプロピルメタクリレート、2−ヒドロキシ−3−シクロヘキシルオキシプロピルメタクリレート等を挙げることができる。 In the present embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing the (A) polyimide precursor include 2-acryloyloxyethyl alcohol and 1-acryloyloxy. -3-propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.
上記光重合性の不飽和二重結合を有するアルコール類に、例えば、メタノール、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、tert−ブタノール、1−ペンタノール、2−ペンタノール、3−ペンタノール、ネオペンチルアルコール、1−ヘプタノール、2−ヘプタノール、3−ヘプタノール、1−オクタノール、2−オクタノール、3−オクタノール、1−ノナノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、テトラエチレングリコールモノメチルエーテル、テトラエチレングリコールモノエチルエーテル、ベンジルアルコールなどの不飽和二重結合を有さないアルコール類を一部混合して用いることもできる。 The alcohols having a photopolymerizable unsaturated double bond include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol. , Neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl Alcohols having no unsaturated double bond such as ether, tetraethylene glycol monoethyl ether, and benzyl alcohol can also be partially mixed and used.
また、ポリイミド前駆体として、上記不飽和二重結合を有さないアルコール類のみで調製された非感光性ポリイミド前駆体を、感光性ポリイミド前駆体と混合して用いてもよい。解像性の観点から、非感光性ポリイミド前駆体は、感光性ポリイミド前駆体100質量部を基準として、200質量部以下であることが好ましい。 Further, as the polyimide precursor, a non-photosensitive polyimide precursor prepared only with alcohols having no unsaturated double bond may be mixed with the photosensitive polyimide precursor and used. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.
上記の好適なテトラカルボン酸二無水物と上記のアルコール類とを、ピリジン等の塩基性触媒の存在下、後述するような溶剤中、温度20〜50℃で4〜10時間撹拌溶解し、混合することにより、酸無水物のエステル化反応が進行し、所望のアシッド/エステル体を得ることができる。 The above-mentioned suitable tetracarboxylic acid dianhydride and the above-mentioned alcohols are dissolved by stirring and dissolving in a solvent as described later in the presence of a basic catalyst such as pyridine for 4 to 10 hours at a temperature of 20 to 50 ° C. and mixed. By doing so, the esterification reaction of the acid anhydride proceeds, and a desired acid / ester compound can be obtained.
(ポリイミド前駆体の調製)
上記アシッド/エステル体(典型的には後述する溶剤中の溶液)に、氷冷下、適当な脱水縮合剤、例えば、ジシクロヘキシルカルボジイミド、1−エトキシカルボニル−2−エトキシ−1,2−ジヒドロキノリン、1,1−カルボニルジオキシ−ジ−1,2,3−ベンゾトリアゾール、N,N’−ジスクシンイミジルカーボネート等を投入混合してアシッド/エステル体をポリ酸無水物とした後、これに、本実施形態で好適に用いられる2価の有機基Y1を含むジアミン類を別途溶媒に溶解又は分散させたものを滴下投入し、アミド重縮合させることにより、目的のポリイミド前駆体を得ることができる。代替的には、上記アシッド/エステル体を、塩化チオニル等を用いてアシッド部分を酸クロライド化した後に、ピリジン等の塩基存在下に、ジアミン化合物と反応させることにより、目的のポリイミド前駆体を得ることができる。
(Preparation of polyimide precursor)
A suitable dehydration condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinolin, is added to the acid / ester compound (typically a solution in a solvent described later) under ice-cooling. 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, etc. are added and mixed to make an acid / ester compound into a polyacid anhydride, which is then mixed. , those diamines containing preferably a divalent organic group Y 1 used in this embodiment were separately dissolved or dispersed in a solvent is dropped on, by engaged amide polycondensation, to obtain a polyimide precursor of interest Can be done. Alternatively, the acid / ester compound is acid-chloride-ized with thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain a desired polyimide precursor. be able to.
本実施形態で好適に用いられる2価の有機基Y1を含むジアミン類としては、上記一般式(21)に示される構造を有するジアミンをはじめ、例えば、p−フェニレンジアミン、m−フェニレンジアミン、4,4−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、3,3’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルフィド、3,4’−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スルフィド、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スルホン、4,4’−ジアミノビフェニル、3,4’−ジアミノビフェニル、3,3’−ジアミノビフェニル、4,4’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン、3,3’−ジアミノベンゾフェノン、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、3,3’−ジアミノジフェニルメタン、1,4−ビス(4−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、1,3−ビス(3−アミノフェノキシ)ベンゼン、ビス〔4−(4−アミノフェノキシ)フェニル〕スルホン、ビス〔4−(3−アミノフェノキシ)フェニル〕スルホン、4,4−ビス(4−アミノフェノキシ)ビフェニル、4,4−ビス(3−アミノフェノキシ)ビフェニル、ビス〔4−(4−アミノフェノキシ)フェニル〕エーテル、ビス〔4−(3−アミノフェノキシ)フェニル〕エーテル、1,4−ビス(4−アミノフェニル)ベンゼン、1,3−ビス(4−アミノフェニル)ベンゼン、9,10−ビス(4−アミノフェニル)アントラセン、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、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、1,4−ビス(3−アミノプロピルジメチルシリル)ベンゼン、オルト−トリジンスルホン、9,9−ビス(4−アミノフェニル)フルオレン、及びこれらのベンゼン環上の水素原子の一部が、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基、ハロゲン等で置換されたもの、例えば3,3’−ジメチル−4,4’−ジアミノビフェニル、2,2’−ジメチル−4,4’−ジアミノビフェニル、3,3’−ジメチル−4,4’−ジアミノジフェニルメタン、2,2’−ジメチル−4,4’−ジアミノジフェニルメタン、3,3’−ジメチトキシ−4,4’−ジアミノビフェニル、3,3’−ジクロロ−4,4’−ジアミノビフェニル、及びそれらの混合物等が挙げられるが、これに限定されるものではない。 The diamines containing divalent organic group Y 1 used suitably in the present embodiment, including the diamine having a structure represented by the general formula (21), for example, p- phenylenediamine, m- phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl , 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1, , 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-amino) biphenyl Phenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10- Bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-Aminophenyl) Fluorene and some of the hydrogen atoms on these benzene rings are substituted with methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., for example, 3,3'-. Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diamino Examples include, but are not limited to, biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.
アミド重縮合反応終了後、当該反応液中に共存している脱水縮合剤の吸水副生物を必要に応じて濾別した後、水、脂肪族低級アルコール、又はそれらの混合液等の貧溶媒を、得られた重合体成分に投入し、重合体成分を析出させ、さらに、再溶解、再沈析出操作等を繰り返すことにより、重合体を精製し、真空乾燥を行い、目的のポリイミド前駆体を単離する。精製度を向上させるために、陰イオン及び/又は陽イオン交換樹脂を適当な有機溶剤で膨潤させて充填したカラムに、この重合体の溶液を通し、イオン性不純物を除去してもよい。 After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added. , The polymer component is added to the obtained polymer component, the polymer component is precipitated, and the polymer is purified and vacuum dried by repeating the redissolving and reprecipitation precipitation operations to obtain the desired polyimide precursor. Isolate. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.
上記(A)ポリイミド前駆体の分子量は、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量で測定した場合に、8,000〜150,000であることが好ましく、9,000〜50,000であることがより好ましい。重量平均分子量が8,000以上である場合、機械物性が良好であり、150,000以下である場合、現像液への分散性が良好で、レリーフパターンの解像性能が良好である。ゲルパーミエーションクロマトグラフィーの展開溶媒としては、テトラヒドロフラン、及びN−メチル−2−ピロリドンが推奨される。また重量平均分子量は標準単分散ポリスチレンを用いて作成した検量線から求める。標準単分散ポリスチレンとしては、昭和電工社製 有機溶媒系標準試料 STANDARD SM−105から選ぶことが推奨される。 The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, preferably 9,000 to 50,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. Is more preferable. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.
(B)光重合開始剤
本実施形態に用いられる(B)光重合開始剤について説明する。光重合開始剤としては、光ラジカル重合開始剤であることが好ましく、ベンゾフェノン、o−ベンゾイル安息香酸メチル、4−ベンゾイル−4’−メチルジフェニルケトン、ジベンジルケトン、フルオレノン等のベンゾフェノン誘導体、2,2’−ジエトキシアセトフェノン、2−ヒドロキシ−2−メチルプロピオフェノン、1−ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体、チオキサントン、2−メチルチオキサントン、2−イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体、ベンジル、ベンジルジメチルケタール、ベンジル−β−メトキシエチルアセタール等のベンジル誘導体、ベンゾイン、ベンゾインメチルエーテル等のベンゾイン誘導体、1−フェニル−1,2−ブタンジオン−2−(o−メトキシカルボニル)オキシム、1−フェニル−1,2−プロパンジオン−2−(o−メトキシカルボニル)オキシム、1−フェニル−1,2−プロパンジオン−2−(o−エトキシカルボニル)オキシム、1−フェニル−1,2−プロパンジオン−2−(o−ベンゾイル)オキシム、1,3−ジフェニルプロパントリオン−2−(o−エトキシカルボニル)オキシム、1−フェニル−3−エトキシプロパントリオン−2−(o−ベンゾイル)オキシム等のオキシム類、N−フェニルグリシン等のN−アリールグリシン類、ベンゾイルパークロライド等の過酸化物類、芳香族ビイミダゾール類、チタノセン類、α−(n−オクタンスルフォニルオキシイミノ)−4−メトキシベンジルシアニド等の光酸発生剤類等が好ましく挙げられるが、これらに限定されるものではない。上記の光重合開始剤の中では、特に光感度の観点で、オキシム類がより好ましい。
(B) Photopolymerization Initiator The (B) photopolymerization initiator used in the present embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and is a benzophenone derivative such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, 2, Acetphenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl- 1,2-Propandione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 Oxims such as − (o-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropantrione-2- (o-benzoyl) oxime, N Light such as N-arylglycines such as −phenylglycine, peroxides such as benzoylparklolide, aromatic biimidazoles, titanocenes, α- (n-octanesulfonyloxyimino) -4-methoxybenzylcyanide, etc. Acid generators and the like are preferably mentioned, but are not limited thereto. Among the above photopolymerization initiators, oximes are more preferable from the viewpoint of photosensitivity.
ネガ型感光性樹脂組成物中の(B)光重合開始剤の配合量は、(A)ポリイミド前駆体100質量部に対して、好ましくは0.1質量部以上20質量部以下であり、より好ましくは1質量部以上8質量部以下である。上記配合量は、光感度又はパターニング性の観点で0.1質量部以上であり、ネガ型感光性樹脂組成物の硬化後の感光性樹脂層の物性の観点から20質量部以下である。 The blending amount of the (B) photopolymerization initiator in the negative photosensitive resin composition is preferably 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. It is preferably 1 part by mass or more and 8 parts by mass or less. The blending amount is 0.1 part by mass or more from the viewpoint of light sensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.
(C)特定の構造を有するシランカップリング剤
本実施形態に用いられる(C)特定の構造を有するシランカップリング剤について説明する。
本実施の形態にかかる(C)特定の構造を有するシランカップリング剤は下記一般式(1)で表される構造を有する。
一般式(1)において、aは、1〜3の整数であれば限定されないが、金属再配線層との接着性などの観点から、2または3が好ましく、3がより好ましい。
nは1〜6の整数であれば限定されないが、金属再配線層との接着性の観点から、1以上4以下が好ましい。現像性の観点から、2以上5以下が好ましい。
R21は炭素数1〜4のアルキル基であれば限定されない。メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t―ブチル基などを例示することができる。
R22は、ヒドロキシル基、または炭素数1〜4のアルキル基であれば限定されない。炭素数1〜4のアルキル基としては、R21と同様のアルキル基を例示することができる。
R20は、エポキシ基、フェニルアミノ基、ウレイド基、イソシアネート基を含む置換基であれば限定されない。これらの中で、現像性や金属再配線層の接着性の観点から、フェニルアミノ基を含む置換基、およびウレイド基を含む置換基からなる群から選択される少なくとも1種であることが好ましく、フェニルアミノ基を含む置換基がより好ましい。
エポキシ基を含有するシランカップリング剤としては、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−グリシドキシプロピルトリエトキシシラン、などを例示することができる。
フェニルアミノ基を含有するシランカップリング剤としては、N−フェニル−3−アミノプロピルトリメトキシシランを例示することができる。
ウレイド基を含有するシランカップリング剤としては、3−ウレイドプロピルトリアルコキシシランを例示することができる
イソシアネート基を含有するシランカップリング剤としては、3−イソシアネートプロピルトリエトキシシランを例示することができる。
(C) Silane Coupling Agent Having a Specific Structure (C) A silane coupling agent having a specific structure used in the present embodiment will be described.
(C) The silane coupling agent having a specific structure according to the present embodiment has a structure represented by the following general formula (1).
In the general formula (1), a is not limited as long as it is an integer of 1 to 3, but 2 or 3 is preferable, and 3 is more preferable from the viewpoint of adhesiveness to the metal rewiring layer.
n is not limited as long as it is an integer of 1 to 6, but is preferably 1 or more and 4 or less from the viewpoint of adhesiveness to the metal rewiring layer. From the viewpoint of developability, 2 or more and 5 or less are preferable.
R 21 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group.
R 22 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, the same alkyl group as R 21 can be exemplified.
R 20 is not limited as long as it is a substituent containing an epoxy group, a phenylamino group, a ureido group, and an isocyanate group. Among these, at least one selected from the group consisting of a substituent containing a phenylamino group and a substituent containing a ureido group is preferable from the viewpoint of developability and adhesiveness of the metal rewiring layer. Substituents containing a phenylamino group are more preferred.
Examples of the silane coupling agent containing an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycyl. Examples thereof include sidoxylpropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
Examples of the silane coupling agent containing a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane.
As the silane coupling agent containing a ureido group, 3-ureidopropyltrialkoxysilane can be exemplified. As the silane coupling agent containing an isocyanate group, 3-isocyanatepropyltriethoxysilane can be exemplified. ..
(D)特定の構造を有する有機溶媒
本実施の形態にかかる有機溶媒は、γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール, アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、及びε―カプロラクトンからなる群から選択される少なくとも1種を含有すれば限定されない。上記有機溶媒を含むことにより、封止材との密着性を十分に発現しうる。その中で、(A)ポリイミド前駆体の溶解性の観点から、γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール, アセト酢酸エチル、ε―カプロラクトンが好ましく、銅表面ボイド抑制の観点から、上記群から選択される有機溶媒を少なくとも2種含むことがより好ましい。
(D) Organic Solvent with Specific Structure The organic solvent according to this embodiment comprises γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. It is not limited as long as it contains at least one selected from the group. By containing the above organic solvent, the adhesion to the encapsulant can be sufficiently exhibited. Among them, γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, and ε-caprolactone are preferable from the viewpoint of (A) solubility of the polyimide precursor, and from the viewpoint of suppressing copper surface voids, from the above group. More preferably, it contains at least two selected organic solvents.
本実施の形態にかかる特定の構造を有する有機溶媒が、封止材との密着性が良好である理由は定かではないが、本発明者らは下記のように推定している。
従来、ポリイミド前駆体を含む感光性樹脂組成物を溶解させる有機溶媒は、N−メチル−2−ピロリドンやN,N−ジメチルアセトアミド、N,N−ジメチルホルムアミドなどのアミド系溶媒が用いられてきた。これらの溶媒は、ポリイミド前駆体の溶解能は極めて高いものの、近年求められている加熱硬化温度が低温(例えば200℃未満)の場合には、生成するポリイミドとの親和性が高いためにフィルム中に多量に残存する傾向にある。そのため、上記(C)特定の構造を有するシランカップリング剤との相互作用などにより、性能を低下させてしまう。一方で、上記の溶媒を含むことにより、加熱硬化温度が低温となっても、加熱硬化後にフィルムに残存する溶媒を十分に低減することができるために、封止材との密着性が良好である傾向にある。
The reason why the organic solvent having a specific structure according to the present embodiment has good adhesion to the encapsulant is not clear, but the present inventors presume as follows.
Conventionally, as an organic solvent for dissolving a photosensitive resin composition containing a polyimide precursor, an amide-based solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, or N, N-dimethylformamide has been used. .. Although these solvents have extremely high dissolving ability of the polyimide precursor, when the heat curing temperature required in recent years is low (for example, less than 200 ° C.), they have high affinity with the polyimide to be produced, so that they are contained in the film. Tends to remain in large quantities. Therefore, the performance is deteriorated due to the interaction with the silane coupling agent having the specific structure (C) described above. On the other hand, by containing the above solvent, even if the heat curing temperature is low, the solvent remaining on the film after heat curing can be sufficiently reduced, so that the adhesion to the encapsulant is good. There is a tendency.
本実施形態のネガ型感光性樹脂組成物において、有機溶媒の使用量は、(A)ポリイミド前駆体100質量部に対して、好ましくは100〜1000質量部であり、より好ましくは120〜700質量部であり、さらに好ましくは125〜500質量部の範囲である。 In the negative photosensitive resin composition of the present embodiment, the amount of the organic solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. Parts, more preferably in the range of 125-500 parts by mass.
(E)熱塩基発生剤
本実施形態のネガ型感光性樹脂組成物は、上記(A)〜(D)成分以外の成分をさらに含有していてもよい。特に、加熱硬化温度の低温化に対応するため、(E)熱塩基発生剤を含むことがより好ましい。
塩基発生剤とは、加熱することで塩基を発生する化合物をいう。熱塩基発生剤を含有することで、感光性樹脂組成物のイミド化をさらに促進することができる。
(E) Thermal Base Generator The negative photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (D). In particular, it is more preferable to contain (E) a thermobase generator in order to cope with lowering the heat curing temperature.
A base generator is a compound that generates a base when heated. By containing the thermal base generator, the imidization of the photosensitive resin composition can be further promoted.
熱塩基発生剤としては、その種類を特に定めるものではないが、tert−ブトキシカルボニル基によって保護されたアミン化合物や、国際公開第2017/038598号公報に開示された熱塩基発生剤等が挙げられる。しかしながら、これらに限定されず、その他にも公知の熱塩基発生剤を用いることができる。 The type of the thermobase generator is not particularly specified, and examples thereof include amine compounds protected by a tert-butoxycarbonyl group, thermobase generators disclosed in International Publication No. 2017/0385898, and the like. .. However, the present invention is not limited to these, and other known thermobase generators can be used.
tert−ブトキシカルボニル基によって保護されたアミン化合物としては、エタノールアミン、3−アミノ−1−プロパノール、1−アミノ−2−プロパノール、2−アミノ−1−プロパノール、4−アミノ−1−ブタノール、2−アミノ−1−ブタノール、1−アミノ−2−ブタノール、3−アミノ−2,2−ジメチル−1−プロパノール、4−アミノ−2−メチル−1−ブタノール、バリノール、3−アミノ−1,2−プロパンジオール、2−アミノ−1,3−プロパンジオール、チラミン、ノルエフェドリン、2−アミノ−1−フェニル−1,3−プロパンジオール、2−アミノシクロヘキサノール、4−アミノシクロヘキサノール、4−アミノシクロヘキサンエタノール、4−(2−アミノエチル)シクロヘキサノール、N−メチルエタノールアミン、3−(メチルアミノ)−1−プロパノール、3−(イソプロピルアミノ)プロパノール、N−シクロヘキシルエタノールアミン、α−[2−(メチルアミノ)エチル]ベンジルアルコール、ジエタノールアミン、ジイソプロパノールアミン、3−ピロリジノール、2−ピロリジンメタノール、4−ヒドロキシピペリジン、3−ヒドロキシピペリジン、4−ヒドロキシ−4−フェニルピペリジン、4−(3−ヒドロキシフェニル)ピペリジン、4−ピペリジンメタノール、3−ピペリジンメタノール、2−ピペリジンメタノール、4−ピペリジンエタノール、2−ピペリジンエタノール、2−(4−ピペリジル)−2−プロパノール、1,4−ブタノールビス(3−アミノプロピル)エーテル、1,2−ビス(2−アミノエトキシ)エタン、2,2’−オキシビス(エチルアミン)、1,14−ジアミノ−3,6,9,12−テトラオキサテトラデカン、1−アザ−15−クラウン 5−エーテル、ジエチレングリコールビス(3−アミノプロピル)エーテル、1,11−ジアミノ−3,6,9−トリオキサウンデカン、又は、アミノ酸及びその誘導体のアミノ基をtert−ブトキシカルボニル基によって保護した化合物が挙げられるが、これらに限定されるものではない。 Amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2 -Amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, barinol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-amino Cyclohexaneethanol, 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, α- [2- (Methylamino) ethyl] benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidin methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidin, 4- (3-hydroxyphenyl) ) Piperidine, 4-piperidin methanol, 3-piperidin methanol, 2-piperidin methanol, 4-piperidin ethanol, 2-piperidin ethanol, 2- (4-piperidyl) -2-propanol, 1,4-butanolbis (3-amino) Propyl) ether, 1,2-bis (2-aminoethoxy) ethane, 2,2'-oxybis (ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15 -Crown 5-ether, diethylene glycol bis (3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or amino groups of amino acids and derivatives thereof were protected by tert-butoxycarbonyl groups. Examples include, but are not limited to, compounds.
(E)熱塩基発生剤の配合量は、(A)ポリイミド前駆体100質量部に対して、好ましくは0.1質量部以上30質量部以下であり、より好ましくは1質量部以上20質量部以下である。上記配合量は、イミド化促進効果の観点で0.1質量部以上であり、ネガ型感光性樹脂組成物の硬化後の感光性樹脂層の物性の観点から20質量部以下であることが好ましい。 The amount of the (E) thermal base generator to be blended is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. It is as follows. The blending amount is preferably 0.1 part by mass or more from the viewpoint of the imidization promoting effect, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative type photosensitive resin composition. ..
本実施形態のネガ型感光性樹脂組成物は、上記(A)〜(E)成分以外の成分をさらに含有していてもよい。
(A)〜(E)成分以外の成分としては、限定されないが、含窒素複素環化合物、ヒンダードフェノール化合物、有機チタン化合物、増感剤、光重合性不飽和モノマー、熱重合禁止剤等が挙げられる。
The negative photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (E).
The components other than the components (A) to (E) are not limited, but include nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors. Can be mentioned.
<含窒素複素環化合物>
本実施形態のネガ型感光性樹脂組成物を用いて銅又は銅合金から成る基板上に硬化膜を形成する場合には、銅上の変色を抑制するために、ネガ型感光性樹脂組成物は、含窒素複素環化合物を任意に含んでよい。具体的には、アゾール化合物、及びプリン誘導体等が挙げられる。
<Nitrogen-containing heterocyclic compound>
When a cured film is formed on a substrate made of copper or a copper alloy using the negative photosensitive resin composition of the present embodiment, in order to suppress discoloration on copper, the negative photosensitive resin composition is used. , Nitrogen-containing heterocyclic compound may be optionally contained. Specific examples thereof include azole compounds and purine derivatives.
アゾール化合物としては、1H−トリアゾール、5−メチル−1H−トリアゾール、5−エチル−1H−トリアゾール、4,5−ジメチル−1H−トリアゾール、5−フェニル−1H−トリアゾール、4−t−ブチル−5−フェニル−1H−トリアゾール、5−ヒドロキシフェニル−1H−トリアゾール、フェニルトリアゾール、p−エトキシフェニルトリアゾール、5−フェニル−1−(2−ジメチルアミノエチル)トリアゾール、5−ベンジル−1H−トリアゾール、ヒドロキシフェニルトリアゾール、1,5−ジメチルトリアゾール、4,5−ジエチル−1H−トリアゾール、1H−ベンゾトリアゾール、2−(5−メチル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−[2−ヒドロキシ−3,5−ビス(α,α−ジメチルベンジル)フェニル]−ベンゾトリアゾール、2−(3,5−ジ−t−ブチル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−(3−t−ブチル−5−メチル−2−ヒドロキシフェニル)−ベンゾトリアゾール、2−(3,5−ジ−t−アミル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−5’−t−オクチルフェニル)ベンゾトリアゾール、ヒドロキシフェニルベンゾトリアゾール、トリルトリアゾール、5−メチル−1H−ベンゾトリアゾール、4−メチル−1H−ベンゾトリアゾール、4−カルボキシ−1H−ベンゾトリアゾール、5−カルボキシ−1H−ベンゾトリアゾール、1H−テトラゾール、5−メチル−1H−テトラゾール、5−フェニル−1H−テトラゾール、5−アミノ−1H−テトラゾール、1−メチル−1H−テトラゾール等が挙げられる。 Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl-5. -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2) -Hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenyl Bentriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl- Examples thereof include 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.
特に好ましくは、トリルトリアゾール、5−メチル−1H−ベンゾトリアゾール、及び4−メチル−1H−ベンゾトリアゾールが挙げられる。また、これらのアゾール化合物は、1種で用いても2種以上の混合物で用いても構わない。 Particularly preferred include triltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used alone or in a mixture of two or more.
プリン誘導体の具体例としては、プリン、アデニン、グアニン、ヒポキサンチン、キサンチン、テオブロミン、カフェイン、尿酸、イソグアニン、2,6−ジアミノプリン、9−メチルアデニン、2−ヒドロキシアデニン、2−メチルアデニン、1−メチルアデニン、N−メチルアデニン、N,N−ジメチルアデニン、2−フルオロアデニン、9−(2−ヒドロキシエチル)アデニン、グアニンオキシム、N−(2−ヒドロキシエチル)アデニン、8−アミノアデニン、6−アミノ‐8−フェニル‐9H−プリン、1−エチルアデニン、6−エチルアミノプリン、1−ベンジルアデニン、N−メチルグアニン、7−(2−ヒドロキシエチル)グアニン、N−(3−クロロフェニル)グアニン、N−(3−エチルフェニル)グアニン、2−アザアデニン、5−アザアデニン、8−アザアデニン、8−アザグアニン、8−アザプリン、8−アザキサンチン、8−アザヒポキサンチン等及びその誘導体が挙げられる。 Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthin, xanthin, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-Methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-Amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Examples thereof include guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahipoxanthin and derivatives thereof.
ネガ型感光性樹脂組成物が上記アゾール化合物又はプリン誘導体を含有する場合の配合量は、(A)ポリイミド前駆体100質量部に対し、0.1〜20質量部であることが好ましく、光感度特性の観点から0.5〜5質量部がより好ましい。アゾール化合物の(A)ポリイミド前駆体100質量部に対する配合量が0.1質量部以上である場合、本実施形態のネガ型感光性樹脂組成物を銅又は銅合金の上に形成した場合に、銅又は銅合金表面の変色が抑制され、一方、20質量部以下である場合には光感度に優れる。 When the negative photosensitive resin composition contains the azole compound or the purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and the light sensitivity. From the viewpoint of characteristics, 0.5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, when the negative photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, Discoloration of the surface of copper or copper alloy is suppressed, while when the amount is 20 parts by mass or less, the light sensitivity is excellent.
<ヒンダードフェノール化合物>
また、銅表面上の変色を抑制するために、ネガ型感光性樹脂組成物は、ヒンダードフェノール化合物を任意に含んでもよい。ヒンダードフェノール化合物としては、2,6−ジ−t−ブチル−4−メチルフェノール、2,5−ジ−t−ブチル−ハイドロキノン、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネ−ト、イソオクチル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、4、4’−メチレンビス(2、6−ジ−t−ブチルフェノール)、4,4’−チオ−ビス(3−メチル−6−t−ブチルフェノール)、4,4’−ブチリデン−ビス(3−メチル−6−t−ブチルフェノール)、トリエチレングリコール−ビス[3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)プロピオネート]、1,6−ヘキサンジオール−ビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、2,2−チオ−ジエチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、N,N’−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナマミド)、2,2’−メチレン−ビス(4−メチル−6−t−ブチルフェノール)、2,2’−メチレン−ビス(4−エチル−6−t−ブチルフェノール)、ペンタエリスリチル−テトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、トリス−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−イソシアヌレイト、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)ベンゼン、1,3,5−トリス(3−ヒドロキシ−2,6−ジメチル−4−イソプロピルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−s−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス[4−(1−エチルプロピル)−3−ヒドロキシ−2,6−ジメチルベンジル]−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス[4−トリエチルメチル−3−ヒドロキシ−2,6−ジメチルベンジル]−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(3−ヒドロキシ−2,6−ジメチル−4−フェニルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−3−ヒドロキシ−2,5,6−トリメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−5−エチル−3−ヒドロキシ−2,6−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−6−エチル−3−ヒドロキシ−2−メチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−6−エチル−3−ヒドロキシ−2,5−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−5,6−ジエチル−3−ヒドロキシ−2−メチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−3−ヒドロキシ−2−メチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−3−ヒドロキシ−2,5−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、1,3,5−トリス(4−t−ブチル−5‐エチル−3−ヒドロキシ−2−メチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン等が挙げられるが、これに限定されるものではない。これらの中でも、1,3,5−トリス(4−t−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン等が特に好ましい。
<Hindered phenol compound>
Further, in order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio -Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrosin) Namamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6- Dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethyl Butyl] -1,3, 5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5- Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3 5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) ) -1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2, 5-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-) 3-Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-3) Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-) 2,5-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl- Examples include, but are not limited to, 3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione and the like are particularly preferable.
ヒンダードフェノール化合物の配合量は、(A)ポリイミド前駆体100質量部に対し、0.1〜20質量部であることが好ましく、光感度特性の観点から0.5〜10質量部であることがより好ましい。ヒンダードフェノール化合物の(A)ポリイミド前駆体100質量部に対する配合量が0.1質量部以上である場合、例えば銅又は銅合金の上に本実施形態のネガ型感光性樹脂組成物を形成した場合に、銅又は銅合金の変色・腐食が防止され、一方、20質量部以下である場合には光感度に優れる。 The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, and 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics with respect to 100 parts by mass of the (A) polyimide precursor. Is more preferable. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, the negative photosensitive resin composition of the present embodiment is formed on, for example, copper or a copper alloy. In some cases, discoloration and corrosion of copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent.
<有機チタン化合物>
本実施形態のネガ型感光性樹脂組成物は、有機チタン化合物を含有してもよい。有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる感光性樹脂層を形成できる。
<Organic titanium compound>
The negative photosensitive resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
使用可能な有機チタン化合物としては、チタン原子に有機化学物質が共有結合又はイオン結合を介して結合しているものが挙げられる。
有機チタン化合物の具体的例を以下のI)〜VII)に示す:
I)チタンキレート化合物:中でも、ネガ型感光性樹脂組成物の保存安定性及び良好なパターンが得られることから、アルコキシ基を2個以上有するチタンキレートがより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n−ブトキサイド)ビス(2,4−ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4−ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
Examples of the organic titanium compound that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n−ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2−エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n−ノニロキサイド)、チタニウムテトラ(n−プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2−(アリロキシメチル)ブトキサイド}]等である。 II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxide), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5−2,4−シクロペンタジエン−1−イル)ビス(2,6−ジフルオロフェニル)チタニウム、ビス(η5−2,4−シクロペンタジエン−1−イル)ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptaneate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
中でも、有機チタン化合物は、上記I)チタンキレート化合物、II)テトラアルコキシチタン化合物、及びIII)チタノセン化合物から成る群から選ばれる少なくとも1種の化合物であることが、より良好な耐薬品性を奏するという観点から好ましく、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)、チタニウムテトラ(n−ブトキサイド)、及びビス(η5−2,4−シクロペンタジエン−1−イル)ビス(2,6−ジフルオロ−3−(1H−ピロール−1−イル)フェニル)チタニウムが特に好ましい。 Among them, the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound, which exhibits better chemical resistance. From this point of view, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3) are preferable. -(1H-pyrrole-1-yl) phenyl) titanium is particularly preferred.
有機チタン化合物を配合する場合の配合量は、(A)ポリイミド前駆体100質量部に対し、0.05〜10質量部であることが好ましく、より好ましくは0.1〜2質量部である。該配合量が0.05質量部以上である場合、良好な耐熱性及び耐薬品性が発現し、一方では10質量部以下である場合、保存安定性に優れる。 When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, the storage stability is excellent.
<増感剤>
本実施形態のネガ型感光性樹脂組成物は、光感度を向上させるために、増感剤を任意に含んでもよい。該増感剤としては、例えば、ミヒラーズケトン、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、2,5−ビス(4’−ジエチルアミノベンザル)シクロペンタン、2,6−ビス(4’−ジエチルアミノベンザル)シクロヘキサノン、2,6−ビス(4’−ジエチルアミノベンザル)−4−メチルシクロヘキサノン、4,4’−ビス(ジメチルアミノ)カルコン、4,4’−ビス(ジエチルアミノ)カルコン、p−ジメチルアミノシンナミリデンインダノン、p−ジメチルアミノベンジリデンインダノン、2−(p−ジメチルアミノフェニルビフェニレン)−ベンゾチアゾール、2−(p−ジメチルアミノフェニルビニレン)ベンゾチアゾール、2−(p−ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3−ビス(4’−ジメチルアミノベンザル)アセトン、1,3−ビス(4’−ジエチルアミノベンザル)アセトン、3,3’−カルボニル−ビス(7−ジエチルアミノクマリン)、3−アセチル−7−ジメチルアミノクマリン、3−エトキシカルボニル−7−ジメチルアミノクマリン、3−ベンジロキシカルボニル−7−ジメチルアミノクマリン、3−メトキシカルボニル−7−ジエチルアミノクマリン、3−エトキシカルボニル−7−ジエチルアミノクマリン、N−フェニル−N’−エチルエタノールアミン、N−フェニルジエタノールアミン、N−p−トリルジエタノールアミン、N−フェニルエタノールアミン、4−モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2−メルカプトベンズイミダゾール、1−フェニル−5−メルカプトテトラゾール、2−メルカプトベンゾチアゾール、2−(p−ジメチルアミノスチリル)ベンズオキサゾール、2−(p−ジメチルアミノスチリル)ベンズチアゾール、2−(p−ジメチルアミノスチリル)ナフト(1,2−d)チアゾール、2−(p−ジメチルアミノベンゾイル)スチレン等が挙げられる。これらは単独で又は例えば2〜5種類の組合せで用いることができる。
<Sensitizer>
The negative photosensitive resin composition of the present embodiment may optionally contain a sensitizer in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-Acetone-7-Dimethylaminocoumarin, 3-ethoxycarbonyl-7-Dimethylaminocoumarin, 3-Benzyloxycarbonyl-7-Dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole and 2- (p-dimethylaminobenzoyl) styrene. These can be used alone or, for example, in a combination of 2 to 5 types.
光感度を向上させるための増感剤をネガ型感光性樹脂組成物が含有する場合の配合量は、(A)ポリイミド前駆体100質量部に対し、0.1〜25質量部であることが好ましい。 When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. preferable.
<光重合性不飽和モノマー>
ネガ型感光性樹脂組成物は、レリーフパターンの解像性を向上させるために、光重合性の不飽和結合を有するモノマーを任意に含んでもよい。このようなモノマーとしては、光重合開始剤によりラジカル重合反応する(メタ)アクリル化合物が好ましく、特に以下に限定するものではないが、ジエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレートなどの、エチレングリコール又はポリエチレングリコールのモノ又はジアクリレート及びメタクリレート、プロピレングリコール又はポリプロピレングリコールのモノ又はジアクリレート及びメタクリレート、グリセロールのモノ、ジ又はトリアクリレート及びメタクリレート、シクロヘキサンジアクリレート及びジメタクリレート、1,4−ブタンジオールのジアクリレート及びジメタクリレート、1,6−ヘキサンジオールのジアクリレート及びジメタクリレート、ネオペンチルグリコールのジアクリレート及びジメタクリレート、ビスフェノールAのモノ又はジアクリレート及びメタクリレート、ベンゼントリメタクリレート、イソボルニルアクリレート及びメタクリレート、アクリルアミド及びその誘導体、メタクリルアミド及びその誘導体、トリメチロールプロパントリアクリレート及びメタクリレート、グリセロールのジ又はトリアクリレート及びメタクリレート、ペンタエリスリトールのジ、トリ、又はテトラアクリレート及びメタクリレート、並びにこれら化合物のエチレンオキサイド又はプロピレンオキサイド付加物等の化合物を挙げることができる。
<Photopolymerizable unsaturated monomer>
The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and Dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its Derivatives, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, etc. Compounds can be mentioned.
レリーフパターンの解像性を向上させるための上記の光重合性の不飽和結合を有するモノマーを感光性樹脂組成物が含有する場合、光重合性の不飽和結合を有するモノマーの配合量は、(A)ポリイミド前駆体100質量部に対し、1〜50質量部であることが好ましい。 When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is ( A) It is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor.
<熱重合禁止剤>
また、本実施形態のネガ型感光性樹脂組成物は、特に溶剤を含む溶液の状態での保存時のネガ型感光性樹脂組成物の粘度及び光感度の安定性を向上させるために、熱重合禁止剤を任意に含んでもよい。熱重合禁止剤としては、例えば、ヒドロキノン、N−ニトロソジフェニルアミン、p−tert−ブチルカテコール、フェノチアジン、N−フェニルナフチルアミン、エチレンジアミン四酢酸、1,2−シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、2,6−ジ−tert−ブチル−p−メチルフェノール、5−ニトロソ−8−ヒドロキシキノリン、1−ニトロソ−2−ナフトール、2−ニトロソ−1−ナフトール、2−ニトロソ−5−(N−エチル−N−スルホプロピルアミノ)フェノール、N−ニトロソ−N−フェニルヒドロキシルアミンアンモニウム塩、N−ニトロソ−N(1−ナフチル)ヒドロキシルアミンアンモニウム塩等が用いられる。
<Thermal polymerization inhibitor>
Further, the negative photosensitive resin composition of the present embodiment is thermally polymerized in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition especially when stored in a solution containing a solvent. A banning agent may be optionally contained. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, and 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-) N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
<硬化レリーフパターンの製造方法及び半導体装置>
また、本発明は、(1)上述した本実施形態のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を上記基板上に形成する工程と、(2)上記感光性樹脂層を露光する工程と、(3)露光後の上記感光性樹脂層を現像してレリーフパターンを形成する工程と、(4)上記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程とを含む、硬化レリーフパターンの製造方法を提供する。
<Manufacturing method of cured relief pattern and semiconductor device>
Further, the present invention comprises (1) a step of applying the negative photosensitive resin composition of the present embodiment described above onto a substrate to form a photosensitive resin layer on the substrate, and (2) the above-mentioned photosensitive. A step of exposing the resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern. Provided is a method for producing a cured relief pattern including and.
(1)感光性樹脂層形成工程
本工程では、本発明のネガ型感光性樹脂組成物を基材上に塗布し、必要に応じて、その後乾燥させて、感光性樹脂層を形成する。塗布方法としては、従来から感光性樹脂組成物の塗布に用いられていた方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法等を用いることができる。
(1) Photosensitive Resin Layer Forming Step In this step, the negative type photosensitive resin composition of the present invention is applied onto a substrate and, if necessary, dried thereafter to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or spray coating with a spray coater. A method or the like can be used.
必要に応じて、ネガ型感光性樹脂組成物を含む塗膜を乾燥させることができる。乾燥方法としては、風乾、オーブン又はホットプレートによる加熱乾燥、真空乾燥等の方法が用いられる。具体的には、風乾又は加熱乾燥を行う場合、20℃〜140℃で1分〜1時間の条件下で乾燥を行うことができる。以上のとおり、基板上に感光性樹脂層(ネガ型感光性樹脂層)を形成できる。 If necessary, the coating film containing the negative photosensitive resin composition can be dried. As the drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Specifically, when air-drying or heat-drying is performed, drying can be performed at 20 ° C. to 140 ° C. under the conditions of 1 minute to 1 hour. As described above, the photosensitive resin layer (negative type photosensitive resin layer) can be formed on the substrate.
(2)露光工程
本工程では、上記で形成したネガ型感光性樹脂層を、コンタクトアライナー、ミラープロジェクション、ステッパー等の露光装置を用いて、パターンを有するフォトマスク又はレチクルを介して又は直接に、紫外線光源等により露光する。
(2) Exposure Step In this step, the negative photosensitive resin layer formed above is exposed to a photomask or reticle having a pattern by using an exposure device such as a contact aligner, a mirror projection, or a stepper, or directly. It is exposed with an ultraviolet light source or the like.
この後、光感度の向上等の目的で、必要に応じて、任意の温度及び時間の組合せによる露光後ベーク(PEB)及び/又は現像前ベークを施してもよい。ベーク条件の範囲については、温度は40℃〜120℃であり、そして時間は10秒〜240秒であることが好ましいが、本発明のネガ型感光性樹脂組成物の諸特性を阻害するものでない限り、この範囲に限らない。 After that, post-exposure bake (PEB) and / or pre-development bake at any combination of temperature and time may be applied, if necessary, for the purpose of improving light sensitivity and the like. Regarding the range of baking conditions, the temperature is preferably 40 ° C. to 120 ° C. and the time is preferably 10 seconds to 240 seconds, but this does not interfere with the properties of the negative photosensitive resin composition of the present invention. As long as it is not limited to this range.
(3)レリーフパターン形成工程
本工程では、露光後の感光性樹脂層のうち未露光部を現像除去する。露光(照射)後の感光性樹脂層を現像する現像方法としては、従来知られているフォトレジストの現像方法、例えば、回転スプレー法、パドル法、超音波処理を伴う浸漬法等の中から任意の方法を選択して使用することができる。また、現像の後、レリーフパターンの形状を調整する等の目的で、必要に応じて、任意の温度及び時間の組合せによる現像後ベークを施してもよい。
(3) Relief pattern forming step In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of the conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by sonication, etc. The method can be selected and used. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.
現像に使用される現像液としては、例えば、ネガ型感光性樹脂組成物に対する良溶媒、又は該良溶媒と貧溶媒との組合せが好ましい。良溶媒としては、例えば、N−メチル−2−ピロリドン、N−シクロヘキシル−2−ピロリドン、N,N−ジメチルアセトアミド、シクロペンタノン、シクロヘキサノン、γ−ブチロラクトン、α−アセチル−γ−ブチロラクトン等が好ましい。貧溶媒としては、例えば、トルエン、キシレン、メタノール、エタノール、イソプロピルアルコール、乳酸エチル、プロピレングリコールメチルエーテルアセテート及び水等が好ましい。良溶媒と貧溶媒とを混合して用いる場合には、ネガ型感光性樹脂組成物中のポリマーの溶解性によって良溶媒に対する貧溶媒の割合を調整することが好ましい。また、各溶媒を2種以上、例えば数種類組合せて用いることもできる。 As the developing solution used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. .. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more kinds of each solvent, for example, several kinds can be used in combination.
(4)硬化レリーフパターン形成工程
本工程では、上記現像により得られたレリーフパターンを加熱して感光成分を希散させるとともに、(A)ポリイミド前駆体をイミド化させることによって、ポリイミドから成る硬化レリーフパターンに変換する。加熱硬化の方法としては、例えば、ホットプレートによるもの、オーブンを用いるもの、温度プログラムを設定できる昇温式オーブンを用いるもの等種々の方法を選ぶことができる。加熱は、例えば、170℃〜400℃で30分〜5時間の条件で行うことができる。加熱硬化時の雰囲気気体としては、空気を用いてもよく、窒素、アルゴン等の不活性ガスを用いることもできる。
(4) Cured relief pattern forming step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) the polyimide precursor is imidized to form a cured relief made of polyimide. Convert to a pattern. As a method of heat curing, various methods can be selected, for example, a method using a hot plate, a method using an oven, and a method using a temperature rising oven in which a temperature program can be set. The heating can be performed, for example, at 170 ° C. to 400 ° C. for 30 minutes to 5 hours. As the atmospheric gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.
<ポリイミド>
上記ポリイミド前駆体組成物から形成される硬化レリーフパターンに含まれるポリイミドの構造は、下記一般式(8)で表される。
一般式(2)中の好ましいX1とY1は、同じ理由により、一般式(8)のポリイミドにおいても好ましい。一般式(8)の繰り返し単位数mは、正の整数であればよく、特に限定は無いが、2〜150の整数、又は3〜140の整数であってもよい。
<Polyimide>
The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (8).
The preferred X 1 and Y 1 in the general formula (2) are also preferable in the polyimide of the general formula (8) for the same reason. The number of repeating units m in the general formula (8) may be a positive integer and is not particularly limited, but may be an integer of 2 to 150 or an integer of 3 to 140.
また、上記で説明されたネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法も本発明の一態様である。 Another aspect of the present invention is also a method for producing polyimide, which comprises a step of converting the negative photosensitive resin composition described above into polyimide.
<半導体装置>
本実施形態では、上述した硬化レリーフパターンの製造方法により得られる硬化レリーフパターンを有する、半導体装置も提供される。したがって、半導体素子である基材と、上述した硬化レリーフパターン製造方法により該基材上に形成されたポリイミドの硬化レリーフパターンとを有する半導体装置が提供されることができる。また、本発明は、基材として半導体素子を用い、上述した硬化レリーフパターンの製造方法を工程の一部として含む半導体装置の製造方法にも適用できる。本発明の半導体装置は、上記硬化レリーフパターン製造方法で形成される硬化レリーフパターンを、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、又はバンプ構造を有する半導体装置の保護膜等として形成し、既知の半導体装置の製造方法と組合せることで製造することができる。
<Semiconductor device>
In the present embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Therefore, it is possible to provide a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like and combining it with a known manufacturing method of a semiconductor device.
<表示体装置>
本実施形態では、表示体素子と該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は上述の硬化レリーフパターンである表示体装置が提供される。ここで、当該硬化レリーフパターンは、当該表示体素子に直接接して積層されていてもよく、別の層を間に挟んで積層されていてもよい。例えば、該硬化膜として、薄膜トランジスタ(TFT)液晶表示素子及びカラーフィルター素子の表面保護膜、絶縁膜、及び平坦化膜、マルチドメイン垂直配向(MVA)型液晶表示装置用の突起、並びに有機エレクトロルミネッセンス(EL)素子陰極用の隔壁を挙げることができる。
<Display device>
In the present embodiment, there is provided a display body device including a display body element and a cured film provided on the upper portion of the display body element, wherein the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them. For example, the cured film includes a surface protective film, an insulating film, and a flattening film for a thin film transistor (TFT) liquid crystal display element and a color filter element, protrusions for a multidomain vertical orientation (MVA) type liquid crystal display device, and organic electroluminescence. (EL) A partition wall for the element cathode can be mentioned.
本発明のネガ型感光性樹脂組成物は、上記のような半導体装置への適用の他、多層回路の層間絶縁、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、及び液晶配向膜等の用途にも有用である。 The negative photosensitive resin composition of the present invention is applied to semiconductor devices as described above, as well as applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is also useful.
以下、実施例により本実施形態を具体的に説明するが、本発明はこれに限定されるものではない。実施例、比較例、及び製造例においては、ポリマー又はネガ型感光性樹脂組成物の物性を以下の方法に従って測定及び評価した。 Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.
<測定及び評価方法>
(1)重量平均分子量
各樹脂の重量平均分子量(Mw)を、ゲルパーミエーションクロマトグラフィー法(標準ポリスチレン換算)を用いて以下の条件下で測定した。
ポンプ:JASCO PU−980
検出器:JASCO RI−930
カラムオーブン:JASCO CO−965 40℃
カラム:昭和電工(株)製Shodex KD−806M 直列に2本、又は
昭和電工(株)製Shodex 805M/806M直列
標準単分散ポリスチレン:昭和電工(株)製Shodex STANDARD SM−105
移動相:0.1mol/L LiBr/N−メチル−2−ピロリドン(NMP)
流速:1mL/min.
<Measurement and evaluation method>
(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured under the following conditions using a gel permeation chromatography method (standard polystyrene conversion).
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Showa Denko Corporation Shodex KD-806M Two in series, or
Showa Denko Co., Ltd. Shodex 805M / 806M series standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105
Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)
Flow velocity: 1 mL / min.
(2)Cu上の硬化レリーフパターンの作製
6インチシリコンウェハー(フジミ電子工業株式会社製、厚み625±25μm)上に、スパッタ装置(L−440S−FHL型、キヤノンアネルバ社製)を用いて200nm厚のTi、400nm厚のCuをこの順にスパッタした。続いて、このウェハー上に、後述の方法により調製したネガ型感光性樹脂組成物をコーターデベロッパー(D−Spin60A型、SOKUDO社製)を用いて回転塗布し、110℃で180秒間ホットプレートにてプリベークを行い、約7μm厚の塗膜を形成した。この塗膜に、テストパターン付マスクを用いて、プリズマGHI(ウルトラテック社製)により500mJ/cm2のエネルギーを照射した。次いで、この塗膜を、現像液としてシクロペンタノンを用いてコーターデベロッパー(D−Spin60A型、SOKUDO社製)でスプレー現像し、プロピレングリコールメチルエーテルアセテートで、リンスすることにより、Cu上のレリーフパターンを得た。
Cu上に該レリーフパターンを形成したウェハーを、昇温プログラム式キュア炉(VF−2000型、光洋リンドバーグ社製)を用いて、窒素雰囲気下、表1に記載のキュア温度で2時間加熱処理することにより、Cu上に約4〜5μm厚の樹脂から成る硬化レリーフパターンを得た。
(2) Preparation of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (manufactured by Fujimi Denshi Kogyo Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, the negative photosensitive resin composition prepared by the method described below is rotationally coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and is placed on a hot plate at 110 ° C. for 180 seconds. Prebaking was performed to form a coating film having a thickness of about 7 μm. This coating film was irradiated with an energy of 500 mJ / cm 2 by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. Got
The wafer in which the relief pattern is formed on Cu is heat-treated for 2 hours at the cure temperature shown in Table 1 under a nitrogen atmosphere using a heating program type curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.). As a result, a cured relief pattern made of a resin having a thickness of about 4 to 5 μm was obtained on Cu.
(3)Cu上の硬化レリーフパターンの解像性評価
上記の方法で得た硬化レリーフパターンを光学顕微鏡下で観察し、最少開口パターンのサイズを求めた。このとき、得られたパターンの開口部の面積が、対応するパターンマスク開口面積の1/2以上であれば解像されたものとみなし、解像された開口部のうち最小面積を有するものに対応するマスク開口辺の長さを解像度とした。
解像度が10μm未満のものを「優」、10μm以上14μm未満のものを「良」、14μm以上18μm未満のものを「可」、18μm以上のものを「不可」とした。
(3) Evaluation of Resolvability of Cured Relief Pattern on Cu The cured relief pattern obtained by the above method was observed under an optical microscope to determine the size of the minimum aperture pattern. At this time, if the area of the opening of the obtained pattern is ½ or more of the corresponding pattern mask opening area, it is considered to be resolved, and the one having the minimum area among the resolved openings is selected. The length of the corresponding mask opening side was taken as the resolution.
A resolution of less than 10 μm was rated as “excellent”, a resolution of 10 μm or more and less than 14 μm was rated as “good”, a resolution of 14 μm or more and less than 18 μm was rated as “possible”, and a resolution of 18 μm or more was rated as “impossible”.
(4)Cu上の硬化レリーフパターンの高温保存(high temperature storage)試験と、その後のボイド面積評価
Cu上に該硬化レリーフパターンを形成したウェハーを、昇温プログラム式キュア炉(VF−2000型、光洋リンドバーグ社製)を用いて、空気中、150℃で168時間加熱した。続いて、プラズマ表面処理装置(EXAM型、神港精機社製)を用いて、Cu上の樹脂層を全てプラズマエッチングにより除去した。プラズマエッチング条件は下記のとおりである。
出力:133W
ガス種・流量:O2:40mL/分 + CF4:1mL/分
ガス圧:50Pa
モード:ハードモード
エッチング時間:1800秒
(4) High temperature storage test of the cured relief pattern on Cu and subsequent evaluation of the void area The wafer on which the cured relief pattern was formed on Cu was placed in a heating program type cure furnace (VF-2000 type, Using a Koyo Lindbergh Co., Ltd.), the mixture was heated in air at 150 ° C. for 168 hours. Subsequently, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all the resin layers on Cu were removed by plasma etching. The plasma etching conditions are as follows.
Output: 133W
Gas type / flow rate: O 2 : 40 mL / min + CF 4 : 1 mL / min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds
樹脂層を全て除去したCu表面を、FE−SEM(S−4800型、日立ハイテクノロジーズ社製)によって観察し、画像解析ソフト(A像くん、旭化成社製)を用いて、Cu層の表面に占めるボイドの面積を算出した。比較例1に記載の感光性樹脂組成物を評価した際のボイドの総面積を100%とした際に、ボイドの総面積比率が50%未満のものを「優」、50%以上75%未満のものを「良」、75%以上100%未満のものを「可」、100%以上のものを「不可」と判定した。 The Cu surface from which all the resin layer has been removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A image-kun, manufactured by Asahi Kasei Co., Ltd.) is used on the surface of the Cu layer. The area of voids occupied was calculated. When the total area of voids when the photosensitive resin composition described in Comparative Example 1 is evaluated is 100%, those having a total area ratio of voids of less than 50% are "excellent", and 50% or more and less than 75%. Those of 75% or more and less than 100% were judged as "good", those of 100% or more were judged as "impossible".
(5)硬化レリーフパターン(ポリイミド塗膜)の耐薬品性評価
Cu上に形成した該硬化レリーフパターンを、レジスト剥離液{ATMI社製、製品名ST−44、主成分:2−(2−アミノエトキシ)エタノール、及び1−シクロヘキシル−2−ピロリドン}を50℃に加熱したものに5分間浸漬し、流水で1分間洗浄し、風乾した。その後、膜表面を光学顕微鏡で目視観察し、クラック等の薬液によるダメージの有無、及び/又は薬液処理後の膜厚の変化率に基づいて耐薬品性を評価した。評価基準として、クラック等のダメージが発生せず、膜厚変化率が薬品浸漬前の膜厚を基準として10%以内のものを「優」、10〜15%のものを「良」、15〜20%のものを「可」とし、クラックが発生したもの、または膜厚変化率が20%を超えるものを「不可」とした。
(5) Chemical resistance evaluation of cured relief pattern (polyimide coating film) The cured relief pattern formed on Cu is subjected to a resist stripping solution {ATMI, product name ST-44, main component: 2- (2-amino). Ethoxy) ethanol and 1-cyclohexyl-2-pyrrolidone} were immersed in a mixture heated to 50 ° C. for 5 minutes, washed with running water for 1 minute, and air-dried. Then, the surface of the film was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage due to the chemical solution such as cracks and / or the rate of change in the film thickness after the chemical solution treatment. As evaluation criteria, those with no damage such as cracks and whose film thickness change rate is within 10% based on the film thickness before chemical immersion are "excellent", those with 10 to 15% are "good", and 15 to 15 Those with 20% were evaluated as "possible", and those with cracks or those with a film thickness change rate of more than 20% were evaluated as "impossible".
(6)封止材との密着性試験
エポキシ系封止材として長瀬ケムテックス社製のR4000シリーズを用意した。
次いで、アルミスパッタしたシリコーンウエハー上に封止材を厚みが約150ミクロンになるようにスピンコートし、130℃で熱硬化させてエポキシ系封止材を硬化させた。 上記エポキシ系硬化膜上に実施例、比較例で作製した感光性樹脂組成物を最終膜厚が10ミクロンになるように塗布した。塗布した感光性樹脂組成物を500mJ/cm2の露光条件で全面を露光した後、180℃2時間熱硬化させて、厚み10ミクロンの1層目の硬化膜を作製した。
上記1層目の硬化膜上に1層目の硬化膜形成で使用した感光性樹脂組成物を塗布し、1層目の硬化膜作製時と同じ条件で全面を露光した後、熱硬化させて、厚み10ミクロンの2層目の硬化膜を作製した。
上記サンプルの感光性樹脂硬化膜上にエポキシ樹脂を塗布し、続いてピンを立て、引取試験機(クワッドグループ社製、セバスチャン5型)を用いて密着性試験を行った。以下の基準に従い、評価した。
評価:接着強度70MPa以上:密着力 優
50MPa以上−70MPa未満:密着力 良
30MPa以上−50MPa未満:密着力 可
30MPa未満:密着力 不可
(6) Adhesion test with sealing material R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based sealing material.
Next, the encapsulant was spin-coated on the aluminum-sputtered silicon wafer so as to have a thickness of about 150 microns, and the epoxy-based encapsulant was cured by thermosetting at 130 ° C. The photosensitive resin compositions prepared in Examples and Comparative Examples were applied onto the epoxy-based cured film so that the final film thickness was 10 microns. The entire surface of the coated photosensitive resin composition was exposed under an exposure condition of 500 mJ / cm 2 , and then heat-cured at 180 ° C. for 2 hours to prepare a first-layer cured film having a thickness of 10 microns.
The photosensitive resin composition used for forming the first-layer cured film was applied onto the first-layer cured film, and the entire surface was exposed under the same conditions as when the first-layer cured film was formed, and then heat-cured. , A second cured film having a thickness of 10 microns was prepared.
An epoxy resin was applied onto the photosensitive resin cured film of the above sample, then a pin was set up, and an adhesion test was conducted using a take-up tester (Quad Group, Sebastian Type 5). Evaluation was made according to the following criteria.
Evaluation: Adhesive strength 70 MPa or more: Excellent adhesion
50 MPa or more and less than -70 MPa: Good adhesion
30 MPa or more and less than -50 MPa: Adhesion is possible
Less than 30 MPa: Adhesion is not possible
製造例1:(A)ポリイミド前駆体としてのポリマーA−1の合成
4,4’−オキシジフタル酸二無水物(ODPA)155.1gを2L容量のセパラブルフラスコに入れ、2−ヒドロキシエチルメタクリレート(HEMA)131.2gとγ−ブチロラクトン400mLを入れて室温下で攪拌し、攪拌しながらピリジン81.5gを加えて反応混合物を得た。反応による発熱の終了後に反応混合物を室温まで放冷し、16時間放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC)206.3gをγ−ブチロラクトン180mLに溶解した溶液を攪拌しながら40分掛けて反応混合物に加え、続いて4,4’−オキシジアニリン(ODA)93.0gをγ−ブチロラクトン350mLに懸濁したものを攪拌しながら60分掛けて加えた。更に室温で2時間攪拌した後、エチルアルコール30mLを加えて1時間攪拌し、次に、γ−ブチロラクトン400mLを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
Production Example 1: (A) Synthesis of Polymer A-1 as Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L volume separable flask, and 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) ( 131.2 g of HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of exotherm by the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-oxydianiline (ODA). ) 93.0 g was suspended in 350 mL of γ-butyrolactone and added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
得られた反応液を3Lのエチルアルコールに加えて、粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン1.5Lに溶解して、粗ポリマー溶液を得た。得られた粗ポリマー溶液を28Lの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状のポリマー(ポリマーA−1)を得た。ポリマー(A−1)の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。 The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A-1). When the molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.
製造例2:(A)ポリイミド前駆体としてのポリマーA−2の合成
製造例1の4,4’−オキシジフタル酸二無水物(ODPA)155.1gに代えて、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)147.1gを用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマー(A−2)を得た。ポリマー(A−2)の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は22,000であった。
Production Example 2: (A) Synthesis of Polymer A-2 as Polyimide Precursor 3,3', 4,4 instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Production Example 1. The reaction was carried out in the same manner as in Production Example 1 described above except that 147.1 g of'-biphenyltetracarboxylic dianhydride (BPDA) was used to obtain a polymer (A-2). When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.
製造例3:(A)ポリイミド前駆体としてのポリマーA−3の合成
製造例1の4,4’−オキシジアニリン(ODA)93.0gに代えて、p−フェニレンジアミン50.2gを用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマー(A−3)を得た。ポリマー(A−3)の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は19,000であった。
Production Example 3: (A) Synthesis of Polymer A-3 as Polyimide Precursor 50.2 g of p-phenylenediamine was used in place of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. A polymer (A-3) was obtained by carrying out the reaction in the same manner as described in Production Example 1 described above except for the above. When the molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 19,000.
製造例4:(A)ポリイミド前駆体としてのポリマーA−4の合成
製造例1の4,4’−オキシジフタル酸二無水物をフルオレン酸二無水物(229.2g)、4,4’−オキシジアニリンを2,2’−ビス(トリフルオロメチル)ベンジジン(TFMB)(148.5g)に変えた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマー(A−4)を得た。ポリマー(A−4)の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は12,000であった。
Production Example 4: (A) Synthesis of Polymer A-4 as Polyimide Precursor The 4,4'-oxydiphthalic dianhydride of Production Example 1 is fluorenic dianhydride (229.2 g), 4,4'-oxy. The reaction was carried out in the same manner as in Production Example 1 described above, except that dianiline was changed to 2,2'-bis (trifluoromethyl) benzidine (TFMB) (148.5 g), and the polymer (A- 4) was obtained. When the molecular weight of the polymer (A-4) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 12,000.
製造例5:(A)ポリイミド前駆体としてのポリマーA−5の合成
製造例1の4,4’−オキシジアニリン(ODA)93.0gに代えて、2,2’−ジメチルビフェニル−4,4’−ジアミン(m−TB)98.6gを用いた以外は、前述の製造例1に記載の方法と同様にして反応を行い、ポリマー(A−5)を得た。ポリマー(A−5)の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は21,000であった。
Production Example 5: (A) Synthesis of Polymer A-5 as Polyimide Precursor 2,2'-Dimethylbiphenyl-4, in place of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The reaction was carried out in the same manner as in Production Example 1 described above except that 98.6 g of 4'-diamine (m-TB) was used to obtain a polymer (A-5). When the molecular weight of the polymer (A-5) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.
製造例6:(E)熱塩基発生剤E−1の合成
容量1Lのナス型フラスコ中へ、ジエチレングリコールビス(3−アミノプロピル)エーテル(東京化成工業株式会社製)100gとエタノール100gを加えてスターラーで混合撹拌して均一溶液とし、氷水で5℃以下に冷却した。これに、二炭酸ジ−tert−ブチル(東京化成工業株式会社製)215gをエタノール120gに溶解したものを滴下ロートにより滴下した。この際、反応液温が50℃以下を保つように滴下速度を調整しながら滴下を行った。滴下終了から2時間後、反応液を50℃で3時間減圧濃縮することにより、目的の化合物E−1を得た。
Production Example 6: (E) Synthesis of Thermal Base Generator E-1 100 g of diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 100 g of ethanol are added to a 1 L eggplant-shaped flask to stirrer. To obtain a uniform solution, the mixture was cooled to 5 ° C. or lower with ice water. To this, 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120 g of ethanol was added dropwise using a dropping funnel. At this time, dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the target compound E-1.
<実施例1>
ポリマーA−1を用いて以下の方法でネガ型感光性樹脂組成物を調製し、調製した組成物の評価を行った。(A)ポリイミド前駆体としてポリマーA−1:100g、(B)光重合開始剤として1−フェニル−1,2−プロパンジオン−2−(O−エトキシカルボニル)−オキシム(光重合開始剤B−1に該当):3gを、(C)KBM−403(1.5g)(D)有機溶剤γ−ブチルラクトン(以下ではGBLと表記):150gに溶解した。得られた溶液の粘度を、少量のGBLをさらに加えることによって、約30ポイズに調整し、ネガ型感光性樹脂組成物とした。該組成物を、前述の方法に従って評価した。結果を表1に示す。
<Example 1>
A negative photosensitive resin composition was prepared using the polymer A-1 by the following method, and the prepared composition was evaluated. (A) Polymer A-1: 100 g as a polyimide precursor, (B) 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photopolymerization initiator B-) as a photopolymerization initiator 1): 3 g was dissolved in (C) KBM-403 (1.5 g) (D) organic solvent γ-butyl lactone (hereinafter referred to as GBL): 150 g. The viscosity of the obtained solution was adjusted to about 30 poises by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.
<実施例2〜13、比較例1〜3>
表1に示すとおりの成分と配合比で調製すること以外は、実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。その結果を表1に示す。表1に記載されている、化合物はそれぞれ以下のとおりである。
<Examples 2 to 13, Comparative Examples 1 to 3>
A negative photosensitive resin composition similar to that of Example 1 was prepared except that it was prepared with the components and compounding ratios shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. The compounds listed in Table 1 are as follows.
B−1:1−フェニル−1,2−プロパンジオン−2−(O−エトキシカルボニル)−オキシム
C−1:3−グリシドキシプロピルトリメトキシシラン(KBM−403)
C−2:N−フェニル−3−アミノプロピルトリメトキシシラン(KBM−573)
C−3:3−ウレイドプロピルトリエトキシシラン(KBE−585)
C−4:3−イソシアネートプロピルトリエトキシシラン(KBE−9007)
C−5:3−アミノプロピルトリメトキシシラン(KBM−903)
D−1:γ−ブチルラクトン(以下ではGBLと表記)
D−2:ジメチルスルホキシド(DMSO)
E−1:製造例5で表される化合物
E−2:1−(tert−ブトキシカルボニル)−4−ヒドロキシピペリジン(東京化成工業株式会社製)
B-1: 1-Phenyl-1,2-Propanedione-2- (O-ethoxycarbonyl) -Oxime C-1: 3-glycidoxypropyltrimethoxysilane (KBM-403)
C-2: N-Phenyl-3-aminopropyltrimethoxysilane (KBM-573)
C-3: 3-Ureidopropyltriethoxysilane (KBE-585)
C-4: 3-Isocyanatepropyltriethoxysilane (KBE-9007)
C-5: 3-Aminopropyltrimethoxysilane (KBM-903)
D-1: γ-Buty lactone (hereinafter referred to as GBL)
D-2: Dimethyl sulfoxide (DMSO)
E-1: Compound represented by Production Example 5 E-2: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)
表1から明らかなように、上記一般式(1)で表される特定構造を有する(C)シランカップリング剤を含む実施例1〜13では、上記一般式(1)で表される特定構造を有する(C)シランカップリング剤を含まない比較例1〜3に比べて、高い耐薬品性および解像度が得られた。さらに、高温保存試験後、Cu層の樹脂層に接する界面でボイドの発生も抑制することができ、封止材との密着性も良好であった。 As is clear from Table 1, in Examples 1 to 13 containing the (C) silane coupling agent having the specific structure represented by the general formula (1), the specific structure represented by the general formula (1). (C) Higher chemical resistance and resolution were obtained as compared with Comparative Examples 1 to 3 containing no silane coupling agent. Further, after the high temperature storage test, the generation of voids could be suppressed at the interface of the Cu layer in contact with the resin layer, and the adhesion to the encapsulant was also good.
本発明によるネガ型感光性樹脂組成物を用いることで、高い耐薬品性と解像性を持つ硬化レリーフパターンを得ることができ、かつ、Cu表面のボイド発生を抑制することができる。本発明は、例えば半導体装置、多層配線基板等の電気・電子材料の製造に有用な感光性材料の分野で好適に利用できる。 By using the negative photosensitive resin composition according to the present invention, a cured relief pattern having high chemical resistance and resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.
Claims (20)
(A)ポリイミド前駆体;
(B)光重合開始剤;
(C)下記一般式(1):
で表されるシランカップリング剤;及び
(D)γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール, アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、及びε―カプロラクトンからなる群から選択される少なくとも1種を含有する、有機溶媒;
を含む、ネガ型感光性樹脂組成物。 The following ingredients:
(A) Polyimide precursor;
(B) Photopolymerization initiator;
(C) The following general formula (1):
Silane coupling agent represented by; and (D) at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone. Seed-containing organic solvent;
Negative type photosensitive resin composition containing.
で表される構造単位を有する、請求項1〜5のいずれか1項に記載のネガ型感光性樹脂組成物。 The polyimide precursor of (A) has the following general formula (2):
The negative photosensitive resin composition according to any one of claims 1 to 5, which has a structural unit represented by.
で表される1価の有機基である、請求項6に記載のネガ型感光性樹脂組成物。 In the general formula (2), at least one of R 1 and R 2 is the following general formula (3):
The negative photosensitive resin composition according to claim 6, which is a monovalent organic group represented by.
で表される構造を含む、請求項6〜10のいずれか1項に記載のネガ型感光性樹脂組成物。 In the general formula (2), Y 1 is the following general formula (21c):
The negative photosensitive resin composition according to any one of claims 6 to 10, which comprises the structure represented by.
で表される構造単位を有する、請求項6又は7に記載のネガ型感光性樹脂組成物。 The polyimide precursor of (A) has the following general formula (4):
The negative photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by.
で表される構造単位を有する、請求項6又は7に記載のネガ型感光性樹脂組成物。 The polyimide precursor of (A) has the following general formula (5):
The negative photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by.
下記一般式(5):
で表される構造単位を同時に含む、請求項6又は7に記載のネガ型感光性樹脂組成物。 The polyimide precursor of (A) has the following general formula (4):
The following general formula (5):
The negative photosensitive resin composition according to claim 6 or 7, further comprising the structural unit represented by.
で表される構造単位を有する、請求項6又は7に記載のネガ型感光性樹脂組成物。 The polyimide precursor of (A) has the following general formula (6):
The negative photosensitive resin composition according to claim 6 or 7, which has a structural unit represented by.
前記(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の前記(B)光重合開始剤と、
前記(A)ポリイミド前駆体100質量部を基準として0.1〜20質量部の前記(C)シランカップリング剤と、
を含む、請求項1〜17のいずれか1項に記載のネガ型感光性樹脂組成物。 With 100 parts by mass of the polyimide precursor (A)
0.1 to 20 parts by mass of the (B) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.
0.1 to 20 parts by mass of the (C) silane coupling agent based on 100 parts by mass of the (A) polyimide precursor.
The negative photosensitive resin composition according to any one of claims 1 to 17, which comprises.
(1)請求項1〜18のいずれか1項に記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を前記基板上に形成する工程;
(2)前記感光性樹脂層を露光する工程;
(3)露光後の前記感光性樹脂層を現像して、レリーフパターンを形成する工程;及び、
(4)前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程;
を含む、硬化レリーフパターンの製造方法。 The following steps:
(1) A step of applying the negative photosensitive resin composition according to any one of claims 1 to 18 onto a substrate to form a photosensitive resin layer on the substrate;
(2) A step of exposing the photosensitive resin layer;
(3) A step of developing the photosensitive resin layer after exposure to form a relief pattern;
(4) A step of heat-treating the relief pattern to form a cured relief pattern;
A method for manufacturing a cured relief pattern, including.
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