CN115516375A - Positive photosensitive resin composition, dry film, pattern coating film, and electronic component - Google Patents
Positive photosensitive resin composition, dry film, pattern coating film, and electronic component Download PDFInfo
- Publication number
- CN115516375A CN115516375A CN202180032905.5A CN202180032905A CN115516375A CN 115516375 A CN115516375 A CN 115516375A CN 202180032905 A CN202180032905 A CN 202180032905A CN 115516375 A CN115516375 A CN 115516375A
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- China
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- action
- photosensitive resin
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title claims description 26
- 238000000576 coating method Methods 0.000 title claims description 26
- 125000006239 protecting group Chemical group 0.000 claims abstract description 68
- 230000009471 action Effects 0.000 claims abstract description 59
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920001721 polyimide Polymers 0.000 claims abstract description 25
- 239000004642 Polyimide Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 16
- 229920002577 polybenzoxazole Polymers 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 8
- 230000005593 dissociations Effects 0.000 claims abstract description 8
- 150000007514 bases Chemical class 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 37
- 125000000962 organic group Chemical group 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- -1 alkyl cyanide Chemical compound 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000005519 fluorenylmethyloxycarbonyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 125000003828 azulenyl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000010408 film Substances 0.000 description 82
- 239000002585 base Substances 0.000 description 57
- 235000013824 polyphenols Nutrition 0.000 description 33
- 229920000642 polymer Polymers 0.000 description 24
- 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 23
- 238000011161 development Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000004985 diamines Chemical class 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 244000061458 Solanum melongena Species 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000013039 cover film Substances 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000007952 growth promoter Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PMOWTIHVNWZYFI-AATRIKPKSA-N trans-2-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1O PMOWTIHVNWZYFI-AATRIKPKSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 2
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- CGCQHMFVCNWSOV-UHFFFAOYSA-N (4-morpholin-4-ylphenyl)-phenylmethanone Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C1=CC=CC=C1 CGCQHMFVCNWSOV-UHFFFAOYSA-N 0.000 description 1
- XUFXKBJMCRJATM-FMIVXFBMSA-N (e)-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1\C=C\C(=O)C1=CC=CC=C1 XUFXKBJMCRJATM-FMIVXFBMSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ZNNRTWIXUUGIFI-UHFFFAOYSA-N 1,5-bis[4-(diethylamino)phenyl]penta-1,4-dien-3-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=CC(=O)C=CC1=CC=C(N(CC)CC)C=C1 ZNNRTWIXUUGIFI-UHFFFAOYSA-N 0.000 description 1
- JWTSVUUPJIIXTO-UHFFFAOYSA-N 1,5-bis[4-(dimethylamino)phenyl]penta-1,4-dien-3-one Chemical compound C1=CC(N(C)C)=CC=C1C=CC(=O)C=CC1=CC=C(N(C)C)C=C1 JWTSVUUPJIIXTO-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- SFXPLYOSNTZJFW-UHFFFAOYSA-N 2,6-bis[[4-(diethylamino)phenyl]methylidene]-4-methylcyclohexan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC(C)C1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 SFXPLYOSNTZJFW-UHFFFAOYSA-N 0.000 description 1
- LIFWPLOFXPGAJJ-UHFFFAOYSA-N 2,6-bis[[4-(diethylamino)phenyl]methylidene]cyclohexan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CCC1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 LIFWPLOFXPGAJJ-UHFFFAOYSA-N 0.000 description 1
- YXQINXKZKRYRQM-UHFFFAOYSA-N 2,6-bis[[4-(dimethylamino)phenyl]methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N(C)C)CC(C)CC1=CC1=CC=C(N(C)C)C=C1 YXQINXKZKRYRQM-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 1
- DWDONSBFIIUPQS-UHFFFAOYSA-N 3-benzoyl-7-(dimethylamino)chromen-2-one Chemical compound O=C1OC2=CC(N(C)C)=CC=C2C=C1C(=O)C1=CC=CC=C1 DWDONSBFIIUPQS-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- HAHWYTLUKCIGPH-UHFFFAOYSA-N 3-methylbutyl 2-(diethylamino)benzoate Chemical compound CCN(CC)C1=CC=CC=C1C(=O)OCCC(C)C HAHWYTLUKCIGPH-UHFFFAOYSA-N 0.000 description 1
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- MEJQNPUKRTVBDA-UHFFFAOYSA-N 3-methylcyclobutane-1,1,2,2-tetracarboxylic acid Chemical compound CC1CC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O MEJQNPUKRTVBDA-UHFFFAOYSA-N 0.000 description 1
- DMFZUPUWYGUECI-UHFFFAOYSA-N 4-(2,5-dioxooxolan-3-yl)benzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1=CC2=CC=CC=C2C2=C1C(=O)OC2=O DMFZUPUWYGUECI-UHFFFAOYSA-N 0.000 description 1
- ODPLCKKBVAJQEP-UHFFFAOYSA-N 4-(2-benzo[e][1,3]benzothiazol-2-ylethenyl)-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C=CC(S1)=NC2=C1C=CC1=CC=CC=C21 ODPLCKKBVAJQEP-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- MVMOMSLTZMMLJR-FMIVXFBMSA-N 4-[(e)-2-(1,3-benzothiazol-2-yl)ethenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=NC2=CC=CC=C2S1 MVMOMSLTZMMLJR-FMIVXFBMSA-N 0.000 description 1
- DQOPDYYQICTYEY-UHFFFAOYSA-N 4-[2-(1,3-benzoxazol-2-yl)ethenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C=CC1=NC2=CC=CC=C2O1 DQOPDYYQICTYEY-UHFFFAOYSA-N 0.000 description 1
- XUWFAPDKIXEUPR-UHFFFAOYSA-N 4-[[3-[[4-(diethylamino)phenyl]methylidene]cyclopentylidene]methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC1)CC1=CC1=CC=C(N(CC)CC)C=C1 XUWFAPDKIXEUPR-UHFFFAOYSA-N 0.000 description 1
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical group CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- QXAMGWKESXGGNV-UHFFFAOYSA-N 7-(diethylamino)-1-benzopyran-2-one Chemical compound C1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 QXAMGWKESXGGNV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- KGUYZCLKIAMWTP-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(2-ethenylphenyl)methanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1C=C KGUYZCLKIAMWTP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- AIJZIRPGCQPZSL-UHFFFAOYSA-N ethylenetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)=C(C(O)=O)C(O)=O AIJZIRPGCQPZSL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- SUTFHRPLCUZXQA-UHFFFAOYSA-N n,n-dimethyl-2-oxochromene-3-carboxamide Chemical compound C1=CC=C2OC(=O)C(C(=O)N(C)C)=CC2=C1 SUTFHRPLCUZXQA-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- JREWFSHZWRKNBM-UHFFFAOYSA-N pyridine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C(C(O)=O)=C1C(O)=O JREWFSHZWRKNBM-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/22—Polybenzoxazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- 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
-
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
A positive photosensitive resin composition which stably provides a good developing contrast is provided. The present invention is a positive photosensitive resin composition comprising: (A) A polyamic acid having a carboxyl group protected with a protecting group which is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base; and (B) a photobase generator obtained by latentizing a basic compound having an acid dissociation constant pKa of 10.8 or more by a covalent bond.
Description
Technical Field
The invention relates to a positive photosensitive resin composition, a dry film, a pattern coating film and an electronic component.
Background
In recent years, polyimide resins and polybenzoxazole resins have attracted attention as heat-resistant resins having excellent mechanical strength and electrical insulation properties, and are widely used as insulating materials for electronic components such as semiconductors and printed wiring boards.
As a method for forming a pattern of polyimide, a method for forming a pattern of negative-type polyimide using a polyimide precursor having a photosensitive group has been known, but recently, a photosensitive resin composition capable of realizing a positive-type pattern film has been proposed. The positive photosensitive resin composition uses a photoacid generator such as a quinonediazide compound, but if the photoacid generator is contained, there is a problem that a circuit is easily corroded. In contrast, the use of a photobase generator has been attempted, and a composition comprising an alkali-soluble resin having a phenolic hydroxyl group, a covalently bonded photobase generator and an esterifying agent for the hydroxyl group (patent document 1), and a composition comprising a polyimide resin having a phenolic hydroxyl group protected by a 9-fluorenylmethyloxycarbonyl group and a photobase generator (patent document 2) have been proposed.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2019-45735
Patent document 2: japanese patent laid-open publication No. 2019-194631
Disclosure of Invention
Problems to be solved by the invention
However, conventional photobase generators may generate a base having a low basicity (a low acid dissociation constant pKa) and may not provide sufficient resolution, and further improvement in development contrast is required for a positive photosensitive resin composition containing the photobase generator. In addition, the development contrast may be lowered by storage, and excellent stability may be required.
Means for solving the problems
As a result of intensive studies in view of the above, the present inventors have found that a positive photosensitive resin composition can stably exhibit a good development contrast by protecting carboxyl groups and phenolic hydroxyl groups in a polymer and combining the protected carboxyl groups and phenolic hydroxyl groups with a specific covalent bond type photobase generator, and have completed the present invention.
In the composition of the present invention, the carboxyl group of the polyamic acid, the phenolic hydroxyl group of the polyimide, and the phenolic hydroxyl group of the polybenzoxazole precursor are protected by the protective group which is eliminated by the action of the base, and therefore, the base solubility is hindered in the unexposed area, while the protective group is easily eliminated in the exposed area by the base generated from the specific covalent bond type photobase generator, and the base solubility is expressed. Due to such a significant difference in alkali solubility between the unexposed portion and the exposed portion, the development contrast can be improved. Further, the present inventors have found that the development contrast is lowered during storage by using a specific covalent bond type photobase generator.
The gist of the present invention is as follows.
[1] A positive photosensitive resin composition comprising:
(A) A polyamic acid having a carboxyl group protected with a protecting group which is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base; and
(B) A photobase generator obtained by latentiating a basic compound having an acid dissociation constant pKa of 10.8 or more by a covalent bond.
[2] The positive photosensitive resin composition according to [1], wherein (B) is a photobase generator represented by the general formula (1).
(wherein Z represents an amino group or an imino group.)
[3] The positive photosensitive resin composition according to [2], wherein in the general formula (1), Z is a group represented by a general formula (Z1) or a group represented by a general formula (Z2),
(wherein, R 1 And R 2 Each independently is a hydrogen atom or an organic group, R 1 And R 2 Optionally together with the nitrogen atom to which they are bonded, form a cyclic structure optionally containing heteroatoms other than the aforementioned nitrogen atoms, R 1 And R 2 Not simultaneously hydrogen atoms. )
-N＝CR 3 R 4 8230a general formula (z 2)
(wherein, R 3 And R 4 Each independently is-NR 5 R 6 or-C (= O) NR 7 R 8 ，R 5 、R 6 、R 7 And R 8 Each independently a hydrogen atom, an alkyl group or an aryl group. ).
[4] The positive photosensitive resin composition according to any one of [1] to [3], wherein (A) comprises a repeating unit represented by the general formula (2), (3) or (4),
(wherein,
X 1 is an organic group having a valence of 4,
Y 1 is an organic group having a valence of 2,
R 1 and R 2 Each independently a hydrogen atom or a protecting group which is detached by the action of a base, with the proviso that R 1 And R 2 Is not a hydrogen atom at the same time,
X 2 is an organic group with valence of (4+p),
Y 2 is an organic group having a valence of (2 +q),
R 3 a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 3 When they are optionally the same or different,
R 4 a plurality of R's being present for a hydrogen atom or a protecting group released by the action of a base 4 When they are optionally the same or different,
p is an integer of 0 to 4,
q is an integer of 0 to 4, but p and q are not simultaneously 0,
OR 3 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
OR 4 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
R 3 and R 4 Not all of them are hydrogen atoms,
X 3 is an organic group having a valence of 2,
Y 3 is an organic radical having a valence of (2+s),
R 5 are hydrogen atoms or protecting groups which are liberated by the action of a base, optionally identical or different,
s is an integer of 2 to 8,
OR 5 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
R 5 not all hydrogen atoms. ).
[5]According to [4]]The positive photosensitive resin composition, wherein R 3 The protecting group removed by action of a base being an alkyl cyanide or an alkyl azulenyl group, R 4 The protecting group released by the action of a base is dialkoxynitrobenzyloxycarbonyl or fluorenylmethyloxycarbonyl, R 5 The protecting group to be detached by the action of a base of (a) is a dialkoxynitrobenzyloxycarbonyl group or a fluorenylmethyloxycarbonyl group.
[6] A dry film comprising a resin layer obtained by applying the positive photosensitive resin composition according to any one of [1] to [5] to a thin film and drying the applied resin layer.
[7] A pattern coating film obtained by exposing, heating and developing a resin layer of the positive photosensitive resin composition according to any one of [1] to [5] or the dry film according to [6], and optionally curing the resin layer.
[8] An electronic part having the pattern coating film according to [7 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a positive photosensitive resin composition stably providing a good development contrast, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a semiconductor element, a printed wiring board, and an electronic component having the cured product.
The resin composition of the present invention comprises: (A) A polyamic acid having a carboxyl group protected by a protecting group which is detached by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group which is detached by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group which is detached by the action of a base; and
(B) A photobase generator obtained by latentiating a basic compound having an acid dissociation constant pKa of 10.8 or more by a covalent bond.
Here, the photobase generator in which the basic compound is latent by a covalent bond means a photobase generator in which the generated base is latent by a covalent bond and generates a base by irradiation of active energy rays such as light and electromagnetic waves, and is a covalent bond type photobase generator.
< polymers of (A) >
(A) The polymer of (b) is a polyamic acid having a carboxyl group protected by a protecting group detached by the action of a base, a polyimide having a phenolic hydroxyl group protected by a protecting group detached by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protecting group detached by the action of a base. (A) The components may be used alone or in combination of 2 or more kinds in an arbitrary ratio.
The polyamic acid having a carboxyl group protected with a protecting group which is eliminated by the action of a base includes a polymer having a repeating unit represented by the general formula (2),
(wherein,
X 1 is an organic group having a valence of 4,
Y 1 is an organic group having a valence of 2,
R 1 and R 2 Each independently a hydrogen atom or a protecting group which is detached by the action of a base, with the proviso that R 1 And R 2 Not simultaneously hydrogen atoms).
X 1 The organic group has a valence of 4, and the number of carbon atoms of the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.
Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton, and examples thereof include, but are not limited to, the following.
Y 1 The organic group has a valence of 2, and the number of carbon atoms of the organic group is preferably 4 to 40, more preferably 6 to 34. Is provided withThe organic group preferably has an aromatic ring.
Examples of the organic group having an aromatic ring include a group containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton, and examples thereof include, but are not limited to, the following.
Examples of the group having an aromatic ring include, but are not limited to, the following.
(wherein A is a single bond, -CH 2 -、-O-、-CO-、-S-、-SO 2 -、-NHCO-、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。)
R 1 And R 2 Each independently a hydrogen atom or a protecting group which is liberated by the action of a base, with the proviso that R is 1 And R 2 Not simultaneously hydrogen atoms. Preferably R 1 And R 2 Both are protecting groups which are detached by the action of a base, and more preferably the same.
The protecting group released by the action of a base in the general formula (2) is a group protecting a carboxylic acid group, and examples thereof include an alkyl cyanide group and an alkyl azulenyl group, and an alkyl cyanide group is preferable. Examples of the alkyl group in these groups include alkyl groups having 1 to 6 carbon atoms. Specific examples of the protecting group to be detached by the action of the base include, but are not limited to, the following.
The polymer of the general formula (2) can be prepared, for example, as follows: acid dianhydride and diamine are mixed in a solution to synthesize polyamic acid, and a protecting group detached by the action of a base is introduced into a carboxyl group of the polyamic acid.
The acid dianhydride may be a compound represented by the general formula (5).
(wherein, X 1 The meaning of the compound is the same as that of the general formula (2). )
Examples of the acid dianhydride include aliphatic tetracarboxylic acid dianhydrides such as 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-dione, ethylenetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, methylcyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride; <xnotran> ,3,3', 4,4' - ,2,2 ',3,3' - ,2,3 ',3,4' - ,3,3', 4,4' - ,2,2 ',3,3' - ,2,3 ',3,4' - ,2,2 ',6,6' - ,2,2- (3,4- ) ,2,2- (2,3- ) , (3,4- ) , (3,4- ) ,1,1- (2,3- ) , (2,3- ) , (3,4- ) ,2,2- (3,4- ) -1,1,1,3,3,3- ,2,2- (2,3- ) -1,1,1,3,3,3- ,1,3- 〔 (3,4- ) 〕 ,1,4- 〔 (3,4- ) 〕 ,2,2- {4- 〔 4- (1,2- ) 〕 } ,2,2- {4- 〔 3- (1,2- ) 〕 } , {4- 〔 4- (1,2- ) 〕 } , </xnotran> <xnotran> {4- 〔 3- (1,2- ) 〕 } ,4,4'- 〔 4- (1,2- ) 〕 ,4,4' - 〔 3- (1,2- ) 〕 , {4- 〔 4- (1,2- ) 〕 } , {4- 〔 3- (1,2- ) 〕 } , {4- 〔 4- (1,2- ) 〕 } , {4- 〔 3- (1,2- ) 〕 } , {4- 〔 4- (1,2- ) 〕 } , {4- 〔 3- (1,2- ) 〕 } ,2,2- {4- 〔 4- (1,2- ) 〕 } -1,1,1,3,3,3- ,2,2- {4- 〔 3- (1,2- ) 〕 } -1,1,1,3,3,3- ,2,3,6,7- ,1,1,1,3,3,3- -2,2- (2,3- 3,4- ) ,1,4,5,8- ,1,2,5,6- ,1,2,3,4- ,3,4,9,10- ,2,3,6,7- ,1,2,7,8- , </xnotran> And aromatic tetracarboxylic dianhydrides such as pyridinetetracarboxylic dianhydride, sulfonyldibenzoic dianhydride, m-terphenyl-3, 3', 4' -tetracarboxylic dianhydride, and p-terphenyl-3, 3', 4' -tetracarboxylic dianhydride.
Among them, preferred are 1, 3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furyl) naphtho [1,2-c ] furan-1, 3-dione, pyromellitic dianhydride, 3', 4' -benzophenonetetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 2',6,6' -biphenyltetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1, 3-hexafluoropropane dianhydride.
When acid dianhydride containing fluorine or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride, physical properties such as solubility and thermal expansion coefficient can be adjusted while maintaining good transparency.
Examples of the diamine that can be used for the production of the polymer of the general formula (2) include compounds represented by the general formula (6).
II 2 N-Y 1 -NII 2 \823080general formula (6)
(wherein, Y 1 The meaning of the compound is the same as that of the general formula (2). )
As Y 1 <xnotran> 2 , ,3,3' - -4,4' - ,2,2 ' - -4,4' - ,3,3' - -4,4' - ,3,3' - -4,4' - ,9,10- (4- ) ,4,4' - ,4,4' - ,3,3' - ,4,4' - ,1,3- (3- ) , 〔 4- (4- ) 〕 , 〔 4- (3- ) 〕 ,4,4' - (4- ) </xnotran><xnotran>, 4,4'- (3- , 〔 4- (4- ) 〕 ,1,1,1,3,3,3- -2,2- (4- ) ,1,1,1,3,3,3- -2,2- 〔 4- (4- ) 〕 ,1,1,1,3,3,3- -2,2- (3- -4- ) , ,4,4' - ,4,4'- ,3,4' - ,1,4- (4- ) ,1,3- (4- ) . </xnotran>
As Y 1 As the diamine having an aliphatic group having a valence of not 2, 1-m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4-diaminoheptamethylenediamine, 1, 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, hexahydro-4, 7-methanoindanyldimethylenediamine, tricyclo [6.2.1.02, 7] methylene]Undecenyldimethyl diamine, 4' -methylenebis (cyclohexylamine), isophoronediamine.
As the diamine, a compound represented by the general formula (7) can also be used.
(wherein, R 28 And R 29 Each independently a hydrocarbyl group having a valence of 2,
R 30 and R 31 Each independently a hydrocarbyl group having a valence of 1,
r is an integer of 1 or more, preferably an integer of 1 to 10. )
As R 28 And R 29 Examples thereof include alkylene groups having 1 to 7 carbon atoms such as methylene, ethylene and propylene, and arylene groups having 6 to 18 carbon atoms such as phenylene.
As R 30 And R 31 Examples thereof include alkyl groups having 1 to 7 carbon atoms such as methyl group and ethyl group, and aryl groups having 6 to 12 carbon atoms such as phenyl group.
The protective group which is released by the action of an alkali can be introduced into the carboxyl group of the polyamic acid by reacting the polyamide with a protecting groupAcids with R 1 X or R 2 X (wherein X is a halogen atom, preferably a chlorine atom) is reacted, but is not limited thereto.
Examples of the polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base include a polymer having a repeating unit represented by the general formula (3),
(wherein,
X 2 is an organic group with valence of (4+p),
Y 2 is an organic group having a valence of (2 +q),
R 3 a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 3 When they are optionally the same or different,
R 4 a plurality of R's being present for a hydrogen atom or a protecting group released by the action of a base 4 When they are optionally the same or different,
p is an integer of 0 to 4,
q is an integer of 0 to 4, but p and q are not simultaneously 0,
OR 3 the carbon atom bonded is a ring-constituting atom of an aromatic ring,
OR 4 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
R 3 and R 4 Not all are hydrogen atoms. ).
X 2 Is (4) + p) valent organic group, the carbon number of the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.
Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton, and examples thereof include the following groups and p (OR) groups bonded to the groups 3 ) But is not limited to these.
Y 2 Is an organic group having a valence of (2 + q), and the number of carbon atoms of the organic group is preferably 4 to 40, more preferably 6 to 34. The organic group preferably has an aromatic ring.
Examples of the organic group having an aromatic ring include groups containing a benzene ring such as a benzene skeleton, a biphenyl skeleton, and a bisphenol skeleton, and examples thereof include the following groups and q (OR) groups bonded thereto 4 ) The group (b) is not limited thereto.
Examples of the group having an aromatic ring include, but are not limited to, the following.
(wherein A is a single bond, -CH 2 -、-O-、-CO-、-S-、-SO 2 -、-NHCO-、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。)
R 3 A plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 3 When used, they are optionally the same or different, preferably the same.
R 4 A plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 4 When used, they are optionally the same or different, preferably the same.
p is an integer of 0 to 4, and q is an integer of 0 to 4, but p and q are not 0 at the same time. Preferably, (p + q) is an integer of 1 to 3, more preferably (p + q) is 2, and particularly preferably p is 2 and q is 0, or p is 0 and q is 2.
In the general formula (3), in the formula,
OR 3 the carbon atom bonded is a ring-constituting atom of an aromatic ring,
OR 4 the carbon atom bonded is a ring-constituting atom of an aromatic ring,
R 3 and R 4 Not all hydrogen atoms, preferably R 3 And R 4 All are protecting groups that are detached by the action of a base.
The protecting group released by the action of the base in the general formula (3) is a protecting group for a phenolic hydroxyl group, and examples thereof include a mono-or dialkoxynitrobenzyloxycarbonyl group and a fluorenylmethyloxycarbonyl group, and a fluorenylmethyloxycarbonyl group is preferable. Specific examples of the protecting group to be detached by the action of the base include, but are not limited to, the following.
The polymers of the general formula (3) can be prepared, for example, as follows: an acid dianhydride having q phenolic hydroxyl groups and a diamine having p phenolic hydroxyl groups are mixed to synthesize a polyamic acid, which is then subjected to ring closure to form a polyimide, and then a protective group that is eliminated by the action of a base is introduced into the phenolic hydroxyl group in the polyimide.
Examples of the acid dianhydride having p phenolic hydroxyl groups include the acid dianhydrides described in relation to the general formula (2) and compounds in which p hydroxyl groups are bonded to the aromatic ring of the acid dianhydride.
The diamine having q phenolic hydroxyl groups includes diamines exemplified in relation to the general formula (2) and compounds in which q hydroxyl groups are bonded to the aromatic ring of the diamine. <xnotran> , , 2,4- ,3,5- ,2,5- ,1,4- -2,5- ,4,6- ,2,5- , (3- -4- ) , (4- -3- ) , (4- -3,5- ) , (3- -4- ) , (4- -3- ) ,2,2- (3- -4- ) ,2,2- (3- -4- ) , (4- -3,5- ) , (3- -4- ) , (4- -3- ) , (4- -3,5- ) ,2,2- (3- -4- ) ,2,2- (4- -3- ) ,2,2- (4- -3,5- ) ,2,2- (3- -4- ) , </xnotran> <xnotran> 3,3'- -4,4' - ,4,4'- -3,3' - ,4,4'- -3,3' - -5,5'- ,4,4' - -3,3'- -5,5' - ,1,4- (3- -4- ) ,1,3- (3- -4- ) ,1,4- (4- -3- ) ,1,3- (4- -3- ) , [4- (3- -4- ) ] , [4- (3- -4- ) ] ,2,2- [4- (3- -4- ) ] , (4- -4- -5- ) , (4- -3- -5- ) , (4- -3- -5- ) ,2,2- (4- -3- -5- ) ,2,2- (4- -3- -5- ) , </xnotran> But is not limited thereto.
In order to introduce a protective group which is released by the action of a base into a phenolic hydroxyl group of polyimide, polyimide and R may be used 3 X or R 4 X (wherein X is a halogen atom, preferably a chlorine atom), but is not limited thereto.
Examples of the polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base include a polymer having a repeating unit represented by the general formula (4),
(wherein,
X 3 is an organic group having a valence of 2,
Y 3 is an organic group having a valence of (2 + s),
R 5 are hydrogen atoms or protecting groups released by the action of a base, optionally identical or different
s is an integer of 2 to 8,
OR 5 the carbon atom bonded is a ring-constituting atom of an aromatic ring,
R 5 not all are hydrogen atoms. ).
X 3 The organic group having a valence of 2 may be an aliphatic group or an aromatic group, preferably an aromatic group, and more preferably bonded to the carbonyl group in the general formula (4) on the aromatic ring. The number of carbon atoms of the aromatic group is preferably 6 to 30, more preferably 6 to 24.
Examples of the aromatic group include, but are not limited to, the following.
(wherein A is a single bond, -CH 2 -、-O-、-CO-、-S-、-SO 2 -、-NHCO-、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。)
Y 3 The organic group having valence of (2 + s) may be an aliphatic group or an aromatic group, preferably an aromatic group. The number of carbon atoms of the aromatic group is preferably 6 to 30, more preferably 6 to 24. More preferably 2 (OR) 5 ) With 2 amino groups in the ortho position on the aromatic ring.
Examples of the aromatic group include the following groups ((OR) 5 ) To 2 of the atomic bonds) OR (s-2) on these groups (OR) 5 ) The group is not limited to these.
R 5 Are hydrogen atoms or protecting groups which are liberated by the action of a base, optionally identical or different, preferably identical.
s is preferably 2.
In the general formula (4), OR 5 The carbon atom bonded is a ring-constituting atom of an aromatic ring.
R 5 Not all are hydrogen atoms, and preferably all are protecting groups which are eliminated by the action of a base.
The protecting group released by the action of the base in the general formula (4) is a group protecting a phenolic hydroxyl group, and examples thereof include a mono-or dialkoxynitrobenzyloxycarbonyl group and a fluorenylmethyloxycarbonyl group, and a fluorenylmethyloxycarbonyl group is preferable. Specific examples of the protecting group to be detached by the action of the base include, but are not limited to, the following.
The polymer of the general formula (4) can be produced, for example, by reacting a dihydroxy diamine with a dicarboxylic acid halide such as dicarboxylic acid chloride to introduce a protecting group, which is released by the action of a base, into a phenolic hydroxyl group in the reaction product.
<xnotran> , , 3,3'- -4,4' - ,4,4'- -3,3' - , (3- -4- ) , (4- -3- ) , (3- -4- ) , (4- -3- ) ,2,2- (3- -4- ) -1,1,1,3,3,3- ,2,2- (4- -3- ) -1,1,1,3,3,3- , . </xnotran> Among them, 2-bis (3-amino-4-hydroxyphenyl) -1, 3-hexafluoropropane is preferable.
<xnotran> , , , ,5- ,5- ,5- ,5- ,2,6- ,4,4' - ,4,4' - ,4,4' - , (4- ) ,2,2- ( ) ,2,2- (4- ) -1,1,1,3,3,3- , , , ,1,2- ,1,4- ,1,3- , . </xnotran> Among them, 4' -dicarboxydiphenyl ether is preferable.
In order to introduce a protective group which is released by the action of a base into a phenolic hydroxyl group of a reactant, a polyimide and R may be used 3 X or R 4 X (wherein X is a halogen atom, preferably a chlorine atom), but is not limited thereto.
(A) The weight average molecular weight of the polymer (b) may be 1000 to 100 ten thousand, preferably 5000 to 10 ten thousand, and more preferably 1 to 5 ten thousand. The weight average molecular weight can be measured by the method described in examples.
[ specific covalent bond type photobase generator of (B) ]
The positive photosensitive resin composition of the present invention contains a photobase generator which is obtained by latent-polymerizing (B) a basic compound having an acid dissociation constant pKa of 10.8 or more by a covalent bond. By containing the specific covalent bond type photobase generator, the dissolution inhibiting effect of the unexposed portion is more excellent than that in the case of containing the ion bonding type photobase generator, and the development contrast can be improved. Further, by using a specific covalent bond type photobase generator, it is also possible to suppress a decrease in development contrast during storage.
The base generated by the covalent bond type photobase generator preferably has an acid dissociation constant pKa of 10.8 or more, more preferably 13.0 or more. The acid dissociation constant pKa is a measured value in an aqueous solution at 25 ℃.
Examples of the base to be generated include, but are not limited to, 1,1, 3-Tetramethylguanidine (TMG), dibutylamine (DBA), 1,5, 7-triazabicyclo [4.4.0] deca-5-ene (TBD), and 2-methyl-2-imidazoline.
Preferably TMG or TBD.
The photobase generator is preferably a photobase generator represented by the general formula (1),
(wherein Z represents an amino group or an imino group). The amino or imino group comprises the residue of the bases exemplified in the above.
Z may be a group represented by the general formula (Z1).
(wherein, R 1 And R 2 Each independently is a hydrogen atom or an organic group, R 1 And R 2 Optionally together with the nitrogen atom to which they are bonded, form a cyclic structure optionally containing heteroatoms other than the aforementioned nitrogen atom, but R 1 And R 2 Not simultaneously hydrogen atoms. )
From the standpoint of the basicity of the base produced, R 1 And R 2 Preferably both alkyl groups, or together with the nitrogen atom to which they are bonded form a cyclic structure, and R 1 And R 2 An alkylene chain is formed in the cyclic structure. The number of carbon atoms constituting the alkyl group or alkylene chain is preferably 1 to 20, more preferably 1 to 8.
Z may be a group represented by the general formula (Z2),
-N＝CR 3 R 4 8230a general formula (z 2)
(wherein, R 3 And R 4 Each independently is-NR 5 R 6 or-C (= O) NR 7 R 8 ，R 5 、R 6 、R 7 And R 8 Each independently a hydrogen atom, an alkyl group or an aryl group. ). The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group and an ethyl group. The aryl group is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and the like. As R 3 、R 4 Examples thereof include an amino group, a mono-or dialkylamino group, a phenylamino group, and an amide group.
The following photobase generators are preferably used, but not limited thereto.
< amount of compounding >
In the positive type resin composition of the present invention, the covalently bonded photobase generator of (B) is preferably 10 to 40 parts by mass per 100 parts by mass of the polymer of (a). Within this range, the development contrast can be sufficiently improved.
< solvent >
The positive photosensitive resin composition of the present invention may contain a solvent, and the solvent is not particularly limited as long as it can dissolve the polymer of (a) and the covalently bonded photobase generator of (B).
Examples of the solvent include N, N '-dimethylformamide, N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, N' -dimethylacetamide (DMAc), diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone or in combination of 2 or more kinds in an arbitrary ratio. The amount of the solvent is not particularly limited, and may be adjusted according to, for example, the coating film thickness, viscosity, and the like. The solvent may be set to 50 to 9000 parts by mass, for example, with respect to 100 parts by mass of the polymer (a).
< other ingredients >
The positive photosensitive resin composition of the present invention may contain a sensitizer. By compounding a sensitizer, the sensitivity can be further improved. The sensitizer is not particularly limited, and may be, for example, there may be mentioned Michler's ketone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -dimethylaminobenzylidene) -4-methylcyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminobenylideninone, p-dimethylaminobenzylidenone, 2- (p-dimethylaminophenylbiphenylylidene) -benzothiazole, 2- (p-dimethylaminobenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isobenzothiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminobenzylidene, 3-ethoxycarbonyl-7-dimethylaminobenzophenone, 3-dimethyl-7-dimethylaminobenzylidene-7-coumarin, 3-dimethylaminoethoxy-7-dimethylaminobenzocoumarin, 3-dimethylaminocarbonylcoumarin, 3-7-dimethylaminoethoxy coumarin, 7-dimethylaminobenzoylcoumarin, 3-7-dimethylaminobenzone, and 3-bis (7-dimethylaminoethoxy) coumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like, and thioxanthones such as 4- (1-methylethyl) -9H-thioxanth-9-one are preferable from the viewpoint of sensitivity. These may be used alone or in combination of 2 or more kinds in an arbitrary ratio. The sensitizer may be used in an amount of, for example, 0.1 to 10 parts by mass per 100 parts by mass of the polymer (a).
The positive photosensitive resin composition of the present invention may contain an alkali multiplying agent. In order to decompose the photobase generator uniformly in the film thickness direction, it is preferable to use an alkali growth promoter in combination. The alkali growth promoter is not particularly limited, and for example, the alkali growth promoters disclosed in Japanese patent laid-open Nos. 2012-237776 and 2006-282657 can be used.
The positive photosensitive resin composition of the present invention may contain a coupling agent. The adhesion to the substrate is improved by the incorporation of the coupling agent. The coupling agent is not particularly limited, and examples thereof include a silane coupling agent and the like, and examples thereof include a silane coupling agent having an alkoxy group, a silane coupling agent having a mercapto group, a silane coupling agent having an epoxy group, a silane coupling agent having an ethylenically unsaturated group, a silane coupling agent having an arylamino group, and the like. Examples of commercially available coupling agents include KBM series and KBE series manufactured by Shin-Etsu Silicones, inc. The coupling agent can be used, for example, in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the polymer (a).
The positive photosensitive resin composition of the present invention may contain a melamine compound. The chemical resistance is improved by blending a melamine compound. The melamine-based compound is not particularly limited, and examples thereof include MW series manufactured by SANWA Chemical co.
The positive photosensitive resin composition of the present invention may contain a crosslinking agent having a methylol group. By compounding a crosslinking agent having a methylol group, resolution and mechanical properties are improved. Examples thereof include TM-BIP-A manufactured by Asahi organic materials Co., ltd, and TML-BPAF-MF manufactured by Kyowa chemical Co., ltd.
The positive photosensitive resin composition of the present invention may contain a filler. The filler is not particularly limited, and may be an inorganic filler or an organic filler. Examples of the filler include powders such as silica and barium sulfate, and fibrous materials such as glass fibers.
The positive photosensitive resin composition of the present invention may contain a colorant. The colorant is not particularly limited, and any known and conventional colorant such as red, cyan, green, yellow, white, black, tea, orange, violet, etc. can be used.
The positive photosensitive resin composition of the present invention may contain a photobase generator which is not of a covalent bond type within a range not impairing the effects of the present invention, and the content is preferably suppressed, and more preferably not contained, from the viewpoint of improving the effective development contrast.
The positive photosensitive resin composition of the present invention may contain a photoacid generator within a range not impairing the effects of the present invention, and the content is preferably suppressed, and more preferably not contained, from the viewpoint of suppressing corrosion of a circuit.
The positive photosensitive resin composition of the present invention may contain other various organic or inorganic low-molecular or high-molecular compounds. For example, dyes, surfactants, leveling agents, plasticizers, microparticles, and the like can be used. Examples of the fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these fine particles may have a porous or hollow structure. Specific examples of the material for obtaining the porous shape and the hollow structure include various pigments, fillers, fibers, and the like.
< Dry film >
The dry film of the present invention has a resin layer obtained by applying the positive photosensitive resin composition of the present invention on a carrier film (support) and drying the applied resin layer. The formation of the resin layer may be performed as follows: the photosensitive resin composition of the present invention is diluted with a solvent to adjust the viscosity to an appropriate value, and then coated on a support film (support film) in a uniform thickness by a comma coater, a knife coater, a lip (lip) coater, a bar coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and thereafter, the coated photosensitive resin composition is dried at a temperature of usually 50 to 130 ℃ for 1 to 30 minutes. The coating film thickness is not particularly limited, and may be usually 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.
As the carrier film (support), a plastic film can be used, and examples thereof include a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, and the like. The thickness of the carrier film is not particularly limited, and may be usually 10 to 150 μm.
After a resin layer formed from the positive photosensitive resin composition of the present invention is formed on a support film (support), a releasable protective film (cover film) is preferably further laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As the peelable protective film (cover film), for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. The protective film (cover film) may be one having a smaller adhesive force than the adhesive force between the resin layer and the carrier film (support film) when the protective film (cover film) is peeled off.
< patterned coating film >
The pattern coating film of the present invention can be prepared, for example, as follows.
[ step 1]
The positive photosensitive resin composition of the present invention is applied to a substrate and dried to obtain a coating film. The coating method is not particularly limited, and for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, a method of spray coating with a spray coater, an inkjet method, or the like can be used. The method of drying the coating film is not particularly limited, and methods such as air drying, heat drying in an oven or a hot plate, and vacuum drying can be used. Specifically, the drying may be natural drying, forced air drying, or heat drying at 20 to 80 ℃ for 1 minute to 1 hour. Drying is preferably carried out on a hot plate for 1 to 20 minutes. Further, the drying may be performed under vacuum, and in this case, the drying may be performed at room temperature for 1 minute to 1 hour.
The base material is not particularly limited, and can be widely used for silicon wafers, wiring boards, various resins, metals, passivation films of semiconductor devices, and the like.
[ step 2]
The coating film formed in step 1 is exposed to light through a photomask having a pattern or directly. As the active energy ray used for the exposure, an active energy ray having a wavelength capable of activating the photobase generator to generate a base can be used, and the maximum wavelength is preferably in the range of 350 to 410 nm. The exposure apparatus is not particularly limited, and a contact type photolithography machine, a mirror projection type exposure machine (mirror projection), a stepper, a laser direct exposure machine (laser direct), or the like can be used.
[ step 3]
The coating film exposed in step 2 is heated to deprotect the protecting group in the coating film. The heating time and heating temperature can be suitably adjusted depending on the type and amount of the polymer (A) and the covalently bonded photobase generator (B), and the coating film thickness, and in the case of a coating film thickness of about 10 μm, the temperature is about 120 to 300 ℃ and about 30 to 60 minutes.
[ step 4]
The coating film heated in step 3 is treated with a developer. (A) When the polymer (b) is a polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base, a patterned coating film can be formed on a substrate.
The developing method is not particularly limited, and for example, a rotary spray method, a paddle method, a dipping method with ultrasonic treatment, or the like can be used. The developer is not particularly limited, and an aqueous solution of an inorganic base such as sodium hydroxide, sodium carbonate, sodium silicate, or aqueous ammonia, an organic amine such as ethylamine, diethylamine, triethylamine, or triethanolamine, or a quaternary ammonium salt such as tetramethylammonium hydroxide or tetrabutylammonium hydroxide may be used. If necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added to these components. Thereafter, the coating film is washed with a washing liquid as necessary to obtain a pattern film. As the rinse solution, distilled water, methanol, ethanol, isopropyl alcohol, or the like can be used, and these may be used alone or in any combination of 2 or more.
[ step 5]
(A) When the polymer of (4) is a polyamic acid having a carboxyl group protected by a protective group which is detached by the action of a base or a polybenzoxazole precursor having a phenolic hydroxyl group protected by a protective group which is detached by the action of a base, the film obtained by the step (4) after development can be heated to form a patterned coating film which is a cured product of polyimide or polybenzoxazole. The heating temperature may be, for example, 150 to 350 ℃, preferably 180 to 300 ℃, and the heating time may be, for example, about 5 to 120 minutes. The heating method is not particularly limited, and examples thereof include a hot plate, an oven, and a temperature-raising oven capable of setting a temperature program. The heating may be performed in an inert atmosphere or in the atmosphere, and examples of the inert gas include nitrogen, argon, and the like.
< use >
The application of the positive photosensitive resin composition of the present invention is not particularly limited, and examples thereof include a paint, a printing ink, an adhesive, and the like. The photosensitive resin composition of the present invention can be suitably used as a material for forming a display device, a semiconductor element, an electronic component, an optical component, a building material, and the like.
Examples of the material for forming the display device include a material for forming a layer such as a color filter, a thin film for a flexible display, a resist material, and an alignment film, and an image forming material.
Examples of the material for forming the semiconductor element include a resist material, a buffer coating film, and a layer forming material such as an insulating film for a rewiring layer of a Wafer Level Package (WLP).
Examples of the material for forming the electronic component include sealing materials and layer forming materials such as printed wiring boards, interlayer insulating films, and wiring cover films.
Examples of the material for forming the optical member include optical materials and layer-forming materials such as holograms, optical waveguides, optical circuits, optical circuit members, and antireflection films.
As a building material, it can be used for paints, coating agents and the like.
The positive photosensitive resin composition of the present invention is preferably used as a pattern forming material, and particularly can be suitably used as a surface protective film, a buffer coating film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for devices having a buffer structure, an interlayer insulating film for multilayer circuits, an insulating material for passive components, a protective film for printed wiring boards such as solder resists and coverlays (coverlays), a liquid crystal alignment film, and the like, in semiconductor devices, display devices, and light emitting devices.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The following "parts" and "%" are all on a mass basis unless otherwise specified.
The measurement and evaluation in the examples were carried out as follows.
< weight average molecular weight >
The weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC) and converted to standard polystyrene.
[ measurement conditions ]
GPC measurement GL7700 (GLscience Co., ltd.)
Using a column: tosoh corporation TSK gel (registered trademark) alpha-2500
α-4000
Column temperature: 40 deg.C
Eluent conditions: 100mmol/LH 3 PO 4 ,10mmol/LLiBr,inNMP
Eluent flow rate: 0.5 mL/min
Calibration standard reagent: polystyrene standard (Showdex corporation)
Sample concentration: 0.1% eluent
A detector: UV (wavelength 260nm and 300 nm), room temperature
< development contrast value >
The photosensitive resin compositions of examples/comparative examples were spin-coated on a silicon wafer, and pre-baked at 60 ℃ for 3 minutes. Subjecting the obtained dried film to 1000mJ/cm 2 Was irradiated with light (365 nm wavelength LED light source), and then, exposed portions and unexposed portions were formed on the film, followed by exposure and heating under the conditions shown in table 1. The developing solution was developed with a 10% aqueous tetramethylammonium hydroxide solution, and the developing contrast value was calculated by the following formula.
The development contrast value of 5 or more was evaluated as good, 2 or more and less than 5 was evaluated as Δ, and less than 2 was evaluated as x.
< storage stability of developing contrast >
The photosensitive compositions of examples and comparative examples were left at 0 ℃ for one week, and the development contrast before and after the left standing was evaluated. Those with unchanged development contrast values before and after leaving alone were evaluated as good, those with a change in development contrast value of 1 to 2 were evaluated as good, and those with a change in development contrast value of 2 or more were evaluated as poor. The development contrast value before standing was less than 2, and the measurement was not performed after standing.
< resolution >
The photosensitive resin compositions of examples/comparative examples were spin-coated on a silicon wafer, and prebaked at 60 ℃/3 minutes. The obtained dried film was subjected to 1000mJ/cm through a mask in which L5/S (line/space) steps of 1 μm in length from 1 μm/1 μm to 20 μm/20 μm in length of line/space were drawn 2 The film was irradiated with light (365 nm wavelength LED light source) to form an exposed portion and an unexposed portion on the film, and then the film was exposed and heated under the conditions shown in table 1. Development was carried out with 10% aqueous tetramethylammonium hydroxide solution to obtain a pattern.
The smallest line width of a pattern that can be formed was regarded as good as resolution, and the resolution was regarded as good as less than 10 μm, Δ was regarded as 10 μm or more and 20 μm or less, and x was regarded as 20 μm or more.
< chemical resistance >
The photosensitive resin compositions of examples/comparative examples were spin-coated on a silicon wafer so that the film thickness after drying was about 3 μm, dried on a hot plate at 100 ℃ for 5 minutes, and then heated at 180 ℃ for 1 hour to obtain a cured film. The obtained film was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution for 1 minute, and the film having an initial film thickness reduction rate of less than 5% with respect to the cured film was evaluated as good, the film having a reduction rate of 5% or more and less than 20% was evaluated as Δ, and the film having a reduction rate of 20% or more was evaluated as x.
The ingredients used in the examples are as follows.
< Synthesis of polyimide having phenolic hydroxyl group (R-1) >
In an eggplant type flask, 7.0g (28 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) propane (AHPP) as a diamine, 9.5g (28 mmol) of 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride (alias: 4,4' - [ p-sulfonylbis (phenylene sulfanyl) ] phthalic anhydride (DSDA)) as an acid dianhydride and 45ml of dry N-methyl-2-pyrrolidone were charged, and the mixture was stirred and reacted at room temperature (23 ℃) for 24 hours, and 55ml of dry N-methyl-2-pyrrolidone and 50ml of toluene were additionally charged in the flask, and the reaction was carried out at 180 ℃ for 9 hours.
The reaction solution was cooled to room temperature, and then, the solution was added dropwise to methanol to precipitate a polymer, which was then filtered and dried to obtain 15g of a target polyimide (R-1) having a phenolic hydroxyl group and having the following repeating unit. The repeating units are as follows.
The weight average molecular weight was measured by GPC and found to be 1.2X 10 in terms of polystyrene 4 。
< Synthesis of polyimide (A-1) having phenolic hydroxyl group protected with protecting group >
1.0g of polyimide (R-1) having a phenolic hydroxyl group, 3.4g (13 mmol) of 9-fluorenylmethyl chloroformate, 50ml of dry THF and 1.3g (16 mmol) of pyridine were put in an eggplant type flask, and the mixture was stirred and reacted at room temperature for 12 hours.
The reaction solution was cooled to room temperature, and then, the solution was added dropwise to methanol to precipitate a polymer, which was then filtered and dried to obtain 1.4g of the objective polyimide (A-1) having the following repeating unit and having a phenolic hydroxyl group protected with a protecting group.
< Synthesis of polybenzoxazole precursor (A-2) having phenolic hydroxyl group protected with protecting group >
In a flask equipped with a stirrer and a thermometer, 10.0g (27.3 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) as a diamine was dissolved in 150ml of dry N-methyl-2-pyrrolidone with stirring. Thereafter, the flask was immersed in an ice bath, the flask was kept at 5 ℃ and 8.78g (29.8 mmol) of 4,4' -diphenyletherdicarboxylic acid dichloride (DEDC) was added thereto, and the mixture was stirred in the ice bath for 30 minutes and reacted at room temperature for 18 hours. The stirred solution was poured into ion-exchanged water, and a precipitate was recovered. Thereafter, the obtained solid was dissolved in acetone and again put into ion-exchanged water. The precipitate was recovered and dried to obtain 16g of a polybenzoxazole precursor (polyhydroxyamide).
The weight average molecular weight of the polycarbonate resin was measured by GPC and found to be 2.9X 10 in terms of polystyrene 4 。
In an eggplant type flask, 1.0g of polybenzoxazole precursor (polyhydroxyamide), 3.4g (13 mmol) of 9-fluorenylmethyl chloroformate, 50ml of dry THF and 1.3g (16 mmol) of pyridine were charged, and the mixture was stirred and reacted at room temperature for 12 hours.
The reaction solution was added dropwise to ion-exchanged water, thereby precipitating a polymer. This was filtered and dried to obtain 1.4g of a desired polybenzoxazole precursor (A-2) having the following repeating unit and having a phenolic hydroxyl group protected with a protecting group.
< Synthesis of Polyamic acid (A-3) having carboxyl group protected with protecting group >
7.0g (22 mmol) of 2,2 '-bis (trifluoromethyl) benzidine (TFMB) as a diamine, 8.1g (18 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA) as an acid anhydride, and 81ml of dry N-methyl-2-pyrrolidone were put into an eggplant type flask, followed by stirring and reaction at room temperature for 24 hours. The reaction solution was dropped into ion-exchanged water to precipitate a polymer, which was then filtered and dried to obtain 13g of a polyamic acid having a carboxyl group.
The weight average molecular weight was measured by GPC and found to be 1.3X 10 in terms of polystyrene 4 。
In an eggplant type flask, 1.0g of a polyamic acid resin having a carboxyl group was dissolved in 10ml of dry N-methyl-2-pyrrolidone, and 0.42g (3.3 mmol) of oxalyl chloride was added dropwise to the solution to carry out a reaction for 3 hours. 0.23g (3.3 mmol) of 2-cyanoethanol was added dropwise to the reaction mixture, and the mixture was immersed in an ice bath. After 0.30g (3.0 mmol) of triethylamine was added dropwise, the reaction was carried out at room temperature for 16 hours.
The reaction solution was dropped into ion-exchanged water to precipitate a polymer, which was then filtered and dried to obtain 1.1g of a polyamic acid resin (A-3) having a carboxyl group protected by a protecting group, which had the following repeating unit.
< Synthesis of covalent bond type photobase Forming agent (B-1) >
1.8g of trans-2-hydroxycinnamic acid, 1.26g of 1, 3-tetramethylguanidine, 2.1g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) as a condensing agent, and Tetrahydrofuran (THF) as a solvent were reacted at room temperature for 15 hours. After the reaction, the organic layer was washed with dilute hydrochloric acid, water and a saturated aqueous solution of sodium hydrogencarbonate in this order, dried over anhydrous magnesium sulfate, then the solvent was removed, and the organic layer was recrystallized from chloroform to obtain a compound having the following chemical structure as a white crystal. The obtained compound was used as a photobase generator (B-1).
< Synthesis of covalent bond type photobase Forming agent (B-2) >
1.8g of trans-2-hydroxycinnamic acid, 1.26g of 2-methyl-2-imidazoline, and 2.1g of EDC were dissolved in THF as a solvent and reacted at room temperature for 15 hours. After the reaction, the organic layer was washed with dilute hydrochloric acid, water and a saturated aqueous solution of sodium hydrogencarbonate in this order, dried over anhydrous magnesium sulfate, then the solvent was removed, and the organic layer was recrystallized from chloroform to obtain a compound having the following chemical structure as a white crystal. The resulting compound was used as the photobase generator (B-2).
< Synthesis of covalent bond type photobase generator (B' -1) >
1.8g of trans-2-hydroxycinnamic acid, 0.99g of cyclohexylamine and 2.1g of EDC were dissolved in THF as a solvent and reacted at room temperature for 15 hours. After the reaction, the organic layer was washed with dilute hydrochloric acid, water and a saturated aqueous solution of sodium hydrogencarbonate in this order, dried over anhydrous magnesium sulfate, then the solvent was removed, and the organic layer was recrystallized from chloroform to obtain a compound having the following chemical structure as a white crystal. The obtained compound was used as the photobase generator (B' -1).
< ion-bonded photobase generator (B' -2) >
As the photobase generator (B' -2), guanidine 2- (3-benzoylphenyl) propionate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was used.
< example >
The photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 3 were obtained by mixing the resins (A-1) to (A-3) and (R-1), the photobase generators (B-1) to (B-2) and (B '-1) to (B' -2), and the solvent (N, N-dimethylacetamide (DMAc) at the mixing ratios shown in Table 1. Various measurements were performed on each photosensitive composition. The results are shown in Table 1.
[ Table 1]
The photosensitive resin compositions of the examples have a large development contrast, excellent resolution, good storage stability of the development contrast, and good chemical resistance.
Claims (8)
1. A positive photosensitive resin composition comprising:
(A) A polyamic acid having a carboxyl group protected with a protecting group which is eliminated by the action of a base, a polyimide having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base, or a polybenzoxazole precursor having a phenolic hydroxyl group protected with a protecting group which is eliminated by the action of a base; and
(B) A photobase generator which comprises a basic compound having an acid dissociation constant pKa of 10.8 or more latent by a covalent bond.
2. The positive photosensitive resin composition according to claim 1, wherein (B) is a photobase generator represented by the general formula (1),
here, Z represents an amino group or an imino group.
3. The positive photosensitive resin composition according to claim 2, wherein in the general formula (1), Z is a group represented by general formula (Z1) or a group represented by general formula (Z2),
wherein R is 1 And R 2 Each independently being a hydrogen atom or an organic group, R 1 And R 2 Optionally together with the nitrogen atom to which they are bonded, form a cyclic structure optionally containing heteroatoms other than said nitrogen atom, with the proviso that R 1 And R 2 Not simultaneously being a hydrogen atom,
-N＝CR 3 R 4 \823080general formula (z 2)
Wherein R is 3 And R 4 Each independently is-NR 5 R 6 or-C (= O) NR 7 R 8 ，R 5 、R 6 、R 7 And R 8 Each independently a hydrogen atom, an alkyl group or an aryl group.
4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein (A) comprises a repeating unit represented by general formula (2), (3) or (4),
wherein,
X 1 is an organic group having a valence of 4,
Y 1 is an organic group having a valence of 2,
R 1 and R 2 Each independently a hydrogen atom or a protecting group which is liberated by the action of a base, with the proviso that R is 1 And R 2 Not simultaneously being a hydrogen atom,
X 2 is an organic group with valence of (4+p),
Y 2 is an organic radical having a valence of (2 q),
R 3 a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 3 When they are optionally the same or different,
R 4 a plurality of R's being present for hydrogen atoms or protecting groups detached by action of a base 4 When they are optionally the same or different,
p is an integer of 0 to 4,
q is an integer of 0 to 4, but p and q are not simultaneously 0,
OR 3 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
OR 4 the carbon atom bonded is a ring-constituting atom of an aromatic ring,
R 3 and R 4 Not all of them are hydrogen atoms,
X 3 is an organic group having a valence of 2,
Y 3 is an organic group having a valence of (2 + s),
R 5 are hydrogen atoms or protecting groups which are liberated by the action of a base, optionally identical or different,
s is an integer of 2 to 8,
OR 5 the bonded carbon atom is a ring-constituting atom of an aromatic ring,
R 5 not all hydrogen atoms.
5. The positive photosensitive resin set according to claim 4A compound of formula (I), wherein R 3 The protecting group released by the action of a base is an alkyl cyanide or an alkyl azulenyl group, R 4 The protecting group released by the action of a base is dialkoxynitrobenzyloxycarbonyl or fluorenylmethyloxycarbonyl, R 5 The protecting group to be detached by the action of a base of (a) is a dialkoxynitrobenzyloxycarbonyl group or a fluorenylmethyloxycarbonyl group.
6. A dry film comprising a resin layer obtained by applying the positive photosensitive resin composition according to any one of claims 1 to 5 to a film and drying the applied film.
7. A pattern coating film obtained by exposing, heating, and developing a resin layer of the positive photosensitive resin composition according to any one of claims 1 to 5 or the dry film according to claim 6, and optionally curing the resin layer.
8. An electronic part having the pattern coating film according to claim 7.
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| JP2020082245A JP2021177210A (en) | 2020-05-07 | 2020-05-07 | Positive type photosensitive resin composition, dry film, pattern coated film and electronic component |
| JP2020-082245 | 2020-05-07 | ||
| PCT/JP2021/017302 WO2021225127A1 (en) | 2020-05-07 | 2021-04-30 | Positive photosensitive resin composition, dry film, patterned coating film and electronic component |
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| JP2019045735A (en) | 2017-09-04 | 2019-03-22 | 学校法人東京理科大学 | Positive photosensitive resin composition and cured product thereof |
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- 2021-04-30 CN CN202180032905.5A patent/CN115516375A/en active Pending
- 2021-04-30 KR KR1020227037823A patent/KR20230006636A/en active Search and Examination
- 2021-04-30 WO PCT/JP2021/017302 patent/WO2021225127A1/en active Application Filing
- 2021-05-07 TW TW110116505A patent/TW202142602A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021177210A (en) | 2021-11-11 |
| WO2021225127A1 (en) | 2021-11-11 |
| KR20230006636A (en) | 2023-01-10 |
| TW202142602A (en) | 2021-11-16 |
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