CN116774524A - Photosensitive resin composition, method for producing pattern cured product, and use thereof - Google Patents
Photosensitive resin composition, method for producing pattern cured product, and use thereof Download PDFInfo
- Publication number
- CN116774524A CN116774524A CN202310776772.3A CN202310776772A CN116774524A CN 116774524 A CN116774524 A CN 116774524A CN 202310776772 A CN202310776772 A CN 202310776772A CN 116774524 A CN116774524 A CN 116774524A
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- CN
- China
- Prior art keywords
- group
- carbon atoms
- photosensitive resin
- resin composition
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 diazonaphthoquinone compound Chemical class 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 47
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 37
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000004642 Polyimide Substances 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000000962 organic group Chemical group 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000004185 ester group Chemical group 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000005354 acylalkyl group Chemical group 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000004427 diamine group Chemical group 0.000 claims description 10
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-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 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- RGVHBPPWCQVMDR-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 RGVHBPPWCQVMDR-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 claims description 3
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 description 43
- 238000003786 synthesis reaction Methods 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- 230000035882 stress Effects 0.000 description 13
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 238000006352 cycloaddition reaction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920001955 polyphenylene ether Polymers 0.000 description 8
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 229960000956 coumarin Drugs 0.000 description 6
- 235000001671 coumarin Nutrition 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- RRHXPUCIXLAHIY-UHFFFAOYSA-N 7-aminochromen-2-one Chemical compound C1=CC(=O)OC2=CC(N)=CC=C21 RRHXPUCIXLAHIY-UHFFFAOYSA-N 0.000 description 5
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 6-hydroxychromen-2-one Chemical compound O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RIUPLDUFZCXCHM-UHFFFAOYSA-N Urolithin A Chemical compound OC1=CC=C2C3=CC=C(O)C=C3OC(=O)C2=C1 RIUPLDUFZCXCHM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 229940018563 3-aminophenol Drugs 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ketene group Chemical group C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- XGQJGMGAMHFMAO-UHFFFAOYSA-N 1,3,4,6-tetrakis(methoxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound COCN1C(=O)N(COC)C2C1N(COC)C(=O)N2COC XGQJGMGAMHFMAO-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KPDMOOCRWQNXAI-UHFFFAOYSA-N 1,5-diaminocyclohexa-2,4-diene-1-carboxylic acid Chemical compound NC1=CC=CC(N)(C(O)=O)C1 KPDMOOCRWQNXAI-UHFFFAOYSA-N 0.000 description 1
- FHMMQQXRSYSWCM-UHFFFAOYSA-N 1-aminonaphthalen-2-ol Chemical compound C1=CC=C2C(N)=C(O)C=CC2=C1 FHMMQQXRSYSWCM-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- UZSDRHVOBLQYCX-UHFFFAOYSA-N 2-amino-6-hydroxybenzoic acid Chemical compound NC1=CC=CC(O)=C1C(O)=O UZSDRHVOBLQYCX-UHFFFAOYSA-N 0.000 description 1
- CXOWHCCVISNMIX-UHFFFAOYSA-N 2-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(N)=CC=C21 CXOWHCCVISNMIX-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LIBFVQBAZPYQCJ-UHFFFAOYSA-N 2-oxaspiro[3.4]octane-1,3-dione Chemical compound O=C1OC(=O)C11CCCC1 LIBFVQBAZPYQCJ-UHFFFAOYSA-N 0.000 description 1
- HHCHLHOEAKKCAB-UHFFFAOYSA-N 2-oxaspiro[3.5]nonane-1,3-dione Chemical compound O=C1OC(=O)C11CCCCC1 HHCHLHOEAKKCAB-UHFFFAOYSA-N 0.000 description 1
- KCCUBRRTVWFOGF-UHFFFAOYSA-N 2-tritylphenol Chemical compound OC1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KCCUBRRTVWFOGF-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- QMAQHCMFKOQWML-UHFFFAOYSA-N 3-[2-[2-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)S(=O)(=O)C=2C(=CC=CC=2)OC=2C=C(N)C=CC=2)=C1 QMAQHCMFKOQWML-UHFFFAOYSA-N 0.000 description 1
- BYHMLZGICSEKIY-UHFFFAOYSA-N 3-amino-2-methylbenzoic acid Chemical compound CC1=C(N)C=CC=C1C(O)=O BYHMLZGICSEKIY-UHFFFAOYSA-N 0.000 description 1
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- YIPRQTYMJYGRER-UHFFFAOYSA-N 3-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=CC(N)=CC(C(O)=O)=C21 YIPRQTYMJYGRER-UHFFFAOYSA-N 0.000 description 1
- OCISOSJGBCQHHN-UHFFFAOYSA-N 3-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(O)=CC2=C1 OCISOSJGBCQHHN-UHFFFAOYSA-N 0.000 description 1
- RSFDFESMVAIVKO-UHFFFAOYSA-N 3-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S)=C1 RSFDFESMVAIVKO-UHFFFAOYSA-N 0.000 description 1
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- ABJQKDJOYSQVFX-UHFFFAOYSA-N 4-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=C1 ABJQKDJOYSQVFX-UHFFFAOYSA-N 0.000 description 1
- HZVWUBNSJFILOV-UHFFFAOYSA-N 4-aminonaphthalen-2-ol Chemical compound C1=CC=C2C(N)=CC(O)=CC2=C1 HZVWUBNSJFILOV-UHFFFAOYSA-N 0.000 description 1
- GTCAZWRERBLCFJ-UHFFFAOYSA-N 4-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(N)=CC=C(C(O)=O)C2=C1 GTCAZWRERBLCFJ-UHFFFAOYSA-N 0.000 description 1
- BSAWDWUYBRFYFY-UHFFFAOYSA-N 4-aminoquinolin-8-ol Chemical compound C1=CC=C2C(N)=CC=NC2=C1O BSAWDWUYBRFYFY-UHFFFAOYSA-N 0.000 description 1
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- PSAGPCOTGOTBQB-UHFFFAOYSA-N 4-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(O)C2=C1 PSAGPCOTGOTBQB-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 description 1
- NKKQTHYUNYPWNL-UHFFFAOYSA-N 5-amino-5-methylcyclohexa-1,3-diene-1-carboxylic acid Chemical compound CC1(N)CC(C(O)=O)=CC=C1 NKKQTHYUNYPWNL-UHFFFAOYSA-N 0.000 description 1
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 description 1
- FSBRKZMSECKELY-UHFFFAOYSA-N 5-aminonaphthalen-2-ol Chemical compound OC1=CC=C2C(N)=CC=CC2=C1 FSBRKZMSECKELY-UHFFFAOYSA-N 0.000 description 1
- FPKNJPIDCMAIDW-UHFFFAOYSA-N 5-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(N)=CC=CC2=C1C(O)=O FPKNJPIDCMAIDW-UHFFFAOYSA-N 0.000 description 1
- YDEUKNRKEYICTH-UHFFFAOYSA-N 5-aminoquinolin-8-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=N1 YDEUKNRKEYICTH-UHFFFAOYSA-N 0.000 description 1
- NYYMNZLORMNCKK-UHFFFAOYSA-N 5-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1O NYYMNZLORMNCKK-UHFFFAOYSA-N 0.000 description 1
- CKSZZOAKPXZMAT-UHFFFAOYSA-N 6-aminonaphthalene-1-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(N)=CC=C21 CKSZZOAKPXZMAT-UHFFFAOYSA-N 0.000 description 1
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 1
- BFBAHPDPLUEECU-UHFFFAOYSA-N 7-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=CC(N)=CC=C21 BFBAHPDPLUEECU-UHFFFAOYSA-N 0.000 description 1
- XABCHXCRWZBFQX-UHFFFAOYSA-N 7-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=C(O)C=C2C(C(=O)O)=CC=CC2=C1 XABCHXCRWZBFQX-UHFFFAOYSA-N 0.000 description 1
- XSECDQPYFOEVPU-UHFFFAOYSA-N 7-nitrochromen-2-one Chemical compound C1=CC(=O)OC2=CC([N+](=O)[O-])=CC=C21 XSECDQPYFOEVPU-UHFFFAOYSA-N 0.000 description 1
- HMNPDEGBVWDHAR-UHFFFAOYSA-N 8-aminonaphthalen-1-ol Chemical compound C1=CC(O)=C2C(N)=CC=CC2=C1 HMNPDEGBVWDHAR-UHFFFAOYSA-N 0.000 description 1
- KVHHMYZBFBSVDI-UHFFFAOYSA-N 8-aminonaphthalen-2-ol Chemical compound C1=C(O)C=C2C(N)=CC=CC2=C1 KVHHMYZBFBSVDI-UHFFFAOYSA-N 0.000 description 1
- OXTCGCGDPOLJDV-UHFFFAOYSA-N 8-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(N)=CC=CC2=C1 OXTCGCGDPOLJDV-UHFFFAOYSA-N 0.000 description 1
- SHOOSJLGRQTMFC-UHFFFAOYSA-N 8-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC(O)=C2C(C(=O)O)=CC=CC2=C1 SHOOSJLGRQTMFC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- RCYOFSOASDZELB-UHFFFAOYSA-N dimethoxymethylsilyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)O[SiH2]C(OC)OC RCYOFSOASDZELB-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 1
- 229960004963 mesalazine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FOQWWRAMUUWXFI-UHFFFAOYSA-N n,n-bis(methoxymethyl)-1,3,5-triazin-2-amine Chemical class COCN(COC)C1=NC=NC=N1 FOQWWRAMUUWXFI-UHFFFAOYSA-N 0.000 description 1
- JDDAMKOBLWFNCZ-UHFFFAOYSA-N n-(2-trimethoxysilylethyl)aniline Chemical compound CO[Si](OC)(OC)CCNC1=CC=CC=C1 JDDAMKOBLWFNCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003462 sulfoxides Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a photosensitive resin composition, a method for producing a pattern cured product, a cured product and application thereof. The photosensitive resin composition comprises: (A) a polyimide precursor resin containing a hydroxyl group, (B) a macromolecular crosslinking agent, (C) a diazonaphthoquinone compound, and (D) a solvent; the component (B) has a structure shown in the following formula 1:in the formula (1), R 5 A 2-valent organic group having 1 to 20 carbon atoms and optionally containing an alicyclic and/or aromatic ring or other hetero atom; r is R 6 A 2-valent organic group which represents a carbon number of 0 to 30 and may contain an alicyclic and/or aromatic ring and other hetero atoms; r is R 7 And R is 8 represents-OH, -COOH or an ester group having 2 to 4 carbon atoms; r is R 9 Represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or an acylalkyl group; x+y is greater than or equal to 1, z is greater than or equal to 2, s and t are positive integers. The photosensitive resin composition has high sensitivity, and the obtained cured film has low stress, high cohesiveness, high elongation, and is combined with a substrateThe adhesion of the material was excellent.
Description
Technical Field
The invention relates to the technical field of photosensitive resin materials, in particular to a photosensitive resin composition, a manufacturing method of a pattern cured film, a cured film and application thereof.
Background
Conventionally, with the development of display light emitting elements and semiconductor elements, a surface protective film for semiconductor elements, an interlayer insulating film, a planarizing film for TFT substrates, a pixel defining layer, and the like are required to have resolution and high sensitivity of μm or less. Resin compositions such as photosensitive polyimide, polybenzoxazole, and phenol resins, which have excellent heat resistance and electrical insulation, have been widely used in this field.
There have been reported photosensitive resin compositions in which heat resistance is improved by using a compound having 2 or more alkoxymethyl groups or hydroxymethyl groups. However, in recent years, with the high integration of semiconductors and display devices, miniaturization and enlargement of the base size, there is a need to reduce thermal stress applied to the semiconductors and display devices during production and manufacturing processes, and to reduce warpage of substrates due to the thickening of insulating materials. These materials have a problem that the substrate warpage becomes large because of a high film shrinkage rate at the time of high-temperature curing and a high stress to the substrate, and thus, the problem has not been solved well.
In view of this, a method of reducing warpage by introducing a flexible group into a polyimide main chain to suppress stress generated when a cured film is produced has been reported in the prior art, but there is a problem that thermal properties and mechanical properties of the cured film material are lowered. When applied to semiconductors and display devices, the film material is reserved as a permanent film in the device, and the thermal performance and mechanical performance of the cured film material are very important. Meanwhile, in order to ensure the reliability of the device package, the connectivity between the cured film material and the substrate is very important, especially in the case of applications such as an insulating film between wiring layers for wafer level packaging. Since the heat-resistant material is generally a rigid main chain structure, and a photosensitizer, a dissolution regulator, an acid generator, and the like contained in the photosensitive composition thereof remain after curing, the connectivity of the resulting cured film to the substrate is often not ideal.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a photosensitive resin composition with low stress, high cohesiveness, good adhesion and high sensitivity for a cured film.
To achieve the above object, a first aspect of the present invention provides a photosensitive resin composition comprising:
(A) A polyimide precursor resin containing hydroxyl groups;
(B) Macromolecular crosslinking agent with molecular weight 600< Mw <4000 and solubility 1-10g/100g in 2.38wt% TMAH;
(C) Diazonaphthoquinone compounds;
(D) A solvent;
the macromolecular crosslinking agent component (B) is a compound shown in a structural formula (1):
in the formula (1), R 5 A 2-valent organic group having 1 to 20 carbon atoms and containing an alicyclic ring and/or aromatic ring and other hetero atoms; r is R 6 A 2-valent organic group having 0 to 30 carbon atoms and containing an alicyclic ring and/or aromatic ring and other hetero atoms; r is R 7 And R is 8 represents-OH, -COOH or an ester group having 2 to 4 carbon atoms; r is R 9 Represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or an acylalkyl group; x+y is more than or equal to 1, z is more than or equal to 2, s and t are positive integers;
the (A) hydroxyl group-containing polyimide precursor resin has a structural unit represented by the following structural formula (2):
in the formula (2), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, and R 1 Represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
Further, D in the structural formula (2) represents a diamine residue comprising one or more combinations of the following structural formula (3):
in the formula (3), R 1 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R 2 Represents alkyl, alkoxy, hydroxy, carboxyl, fluorine, chlorine and bromine substituent groups with 1-3 carbon atoms; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine or bromine; s represents a linking group, which is a tetravalent linking group having 0 to 30 carbon atoms and containing alicyclic and/or aromatic rings and other hetero atoms; r is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, other 2-valent organic groups with 1 to 10 carbon atoms or 2-valent organic groups formed by bonding more than 2 of the above groups; p represents an integer of 0 to 2, and q represents an integer of 0 to 1.
Preferably, D in formula (2) represents a combination comprising one or more of the following diamine residues as shown in formula (4):
in the formula (4), R 1 An alkyl group having 1 to 3 carbon atoms and a hydrogen atom; r is R 2 Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine, or bromine; p represents an integer of 0 to 2.
Further, Q in the structural formula (2) represents a combination comprising one or more of the following dianhydride residues corresponding to tetracarboxylic dianhydrides: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 3',4' -tetracarboxylic diphenyl ether dianhydride, 3',4' -tetracarboxylic benzophenone dianhydride, 3',4,4' -tetracarboxylic acid diphenyl sulfonyl dianhydride, 4' -hexafluoroisopropyl phthalic anhydride (6 FDA), 4' -isopropyl phthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutane tetracarboxylic dianhydride (CBDA), cyclohexane tetracarboxylic dianhydride.
Preferably, in the macromolecular crosslinking agent having a structure represented by the above formula (1), R 5 Is one or more of the following structural formulas (5):
further, the amount of the macromolecular crosslinking agent to be used is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the hydroxyl group-containing polyimide precursor resin (a).
A second aspect of the present invention provides a method for producing a pattern cured product, comprising the steps of forming a pattern having a resin coating layer using the photosensitive resin composition, comprising:
Step one: coating the photosensitive resin composition on a substrate to form a photosensitive resin coating, and pre-baking the photosensitive resin coating on a hot plate at 80-120 ℃ for 2-60min to form a photosensitive coating;
step two: exposing the photosensitive film by using an exposure mask plate;
step three: removing the exposed part of the photosensitive film by using an alkaline developer, and developing;
step four: curing the developed film at a temperature of 100-300 ℃ to obtain a cured film.
The third aspect of the present invention provides a cured product prepared from the photosensitive resin composition described above, which is a pattern cured product.
A fourth aspect of the present invention provides use of a cured product applied to an insulating layer, a pixel defining layer, a planarizing layer, or/and a surface protecting layer, an insulating layer of a semiconductor device of an organic electroluminescent element.
Compared with the prior art, the invention has the following beneficial effects: the high-sensitivity photosensitive resin composition provided by the invention adopts the structure shown in the formula (1) as a macromolecular crosslinking agent, and is matched with polyimide precursor resin containing hydroxyl and a photosensitizer, so that the sensitivity is improved, and meanwhile, excellent characteristics such as chemical resistance, low stress and the like of a cured film can be provided; the macromolecular crosslinking agent contains ether bonds, and after thermal crosslinking reaction with resin, a compact and stable crosslinked network structure is obtained, so that the adhesiveness, thermal stability, mechanical strength and other properties of the cured film can be greatly improved, and the adhesiveness between the film layer and the base material is improved.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
< photosensitive resin composition >
The photosensitive resin composition of the present invention contains (a) a polyimide precursor resin containing a hydroxyl group, (B) a macromolecular crosslinking agent, (C) a diazonaphthoquinone compound, and (D) a solvent, and the respective components constituting the photosensitive resin composition will be specifically described below.
(A) Polyimide precursor resin containing hydroxyl group
In the present invention, (a) the hydroxyl group-containing polyimide resin precursor is an alkali-soluble resin, and in the present invention, alkali-solubility means: coating resin dissolved in solvent or mixed solvent on silicon wafer or glass sheet, baking at 120deg.C for 3min to form pre-baked film with thickness of 10 μm + -0.5 μm; the pre-baked film was developed in 2.38wt% aqueous tetramethylammonium hydroxide (TMAH) solution for 60s, followed by water washing for 30s, and the surface water stain was dried, and the alkali-solubility of the pre-baked film was obtained according to the film reduction at this time.
In the present invention, (a) the polyimide in the polyimide precursor resin containing a hydroxyl group is not particularly limited as long as it has a polyimide ring, and the polyimide precursor is not particularly limited as long as it has a polyimide structure having an imide ring by dehydration ring closure; the hydroxyl group-containing polyimide precursor resin of the present invention has a structural unit represented by the following structural formula (2):
in the formula (2), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, and R 1 Represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
The polyimide resin precursor (A) containing hydroxyl groups in the present invention is obtained by reacting a diamine compound with a tetracarboxylic dianhydride under certain conditions.
In the invention, at least 1 diamine compound has a molecular structure containing hydroxyl; further, D in the structural formula (2) represents a diamine residue comprising one or more combinations of the following structural formula (3):
in the formula (3), R 1 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R 2 Represents alkyl, alkoxy, hydroxy, carboxyl, fluorine, chlorine and bromine substituent groups with 1-3 carbon atoms; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine or bromine; s represents a linking group, which is a tetravalent linking group having 0 to 30 carbon atoms and containing alicyclic and/or aromatic rings and other hetero atoms; r is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, or other 2-valent organic group having 1 to 10 carbon atoms, or it More than 2 of them are bonded to form a 2-valent organic group; p represents an integer of 0 to 2, and q represents an integer of 0 to 1.
The diamine compound containing hydroxyl is favorable for enhancing the solubility of the photosensitive resin in alkaline aqueous developer, and ensures that alkaline aqueous developer such as TMAH aq, naOH aq and Na are used 2 CO 3 aq, etc., the resin in the exposed area after exposure can be washed off completely, so as to reduce the influence of residue and improve the exposure sensitivity. The inventors have found that the macromolecular crosslinking agent of the present invention is blended with a hydroxyl group-containing polyimide resin precursor composed of diamine of the structure of formula (3), and that the photosensitive resin has high sensitivity, high elongation and low stress after film formation, and excellent heat and chemical resistance.
In the present invention, at least 1 diamine compound has a hydroxyl group in its molecular structure, and preferably, D in the structural formula (2) represents a diamine residue comprising one or more combinations of the following diamine residues represented by the structural formula (4):
in the formula (4), R 1 An alkyl group having 1 to 3 carbon atoms and a hydrogen atom; r is R 2 Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine, or bromine; p represents an integer of 0 to 2.
The diamine compound containing alicyclic ring and/or aromatic ring is beneficial to improving the mechanical property of the photosensitive resin, the diamine compound containing functional groups such as sulfonyl, sulfoxide, siloxane bond, hexafluoropropyl and the like is beneficial to improving the light transmittance of the photosensitive resin, and the diamine compound containing the ether group and the siloxane bond is beneficial to improving the adhesiveness of the photosensitive resin.
The diamine compound of the present invention further comprises a conventional diamine compound in the art, which is directly available commercially or directly available through other routes, that is, D in the above structural formula (2) represents a combination of one or more of the diamine residues corresponding to the following diamine compound: p-phenylenediamine, m-phenylenediamine, 3-carboxym-phenylenediamine, 3-hydroxy-m-phenylenediamine benzidine, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfide, 4 '-diaminodiphenyl sulfide, 1, 4-di (4-aminophenoxy) benzene bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, 1, 4-bis (4-aminophenoxy) benzene, 3' -dimethyl-4, 4 '-diaminobiphenyl 2,2' -dimethyl-4, 4 '-diaminobiphenyl, 2' -di (trifluoromethyl) -4,4 '-diaminobiphenyl, 2, 3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4,4 '-tetramethyl-4, 4' -diaminobiphenyl, and cycloalkyl-and halogen-substituted aromatic compounds.
Preferably, the conventional diamine compound of the present invention comprises 4,4 '-diaminodiphenyl ether, i.e., D in the above structural formula (2) represents a diamine residue corresponding to the 4,4' -diaminodiphenyl ether.
Although the reactant for synthesizing the hydroxyl group-containing polyimide precursor resin (a) in the present invention contains the above-mentioned conventional diamine compound, the functional compound in the reactant for synthesizing the hydroxyl group-containing polyimide precursor resin in the present invention is mainly a diamine compound corresponding to the diamine residue represented by the structural formula (3), the content of which is 10mol% or more, preferably 50mol% or more, and the introduction of the structural compound is advantageous in improving the exposure development effect, heat resistance and mechanical properties of the resin.
The tetracarboxylic dianhydride used in the present invention is not limited in structure, and any tetracarboxylic dianhydride conventional in the art can be used.
In order to obtain a polyimide resin precursor having excellent heat resistance, it is preferable that an aromatic ring or an aromatic heterocyclic ring-containing organic group, that is, Q in the above structural formula (2) represents a combination comprising one or more of the dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 3',4' -tetracarboxylic diphenyl ether dianhydride, 3',4' -tetracarboxylic benzophenone dianhydride, 3',4,4' -tetracarboxylic acid diphenyl sulfonyl dianhydride, 4' -hexafluoroisopropyl phthalic anhydride (6 FDA), 4' -isopropyl phthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutane tetracarboxylic dianhydride (CBDA), cyclohexane tetracarboxylic dianhydride.
In the present invention, in order to ensure proper solubility of the polyimide precursor resin in an alkaline developer and good heat resistance and elongation of the resin after heat treatment, the number of repeating units of the structural unit is preferably in the range of 10 to 1000, more preferably 20 to 500, particularly preferably 50 to 200; wherein the proportion of the hydroxyl-containing repeating units relative to all the repeating units is preferably between 5% and 100%, more preferably between 40% and 80%; the dissolution rate of the resin in the alkaline developer is controlled by adjusting the proportion of hydrophilic hydroxyl groups in the resin structure relative to hydrophobic groups of the resin, namely aromatic groups and alkane groups, and the dissolution rate of the unexposed film in the alkaline developer is 10-3000 nm/min by matching with a photosensitizer, and the dissolution rate of the film in the alkaline developer after exposure is 200-50000 nm/min.
In the present invention, the weight average molecular weight Mw and the number average molecular weight Mn of the hydroxyl group-containing polyimide precursor resin (A) are measured as values in terms of polystyrene by Gel Permeation Chromatography (GPC), light scattering method, small angle X-ray scattering method, or the like.
In addition, in order to better adjust the molecular weight of the hydroxyl group-containing polyimide precursor resin of the present invention, a certain end-capping agent may be added at the time of polymerization, and specific examples thereof may be, but are not limited to, one or more combinations of the following exemplified compounds:
Monofunctional aromatic amines: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4, 6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline.
Monofunctional aromatic anhydrides: anhydride such as maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride and cyclopentane dicarboxylic anhydride.
Monofunctional aromatic acids: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.
The above-mentioned end-capping agent is added in a proportion of 0.005 to 0.5, further 0.01 to 0.4, based on the molar total of all diamine compounds and tetracarboxylic dianhydrides added; in the above range, a resin composition having a moderate solution viscosity and excellent film properties can be obtained.
(B) Macromolecular crosslinking agent
The macromolecular crosslinking agent is one of the key points of the invention, and contains ether bonds, so that when the photosensitive resin is subjected to heat treatment, the macromolecular crosslinking agent can form a crosslinked structure among the resins, thereby not only reducing the shrinkage rate of the film during curing, but also greatly improving the performances of adhesiveness, thermal stability, mechanical strength, chemical resistance and the like of the cured film, and the bonding reliability and the adhesion between the film layer and the substrate.
The macromolecular crosslinking agent used in the invention is a compound which is shown in the structural formula (1) and contains hydroxyl, carboxyl or ester groups in the molecule; a molecular weight 600< Mw <4000, a solubility in 2.38wt% TMAH of 1-10g/100g;
in the formula (1), R 5 A 2-valent organic group having 1 to 20 carbon atoms and containing an alicyclic ring and/or aromatic ring and other hetero atoms; r is R 6 A 2-valent organic group having 0 to 30 carbon atoms and containing an alicyclic ring and/or aromatic ring and other hetero atoms; r is R 7 And R is 8 represents-OH, -COOH or an ester group having 2 to 4 carbon atoms; r is R 9 Represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or an acylalkyl group; x+y is more than or equal to 1, z is more than or equal to 2, s and t are positive integers;
the macromolecular crosslinking agent contains hydroxyl, carboxyl or ester groups, so that the solubility of the resin in alkaline aqueous developer can be enhanced, and the exposure sensitivity can be improved. The solubility of the macromolecular crosslinking agent in 2.38wt% TMAH is 1-10g/100g, when the solubility is less than 1g/100g, the required exposure amount for forming a cured film is large, and when the solubility is more than 10g/100g, the residual film of the composition film after heat treatment is poor.
The macromolecular crosslinking agent of the invention firstly carries out nucleophilic substitution reaction on a compound containing dihydroxyl and coumarin, 2, 6-dimethyl-1, 4-benzenediol and a compound containing difluoro, dibromo or dichloro to obtain a random copolymerization polyphenyl ether solid; then dissolving polyphenyl ether solid in a solvent, adding AIBN and NBS, stirring for reaction, separating an organic phase, washing, filtering and drying to obtain benzyl brominated polyphenyl ether; and finally, dissolving benzyl brominated polyphenyl ether solid in a solvent, adding sodium methoxide or NaOH, stirring for reaction, adjusting the pH to about 5-6, filtering, washing with water, and drying to obtain the final macromolecular crosslinking agent.
Further, in the macromolecular crosslinking agent having a structure represented by the above formula (1), R 5 Is one or more of the following structural formulas (5):
the macromolecular crosslinking agent may be used alone or in combination of 2 or more. The inventors have found through extensive studies that the alkyl flexible chain in formula (5) not only provides low stress characteristics to the cured film but also improves the adhesion reliability and the adhesiveness of the film, and that the alicyclic and/or aromatic ring-containing compound contributes to improvement of mechanical properties and heat resistance of the cured film.
For the macromolecular crosslinking agent of the present invention, the molecular weight of the macromolecular crosslinking agent should be greater than 600 in order to provide better low stress, mechanical properties and chemical resistance to the film, and the molecular weight of the crosslinking agent should be less than 4000 in order to maintain the exposure sensitivity of the film. In order to improve mechanical properties and heat resistance, the content of the macromolecular crosslinking agent is preferably 0.1 part or more per 100 parts by mass of the resin, and in order to maintain low stress of the film, adhesion reliability and adhesion between the film layer and the substrate, the content of the macromolecular crosslinking agent is preferably 20 parts or less, and the amount of the macromolecular crosslinking agent of the present invention is preferably 0.1 to 20 parts by mass.
(C) Diazonaphthoquinone compound
The diazonaphthoquinone compound contained in the photosensitive resin composition of the present invention is an esterified diazonaphthoquinone compound, and by adding the esterified diazonaphthoquinone compound, a positive pattern in which the exposed portion is removed by an alkaline developer can be formed.
Esterified diazonaphthoquinone compounds, specifically photosensitizers formed by ester bond connection of polyhydroxy phenol compounds and 4-or 5-diazonaphthoquinone groups; when ultraviolet light irradiates the compound, diazonaphthoquinone groups undergo degradation rearrangement to generate an ketene structure, and the ketene structure reacts with water to generate indene acid, so that the dissolution rate is converted, and the conversion is realized as shown in the following reaction formula. The functional groups of these polyhydroxy compounds may not be entirely substituted with diazonium quinone, but from the viewpoint of contrast of the exposed portion and the unexposed portion, it is preferable that 60 mol% or more of the entire functional groups are substituted with diazonium quinone. By using the diazonaphthoquinone compound, a positive photosensitive resin composition that is sensitive to light at the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a conventional ultraviolet mercury lamp can be obtained.
Among them, polyhydric phenol compounds used for preparing the photosensitizer include, but are not limited to, bisphenol a, bisphenol AF, bisphenol AP, naphthol, trihydroxybenzophenone, fluorenyl-containing phenol, trityl phenol, phenolic resin oligomer, and the like. They can be used alone or in combination. The amount of the diazonaphthoquinone compound added is 0.01 to 0.70, more preferably 0.05 to 0.50, relative to the mass of the hydroxyl group-containing polyimide precursor resin used.
(D) Solvent(s)
The solvent used in the photosensitive resin composition is a solvent with a boiling point lower than 230 ℃, and the solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide, gamma-butyrolactone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol, N-butanol, cyclohexanone, ethyl lactate and butyl lactate; the amount of the solvent to be added is 3 to 50 times, more preferably 3 to 20 times, the mass of the hydroxyl group-containing polyimide precursor resin.
(E) Other additives
The photosensitive composition of the present invention may further contain an epoxy resin in terms of film physical properties such as bending resistance, wherein the epoxy resin is preferably bisphenol a epoxy resin or bisphenol F epoxy resin, and the amount of the epoxy resin added is preferably 0 to 0.2 relative to the mass of the hydroxyl group-containing polyimide precursor resin.
In order to improve the adhesiveness of the resin film forming and the substrate, the photosensitive resin composition provided by the embodiment of the invention further comprises an adhesion promoter and a surfactant; wherein the adhesion promoter is preferably a silane coupling agent to improve the adhesion of the film to the substrate during development and inhibit pattern peeling during development, preferably comprising one or more combinations of methacryloxydimethoxymethylsilane, 3-aminopropyl trimethoxysilane, vinyl triacyloxy silane, N-phenylaminoethyl trimethoxysilane, and the like; the addition amount of the adhesion promoter is preferably 0.001 to 0.2 relative to the mass of the hydroxyl group-containing polyimide precursor resin;
The surfactant selected in the invention is fluorine-containing surfactant, silicon-containing surfactant and acrylic ester surfactant; the amount of the surfactant added is 0.0003 to 0.05 relative to the mass of the hydroxyl group-containing polyimide precursor resin.
< method for producing a cured Pattern Using a photosensitive resin composition >
A second aspect of the present invention provides a method for producing a pattern cured product, comprising the steps of:
step one: coating the photosensitive resin composition on a substrate to form a photosensitive resin coating, and pre-baking the photosensitive resin coating on a hot plate at 80-120 ℃ for 2-60min to form a photosensitive coating;
step two: exposing the photosensitive film by using an exposure mask plate;
step three: removing the exposed part of the photosensitive film by using an alkaline developer, and developing;
step four: curing the developed film at a temperature of 100-300 ℃ to obtain a cured film.
First, in step one, a photosensitive resin is coated on a substrate to have a uniform thickness, and examples of the substrate may include a substrate, a silicon wafer, a base material having a metal coating on the surface thereof by ion sputtering or electroplating, and the like; the coating mode can be dip coating, spin coating, roller coating, slit coating, spray coating and the like, and the methods can be combined; in order to make the thickness of the coating more uniform, the invention can adopt a glue homogenizing machine to control the uniform film thickness, but is not limited to the method. The film is preferably formed by prebaking under 80-120deg.C hot plate for 2-60min.
The second and third steps are exposure development steps, wherein exposure radiation preferably has a wavelength of 190nm to 500nm, and the exposure dose is 10-5000mJ/cm 2 。
And step four, curing the patterned resin film, wherein the curing process, particularly the temperature change under high temperature conditions, has a great influence on the crosslinking degree of the resin film, and also directly influences the properties of the cured film, such as heat resistance, mechanical strength and the like. The invention cures the developed film at a temperature of 100-300 ℃ to obtain a cured film.
The most preferred embodiments are: and (3) placing the developed film under a nitrogen flow at 100 ℃, heating to 270-300 ℃ at a heating rate of 1-10 ℃/min, solidifying at 270-300 ℃ for 60-100min, naturally cooling to a room of 25 ℃, and separating the coating film from the substrate to obtain the solidified film.
< cured product >
A third aspect of the present invention provides a cured product formed from the photosensitive resin composition, which is a pattern cured product.
< application of cured product >
The photosensitive resin film of the present invention exhibits excellent heat resistance, chemical resistance, low stress property and low thermal expansion coefficient property, and thus can be applied to a surface protective film of a semiconductor element, an interlayer insulating film, an insulating film of an organic electroluminescent element, and the like.
The above and other advantages of the present invention will be better understood by the following examples, which are not intended to limit the scope of the present invention.
Examples
The following examples are given to illustrate the invention, but the invention is not limited to the following examples.
The relevant abbreviations in the examples are as follows:
6FDA:4,4' -hexafluoroisopropyl phthalic anhydride;
CBDA: cyclobutane tetracarboxylic dianhydride;
ODA:4,4' -diaminodiphenyl ether;
b7: tetramethoxymethyl glycoluril
B8:2,4, 6-tris [ bis (methoxymethyl) amino ] -1,3, 5-triazines
The above compounds are all obtained by commercial means.
< preparation of diamine Compound monomer >
Synthesis example 1
Synthesis of coumarin-like structure derived amine diamine compound (M1)
The hydrochloride of 7-aminocoumarin (3.9 g,20 mmol) was suspended in 30mL of n-hexane, irradiated with a 250-450nm high pressure mercury lamp for 48h, and filtered to give the [2+2] cyclized product of the hydrochloride of 7-aminocoumarin. The pH of the product is regulated to be neutral by saturated aqueous solution of sodium bicarbonate, and the [2+2] cyclization product diamine compound M1 of 7-aminocoumarin is obtained.
Synthesis example 2
Synthesis of coumarin-like structure derived amine diamine compound (M2)
Under the protection of nitrogen flow, the [2+2] cyclized product (10.0 g,31 mmol) of 7-aminocoumarin is dissolved in 100mL of ethanol, 10mL of 0.01mol/mL NaOH aqueous solution is added dropwise, the temperature is raised to 60 ℃, the reaction is carried out for 6 hours, the pH is regulated to 5-6 by dilute hydrochloric acid, the extraction is carried out by ethyl acetate, and the concentration is carried out, thus obtaining the diamine compound M2.
Synthesis example 3
Synthesis of coumarin-like structure derived amine hydrolysate diamine compound (M3)
Under the protection of nitrogen flow, the [2+2] cyclized product (10.0 g,31 mmol) of 7-aminocoumarin is dissolved in 100mL of ethanol, sodium methoxide (5.4 g,100 mmol) is added, the temperature is raised to 60 ℃, the reaction is carried out for 8 hours, the pH is regulated to 5-6 by dilute hydrochloric acid, the extraction is carried out by ethyl acetate, and the concentration is carried out, thus obtaining the diamine compound M3.
Synthesis example 4
Synthesis of benzocyclobutene and coumarin cycloaddition derivative diamine compound (M4)
Into a pressure-resistant sealed vessel, 1, 3-bis (3-benzocyclobutene) -1, 3-tetramethyldisiloxane benzene (3.38 g,10 mmol), 7-nitrocoumarin (3.82 g,20 mmol), and N, N' -dimethylformamide were added 30mL. After the temperature is raised to 200 ℃ for reaction for 36 hours, pouring the reaction product into water, extracting the reaction product by using ethyl acetate, and concentrating the reaction product to obtain the dinitro compound. Dissolving in 50mL of ethanol, adding 0.1g of 10wt% Pd/C, introducing hydrogen, reacting at 50 ℃ for 12 hours, filtering Pd/C, concentrating, and recrystallizing to obtain a diamine compound M4.
Synthesis example 5
Synthesis of benzocyclobutene and coumarin cycloaddition derivative diamine compound (M5)
Diamine compound M4 (19.80 g,30 mmol) was dissolved in 100mL of methanol under nitrogen flow protection, sodium methoxide (5.4 g,100 mmol) was added, the temperature was raised to 60℃for reaction for 8 hours, pH was adjusted to 5-6 with dilute hydrochloric acid, extraction was performed with ethyl acetate, and concentration was performed to obtain diamine compound M5.
Synthesis example 6
Synthesis of hydroxyl group-containing diamine Compound (M6)
BAHF (14.64 g,40 mmol) was dissolved in 100mL of acetone, propylene oxide (13.9 g,239 mmol) and cooled to-15 ℃. A solution of 4-nitrobenzoyl chloride (14.84 g,80 mmol) dissolved in 100mL of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at-15℃for 4 hours, and then the reaction was allowed to return to room temperature. The white solid precipitated was filtered and dried in vacuo at 50 ℃.
20g of the obtained solid was charged into a 300mL stainless steel autoclave, dispersed in 200mL propylene glycol methyl ether, and 1g of 5% palladium on carbon was added. Hydrogen was introduced and stirred vigorously. After about 5 hours, the reaction was completed, the palladium compound was removed by filtration, and the mixture was concentrated by a rotary evaporator to obtain a diamine compound M6.
< Synthesis of macromolecular crosslinking agent >
Synthesis example 7
Synthesis of macromolecular crosslinker B1
3, 8-dihydroxy-6H-dibenzo [ B, D ] pyran-6-one (11.4 g,50 mmol), 1, 4-difluorobenzene (12.5 g,110 mmol), 2, 6-dimethyl-1, 4-benzenediol (6.9 g,50 mmol) were dissolved in 80mL of LDMAc, nitrogen was introduced, potassium carbonate (41.5 g,300 mmol) was added, the temperature was raised to 90℃and the reaction was stirred for 24 hours, the water was poured, the solid was filtered, washed three times with water, and dried at 80℃to obtain a polyphenylene ether solid.
10g of the above polyphenylene ether solid was dissolved in 100mL of carbon tetrabromide, AIBN (0.12 g,0.74 mmol) and NBS (17.8 g,100 mmol) were added, the temperature was raised to 60℃and after stirring for 8 hours, the reaction was poured into water, the organic phase was separated and washed three times with water, then the carbon tetrabromide solution was dropped into methanol, the precipitated solid was collected by filtration, and dried at 80℃to obtain benzyl brominated polyphenylene ether.
10g of the benzyl brominated polyphenylene ether is dissolved in 100ml of LDMAc, sodium methoxide (8.1 g,150 mmol) is added, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 20 hours, then the mixture is poured into water, the pH is regulated to about 5 by acetic acid, the mixture is stirred, the solid is filtered, washed three times by water, and the final macromolecular crosslinking agent B1 is obtained by drying at 80 ℃.
Synthesis example 8
Synthesis of macromolecular crosslinker B2
1, 4-difluorobenzene is changed into 1, 2-dibromoethane, and the synthesis is carried out according to the synthesis step of the macromolecular crosslinking agent B1.
Synthesis example 9
Synthesis of macromolecular crosslinker B3
3, 8-dihydroxy-6H-dibenzo [ B, D ] pyran-6-one (11.4 g,50 mmol), 2' -dibromodiethyl ether (20.79 g,90 mmol), 2, 6-dimethyl-1, 4-benzenediol (6.9 g,50 mmol) were dissolved in 80mL of DMAc, nitrogen was introduced, potassium carbonate (41.5 g,300 mmol) was added, the temperature was raised to 90℃and the reaction was stirred for 24 hours, poured into water, the solid was filtered, washed three times with water and dried at 80℃to obtain a polyphenylene ether solid.
10g of the above polyphenylene ether solid was dissolved in 100mL of carbon tetrabromide, AIBN (0.12 g,0.74 mmol) and NBS (17.8 g,100 mmol) were added, the temperature was raised to 60℃and after stirring for 8 hours, the reaction was poured into water, the organic phase was separated and washed three times with water, then the carbon tetrabromide solution was dropped into methanol, the precipitated solid was collected by filtration, and dried at 80℃to obtain benzyl brominated polyphenylene ether.
10g of the benzyl brominated polyphenylene ether is dissolved in 100mL of ethanol, 10mL of 0.01mol/mL NaOH aqueous solution is added dropwise, the temperature is raised to 50 ℃, the reaction is carried out for 8 hours, the pH is regulated to 6 by dilute hydrochloric acid, the extraction is carried out by ethyl acetate, and the concentration is carried out, thus obtaining the final macromolecular crosslinking agent B3.
Synthesis example 10
Synthesis of macromolecular crosslinker B4
1, 4-difluorobenzene is changed into bromo-tetra polyethylene glycol-bromo, and the synthesis is carried out according to the synthesis step of the macromolecular crosslinking agent B1.
Synthesis example 11
Synthesis of macromolecular crosslinker B5
3, 8-dihydroxy-6H-dibenzo [ B, D ] pyran-6-ketone is changed into a cycloaddition product of benzocyclobutene and coumarin, and the synthesis is carried out according to the synthesis step of the macromolecular crosslinking agent B1.
The cycloaddition product of benzocyclobutene and coumarin is prepared as follows:
into a pressure-resistant sealed vessel, tricyclo [6.2.0.03,6] deca-1, 3 (6), 7-triene (10 mmol), 6-hydroxycoumarin (20 mmol), and N, N-dimethylformamide (10 mL) were charged. Heating to 220 ℃ for reaction for 36 hours, pouring into water, extracting with ethyl acetate, and concentrating to obtain a cycloaddition product of benzocyclobutene and coumarin.
Synthesis example 12
Synthesis of macromolecular crosslinker B6
3, 8-dihydroxy-6H-dibenzo [ B, D ] pyran-6-ketone is changed into cycloaddition product containing siloxane bis (enophile compound) and coumarin, and the synthesis is carried out according to the synthesis step of macromolecular crosslinking agent B1.
Cycloaddition products of siloxane-containing bis (enophile compounds) with coumarin are prepared as follows:
under nitrogen flow protection, siloxane-containing bis (enophile compound) (10 mmol), 6-hydroxycoumarin (20 mmol), N, N' -dimethylformamide (10 mL) were added. After reaction for 36h at 30 ℃, pouring into water, extracting with ethyl acetate, concentrating to obtain cycloaddition product containing siloxane bis (enophile compound) and coumarin.
< Synthesis of diazonaphthoquinone Compound >
Synthesis example 13
Synthesis of diazonaphthoquinone Compound (C1)
Under the protection of dry nitrogen flow, raw material phenol (57.6 g,100 mmol) and 5-diazonaphthoquinone sulfonyl chloride (93.9 g,350 mmol) are dissolved in 500mL of dioxane, 50mL of dioxane/30 mL of triethylamine mixed reagent is dropwise added under the condition that the system temperature is not higher than 30 ℃, reaction is carried out for 3h, triethylamine salt is filtered out, a filtrate is dripped into water, and diazonaphthoquinone compound C1 is obtained by filtering, precipitating and drying.
Synthesis example 14
Synthesis of diazonaphthoquinone Compound (C2)
D is->Or H
Bisphenol AF (33.6 g,100mmo 1) and 2,1, 5-diazonaphthoquinone sulfonyl chloride (51.1 g,190 mmol) were dissolved in 400mL of dioxane under the protection of a dry nitrogen stream, and 15g of triethylamine in 100mL of THF was added dropwise at a system temperature of not more than 30 ℃. After the completion of the dropwise addition, the reaction was further carried out for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Next, the precipitated precipitate was filtered and collected, and dried to obtain 55g of diazonaphthoquinone compound C2.
< Synthesis of polyimide precursor resin containing hydroxyl group >
Synthesis example 15
Synthesis of hydroxyl group-containing polyimide precursor resin A1
Under a dry nitrogen stream, diamine compound M1 (3.222 g,10 mmol), diamine compound M2 (28.650 g,80 mmol), capping agent M-aminophenol (2.181 g,20 mmol), ODA (0 g,0 mmol) were dissolved in 200g of N-methylpyrrolidone (NMP), stirred at room temperature for 0.2h, 6FDA (35.36 g,80mmo 1), CBDA (3.92 g,20 mmol) were added thereto, stirred at room temperature for 8h, and then heated to 90℃for reaction for 6h. The solution was then poured into 2L ethanol and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum drying oven at 60℃for 24 hours to give resin precursor A1.
Synthesis examples 16 to 24 resin precursors A2 to 10
The synthesis method of the resin precursors A2 to 10 was the same as that of the resin precursor A1, except for the difference in the diamine compound and the imidization method, and is specifically shown in Table 1.
TABLE 1
Example 1
Resin precursor A1 (2.0 g), macromolecular crosslinking agent B1 (0.3 g), diazonaphthoquinone compound C1 (0.5 g), C2 (0.1 g), bisphenol F epoxy resin (0.1 g), silane coupling agent, i.e., 3-aminopropyl trimethoxysilane (0.02 g), and surfactant TEGO GLIDE 300 (0.01 g) were dissolved in gamma-butyrolactone 5.39g and ethyl lactate 2.31g, and after stirring at room temperature for 3 hours, the mixture was filtered through an organic filter membrane having a pore size of 0.45 μm to obtain a photosensitive resin composition slurry.
The photosensitive resin composition slurry is coated on a silicon wafer or a glass substrate, baked for 3min at 120 ℃, exposed to light, developed for 60s by a 2.38wt% tetramethylammonium hydroxide (TMAH) aqueous solution, washed for 30s by water to obtain a patterned film, and subjected to heat treatment for 1h at 300 ℃ to obtain a film finally used for performance evaluation.
Examples 2 to 16, comparative examples 1 to 6
The synthesis methods of examples 2-16 and comparative examples 1-6 were the same as in example 1, except that the raw materials were selected and the proportions were different, and the specific formulations are shown in Table 2. The photosensitive resin compositions prepared in examples 1 to 16 and comparative examples 1 to 6 were evaluated for properties such as image forming ability, stress, adhesion, elongation at break, heat resistance, and chemical resistance, and the results are shown in table 2.
< evaluation method >
(1) Imaging capability
Detecting the etched line state of the developed film by using SEM (JEOL JSM-6510), and clearly etching the developed film by using a line with the width smaller than 5 mu m, wherein the developed film has no bending and no defect, and the line width is better than the line width consistent with the design of a mask plate; the line with the width of 5-10 mu m can be clearly etched, has no bending and no defect, and has a line width which is consistent with the design of the mask plate; only the lines with the width of more than 10 mu m can be clearly etched, the lines are free from bending and defect, and the line width is inferior to the line width which is consistent with the design of a mask plate.
(2) Evaluation of stress
Uniformly dropping the photosensitive resin composition slurry on a silicon wafer, uniformly spinning at a rotation speed of 300r/min by using a spin coater, pre-baking at 120 ℃ for 3min on a hot plate, performing exposure and development, heating from 100 ℃ to 300 ℃ at 5 ℃/min, curing at 300 ℃ for 1 hour to obtain a film thickness of 10 μm, taking out the silicon wafer when the temperature becomes 50 ℃ or lower, and confirming the stress of the cured film by using a stress measuring device FLX2908 (manufactured by KLATencor).
(3) Adhesion properties
The developed film was observed with an optical microscope (OLS 5000) for the occurrence of line drop, and it was preferable that only lines with a line width of 2 μm or less were observed, that only lines with a line width of 10 μm or less were observed, and that only lines with a line width of 5 μm or more were observed.
(4) Evaluation of adhesion Property
10 rows and 10 columns of checkered cuts were cut at 2mm intervals in the cured film on the substrate using a single blade knife. The diced cured film substrate was placed in a Pressure Cooker Test (PCT) apparatus (HAST character ehs-211MD, manufactured by Tabai Espec, ltd.) and subjected to PCT treatment at 121 ℃ under saturated conditions of 2 atmospheres for 400 hours, and then the number of peeled off of 100 cells caused by peeling with a transparent adhesive tape was counted to evaluate the adhesion characteristics between the metal material and the resin cured film. The peel test described above. The number of peels in the peeling test is preferably 10 or more and less than 20 or more, and is preferably good and less than 20 or more.
(5) Heat resistance
A small amount of the sample was taken and analyzed by a thermogravimetric analyzer (TGA, NETZSCH STA2500 Regulus) to determine the residual weight ratio (R 400 ). By R 400 >80% is preferably 75%<R 400 <80% is good, R 400 <75% is inferior.
(6) Chemical resistance
The heat-treated film (area greater than 5 x 5cm, thickness 2 μm) was placed in the middle for 72h and the film thickness change of the film sample before and after soaking in N-methylpyrrolidone at 40 ℃ for 120s was measured. Δthk= (THK) 1 -THK 0 )/THK 0 X 100%, where ΔTHK represents the film thickness change rate, THK 1 The film thickness after immersion was shown, and THK was the film thickness before immersion. With DeltaTHK<1% is preferably 1%<ΔTHK<2% is good, ΔTHK>2% is inferior.
(7) Elongation at break test
The photosensitive resin composition paste was coated on an 8-inch silicon wafer by spin coating and pre-baked at 120 ℃/3 minutes to a film thickness of 10 μm after the pre-baking, and then heated to 300 ℃ at 3 ℃/minute under the condition of an oxygen concentration of 100ppm or less using an inert gas oven for 1 hour at 300 ℃. When the temperature reached 50 ℃ or lower, the wafer was taken out, cooled slowly, and immersed in 0.5 mass% hydrofluoric acid for 30 minutes, whereby the film of the resin composition was peeled from the wafer. The film was cut into a long strip having a width of 1cm and a length of 10cm, and the film was stretched at a stretching speed of 50 mm/min at a temperature of 23.0℃and a humidity of 45.0% RH using a tensile machine, and the elongation at break was measured. For each specimen, 10 strips were measured, and the average value of the higher 5 points was obtained from the results. The case where the elongation at break point was 20% or more was evaluated as "excellent", the case where it was 10% or more and less than 20% was evaluated as "good", and the case where it was less than 10% was evaluated as "inferior".
TABLE 2
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A photosensitive resin composition, characterized by comprising:
(A) A polyimide precursor resin containing hydroxyl groups;
(B) Macromolecular crosslinking agent with molecular weight 600< Mw <4000 and solubility 1-10g/100g in 2.38wt% TMAH;
(C) Diazonaphthoquinone compounds;
(D) A solvent;
the macromolecular crosslinking agent component (B) is a compound shown in a structural formula (1):
in the formula (1), R 5 Representing the number of carbon atoms in1-20 may comprise alicyclic and/or aromatic rings, other heteroatom-containing 2 valent organic groups; r is R 6 A 2-valent organic group having 0 to 30 carbon atoms and containing an alicyclic ring and/or aromatic ring and other hetero atoms; r is R 7 And R is 8 represents-OH, -COOH or an ester group having 2 to 4 carbon atoms; r is R 9 Represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or an acylalkyl group; x+y is greater than or equal to 1, z is greater than or equal to 2, s and t are positive integers.
2. The photosensitive resin composition according to claim 1, wherein the (a) hydroxyl group-containing polyimide precursor resin has a structural unit represented by the following structural formula (2):
in the formula (2), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, and R 1 Represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
3. The photosensitive resin composition according to claim 2, wherein D in the structural formula (2) represents a composition comprising one or more of the following diamine residues represented by the structural formula (3):
in the formula (3), R 1 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, R 2 Represents alkyl, alkoxy, hydroxy, carboxyl, fluorine, chlorine and bromine substituent groups with 1-3 carbon atoms; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine or bromine; s represents a linking group, which is a tetravalent linking group having 0 to 30 carbon atoms and containing alicyclic and/or aromatic rings and other hetero atoms; r is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, or other carbon number 1 to10, or a 2-valent organic group formed by bonding 2 or more of them; p represents an integer of 0 to 2, and q represents an integer of 0 to 1.
4. A photosensitive resin composition according to claim 2 or 3, wherein D in the structural formula (2) represents a composition comprising one or more of the following diamine residues represented by the structural formula (4):
in the formula (4), R 1 An alkyl group having 1 to 3 carbon atoms and a hydrogen atom; r is R 2 Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a substituent of fluorine, chlorine, or bromine; p represents an integer of 0 to 2.
5. A photosensitive resin composition according to claim 2 or 3, wherein Q in the structural formula (2) represents a combination comprising one or more of the dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2', 3' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic dianhydride, 3',4' -tetracarboxylic diphenyl ether dianhydride, 3',4' -tetracarboxylic benzophenone dianhydride, 3',4,4' -tetracarboxylic acid diphenyl sulfonyl dianhydride, 4' -hexafluoroisopropyl phthalic anhydride (6 FDA), 4' -isopropyl phthalic anhydride, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, cyclobutane tetracarboxylic dianhydride (CBDA), cyclohexane tetracarboxylic dianhydride.
6. The photosensitive resin composition according to claim 1 or 2, wherein R in the macromolecular crosslinking agent having a structure represented by formula (1) 5 Is one or more combination of the following structural formulas (5):
7. the photosensitive resin composition according to claim 1 or 2, wherein the amount of the (B) macromolecular crosslinking agent is 0.1 to 20 parts by mass relative to 100 parts by mass of the (a) hydroxyl group-containing polyimide precursor resin.
8. A method for producing a pattern cured product, characterized in that a pattern having a resin coating layer is formed from the photosensitive resin composition according to any one of claims 1 to 7, comprising the steps of:
step one: coating the photosensitive resin composition on a substrate to form a photosensitive resin coating, and pre-baking the photosensitive resin coating on a hot plate at 80-120 ℃ for 2-60min to form a photosensitive coating;
step two: exposing the photosensitive film by using an exposure mask plate;
step three: removing the exposed part of the photosensitive film by using an alkaline developer, and developing;
step four: curing the developed film at a temperature of 100-300 ℃ to obtain a cured film.
9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 7, which is a patterned cured product.
10. The use of the cured product according to claim 9, wherein the cured product is applied to an insulating layer, a pixel defining layer, a planarizing layer, or/and a surface protecting layer, an insulating layer of a semiconductor device of an organic electroluminescent element.
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