CN117534836A - Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition - Google Patents
Polybenzoxazole precursor, process for producing the same, and photosensitive resin composition Download PDFInfo
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- CN117534836A CN117534836A CN202311742225.XA CN202311742225A CN117534836A CN 117534836 A CN117534836 A CN 117534836A CN 202311742225 A CN202311742225 A CN 202311742225A CN 117534836 A CN117534836 A CN 117534836A
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- Prior art keywords
- polybenzoxazole precursor
- formula
- dicarboxylic acid
- group
- acid
- Prior art date
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- 239000002243 precursor Substances 0.000 title claims abstract description 133
- 229920002577 polybenzoxazole Polymers 0.000 title claims abstract description 132
- 239000011342 resin composition Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title description 3
- -1 diamine compound Chemical class 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 150000004985 diamines Chemical class 0.000 claims abstract description 58
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 34
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 125000000962 organic group Chemical group 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 6
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims description 3
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 claims description 3
- HDFKMLFDDYWABF-UHFFFAOYSA-N 3-phenyloxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1=CC=CC=C1 HDFKMLFDDYWABF-UHFFFAOYSA-N 0.000 claims description 3
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 claims description 3
- SQJQLYOMPSJVQS-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C=C1 SQJQLYOMPSJVQS-UHFFFAOYSA-N 0.000 claims description 3
- ATZHGRNFEFVDDJ-UHFFFAOYSA-N 4-propylbenzoic acid Chemical compound CCCC1=CC=C(C(O)=O)C=C1 ATZHGRNFEFVDDJ-UHFFFAOYSA-N 0.000 claims description 3
- JATKASGNRMGFSW-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(Br)=CC(C(O)=O)=C1 JATKASGNRMGFSW-UHFFFAOYSA-N 0.000 claims description 3
- PLPFTLXIQQYOMW-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(Cl)=CC(C(O)=O)=C1 PLPFTLXIQQYOMW-UHFFFAOYSA-N 0.000 claims description 3
- AUIOTTUHAZONIC-UHFFFAOYSA-N 5-fluorobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(F)=CC(C(O)=O)=C1 AUIOTTUHAZONIC-UHFFFAOYSA-N 0.000 claims description 3
- BJLUCDZIWWSFIB-UHFFFAOYSA-N 5-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(O)=O)=C1 BJLUCDZIWWSFIB-UHFFFAOYSA-N 0.000 claims description 3
- YIHKILSPWGDWPR-UHFFFAOYSA-N 6708-37-8 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C=C2 YIHKILSPWGDWPR-UHFFFAOYSA-N 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 claims description 3
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004185 ester group Chemical group 0.000 claims description 2
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- 239000002244 precipitate Substances 0.000 claims description 2
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- 239000000126 substance Substances 0.000 abstract description 29
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- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 abstract 2
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- VSZMHWHJMHITJR-UHFFFAOYSA-N [3-(3-amino-4-phenoxybenzoyl)phenyl]-(3-amino-4-phenoxyphenyl)methanone Chemical compound NC1=CC(C(=O)C=2C=C(C=CC=2)C(=O)C=2C=C(N)C(OC=3C=CC=CC=3)=CC=2)=CC=C1OC1=CC=CC=C1 VSZMHWHJMHITJR-UHFFFAOYSA-N 0.000 description 1
- JYYBEGXDDHNJMX-UHFFFAOYSA-N [3-(4-amino-3-phenoxybenzoyl)phenyl]-(4-amino-3-phenoxyphenyl)methanone Chemical compound NC1=CC=C(C(=O)C=2C=C(C=CC=2)C(=O)C=2C=C(OC=3C=CC=CC=3)C(N)=CC=2)C=C1OC1=CC=CC=C1 JYYBEGXDDHNJMX-UHFFFAOYSA-N 0.000 description 1
- WYYLAHMAYZBJOI-UHFFFAOYSA-N [3-[4-(3-aminophenoxy)benzoyl]phenyl]-[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=C(C=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WYYLAHMAYZBJOI-UHFFFAOYSA-N 0.000 description 1
- QWCHFDRTENBRST-UHFFFAOYSA-N [3-[4-(4-aminophenoxy)benzoyl]phenyl]-[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=C(C=CC=2)C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 QWCHFDRTENBRST-UHFFFAOYSA-N 0.000 description 1
- CTEMSXOAFRWUOU-UHFFFAOYSA-N [4-(3-amino-4-phenoxybenzoyl)phenyl]-(3-amino-4-phenoxyphenyl)methanone Chemical compound NC1=CC(C(=O)C=2C=CC(=CC=2)C(=O)C=2C=C(N)C(OC=3C=CC=CC=3)=CC=2)=CC=C1OC1=CC=CC=C1 CTEMSXOAFRWUOU-UHFFFAOYSA-N 0.000 description 1
- VQXJDOIQDHMFPQ-UHFFFAOYSA-N [4-(4-amino-3-phenoxybenzoyl)phenyl]-(4-amino-3-phenoxyphenyl)methanone Chemical compound NC1=CC=C(C(=O)C=2C=CC(=CC=2)C(=O)C=2C=C(OC=3C=CC=CC=3)C(N)=CC=2)C=C1OC1=CC=CC=C1 VQXJDOIQDHMFPQ-UHFFFAOYSA-N 0.000 description 1
- JAGJCSPSIXPCAK-UHFFFAOYSA-N [4-[4-(3-aminophenoxy)benzoyl]phenyl]-[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 JAGJCSPSIXPCAK-UHFFFAOYSA-N 0.000 description 1
- WYBZFSGKJOYRQH-UHFFFAOYSA-N [nitro(phenyl)methyl] carbamate Chemical group NC(=O)OC([N+]([O-])=O)C1=CC=CC=C1 WYBZFSGKJOYRQH-UHFFFAOYSA-N 0.000 description 1
- FOLJMFFBEKONJP-UHFFFAOYSA-N adamantane-1,3-diamine Chemical compound C1C(C2)CC3CC1(N)CC2(N)C3 FOLJMFFBEKONJP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000006307 alkoxy benzyl group Chemical group 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 description 1
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004294 cyclic thioethers Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UHYNYIGCGVDBTC-UHFFFAOYSA-N ethyl 1h-imidazole-2-carboxylate Chemical compound CCOC(=O)C1=NC=CN1 UHYNYIGCGVDBTC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 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
- 238000005507 spraying Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003553 thiiranes Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing 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
- C08G73/22—Polybenzoxazoles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Disclosed herein are a benzoxazole precursor, a method of preparing the same, and a photosensitive resin composition, wherein the benzoxazole precursor is formed by reacting a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound shown in a formula (1), and the dicarboxylic acid monomer has a structure shown in a formula (2). When the polybenzoxazole precursor is used for preparing a black matrix, the polybenzoxazole precursor has good light shielding performance, good photoetching performance, mechanical performance, thermal performance and chemical corrosion resistance.
Description
Technical Field
The application relates to the technical field of photosensitive polymers, in particular to a polybenzoxazole precursor, a preparation method of the polybenzoxazole precursor and a photosensitive resin composition.
Background
Liquid crystal panel (LCD) photoresists are a technology intensive industry with high technology barriers. Only a small number of manufacturers in japan, korea, taiwan, etc. currently have the capability to mass-produce LCD photoresists. In recent years, with the development of liquid crystal display device technology, the contrast requirements are increasing. And placing a black matrix in the gaps between the color filter and the dots, wherein the black matrix plays roles of shielding light and constructing a frame for the red, green and blue three-primary-color photoresist coated subsequently, and the quality of the black matrix directly influences the color development performance of the color filter.
In order to improve contrast of the liquid crystal display device, chromium is used in a black matrix, mainly by depositing chromium on a surface of a glass substrate and then patterning by an etching method. Although this method makes the black matrix have higher optical density and stronger mechanical properties, it also has problems of high cost, high reflectivity of chromium, environmental pollution caused by chromium-containing wastewater, and the like. Then, researchers have proposed using pigments to prepare photoresist compositions having black matrices, but have faced problems of not being dissolved by a developing solution, long developing time, poor developing effect, etc., resulting in failure to obtain high resolution patterns, and the introduction of carbon materials and organic dyes significantly reduces the electrical insulation properties of black matrices. Although there have also been researchers to prepare black matrices using non-carbon black color pigments, black matrix photoresist compositions require high mixing ratios due to poor light shielding of the color pigments, resulting in increased viscosity of the composition and reduced strength of the formed film.
Disclosure of Invention
The purpose of the application is to provide a polybenzoxazole precursor, a preparation method thereof and a photosensitive resin composition, which not only have good light shielding performance, but also have good photoetching performance, mechanical performance, thermal performance and chemical corrosion resistance when being used for preparing a black matrix.
In order to achieve the above object, the technical solution of the present application provides a polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound represented by formula (1):
wherein R is 1 ~R 4 Respectively selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester group, phenyl and 4-aminophenylamino;
the dicarboxylic acid monomer has a structure represented by formula (2):
in formula (2), X is a divalent organic group that is an aliphatic group or an aromatic group; z is selected from hydroxyl or halogen groups.
In some embodiments of the present application, X is a C6-C48 aromatic group; preferably, the X isWherein A is selected from the group consisting of single bond, alkylene, -O-, -and->-S-、/>-C(CF 3 ) 2 -and-C (CH) 3 ) 2 Represents a linkage to the carbonyl group in formula (2).
In some embodiments of the present application, the dicarboxylic acid monomer is selected from the group consisting of a dicarboxylic acid having an aromatic ring, a dihalide of the dicarboxylic acid having an aromatic ring, a dicarboxylic acid ester of the dicarboxylic acid having an aromatic ring, an aliphatic dicarboxylic acid, a dihalide of the aliphatic dicarboxylic acid, and a dicarboxylic acid ester of the aliphatic dicarboxylic acid; preferably, the method comprises the steps of, the dicarboxylic acid monomer is selected from isophthalic acid, terephthalic acid, 5-tertiary butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4 '-dicarboxybiphenyl, 4' -dicarboxybiphenyl ether, 4 '-diacid chloride diphenyl ether, and 4, 4' -dicarboxyltetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid.
In some embodiments of the present application, the diamine monomer further comprises a diamine compound represented by formula (3):
H 2 N——Y——NH 2
formula (3);
in the formula (3), Y is a tetravalent organic group having at least two or more hydroxyl groups, the tetravalent organic group being an aliphatic group or an aromatic group; the tetravalent organic group is preferably an aromatic group.
In some embodiments of the present application, the Y is selected from the following tetravalent organic groups:
wherein one of 1 and 2 represents a linking moiety with an amino group in formula (3), and the other represents a linking moiety with a hydroxyl group in formula (3) Y.
In some embodiments of the present application, the polybenzoxazole precursor has a structural formula shown in formula (4):
in the formula (4), m is 1 to 100, n is 0 to 100, preferably, m is 1 to 40, and n is 15 to 40.
The application also provides a preparation method of the polybenzoxazole precursor, which comprises the following steps: s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compound shown in formula (1) in the diamine monomer is 0.1% -100%; s2: and (3) adding a dicarboxylic acid monomer shown in the formula (2) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
In some embodiments of the present application, the first solvent is selected from at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone, γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethylene lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methylpropyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; and/or, step S2 satisfies one of the following conditions: 1) Adding dicarboxylic acid monomers shown in the formula (2) under the ice bath condition of 0-10 ℃, wherein the polymerization reaction temperature is 0-35 ℃ and the polymerization reaction time is 2-10 hours; 2) The molar ratio of the diamine monomer to the dicarboxylic acid monomer represented by the formula (2) is 1 (0.5-1).
In some embodiments of the present application, the method of preparing further comprises: step S3: adding a blocking agent into the polybenzoxazole precursor solution to carry out a blocking reaction to obtain a blocked polybenzoxazole precursor solution, wherein the blocking reaction at least meets one of the following conditions: a. the mole ratio of the end-capping agent to the diamine monomer is (0.02-0.2): 1; b. the temperature of the end capping reaction is 10-35 ℃ and the time is 1-4 hours; preferably, the end-capping agent is selected from at least one of Phthalic Anhydride (PA), maleic Anhydride (MA), succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynyl phthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride; step S4: and (3) dripping the system obtained in the step (S2) or the step (S3) into deionized water, and cleaning and drying the precipitate to obtain the dried polybenzoxazole precursor.
The application also provides a photosensitive resin composition which comprises the following components in parts by weight: 100 parts of polybenzoxazole precursor, 5 to 40 parts of photosensitizer and 30 to 10000 parts of second solvent; preferably, the photosensitizer comprises at least one of photoacid generator, photobase generator, crosslinking agent, thermal acid generator, sensitizer, thickener, surfactant, leveling agent, and fine particles. Preferably, the second solvent includes at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether.
Compared with the prior art, the polybenzoxazole precursor, the preparation method thereof and the photosensitive resin composition have the following beneficial effects:
because the polybenzoxazole precursor is introduced into the anthraquinone structure, a cured film formed by the photosensitive resin composition comprising the polybenzoxazole precursor has better light shielding performance, and also has better photoetching performance, mechanical performance, thermal performance and chemical corrosion resistance.
The preparation method of the polybenzoxazole precursor has the advantages of convenient and easily obtained raw materials, simple preparation steps and process conditions, easy control and convenient industrialized popularization and application.
Drawings
The following figures describe in detail exemplary embodiments disclosed in the present application. Wherein like reference numerals refer to like structure throughout the several views of the drawings. Those of ordinary skill in the art will understand that these embodiments are non-limiting, exemplary embodiments, and that the drawings are for illustration and description purposes only and are not intended to limit the scope of the present application, other embodiments may equally well accomplish the intent of the invention in this application. It should be understood that the drawings are not to scale. Wherein:
FIG. 1 is a preparation route diagram of a polybenzoxazole precursor according to an embodiment of the application;
FIG. 2 is a FT-IR chart of a polybenzoxazole precursor prepared in example 7 of this application;
FIG. 3 is a graph showing a photolithography performance test of the photosensitive resin composition prepared in example 1 of the present application;
FIG. 4 is a graph showing the photolithography performance test of the photosensitive resin composition prepared in example 4 of the present application;
fig. 5 is a 3D view of the film surface of the cured film of example 14 of the present application after soaking in N-methyl pyrrolidone.
Detailed Description
The following description provides specific applications and requirements to enable any person skilled in the art to make and use the teachings of the present application. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the application. Thus, the present application is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
At present, some technical schemes adopt 4,4 '-diaminodiphenylamine or 4, 4' -diaminodiphenyl ether as diamine monomers to prepare an intrinsic black polyimide film, but the intrinsic black polyimide film has poor light-shielding property and poor mechanical property.
Based on the above, the technical scheme of the application introduces diamine with an anthraquinone structure into the polybenzoxazole precursor, and the anthraquinone structure can absorb visible light, so that when the photosensitive resin composition prepared from the polybenzoxazole precursor is used for a black matrix, the photosensitive resin composition has good light shielding property, and simultaneously has good photoetching performance, mechanical performance, thermal performance, electrical performance and chemical corrosion resistance.
Referring to fig. 1, an embodiment of the present application provides a polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer. Wherein the diamine monomer comprises a diamine compound (1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone) represented by formula (1):
wherein R is 1 ~R 4 And is selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester, phenyl and 4-aminophenylamino.
The dicarboxylic acid monomer has a structure represented by formula (2):
in formula (2), X is a divalent organic group, which may be an aliphatic group or an aromatic group, preferably an aromatic group. The number of carbon atoms of X is preferably 6 to 48, more preferably 6 to 24.
In some preferred embodiments, X isWherein A is selected from the group consisting of single bond, alkylene, -O-, -and->-S-、/>-C(CF 3 ) 2 -and-C (CH) 3 ) 2 -, represents a carbonyl group of formula (2)>Is provided.
In some preferred embodiments, in order to further improve the developability of the photosensitive resin composition and the mechanical properties of the cured film, A is-O-, the divalent organic group has the structural formula
In formula (2), Z is selected from hydroxyl or halogen groups. In order to further increase the yield in the preparation, Z is preferably a halogen radical.
In some embodiments, the dicarboxylic acid monomer is selected from the group consisting of a dicarboxylic acid having an aromatic ring, a dihalide of the dicarboxylic acid having an aromatic ring, a dicarboxylic acid ester of the dicarboxylic acid having an aromatic ring, an aliphatic dicarboxylic acid, a dihalide of the aliphatic dicarboxylic acid, and a dicarboxylic acid ester of the aliphatic dicarboxylic acid; preferably, the method comprises the steps of, the dicarboxylic acid monomer is selected from isophthalic acid, terephthalic acid, 5-tertiary butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4 '-dicarboxybiphenyl, 4' -dicarboxybiphenyl ether, 4 '-diacid chloride diphenyl ether, and 4, 4' -dicarboxyltetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid.
In some embodiments, the dicarboxylic acid-based monomer is preferably 4,4 ' -dicarboxydiphenyl ether (i.e., 4 ' -diphenylether dicarboxylic acid) and dihalides thereof (e.g., 4 ' -diacyldiphenyl ether chloride) in order to further improve the developability of the photosensitive resin composition and the mechanical properties of the cured film.
In some embodiments, the diamine monomer further comprises a diamine compound of formula (3):in formula (3), Y is a tetravalent organic group having at least two or more hydroxyl groups. The tetravalent organic group may be an aliphatic groupA group or an aromatic group, preferably an aromatic group. The positional relationship of the hydroxyl group in Y and the amino group in formula (3) is preferably ortho-position. The number of carbon atoms of Y is preferably 6 to 48, more preferably 6 to 24.
In some preferred embodiments, the Y is selected from the following tetravalent organic groups:
in the above tetravalent organic group, one of 1 and 2 represents an amino group (-NH) in formula (3) 2 ) The other represents a linking part with a hydroxyl group in Y of formula (3).
In some preferred embodiments, to further increase the solubility of the polybenzoxazole precursor in an alkaline developer and photosensitivity, the tetravalent organic group isThe diamine compound shown in the formula (3) is 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, and the structural formula is as follows:
In some preferred embodiments, the diamine compound of formula (3) is 4, 4-methylenebis (2-aminophenol) having the structural formula:
in some preferred embodiments, the diamine compound of formula (3) is 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane having the following structural formula:
in some preferred embodiments, the diamine compound of formula (3) is 2, 2-bis (4-hydroxy-3-aminophenyl) propane having the formula:
in some preferred embodiments, the diamine compound of formula (3) is 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol having the formula:
in some embodiments, the polybenzoxazole precursor has a structural formula shown in formula (4):
in formula (4), m is an integer of 1 or more. Preferably, m is 1 to 100, more preferably, m is 1 to 40.n is an integer of 0 or more. Preferably, n is 1 to 100, more preferably, n is 15 to 40.
In some preferred embodiments, in order to improve the solubility of the photosensitive resin composition in an alkali developer, the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 2000 to 40000, more preferably 3000 to 20000. The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 4000 to 80000, more preferably 6000 to 40000. The Mw/Mn of the polybenzoxazole precursor is preferably 1 to 5, more preferably 1 to 3. In the examples herein, the number average molecular weight and the weight average molecular weight are both values measured by Gel Permeation Chromatography (GPC).
In some preferred embodiments, in order to further improve the light-shielding property of the cured film formed from the photosensitive resin composition, m/(m+n) ×100% is made 0.1% or more in the structural formula of the polybenzoxazole precursor. More preferably, m/(m+n). Times.100%. Gtoreq.5%. Wherein m/(m+n). Times.100% also represents the length ratio of the polymer segment formed by polymerizing the diamine having an anthraquinone structure with the dicarboxylic acid-based monomer in the total molecular chain, and also represents the molar percentage of the diamine compound having an anthraquinone structure in the diamine monomer. For example, in some preferred embodiments, the molar percentage of the diamine compound having an anthraquinone structure is 0.1%,0.3%,0.5%,1.0%,1.5%,2.0%,2.5%,3.0%,3.5%,4.0%,4.5%,5.0%,5.5%,6.0%,6.5%,7.0%,7.5%,8.0%,8.5%,9.0%,9.5%,10.0%,10.5%,11.0%,11.5%,12.0%,12.5%,13.0%,13.5%,14.0%,14.5%,15.0%,15.5%,16.0%,16.5%,17.0%,17.5%,18.0%,18.5%,19.0%,19.5%,20.0%,20.5%,21.0%,21.5%,22.0%,22.5%,23.0%,23.5%,24.0%,24.5%, 24.25%, 26.25%, 26.5%,27.0%,27.5%,28.0%,28.5%,29.0%,29.5%,30.0%,31.5%,32.0%,32.5%,33.0%,33.5%,34.0%,34.5%,35.0%,35.5%,36.0%,36.5%,37.0%,37.5%,38.0%,38.5%,39.0%,40.0%,40.5%,41.0%,41.5%,42.0%,42.5%,43.0%,43.5%,44.0%,44.5%,45.0%,45.5%,46.0%,46.5%,47.0%,47.5%,48.0%,48.5%,49.0%,49.5%,50.0%,55.0%,60.0%,65.0%,70.0%,75.0%,80.0%,85.0%,90.0%,95.0%,100.0%, or any range between any two of them.
In some embodiments, the diamine monomer may include at least one of the following diamine compounds in addition to the diamine compound represented by formula (1) and the diamine compound represented by formula (3): 4,4' -bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl ] ketone, bis [4- (3-aminophenoxy) phenyl ] sulfide bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3 ' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3 ' -diaminodiphenyl sulfide, 3 ' -diaminodiphenyl sulfoxide, and 3, 4' -diaminodiphenyl sulfoxide, 4' -diaminodiphenyl sulfoxide, 3 ' -diaminodiphenyl sulfone, 3, 4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone 3,3 ' -diaminobenzophenone, 3, 4' -diaminobenzophenone, 4' -diaminobenzophenone, 3 ' -diaminodiphenylmethane 3, 4' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl ] methane, 1-bis [4- (4-aminophenoxy) phenyl ] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl ] ethane, 1-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1-bis [4- (4-aminophenoxy) phenyl ] butane, 1, 3-bis [4- (4-aminophenoxy) phenyl ] butane, 1, 4-bis [4- (4-aminophenoxy) phenyl ] butane, 2-bis [4- (4-aminophenoxy) phenyl ] butane, 2, 3-bis [4- (4-aminophenoxy) phenyl ] butane 2- [4- (4-aminophenoxy) phenyl ] -2- [4- (4-aminophenoxy) -3-methylphenyl ] propane, 2-bis [4- (4-aminophenoxy) -3-methylphenyl ] propane, 2- [4- (4-aminophenoxy) phenyl ] -2- [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] propane 2, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ketone, bis [4- (4-aminophenoxy) phenyl ] sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfoxide, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] ether, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) benzoyl ] benzene, 4' -bis [ (3-aminophenoxy) benzoyl ] benzene, 1-bis [4- (3-aminophenoxy) phenyl ] propane, 1, 3-bis [4- (3-aminophenoxy) phenyl ] propane, 3, 4' -bis [4- (4-aminophenoxy) phenyl ] ether, bis [2, 3-aminophenoxy ] propane, 1, 3-bis [ 3-aminophenoxy ] methane, 1, 3-bis [4- (3-aminophenoxy) phenyl ] propane, 1, 2-bis [4- (3-aminophenoxy) phenyl ] ethane, bis [4- (3-aminophenoxy) phenyl ] sulfoxide, 4 '-bis [3- (4-aminophenoxy) benzoyl ] diphenyl ether, 4' -bis [3- (3-aminophenoxy) benzoyl ] diphenyl ether, 4 '-bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] benzophenone, 4' -bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy } phenyl ] sulfone, 1, 4-bis [4- (4-aminophenoxy) phenoxy-alpha, alpha-dimethylbenzyl ] benzene, 1, 3-bis [4- (4-amino-6-trifluoromethylphenoxy) -alpha, alpha-dimethylbenzyl ] benzene, 1, 3-bis [4- (4-amino-alpha, alpha-dimethylbenzyl) -benzene, alpha, 1, 4-bis [4- (4-aminophenoxy) -alpha, 6-dimethylbenzyl ] benzene, alpha, 1, 3-bis [4- (4-aminophenoxy) -alpha, 6-dimethylbenzyl) benzene, alpha-dimethylbenzyl ] benzene, 3 '-diamino-4, 4' -diphenoxybenzophenone, 4 '-diamino-5, 5' -diphenoxybenzophenone, 3,4 '-diamino-4, 5' -diphenoxybenzophenone, 3 '-diamino-4-phenoxybenzophenone, and 4,4' -diamino-5-phenoxybenzophenone, 3,4 '-diamino-4-phenoxybenzophenone, 3, 4' -diamino-5 '-phenoxybenzophenone, 3' -diamino-4, 4 '-diphenoxybenzophenone, 4' -diamino-5, 5 '-diphenoxybenzophenone, 3, 4' -diamino-4, 5 '-biphenoxybenzophenone, 3' -diamino-4-biphenoxybenzophenone, 4 '-diamino-5-biphenoxybenzophenone, 3, 4' -diamino-4-biphenoxybenzophenone, 3,4 '-diamino-5' -biphenoxybenzophenone, 1, 3-bis (3-amino-4-phenoxybenzoyl) benzene, 1, 4-bis (3-amino-4-phenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-phenoxybenzoyl) benzene, 1, 4-bis (4-amino-5-phenoxybenzoyl) benzene, 1, 3-bis (3-amino-4-biphenoxybenzoyl) benzene, and an aromatic diamine in which all or part of hydrogen atoms on an aromatic ring in the aromatic diamine are replaced with a halogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, a cyano group, or a haloalkyl group or an alkoxy group having 1 to 3 carbon atoms, in which all or part of hydrogen atoms of the alkyl group or the alkoxy group are replaced with a halogen atom, and the like, and wherein 1, 4-bis (3-amino-4-diphenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-diphenoxybenzoyl) benzene, 2, 6-bis [4- (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) phenoxy ] benzonitrile, and the like; aliphatic diamines such as 4,4' -methylenebis (cyclohexylamine), isophorone diamine, trans-1, 4-diaminocyclohexane, cis-1, 4-diaminocyclohexane, 1, 4-cyclohexanediamine, 2, 5-bis (aminomethyl) bicyclo [2, 1] heptane, 2, 6-bis (aminomethyl) bicyclo [2, 1] heptane, 3, 8-bis (aminomethyl) tricyclo [5,2,1,0] decane, 1, 3-diaminoadamantane, 2-bis (4-aminocyclohexyl) propane, 2-bis (4-aminocyclohexyl) hexafluoropropane, 1, 3-propane diamine, 1, 4-tetramethylene diamine, 1, 5-pentamethylene diamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylene diamine, and 1, 9-nonamethylene diamine.
The embodiment of the application also provides a preparation method of the polybenzoxazole precursor, which comprises the following steps:
s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compound shown in formula (1) in the diamine monomer is 0.1% -100%;
s2: and (3) adding a dicarboxylic acid monomer shown in the formula (2) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
In some embodiments, in step S1, the first solvent is selected from at least one of N-methylpyrrolidone, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone (DMI), γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate.
In some preferred embodiments, in step S2, the dicarboxylic acid monomer represented by formula (2) is added under ice bath conditions of 0 to 10 ℃ and the polymerization temperature is 0 to 35 ℃ and the polymerization time is 2 to 10 hours.
In some preferred embodiments, the molar ratio of the diamine monomer to the dicarboxylic acid monomer of formula (2) is 1 (0.5 to 1).
In some embodiments, the method of preparing further comprises step S3: and adding a blocking agent into the polybenzoxazole precursor solution to carry out a blocking reaction. In some preferred embodiments, the capping reaction satisfies at least one of the following conditions: a. the mole ratio of the end-capping agent to the diamine monomer is (0.02-0.2): 1; b. the temperature of the end capping reaction is 10-35 ℃ and the time is 1-4 hours. In some embodiments, the capping agent is selected from at least one of Phthalic Anhydride (PA), maleic Anhydride (MA), succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynyl phthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride.
In some embodiments, the method of making further comprises: dropping the system obtained in the step S2 or the step S3 into deionized water to separate out solid resin; and cleaning and drying the solid resin to obtain the dry polybenzoxazole precursor containing anthraquinone diamine. In some embodiments, the cleaning liquid for cleaning the solid resin may be selected from at least one of distilled water, methanol, ethanol, isopropanol, and the like. The drying may be performed by at least one of a forced air oven, a vacuum oven, a freeze dryer, a fluidized dryer, and the like.
The embodiment of the application also provides a photosensitive resin composition which comprises the polybenzoxazole precursor with anthraquinone diamine and a photosensitizer. By introducing diamine monomer with anthraquinone, the prepared polybenzoxazole precursor has intrinsic black characteristic and excellent light absorption at 550 nm.
In some embodiments, the photosensitive resin composition may further include other polybenzoxazole precursors in addition to the polybenzoxazole precursors having anthraquinone diamine described above.
In some preferred embodiments, the polybenzoxazole precursor with anthraquinone diamine accounts for 50 to 99% of the total mass of the nonvolatile components in the photosensitive resin composition, and more preferably, 60 to 90%.
In some embodiments, in the photosensitive resin composition, the polybenzoxazole precursor having anthraquinone diamine is 100 parts by weight, and the sensitizer is preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight.
In some embodiments, the photosensitizer includes a photoacid generator and/or a photobase generator, or the like. In order to further improve the resolution, the sensitizer is preferably a photoacid generator. The photoacid generator is a compound that generates an acid by light irradiation of ultraviolet rays, visible light, or the like, as an example: naphthoquinone diazide compounds, diaryl sulfonium salts, triarylsulfonium salts, dialkyl phenacylsulfonium salts, diaryl iodonium salts, aryl diazonium salts, aromatic tetracarboxylic esters, aromatic sulfonic esters, nitrobenzyl esters, aromatic N-oxybutylene sulfinates, aromatic sulfonamides, benzoquinone diazonium sulfonates, and the like. Further preferably, the photoacid generator is preferably a naphthoquinone diazide compound. The naphthoquinone diazide compound may be, for example, a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593, made by Mitsubao chemical research, inc.), a naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599, made by Mitsubao chemical research, inc.), a naphthoquinone diazide adduct of 4- {4- [1, 1-bis (4-hydroxyphenyl) ethyl ] - α, α -dimethylbenzyl } phenol (for example, TKF-428, TKF-528, made by Mitsubao chemical research, inc.), or the like.
The photobase generator is a compound that generates one or more alkaline substances (secondary amine, tertiary amine, etc.) by changing the molecular structure or splitting the molecule by irradiation with ultraviolet light, visible light, etc. The photobase generator may be an ionic photobase generator or a nonionic photobase generator. In order to further improve the sensitivity of the photosensitive resin composition, the photobase generator is preferably an ionic photobase generator. Examples of the ionic photobase generator include salts of carboxylic acids and tertiary amines containing aromatic components, and examples of the commercial products include WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300, which are commercially available from Wako pure chemical industries, ltd. Examples of the nonionic photobase generator include an α -aminoacetophenone compound, an oxime ester compound, a compound having a substituent such as an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group. As other photobase generators, WPBG-018 (trade name: 9-tetrahydroxymethyl N, N' -diethyl arbamate), WPBG-027 (trade name: E) -1- [3- (2-hydroxyphenyl) -2-propenyl ] piperidine, WPBG-140 (trade name: 1- (antimicrobial-2-yl) ethyl imidazolecarboxylate) and WPBG-165, etc. manufactured by Wako pure chemical industries, ltd.
In some embodiments, the photosensitive resin composition may further include a crosslinking agent. The addition of the crosslinking agent can sufficiently cure the photosensitive resin composition even under a low-temperature curing condition of about 220 ℃. In some preferred embodiments, in the photosensitive resin composition, the polybenzoxazole precursor having anthraquinone diamine is 100 parts by weight, and the crosslinking agent is preferably 0.1 to 30 parts by weight, and more preferably 0.1 to 20 parts by weight.
The crosslinking agent is preferably at least one compound capable of forming a crosslinked structure by reacting with a phenolic hydroxyl group in the polybenzoxazole precursor, for example, a crosslinking agent having a cyclic ether group such as an epoxy group, a cyclic thioether group such as an episulfide group, a crosslinking agent having an alcoholic hydroxyl group obtained by bonding an alkylene group having 1 to 12 carbon atoms such as a hydroxymethyl group to a hydroxyl group, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, a urea-based crosslinking agent, or the like. Further preferably, the crosslinking agent is at least one of a crosslinking agent having a cyclic ether group, particularly an epoxy group, and a crosslinking agent having an alcoholic hydroxyl group, particularly a hydroxymethyl group to which a hydroxyl group is bonded.
In some preferred embodiments, the crosslinking agent comprises a crosslinking agent having an epoxy group that thermally reacts with the hydroxyl groups in the polybenzoxazole precursor to form a crosslinked structure. The number of functional groups of the crosslinking agent having an epoxy group is preferably 2 to 4. Among the crosslinking agents having an epoxy group, epoxy compounds having a naphthalene skeleton with a difunctional group number of not less are preferable, and not only can an insulating film having more excellent flexibility and chemical resistance be obtained, but also a low CTE in the opposite relationship with flexibility can be achieved, and warpage and crack occurrence of the insulating film can be suppressed. In addition, bisphenol a type epoxy compounds may be suitably used as the crosslinking agent in view of flexibility.
In some preferred embodiments, the crosslinking agent comprises a crosslinking agent having hydroxymethyl groups, preferably having more than 2 hydroxymethyl groups.
In some preferred embodiments, the photosensitive resin composition may further include a thermal acid generator in order to further promote the cyclization reaction of the polybenzoxazole precursor. In some preferred embodiments, the photosensitive resin composition may further include a sensitizer in order to improve photosensitivity. In some preferred embodiments, the photosensitive resin composition may further include a binder such as a silane coupling agent in order to further improve adhesion to a substrate. In some preferred embodiments, various organic or inorganic low-molecular or high-molecular compounds may be added to further improve the processing characteristics and various functionalities of the photosensitive resin composition. For example, surfactants, leveling agents, fine particles, and the like can be used. The fine particles include organic fine particles of polystyrene, polytetrafluoroethylene, and the like, and inorganic fine particles of silica, carbon, layered silicate, and the like. In addition, various colorants, fibers, and the like may be blended into the photosensitive resin composition.
In some embodiments, the photosensitive resin composition further comprises a second solvent. The second solvent is not limited in kind as long as each component can be dissolved, and includes, for example, at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, diethylene glycol monomethyl ether, and the like.
In some embodiments, in the photosensitive resin composition, the polybenzoxazole precursor having anthraquinone diamine is 100 parts by weight and the second solvent is 30 to 10000 parts by weight.
The photosensitive resin composition can be used for preparing photoresist.
The present embodiment also provides a dry film, which is a resin layer formed by drying the photosensitive resin composition, and the thickness thereof is not particularly limited, and may be, for example, 0.1 μm to 150 μm, as determined according to practical applications. The coating method is not limited, and for example, spin coater, bar coater, blade coater, curtain coater, screen printer, etc. may be used, or spray coater may be used for spray coating, ink jet method, etc. The drying method may be air drying, thermal drying using an oven or a hot plate, vacuum drying, or the like. In addition, drying is preferably performed under conditions that do not cause ring closure of the polybenzoxazole precursor in the photosensitive resin composition. In some preferred embodiments, natural drying, air drying, or heat drying is performed at 70℃to 140℃for 1 minute to 30 minutes. In order to simplify the operation method, a hot plate is preferably used, and drying is performed for 1 to 20 minutes. Alternatively, the vacuum drying may be performed at room temperature for 20 minutes to 1 hour.
The embodiment of the application also provides a cured film, and the preparation method of the cured film comprises the following steps:
s10: exposing and developing the dry film to form a pattern film;
s20: and heating and curing the pattern film.
In step S10, the wavelength of the light source employed at the time of exposure may be the wavelength at which the photoacid generator is activated. Preferably, the maximum wavelength is 350nm to 450 nm. The exposure amount is determined by the film thickness and the like, and can be usually set to 10mJ/cm 2 ~10000mJ/cm 2 Preferably, the ratio is 50mJ/cm 2 ~3000mJ/cm 2 Within a range of (2). The exposure machine used for exposure may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in a range of 350nm to 450 nm.
For development, a known method for developing a photoresist, for example, a spin spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, or the like can be used. The developer may be an aqueous solution of inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, a proper amount of a water-soluble organic solvent such as methanol, ethanol, or isopropanol, or a surfactant may be added to the aqueous solution.
After the pattern film is formed, the pattern film may be further cleaned with a rinse solution. The flushing liquid is at least one selected from distilled water, methanol, ethanol, isopropanol and the like.
In step S20, the polybenzoxazole precursor contained in the photosensitive resin composition is subjected to cyclization reaction by heating, thereby forming polybenzoxazole. The heating condition is preferably 220-350 deg.c for 5-120 min. For heating, a hot plate, an oven, or a temperature-raising oven capable of setting a temperature program may be used, and heating under an inert gas such as nitrogen or argon is preferable.
The technical solutions of the present application will be clearly and completely described below in connection with the embodiments of the present application. The reagents and starting materials used were purchased commercially, unless otherwise indicated. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
Preparing a polybenzoxazole precursor:
(1) 8.4000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are completely dissolved in 95.1000g of N, N-dimethylacetamide to obtain diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 8.5550g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 2
Preparing a polybenzoxazole precursor:
(1) 8.4000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are completely dissolved in 97.4600g of N, N-dimethylacetamide to obtain diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 3
Preparing a polybenzoxazole precursor:
(1) 8.4000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are completely dissolved in 99.8200g of N, N-dimethylacetamide to obtain diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.7350g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 4
Preparing a polybenzoxazole precursor:
(1) 7.7000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 6.7500g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are completely dissolved in 97.6600g of N, N-dimethylacetamide to obtain diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 5
Preparing a polybenzoxazole precursor:
(1) 7.0000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 7.5000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are completely dissolved in 97.8600g of N, N-dimethylacetamide to obtain diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 6
Preparing a polybenzoxazole precursor:
(1) 6.9000g of 4, 4-methylenebis (2-aminophenol) and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone are taken and completely dissolved in 99.6200g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 7
Preparing a polybenzoxazole precursor:
(1) 10.9800g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone were completely dissolved in 107.7800g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
The polybenzoxazole precursor prepared in example 7 was coated and baked to prepare a dry film, and was cured at a low temperature for 1 hour in an oxygen-free environment having an oxygen content of less than 100ppm at 350 ℃ to obtain a cured PBO film. The PBO films were subjected to fourier transform infrared spectroscopy (FT-IR) testing: the sample iS tested by adopting a Nicolet iS5 type Fourier infrared spectrometer of ThermoFisher technology Co, and the test range covers 4000-500 cm -1 The number of tests was set to 32, and the sample was directly placed on the ATR module at the time of the test, to obtain the FT-IR diagram shown in fig. 2. As shown in FIG. 2, 1052cm -1 The C-O bond on the oxazole ring stretches out and draws back the vibration peak, but 1539cm -1 The peak of the amide bond at the site had disappeared, demonstrating that the PBO membrane had been completely cyclized.
Example 8
Preparing a polybenzoxazole precursor:
(1) 7.7400g of 2, 2-bis (4-hydroxy-3-aminophenyl) propane and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone were completely dissolved in 94.8200g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 9
Preparing a polybenzoxazole precursor:
(1) 8.9400g of 2,2 '-diamino-4, 4' - (cyclohexyl-1, 1-diyl) diphenol and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone were completely dissolved in 99.6200g of N-methylpyrrolidone, and diamine monomer solution was obtained;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4,4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Example 10
Preparing a polybenzoxazole precursor:
(1) 7.7400g of 2, 2-bis (4-hydroxy-3-aminophenyl) propane and 6.0000g of 1, 8-dihydroxy-2, 4,5, 7-tetraminoanthraquinone were completely dissolved in 99.8200g of N-methylpyrrolidone to give a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 9.1450g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 0.8200g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Comparative example 1
Preparing a polybenzoxazole precursor:
(1) 14.000g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone was completely dissolved in 109.9800g of N, N-dimethylacetamide to obtain a diamine monomer solution;
(2) Under the nitrogen atmosphere and the ice bath condition at the temperature of 5 ℃, 12.0950g of 4, 4' -diacyl chloride diphenyl ether solid is poured into the diamine monomer solution, after the pouring is finished, the ice bath is removed, and the polybenzoxazole precursor solution is obtained after the reaction for 4 hours under the nitrogen atmosphere and the temperature of 25 ℃;
(3) Pouring 1.4000g of norbornene dianhydride solid into the polybenzoxazole precursor solution under nitrogen atmosphere at 25 ℃ to react for 2 hours for end-capping reaction;
(4) And uniformly dripping the end-capped product system into deionized water, filtering, replacing the deionized water, soaking, washing again, filtering, repeating for a plurality of times, and drying to obtain the dry polybenzoxazole precursor containing anthraquinone diamine.
Preparation of photosensitive resin composition:
10g of the polybenzoxazole precursor prepared in this example, 2g of naphthoquinone diazide adduct of TS533 (tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, sanbao chemical), 0.5g of gamma-glycidoxypropyl trimethoxysilane and 18g N-methylpyrrolidone were taken and stirred uniformly to obtain a photosensitive resin composition.
Weight average molecular weight (Mw) and molecular weight distribution index (PDI) measurements
The polybenzoxazole precursors prepared in examples 1 to 10 were examined for weight average molecular weight (Mw) and molecular weight distribution index (PDI) by Gel Permeation Chromatography (GPC). The testing method comprises the following steps: filling a chromatographic column with DMAc to occupy all gaps among carrier particles and cavities in the particles, adding a sample solution prepared by the same solvent from a column head, eluting by the same solvent, collecting the eluting liquid at the micro end of the chromatographic column, calculating the volume and the concentration of the eluting liquid, and calling the total volume of the received eluting liquid as the eluting volume. The leached volume of solute is related to its molecular weight, and the larger the molecular weight, the smaller the leached volume. If the sample is polydisperse, a series of fractions of molecular weight ranging from large to small can be collected in the order of leaching. The test results are shown in Table 1.
TABLE 1 Mw and PDI of polybenzoxazole precursors prepared in examples 1 to 10
Group of | Mw | PDI |
Example 1 | 8876 | 1.37 |
Example 2 | 11759 | 1.51 |
Example 3 | 15262 | 1.70 |
Example 4 | 13754 | 1.59 |
Example 5 | 16210 | 1.78 |
Example 6 | 12010 | 1.55 |
Example 7 | 12172 | 1.55 |
Example 8 | 10997 | 1.47 |
Example 9 | 12851 | 1.57 |
Example 10 | 11774 | 1.53 |
Comparative example 1 | 13010 | 1.57 |
Light absorption Performance test
The polybenzoxazole precursors prepared in examples 1 to 10 were dissolved in N-methylpyrrolidone, respectively, the completely dissolved solutions were press-filtered to remove insoluble matters, and defoamed under vacuum, and then cured at high temperature (350 ℃) to obtain test pieces, and the rotation speed of the coating process was adjusted to obtain films of different thicknesses. The test pieces of examples 1 to 10 were tested for OD at 550nm, and table 2 shows the results of the visible light absorbance test of the thin film of example 1 at different film thicknesses.
The visible light absorbance test method comprises the following steps: the absorbance of the film at 550mn was measured using Shimadzu UV-1900i, which is the OD value of the film at 550 nm.
TABLE 2 OD test results of the films of example 1 at different film thicknesses
As can be seen from table 2, the regression equation of the two is calculated as y=0.5529x+0.0159, where the slope represents the strong or weak absorption capacity of the polybenzoxazole precursor to visible light, and the larger the slope represents the stronger the absorption capacity of the polybenzoxazole precursor to visible light, taking the film thickness as an independent variable x and the OD value as an independent variable y. From this, the slopes corresponding to the polybenzoxazole precursors prepared in examples 1 to 10 can be calculated as shown in table 3.
TABLE 3 visible light absorption slope for polybenzoxazole precursors prepared in examples 1 to 10
Group of | Visible light (550 nm) absorption slope |
Example 1 | 0.5529 |
Example 2 | 0.5534 |
Example 3 | 0.5601 |
Example 4 | 0.6311 |
Example 5 | 0.7526 |
Example 6 | 0.5621 |
Example 7 | 0.5472 |
Example 8 | 0.5637 |
Example 9 | 0.5702 |
Example 10 | 0.5527 |
Comparative example 1 | 0.0013 |
As can be seen from table 3, comparative example 1, in which anthraquinone diamine was not added, had an extremely low visible light absorption slope at 550nm, indicating that the polybenzoxazole precursor in which anthraquinone diamine was not added did not have the characteristic of absorbing visible light. The slope of the visible light absorption mainly depends on the feeding ratio of 1, 8-dihydroxyl-2, 4,5, 7-tetraminoanthraquinone in diamine monomers, but the ratio is not greatly related to the type of another diamine compound, the reaction solvent and the molecular weight of the polymer, and the higher the feeding ratio of 1, 8-dihydroxyl-2, 4,5, 7-tetraminoanthraquinone is, the stronger the absorbing capacity of the polybenzoxazole precursor to visible light at 550nm is.
Lithographic performance test
The photosensitive resin compositions prepared in example 1 and example 4 were subjected to pressure filtration to remove insoluble matters, and defoamed under vacuum to obtain a photosensitive resin composition solution, which was spin-coated on a silicon wafer, and then placed on a hot plate at 120 ℃ and pre-baked for 180s, and most of the solvent was volatilized to obtain a dry film. Exposing the dry film by adopting a stepping photoetching machine SSB320/10, wherein the exposure is 500-1500 mJ/cm 2 Developing with 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution for 40s times 2 times, and observing under microscopeAnd (3) a pattern.
The patterns after development by exposure using the photosensitive resin compositions of example 1 and example 4 are shown in fig. 3 and fig. 4, respectively. As is clear from the figures, the photosensitive resin compositions prepared in example 1 and example 4 showed no residual gum in the pattern holes, the opening size was consistent with the set size, and the pattern holes had a higher resolution (3. Mu. m@3. Mu.m, i.e., 3 μm openings with a film thickness of 3. Mu.m), and as a result, it was revealed that the polybenzoxazole precursor containing anthraquinone diamine had excellent lithographic properties.
Example 11
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured in an oxygen-free atmosphere at 300 ℃ and an oxygen content of less than 100ppm for 1 hour, to obtain cured PBO bars.
Example 12
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured in an oxygen-free atmosphere at 320 ℃ and an oxygen content of less than 100ppm for 1 hour, to obtain cured PBO bars.
Example 13
The photosensitive resin composition prepared in example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured in an oxygen-free atmosphere at 350 ℃ and an oxygen content of less than 100ppm for 1 hour, to obtain cured PBO bars.
Comparative example 2
The photosensitive resin composition prepared in comparative example 1 was subjected to film coating, baking, exposure, and development to prepare dumbbell-shaped bars, which were cured in an oxygen-free atmosphere at 350 ℃ and an oxygen content of less than 100ppm for 1 hour, to obtain cured PBO bars.
Cyclisation test
The PBO splines of examples 11-13 were tested in attenuated total reflection mode using a ThermoFisher technology Co., ltd. Nicolet iS5 type Fourier infrared spectrometer for cyclization degree verification. By measuring 1052cm -1 The cyclization ratio of the PBO membrane was monitored for the signal intensity of the c—o bond on the oxazole ring, and the cyclization ratio was obtained as shown in table 4 with the signal intensity of example 13 being 100% as the cyclization ratio. Cyclization ratio resultsIt is shown that the degree of cyclization of the examples of the present application has been near complete cure.
Mechanical property test
The tensile properties, thermal expansion coefficients and dynamic thermo-mechanical properties (DMA) of the PBO bars of examples 11 to 13 and comparative example 2 were tested, and the test results are shown in table 4.
Tensile property test: the tensile strength, young's modulus and elongation at break of the bars were characterized using a universal tensile machine of the type CMT-1104, mitsui electric equipments Co., ltd. In bead sea, the test was performed according to the Standard test method for Plastic tensile Property (ASTM-D638), and the stretching was performed at a stretching speed of 5mm/min until the bars break. The final data were averaged over 5 measurements.
TMA test: the Coefficient of Thermal Expansion (CTE) of the bars was characterized using a TA Instruments model Q400 static thermo-mechanical analyzer to determine their dimensional stability over the normal operating temperature range. In the stretching mode, the temperature was raised to 300℃in a nitrogen atmosphere at a temperature-raising rate of 30℃per minute and left for 5 minutes to eliminate residual thermal potential, followed by cooling to room temperature at the same rate, followed by a secondary temperature rise to 390℃at a temperature-raising rate of 5℃per minute. The static force is set to be 0.05N, and the final CTE value is 50-150 ℃.
DMA test: the glass transition temperature (Tg) of the bars was characterized using a dynamic thermo-mechanical analyzer model Q800 from TA Instruments ltd in the united states to determine their upper normal operating temperature limit. In the dynamic pull-up mode, the temperature was raised to 500℃in a nitrogen atmosphere at a temperature-raising rate of 5℃per minute, and the test frequency was set at 1Hz.
Table 4 mechanical properties test results for examples 11 to 13 and comparative example 2
Table 4 shows the mechanical properties of the anthraquinone diamine containing polybenzoxazole precursor prepared in example 1 at different curing temperatures and the mechanical properties of comparative example 2 at 350 c curing conditions. The results show that the polybenzoxazole precursor containing anthraquinone diamine has excellent mechanical properties.
Thermal performance testing
Thermal weight tests were performed on the PBO splines of examples 11 to 13 and comparative example 2, and the test results are shown in Table 5.
Stability of the instrumented materials was analyzed using a thermal gravimetric analysis model TGA55, incorporated by TA Instruments, USA. Weighing 10-15mg of sample, carefully placing in an alumina high-temperature crucible, heating to 120 ℃ at a heating rate of 20 ℃/min under nitrogen atmosphere, keeping for 10min to remove trace moisture contained in the sample, cooling to room temperature, heating to 800 ℃ at a heating rate of 10 ℃/min for a second time, and heating to a nitrogen pressure of not more than 0.1MPa. The test results are shown in Table 5.
Table 5 thermal performance test results for examples 11-13 and comparative example 2
Project | Curing temperature | Td1%(℃) | Td3%(℃) | Td5%(℃) |
Example 11 | 300℃ | 344.14 | 406.66 | 452.56 |
Example 12 | 320℃ | 362.35 | 423.62 | 466.59 |
Example 13 | 350℃ | 385.13 | 448.31 | 488.23 |
Comparative example 2 | 350℃ | 382.41 | 443.65 | 486.67 |
Table 5 shows the thermal performance test results of the anthraquinone diamine-containing polybenzoxazole precursor prepared in example 1 at different curing temperatures and the thermal performance test results of comparative example 2 at 350 ℃ curing conditions. From the test results, it was found that Td of the polybenzoxazole precursor increased with the increase of the curing temperature and all exceeded 250 ℃. Therefore, the polybenzoxazole precursor prepared by the embodiment of the application has excellent thermal properties, and meets the use requirements.
Chemical corrosion resistance test
Example 14
Spin-coating the photosensitive resin composition of example 1 on a silicon wafer, pre-baking for 180s at 120deg.C on a hot plate, volatilizing most of the solvent to obtain a dry film, exposing the dry film to light with a stepper SSB320/10 at an exposure dose of 500-1500 mJ/cm 2 Then, developing is carried out by using a TMAH (tetramethyl ammonium hydroxide) aqueous solution with the mass fraction of 2.38%, the development time is 40s times 2, and the uncured positive resin pattern is obtained after rinsing by using leacheate. The silicon wafer with the uncured positive resin pattern was placed in a nitrogen-protected air-blown oven (oxygenA concentration of 100ppm or less) was cured at 150℃for 30 minutes, followed by heating to 300℃and curing for 1 hour, to obtain a cured film.
Example 15
The silicon wafer with the uncured positive resin pattern of example 14 was placed in a nitrogen-protected air-blown oven (oxygen concentration of 100ppm or less) to be cured at 150 ℃ for 30min, followed by heating to 320 ℃ to be cured for 1h, to obtain a cured film.
Example 16
The silicon wafer with the uncured positive resin pattern of example 14 was placed in a nitrogen-protected air-blown oven (oxygen concentration of 100ppm or less) to be cured at 150 ℃ for 30min, followed by heating to 350 ℃ to be cured for 1h, to obtain a cured film.
Comparative example 3
Spin-coating the photosensitive resin composition of comparative example 1 on a silicon wafer, pre-baking for 180s at 120deg.C on a hot plate, volatilizing most of the solvent to obtain a dry film, exposing the dry film to light with a stepper SSB320/10 at an exposure dose of 500-1500 mJ/cm 2 Then, developing is carried out by using a TMAH (tetramethyl ammonium hydroxide) aqueous solution with the mass fraction of 2.38%, the development time is 20s times 2, and the uncured positive resin pattern is obtained after rinsing by using leacheate. The silicon wafer with the uncured positive resin pattern was placed in a nitrogen-protected air-blast oven (oxygen concentration below 100 ppm) to be cured at 150 ℃ for 30min, and then heated to 350 ℃ to be cured for 1h, to obtain a cured film.
The silicon wafers with cured films obtained in examples 14 to 16 and comparative example 3 were subjected to the respective organic reagents of acetone (25 ℃ C., 60 s), ammonia (25 ℃ C., 60 s), HCl (25 ℃ C., 60 s), H 2 SO 4 And H 2 O 2 Soaking the mixture (25 ℃ for 180 seconds) and N-methylpyrrolidone (25 ℃ for 30 minutes), washing with water, drying by blowing, measuring the change of film thickness before and after soaking the silicon wafer with the solidified film by using a film thickness meter, observing patterns by using an optical microscope, and evaluating the chemical corrosion resistance of the silicon wafer.
The chemical resistance was evaluated as a for the film thickness change of not more than 5% before and after immersion, as B for the film thickness change of not more than 5% before and after immersion, and as C for the film surface crack, pattern corner crack, pattern edge chemical penetration or peeling of the cured film from the substrate, and the test results can be seen in table 6.
TABLE 6 chemical resistance test results for examples 14-16 and comparative example 3
As can be seen from Table 6, the anthraquinone diamine-containing polybenzoxazole precursors prepared in the examples of this application have good chemical resistance.
Fig. 5 shows a 3D map of the film surface after soaking the cured film of example 14 in N-methyl pyrrolidone (25 ℃,30 min). As can be seen from fig. 5, the film surface was flat, no cracks were generated, and the cured film was proved to have excellent chemical resistance.
The embodiments are described above in order to facilitate the understanding and application of the present application by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications can be made to these embodiments and that the general principles described herein may be applied to other embodiments without the use of inventive faculty. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications without departing from the scope and spirit of the present application.
Claims (10)
1. A polybenzoxazole precursor formed by the reaction of a diamine monomer and a dicarboxylic acid monomer; wherein the diamine monomer comprises a diamine compound represented by formula (1):
Wherein R is 1 ~R 4 Respectively selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester group, phenyl and 4-aminophenylamino;
the dicarboxylic acid monomer has a structure represented by formula (2):
in formula (2), X is a divalent organic group that is an aliphatic group or an aromatic group; z is selected from hydroxyl or halogen groups.
2. The polybenzoxazole precursor according to claim 1 wherein X is a C6 to C48 aromatic group; preferably, the X isWherein A is selected from the group consisting of single bond, alkylene, -O-, -and->-S-、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 Represents a linkage to the carbonyl group in formula (2).
3. The polybenzoxazole precursor according to claim 1, wherein said dicarboxylic acid monomer is selected from the group consisting of a dicarboxylic acid having an aromatic ring, a dihalide of said dicarboxylic acid having an aromatic ring, a dicarboxylic acid ester of said dicarboxylic acid having an aromatic ring, an aliphatic dicarboxylic acid, a dihalide of said aliphatic dicarboxylic acid or a dicarboxylic acid ester of said aliphatic dicarboxylic acid; preferably, the method comprises the steps of, the dicarboxylic acid monomer is selected from isophthalic acid, terephthalic acid, 5-tertiary butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalene dicarboxylic acid, 4 '-dicarboxybiphenyl, 4' -dicarboxybiphenyl ether, 4 '-diacid chloride diphenyl ether, and 4, 4' -dicarboxyltetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 2-bis (4-carboxyphenyl) -1, 3-hexafluoropropane oxalic acid, malonic acid, succinic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid.
4. A polybenzoxazole precursor according to any of claims 1 to 3 where said diamine monomer further comprises a diamine compound represented by formula (3):
H2N—Y——NH2
(3)
In the formula (3), Y is a tetravalent organic group having at least two or more hydroxyl groups, the tetravalent organic group being an aliphatic group or an aromatic group; the tetravalent organic group is preferably an aromatic group.
5. The polybenzoxazole precursor according to claim 4 where Y is selected from the following tetravalent organic groups:
wherein one of 1 and 2 represents a linking moiety with an amino group in formula (3), and the other represents a linking moiety with a hydroxyl group in formula (3) Y.
6. The polybenzoxazole precursor as defined in claim 4 which has a structural formula shown in formula (4):
in the formula (4), m is 1 to 100, n is 0 to 100, preferably, m is 1 to 40, and n is 15 to 40.
7. A process for preparing a polybenzoxazole precursor according to any of claims 1 to 6 including the steps of:
s1: dissolving diamine monomer in a first solvent to obtain diamine monomer solution, wherein the mole percentage of diamine compound shown in formula (1) in the diamine monomer is 0.1% -100%;
S2: and (3) adding a dicarboxylic acid monomer shown in the formula (2) into the diamine monomer solution, and performing polymerization reaction to obtain a polybenzoxazole precursor solution.
8. The production method according to claim 7, wherein the first solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1, 3-dimethyl-2-imidazolidinone, γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate;
and/or, step S2 satisfies one of the following conditions: 1) Adding dicarboxylic acid monomers shown in the formula (2) under the ice bath condition of 0-10 ℃, wherein the polymerization reaction temperature is 0-35 ℃ and the polymerization reaction time is 2-10 hours; 2) The molar ratio of the diamine monomer to the dicarboxylic acid monomer represented by the formula (2) is 1 (0.5-1).
9. The method of manufacturing according to claim 7, further comprising:
step S3: adding a blocking agent into the polybenzoxazole precursor solution to carry out a blocking reaction to obtain a blocked polybenzoxazole precursor solution, wherein the blocking reaction at least meets one of the following conditions: a. the mole ratio of the end-capping agent to the diamine monomer is (0.02-0.2): 1; b. the temperature of the end capping reaction is 10-35 ℃ and the time is 1-4 hours; preferably, the end-capping agent is selected from at least one of Phthalic Anhydride (PA), maleic Anhydride (MA), succinic anhydride, 2, 3-pyrazinedicarboxylic anhydride, tetrafluorophthalic anhydride, 2, 3-naphthalenedicarboxylic anhydride, hexahydrophthalic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, 4-phenylalkynyl phthalic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, phenylsuccinic anhydride, 2' -biphenyldicarboxylic anhydride;
step S4: and (3) dripping the system obtained in the step (S2) or the step (S3) into deionized water, and cleaning and drying the precipitate to obtain the dried polybenzoxazole precursor.
10. A photosensitive resin composition is characterized by comprising the following components in parts by weight: 100 parts of the polybenzoxazole precursor according to any of claims 1 to 6, 5 to 40 parts of a sensitizer and 30 to 10000 parts of a second solvent; preferably, the photosensitizer comprises at least one of photoacid generator, photobase generator, crosslinking agent, thermal acid generator, sensitizer, thickener, surfactant, leveling agent, and fine particles; preferably, the second solvent includes at least one of N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether.
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