CN114479075A - Polyimide precursor resin, photosensitive resin composition, and use of photosensitive resin composition - Google Patents
Polyimide precursor resin, photosensitive resin composition, and use of photosensitive resin composition Download PDFInfo
- Publication number
- CN114479075A CN114479075A CN202111647340.XA CN202111647340A CN114479075A CN 114479075 A CN114479075 A CN 114479075A CN 202111647340 A CN202111647340 A CN 202111647340A CN 114479075 A CN114479075 A CN 114479075A
- Authority
- CN
- China
- Prior art keywords
- polyimide precursor
- resin composition
- precursor resin
- photosensitive resin
- carbon atoms
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 71
- 239000004642 Polyimide Substances 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000002243 precursor Substances 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 125000000962 organic group Chemical group 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- -1 n-octyl Chemical group 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 9
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VXTJVMWIVSZHNI-UHFFFAOYSA-N 2-amino-4-propylphenol Chemical compound CCCC1=CC=C(O)C(N)=C1 VXTJVMWIVSZHNI-UHFFFAOYSA-N 0.000 claims description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000003518 tetracenes Chemical class 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 12
- 206010059866 Drug resistance Diseases 0.000 abstract description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 239000009719 polyimide resin Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- GJIZHYHGIAPLJN-UHFFFAOYSA-N 3-hydroxy-4-nitrobenzoyl chloride Chemical compound OC1=CC(C(Cl)=O)=CC=C1[N+]([O-])=O GJIZHYHGIAPLJN-UHFFFAOYSA-N 0.000 description 16
- 150000004985 diamines Chemical class 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- YQNRVGJCPCNMKT-LFVJCYFKSA-N 2-[(e)-[[2-(4-benzylpiperazin-1-ium-1-yl)acetyl]hydrazinylidene]methyl]-6-prop-2-enylphenolate Chemical compound [O-]C1=C(CC=C)C=CC=C1\C=N\NC(=O)C[NH+]1CCN(CC=2C=CC=CC=2)CC1 YQNRVGJCPCNMKT-LFVJCYFKSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 101000838335 Homo sapiens Dual specificity protein phosphatase 2 Proteins 0.000 description 6
- 101001080401 Homo sapiens Proteasome assembly chaperone 1 Proteins 0.000 description 6
- 229960005552 PAC-1 Drugs 0.000 description 6
- 102100027583 Proteasome assembly chaperone 1 Human genes 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229940116333 ethyl lactate Drugs 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NDMUQNOYNAWAAL-UHFFFAOYSA-N 3-diazo-1,4-dioxonaphthalene-2-sulfonic acid Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])C(S(=O)(=O)O)C(=O)C2=C1 NDMUQNOYNAWAAL-UHFFFAOYSA-N 0.000 description 4
- XLDLRRGZWIEEHT-UHFFFAOYSA-N 3-hydroxy-4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C(O)=C1 XLDLRRGZWIEEHT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- OZPOTRRLBSVXKP-UHFFFAOYSA-N 1-ethoxypropan-2-yl formate Chemical compound CCOCC(C)OC=O OZPOTRRLBSVXKP-UHFFFAOYSA-N 0.000 description 1
- VIOQEHXYEOORLQ-UHFFFAOYSA-N 1-methoxypropan-2-yl formate Chemical compound COCC(C)OC=O VIOQEHXYEOORLQ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- FOLJMFFBEKONJP-UHFFFAOYSA-N adamantane-1,3-diamine Chemical compound C1C(C2)CC3CC1(N)CC2(N)C3 FOLJMFFBEKONJP-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Materials For Photolithography (AREA)
Abstract
The application specifically discloses a polyimide precursor resin, a photosensitive resin composition and application of the photosensitive resin composition. The polyimide precursor resin composition/product comprises a polyimide precursor resin and is characterized by comprising the following structural units
Wherein R is1Is a 4-8 valent organic group containing aromatic ring and having 6-30 carbon atoms or a 4-8 valent organic group containing aliphatic ring structure and having 3-20 carbon atoms; p is the number of hydroxyl groups bonded to R1, and p is an integer of 0 to 4. The photosensitive resin composition comprises polyimide precursor resin, a solvent, an auxiliary agent and a photoacid generator. The photosensitive resin composition has the advantages of high transmittance and good drug resistance.
Description
Technical Field
The present application relates to the field of photosensitive resins, and more particularly, to a polyimide precursor resin, a photosensitive resin composition, and uses of the photosensitive resin composition
Background
Polyimide has excellent high and low temperature resistance, mechanical property, dielectric property, biocompatibility, low thermal expansion coefficient and other properties, and is widely used in the fields of electronic appliance industry, aerospace industry, advanced composite materials, fibers, engineering plastics, photoresist and the like. With the development of thinner, smaller and flexible devices such as display panels and semiconductors, higher and higher requirements are put forward on corresponding materials, packaging technologies and processes.
Photosensitive polyimides are mainly used in photoresists in the field of microelectronics. Compared with the common polyimide, the photosensitive polyimide can simplify the photoetching process to a great extent, and is widely applied to large-scale integrated circuits, insulating interlayers, surface passivation layers, ion implantation masks and the like because of the characteristics of good heat resistance, mechanical property, electrical property, corrosion resistance and the like; specifically, rdl (redistribution layer), Bump layer, etc. in the IC device; in OLED fabrication, it is used for the fabrication of interlayer insulation, device protection, planarization layer (PLN, buffer function) Pixel Division Layer (PDL), and the like.
The synthesis steps of the photosensitive polyimide resin in the related art are generally: the dianhydride and diamine are polymerized to form a polyamic acid precursor, and then the polyamic acid is esterified to obtain the polyamic acid/polyesteramide composition. In the esterification process, a part of polyamic acid can generate imidization side reaction, thereby causing the light transmittance of the photosensitive composition to be reduced, the sensitivity to be reduced and influencing the development effect.
Therefore, it is required to develop a polyimide resin which is effective in improving light transmittance and exposure sensitivity.
Disclosure of Invention
In order to reduce sensitivity reduction caused by partial imidization of a photosensitive polyimide resin during esterification, the present application provides a polyimide precursor resin, a photosensitive resin composition, and uses of the photosensitive resin composition.
In a first aspect, the present application provides a polyimide precursor resin, which employs the following technical scheme:
the polyimide precursor resin comprises a structural unit shown as a formula (I)
In the formula (I)
R1Is composed ofA 4-8 valent organic group having 6-30 carbon atoms of an aromatic ring or a 4-8 valent organic group having 3-20 carbon atoms of an aliphatic ring structure;
p is the number of hydroxyl groups connected to R1, and p is an integer of 0-4;
r2 has a structure shown in formula (II)
R3 is a hydrogen atom or a C1-8 alkyl group;
in the formula (II), R' is selected from any one of the following structures
R4Is 1, 2, or 3, R4Selected from any one of halogen atom, trifluoromethyl, methyl, hydroxyl and alkoxy.
By introducing a high-light-transmittance structure and a hydroxyl site with alkali solubility and crosslinking functions into a diamine compound, the problems that the prior ester ring structure has high transmittance, but has limited application of alkali-free soluble groups in a photosensitive structure and large difference of reactivity compared with an aromatic diamine monomer are solved, and crosslinking sites are increased, so that the components of the photosensitive resin composition are more likely to have crosslinking reaction, and the interlayer insulating material with high transmittance, high heat resistance, high drug resistance and other performances is obtained.
Preferably, the polyimide precursor resin further includes a repeating structural unit represented by the formula (III)
In the formula (III)
R1Is a C6-30 organic group having a valence of 4 to 8 containing an aromatic ring or a C atom containing an aliphatic ring structure4-8 valent organic groups with the sub number of 3-20;
p is attached to R1The number of the hydroxyl groups is 0 to 4;
R3is a hydrogen atom or a C1-8 alkyl group;
R5derived from any one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenylsulfone, diaminodiphenylether, 2-bis (4-hydroxy-3-aminophenyl) propane, 4' -cyclohexanediamine, 1, 4-bis (4' -aminophenoxy).
Preferably, the 4-to 8-valent organic group having 6 to 30 carbon atoms and containing an aromatic ring is derived from benzene, biphenyl, terphenyl, furan, thiophene, pyrrole, pyridine, naphthalene, anthracene, phenanthrene, indene, fluorene, fluoranthene, triphenylene, perylene, and the like,
And (c) any of tetracenes.
Preferably, the organic group having a valence of 4 to 8 and having 3 to 20 carbon atoms and containing an alicyclic structure is derived from any one of cyclobutane, cyclopentane, cyclohexane and cycloheptane.
Preferably, said C1-8The alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl and n-octyl.
Preferably, the number average molecular weight of the precursor resin is 2000-50000.
In a second aspect, the present application provides a polyimide precursor resin, which adopts the following technical scheme:
a photosensitive resin composition is prepared using the above polyimide precursor resin.
Preferably, the photosensitive resin composition comprises, by weight, 5% to 30% of the polyimide precursor resin, 61.5% to 94% of the solvent, 0.01% to 0.5% of the auxiliary agent, and 0.5% to 8% of the photoacid generator.
Preferably, the amount of the polyimide precursor resin is 6 wt% to 20 wt%.
The solvent comprises one or more of gamma-butyrolactone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, ethyl lactate, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the auxiliary agent comprises at least one of a leveling agent, a silane coupling agent and a surfactant.
These auxiliaries contribute to the effects of improving the degree of planarization of the film, the adhesion between the resist compound and the substrate, and reducing the residual film after development.
Preferably, the surfactant comprises a fluorosurfactant and/or a surfactant comprising a polyethylene glycol structure.
Typical photoacid generators include diazonaphthoquinone sulfonates, which may be selected from any one or a combination of at least two of the following compounds:
wherein D is a diazonaphthoquinone sulfonic acid (DNQ) group, q is an integer of 1-3, and the structure of the compound contains at least one DNQ group.
The DNQ group is:
in the photosensitive resin composition of the present invention, the weight percentage of the polyimide precursor resin may be selected from 5.3 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%.
The weight percentage of the photoacid generator is 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, or the like.
The weight percentage of the auxiliary agent is 0.02 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, etc.
The solvent is present in a weight percentage of 61.5 wt% to 95 wt%, such as 62 wt%, 65 wt%, 68 wt%, 70 wt%, 71 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 86 wt%, 88 wt%, 90 wt%, or 94 wt%, and the like.
Preferably, the photosensitive resin composition has a solid content of 5 wt% to 38.5 wt%, such as 6 wt%, 8 wt%, 10 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, or 36 wt%, etc., preferably 8 wt% to 30 wt%.
The solid content refers to a ratio of the sum of the mass of all substances except the solvent in the photosensitive resin composition in the composition.
In the present invention, the solid content is preferably 5 to 38.5 wt%, and too low solid content may affect the continuity and uniformity of the film when the photosensitive resin composition is formed into a film, while too high solid content may cause too high viscosity and further cause problems such as generation of bubbles during the film coating process, deterioration of flatness, and the like.
In a third aspect, the present application provides a polyimide precursor resin, which adopts the following technical scheme:
use of a photosensitive resin composition for the preparation of an optical element.
In summary, the present application has the following beneficial effects:
1. by designing the diamine compound, a high-transmittance structure and hydroxyl sites with a crosslinking effect are introduced into the diamine compound, so that the reactivity is improved, and the components of the photosensitive resin are more easily crosslinked, so that the photosensitive resin has high transmittance and high drug resistance.
2. In the present application, it is preferable to adjust the solid content of the photosensitive resin composition, thereby improving the film continuity and uniformity of the photosensitive resin composition when the film is formed, and allowing the photosensitive resin composition film to have a higher flatness.
Detailed Description
The raw materials used in the application can be obtained from the market
The formula of the photoacid generator PAC-1 used in the application is shown as a formula a,
wherein DNQ is a diazonaphthoquinone sulfonic acid (DNQ) group;
the diazonaphthoquinone sulfonic acid (DNQ) group is:
preparation of diamine compound
Preparation example 1
Weighing 18.31g (0.1mol) of 3-hydroxy-4-nitrobenzoic acid, dissolving in 100ml of Tetrahydrofuran (THF), adding 23.79g (0.2mol) of thionyl chloride, stirring and reacting at room temperature for 12h, and removing the solvent by rotary evaporation to obtain an intermediate 3-hydroxy-4-nitrobenzoyl chloride;
in the nitrogen atmosphere, 13.02g (0.1mol) of 2,5' -cyclohexanol diamine is dissolved in 50mL of gamma-butyrolactone, the temperature is reduced to-15 ℃, then the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride is dripped into the system (the reaction is exothermic, and the reaction temperature is kept lower than-5 ℃ in the dripping process), and the reaction is continued for 5 hours after the dripping is finished. Removing the solvent by using a rotary evaporator to obtain a corresponding nitro intermediate;
the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride was prepared by dissolving 40.31g (0.2mol) of 3-hydroxy-4-nitrobenzoyl chloride in 50mL of gamma-butyrolactone and mixing thoroughly.
Dissolving the dinitro compound in Tetrahydrofuran (THF), adding 1g C-Pd catalyst, stirring under 1 standard atmospheric pressure in hydrogen atmosphere, stirring for 6h, stopping reaction, filtering to remove C-Pd catalyst, rotary evaporating to remove most solvent, vacuum drying at 40 deg.C for 8h to obtain diamine compound 1,
the above C-Pd catalyst is composed of 5% by weight of palladium and 95% by weight of carbon.
Confirmation of structure of diamine compound 1:
mass spectrum: ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z value (M + 1): 401.
the structural formula of the diamine compound 1 is shown as a formula (IV) after being confirmed.
Preparation example 2
Weighing 18.31g (0.1mol) of 3-hydroxy-4-nitrobenzoic acid, dissolving in 100ml of THF, adding 23.79g (0.2mol) of thionyl chloride, stirring and reacting for 12h at room temperature, and removing the solvent by rotary evaporation to obtain an intermediate 3-hydroxy-4-nitrobenzoyl chloride;
under the nitrogen atmosphere, 14.22g (0.1mol) of 1, 4-cyclohexane dimethylamine is dissolved in 50mL of gamma-butyrolactone, the temperature is reduced to-15 ℃, then the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride is dripped into the system (the reaction is exothermic, and the reaction temperature is kept lower than-5 ℃ in the dripping process), and the reaction is continued for 5 hours after the dripping is finished. Removing the solvent by using a rotary evaporator to obtain a corresponding nitro intermediate;
the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride was prepared by dissolving 40.31g (0.2mol) of 3-hydroxy-4-nitrobenzoyl chloride in 50mL of gamma-butyrolactone and mixing well.
Dissolving the dinitro compound in Tetrahydrofuran (THF), adding 1g C-Pd catalyst, stirring in hydrogen atmosphere with 1 standard atmospheric pressure, stopping reaction after stirring for 6h, filtering to remove C-Pd catalyst, removing most of solvent by rotary evaporation, and drying in vacuum at 40 ℃ for 8h to obtain diamine compound 2.
The above C-Pd catalyst is composed of 5% by weight of palladium and 95% by weight of carbon.
Confirmation of diamine compound 2:
mass spectrum: ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z value (M + 1): 413.
the structural formula of the diamine compound 2 is confirmed to be shown as the formula (V)
Preparation example 3
Weighing 18.31g (0.1mol) of 3-hydroxy-4-nitrobenzoic acid, dissolving in 100ml of THF, adding 23.79g (0.2mol) of thionyl chloride, stirring and reacting for 12h at room temperature, and removing the solvent by rotary evaporation to obtain an intermediate 3-hydroxy-4-nitrobenzoyl chloride;
21.04g (0.1mol) of 4, 4-methylene dicyclohexylamine is dissolved in 50mL of gamma-butyrolactone in the nitrogen atmosphere, the temperature is reduced to-15 ℃, then a gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride is dripped into the system (the reaction is exothermic, and the reaction temperature is kept lower than-5 ℃ in the dripping process), and the reaction is continued for 5 hours after the dripping is finished. Removing the solvent by using a rotary evaporator to obtain a corresponding nitro intermediate;
the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride was prepared by dissolving 40.31g (0.2mol) of 3-hydroxy-4-nitrobenzoyl chloride in 50mL of gamma-butyrolactone and mixing thoroughly.
Dissolving the dinitro compound in Tetrahydrofuran (THF), adding 1g of 5% C-Pd catalyst, stirring in a hydrogen atmosphere with the pressure of 1 standard atmosphere, stopping the reaction after stirring for 6h, filtering to remove the C-Pd catalyst, removing most of the solvent by rotary evaporation, and drying in vacuum at 40 ℃ for 8h to obtain the diamine compound 3.
The above C-Pd catalyst is composed of 5% by weight of palladium and 95% by weight of carbon.
Confirmation of diamine compound 3:
mass spectrum: ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z value (M + 1): 481.
the structural formula of the diamine compound 3 is confirmed to be shown as the formula (VI)
Preparation example 4
Weighing 18.31g (0.1mol) of 3-hydroxy-4-nitrobenzoic acid, dissolving in 100ml of THF, adding 23.79g (0.2mol) of thionyl chloride, stirring and reacting for 12 hours at room temperature, and removing the solvent by rotary evaporation to obtain an intermediate 3-hydroxy-4-nitrobenzoyl chloride;
under the nitrogen atmosphere, 16.63g (0.1mol) of 1, 3-adamantane diamine is dissolved in 50mL of gamma-butyrolactone, the temperature is reduced to-15 ℃, then the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride is dripped into the system (the reaction is exothermic, and the reaction temperature is kept lower than-5 ℃ in the dripping process), and the reaction is continued for 5 hours after the dripping is finished. Removing the solvent by using a rotary evaporator to obtain a corresponding nitro intermediate;
the gamma-butyrolactone solution of 3-hydroxy-4-nitrobenzoyl chloride was prepared by dissolving 40.31g (0.2mol) of 3-hydroxy-4-nitrobenzoyl chloride in 50mL of gamma-butyrolactone and mixing thoroughly.
Dissolving the dinitro compound in Tetrahydrofuran (THF), adding 1g of 5% C-Pd catalyst, stirring in a hydrogen atmosphere with the pressure of 1 standard atmosphere, stopping the reaction after stirring for 6h, filtering to remove the C-Pd catalyst, removing most of the solvent by rotary evaporation, and drying in vacuum at 40 ℃ for 8h to obtain a diamine compound 4.
The above C-Pd catalyst is composed of 5% by weight of palladium and 95% by weight of carbon.
Confirmation of diamine compound 4:
mass spectrum: ZAB-HS type mass spectrometer (manufactured by Micromass, UK) M/Z value (M + 1): 437.
the structural formula of the diamine compound 3 is shown as the formula (VII) after being confirmed
Preparation of polyimide precursor resin
Preparation example 5
6.03g (15mmol) of the diamine compound 1 and 5.01g (25mmol) of 4,4' -diaminodiphenyl ether were weighed out and charged into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Quickly dropwise adding a diacid solution into the system, stirring and reacting for 3h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 3h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24h to obtain the polyimide precursor resin 1.
The molecular weight was measured using a gel permeation chromatograph (shimadzu LC-20A, shimadzu, japan) according to the GPC method, and the number average molecular weight of the polyimide precursor resin 1 was determined to be 8000.
Preparation of the diacid solution: 15.51g (50mmol) of 4,4' -oxydiphthalic anhydride monomer were mixed with 35mL of N-methylpyrrolidone (NMP).
Preparation example 6
6.21g (15mmol) of the diamine compound 2 and 5.01g (25mmol) of 4,4' -diaminodiphenyl ether were weighed out and put in a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Quickly dropwise adding a diacid solution into the system, stirring and reacting for 3h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 3h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24h to obtain the polyimide precursor resin 2.
The molecular weight was measured using a gel permeation chromatograph (shimadzu LC-20A, shimadzu, japan) according to the method of GPC, and the number average molecular weight of the polyimide precursor resin 2 was determined to be 8000.
Preparation of the diacid solution: 15.51g (50mmol) of 4,4' -oxydiphthalic anhydride monomer were mixed with 35mL of N-methylpyrrolidone (NMP).
Preparation example 7
7.23g (15mmol) of the diamine compound 3 and 5.01g (25mmol) of 4,4' -diaminodiphenyl ether were weighed out, and charged into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Quickly dropwise adding a diacid solution into the system, stirring and reacting for 3h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 3h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24h to obtain the polyimide precursor resin 3.
The molecular weight was measured by using a gel permeation chromatograph (shimadzu LC-20A, shimadzu, japan) according to the GPC method, and the number average molecular weight of the polyimide precursor resin 3 was measured to be 8400.
Preparation of the diacid solution: 15.51g (50mmol) of 4,4' -oxydiphthalic anhydride monomer were mixed with 35mL of N-methylpyrrolidone (NMP).
Preparation example 8
6.57g (15mmol) of the diamine compound 4 and 5.01g (25mmol) of 4,4' -diaminodiphenyl ether were weighed out and put in a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Quickly dropwise adding a diacid solution into the system, stirring and reacting for 3h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 3h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24h to obtain the polyimide precursor resin 4.
The molecular weight was measured by using a gel permeation chromatograph (shimadzu LC-20A, shimadzu, japan) according to the GPC method, and the number average molecular weight of the polyimide precursor resin 4 was detected to be 8200.
Preparation of diacid solution: 15.51g (50mmol) of 4,4' -oxydiphthalic anhydride monomer were mixed with 35mL of N-methylpyrrolidinone (NMP).
Preparation of photosensitive polyimide resin composition
Example 1
A photosensitive polyimide resin composition is prepared by the following method:
weighing 5g of polyimide precursor resin 1, dissolving in 50mL of mixed solvent, adding 1g of photoacid generator PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant, stirring and dissolving, and filtering through a 0.45 micrometer filter to obtain the photosensitive polyimide resin composition 1.
The mixed solvent consisted of 10 v% of gamma-butyrolactone, 20 v% of ethyl lactate, and 70 v% of propylene glycol monomethyl ether.
Example 2
A photosensitive polyimide resin composition is prepared by the following method:
5g of polyimide precursor resin 2 is weighed and dissolved in 50mL of mixed solvent, 1g of photoacid generator PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant are added, stirred and dissolved, and then filtered through a 0.45 micron filter, so that the photosensitive polyimide resin composition 2 is obtained.
The mixed solvent consisted of 10 v% of gamma-butyrolactone, 20 v% of ethyl lactate, and 70 v% of propylene glycol monomethyl ether.
Example 3
A photosensitive polyimide resin composition is prepared by the following method:
weighing 5g of polyimide precursor resin 3, dissolving in 50mL of mixed solvent, adding 1g of photoacid generator PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant, stirring and dissolving, and filtering through a 0.45 micrometer filter to obtain the photosensitive polyimide resin composition 3.
The mixed solvent consisted of 10 v% of gamma-butyrolactone, 20 v% of ethyl lactate, and 70 v% of propylene glycol monomethyl ether.
Example 4
A photosensitive polyimide resin composition is prepared by the following method:
5g of polyimide precursor resin 4 is weighed and dissolved in 50mL of mixed solvent, 1g of photoacid generator PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant are added, stirred and dissolved, and then filtered through a 0.45 micron filter, so as to obtain the photosensitive polyimide resin composition 4.
The mixed solvent consisted of 10 v% of gamma-butyrolactone, 20 v% of ethyl lactate, and 70 v% of propylene glycol monomethyl ether.
Comparative example
Preparation of comparative polyimide precursor resin
8.02g (40mmol) of 4,4' -diaminodiphenyl ether was weighed out and charged into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Quickly dropwise adding a diacid solution into the system, stirring and reacting for 3h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 3h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24h to obtain the comparative polyimide precursor resin 1.
The molecular weight was measured by gel permeation chromatography (Shimadzu LC-20A, Shimadzu, Japan) according to the GPC method, and the number average molecular weight of the polyimide precursor resin was determined and compared to 8200.
Preparation of diacid solution: 15.51g (50mmol) of 4,4' -oxydiphthalic anhydride monomer were mixed with 35mL of N-methylpyrrolidone (NMP).
A comparative photosensitive polyimide resin composition was prepared by the following method:
5g of comparison polyimide precursor resin is weighed and dissolved in 50mL of mixed solvent, 1g of PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant are added, and after stirring and dissolving, the mixture is filtered through a 0.45 micron filter to obtain a comparison photosensitive polyimide resin composition 1.
The mixed solvent is formed by mixing 10 v% of gamma-butyrolactone, 20 v% of ethyl lactate and 70 v% of propylene glycol monomethyl ether.
Performance test
Detection method/test method
The photosensitive polyimide resin compositions obtained in examples 1 to 4 and comparative example 1 were examined
1. And (3) testing the photoetching performance:
the prepared photosensitive polyimide resin composition was spin-coated (rotational speed 250r/min, coating time 15s) in 5ml on a 5-inch square glass substrate, prebaked at 120 ℃ for 160s to remove most of the solvent, then exposed to ultraviolet light in an ultraviolet exposure machine (g, h, i rays), and developed with 2.38% tetramethylammonium hydroxide (2.38 wt% TMAH) to obtain a photo-etched pattern having a sensitivity of the minimum exposure required for developing a complete pattern within 60s development time.
2. And (3) transmittance test:
the prepared photosensitive polyimide resin composition was spin-coated on a 5-inch square glass substrate, pre-baked at 120 ℃ for 160s to remove most of the solvent, and then cured in a nitrogen clean oven (oxygen concentration <20ppm) at 250 ℃ for 1h to obtain a cured polyimide film, which was tested for light transmittance at wavelengths of 400nm to 700 nm.
3. And (3) drug resistance testing:
the prepared photosensitive resin composition was spin-coated (rotation speed 250r/min, coating time 15s) on a 5-inch square glass substrate, pre-baked at 120 ℃ for 160s to remove most of the solvent, then cured in a nitrogen clean oven (oxygen concentration <20ppm) at 250 ℃ for 1h, and the film thickness was measured with an ellipsometer t 1. The coated glass substrate is respectively soaked in 2.38 wt% of TMAH developing solution or striper solution for 30min at room temperature, is washed by deionized water after being taken out, is baked for 30min in a nitrogen clean oven (oxygen concentration is less than 20ppm) at 230 ℃, is tested for the film thickness t2 by an ellipsometer, and is calculated to obtain the film thickness change rate delta t before and after etching (t1-t2)/t1 is 100%.
The results are shown in Table 1
TABLE 1 test of photoetching Performance, transmittance, and chemical resistance of examples 1 to 4 and comparative example 1
In combination with table 1, it can be seen that the diamine compounds prepared in preparation examples 1, 2, 3 and 4 can be further used to synthesize a polyimide precursor resin, and a photosensitive polyimide resin composition can be further obtained from the polyimide precursor resin. The polyimide resin composition has good exposure sensitivity, and the minimum exposure amount is lower than 85mJ/cm in the comparative example2The minimum exposure of example 4 was 55mJ/cm2。
Meanwhile, the photosensitive polyimide resin compositions obtained in examples 1 to 4 also have good transmittance, and the photosensitive resin compositions have low film thickness reduction rate after being soaked in TMAH developer or striper, which indicates that the photosensitive polyimide resin compositions have good drug resistance.
The photosensitive resin composition prepared by the application can be applied to the preparation of organic electroluminescent elements or semiconductor elements, such as RDL (discriminant layer) and Bump layers in semiconductor devices; or in the field of interlayer insulation and device protection in OLED manufacturing, and manufacturing a planarization layer (PLN, buffer function) Pixel Division Layer (PDL) and the like.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The polyimide precursor resin is characterized by comprising a structural unit shown as a formula (I)
In the formula (I)
R1Is a 4-8 valent organic group containing aromatic ring and having 6-30 carbon atoms or a 4-8 valent organic group containing aliphatic ring structure and having 3-20 carbon atoms;
p is the number of hydroxyl groups connected to R1, and p is an integer of 0-4;
r2 has a structure shown in formula (II)
R3 is a hydrogen atom or a C1-8 alkyl group;
in the formula (II), R' is selected from any one of the following structures
R4Is 1, 2 or 3, R4Selected from any one of halogen atom, trifluoromethyl, methyl, hydroxyl and alkoxy.
2. The polyimide precursor resin according to claim 1, wherein: the polyimide precursor resin also comprises a repeating structural unit shown as a formula (III)
In the formula (III)
R1Is a 4-8 valent organic group containing aromatic ring and having 6-30 carbon atoms or a 4-8 valent organic group containing aliphatic ring structure and having 3-20 carbon atoms;
p is attached to R1The number of the hydroxyl groups is 0 to 4;
R3is a hydrogen atom or an alkyl group of C1-8;
R5derived from any one of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenylsulfone, diaminodiphenylether, 2-bis (4-hydroxy-3-aminophenyl) propane, 4' -cyclohexanediamine, 1, 4-bis (4' -aminophenoxy).
3. The polyimide precursor resin according to claim 1 or 2, characterized in that: the 4-8 valent organic group containing aromatic ring and having 6-30 carbon atoms is derived from benzene, biphenyl, terphenyl, furan, thiophene, pyrrole, pyridine, naphthalene, anthracene, phenanthrene, indene, fluorene, fluoranthene, triphenylene, perylene,
And (c) any of tetracenes.
4. The polyimide precursor resin according to claim 1 or 2, characterized in that: the organic group with 4-8 valences and 3-20 carbon atoms containing the aliphatic ring structure is derived from any one of cyclobutane, cyclopentane, cyclohexane and cycloheptane.
5. The polyimide precursor resin according to claim 1 or 2, characterized in that: said C is1-8The alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl and n-octyl.
6. The polyimide precursor resin according to claim 1 or 2, characterized in that: the number average molecular weight of the precursor resin is 2000-50000.
7. A photosensitive resin composition prepared using the polyimide precursor resin according to any one of claims 1 to 6.
8. The photosensitive resin composition according to claim 7, wherein the photosensitive resin composition comprises, by weight, 5 wt% to 30 wt% of the polyimide precursor resin, 61.5 wt% to 94 wt% of the solvent, 0.01 wt% to 0.5 wt% of the assistant, and 0.5 wt% to 8 wt% of the photoacid generator.
9. The photosensitive resin composition of claim 8, wherein the auxiliary agent comprises at least one of a leveling agent, a silane coupling agent, and a surfactant.
10. Use of the photosensitive resin composition according to any one of claims 7 to 9 for producing an organic electroluminescent element or a semiconductor element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795283A (en) * | 2014-09-02 | 2017-05-31 | 东丽株式会社 | Resin and photosensitive polymer combination |
| JP2017179000A (en) * | 2016-03-28 | 2017-10-05 | 株式会社カネカ | Polyamide acid, polyimide, polyamide acid solution and use of polyimide |
| JP2018123103A (en) * | 2017-02-03 | 2018-08-09 | 東レ株式会社 | Diamine compound, and heat-resistant resin and resin composition using the same |
| CN111171317A (en) * | 2018-11-13 | 2020-05-19 | 北京鼎材科技有限公司 | Modified polyimide precursor resin, photosensitive resin composition containing same and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795283A (en) * | 2014-09-02 | 2017-05-31 | 东丽株式会社 | Resin and photosensitive polymer combination |
| JP2017179000A (en) * | 2016-03-28 | 2017-10-05 | 株式会社カネカ | Polyamide acid, polyimide, polyamide acid solution and use of polyimide |
| JP2018123103A (en) * | 2017-02-03 | 2018-08-09 | 東レ株式会社 | Diamine compound, and heat-resistant resin and resin composition using the same |
| CN111171317A (en) * | 2018-11-13 | 2020-05-19 | 北京鼎材科技有限公司 | Modified polyimide precursor resin, photosensitive resin composition containing same and application |
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