CN111909045A - End-capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof - Google Patents
End-capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof Download PDFInfo
- Publication number
- CN111909045A CN111909045A CN201910384714.XA CN201910384714A CN111909045A CN 111909045 A CN111909045 A CN 111909045A CN 201910384714 A CN201910384714 A CN 201910384714A CN 111909045 A CN111909045 A CN 111909045A
- Authority
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- China
- Prior art keywords
- group
- polyimide precursor
- characteristic peak
- modified polyimide
- resin composition
- 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 126
- 239000004642 Polyimide Substances 0.000 title claims abstract description 105
- 239000002243 precursor Substances 0.000 title claims abstract description 97
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 239000002981 blocking agent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 125000000962 organic group Chemical group 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 57
- 238000003786 synthesis reaction Methods 0.000 abstract description 57
- 238000000034 method Methods 0.000 abstract description 43
- 238000004132 cross linking Methods 0.000 abstract description 24
- 239000009719 polyimide resin Substances 0.000 abstract description 21
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 18
- 239000003431 cross linking reagent Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004017 vitrification Methods 0.000 abstract description 2
- 239000003039 volatile agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 72
- 239000000203 mixture Substances 0.000 description 41
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 40
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 33
- 238000012512 characterization method Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 23
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 23
- 239000002904 solvent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 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 14
- 239000000178 monomer Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 7
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 238000001308 synthesis method Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910003896 H2xO Inorganic materials 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 4
- -1 phenol compound Chemical class 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 description 3
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical group C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 description 3
- IKFWPXJYAIJZES-UHFFFAOYSA-N 3,5-bis(hydroxymethyl)phenol Chemical compound OCC1=CC(O)=CC(CO)=C1 IKFWPXJYAIJZES-UHFFFAOYSA-N 0.000 description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 2
- 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
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 2
- IYTXQZMZTQHONB-UHFFFAOYSA-N 4-[(4-aminophenoxy)-dimethylsilyl]oxyaniline Chemical compound C=1C=C(N)C=CC=1O[Si](C)(C)OC1=CC=C(N)C=C1 IYTXQZMZTQHONB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- UXOOFXUEODCAIP-UHFFFAOYSA-N 1,2,3-tribromo-5-(3,4,5-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC(C=2C=C(Br)C(Br)=C(Br)C=2)=C1 UXOOFXUEODCAIP-UHFFFAOYSA-N 0.000 description 1
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 description 1
- QCKHVNQHBOGZER-UHFFFAOYSA-N 1,2,4,5-tetrabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C=C1Br QCKHVNQHBOGZER-UHFFFAOYSA-N 0.000 description 1
- FXJXZYWFJAXIJX-UHFFFAOYSA-N 1,3-dibromo-5-(3,5-dibromophenyl)benzene Chemical group BrC1=CC(Br)=CC(C=2C=C(Br)C=C(Br)C=2)=C1 FXJXZYWFJAXIJX-UHFFFAOYSA-N 0.000 description 1
- 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
- ZWEYMNHQUMTRGY-UHFFFAOYSA-N 2,3,6,7-tetrabromonaphthalene Chemical compound BrC1=C(Br)C=C2C=C(Br)C(Br)=CC2=C1 ZWEYMNHQUMTRGY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NDMUQNOYNAWAAL-UHFFFAOYSA-N 3-diazo-1,4-dioxonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C(=[N+]=[N-])C(S(=O)(=O)O)C(=O)C2=C1 NDMUQNOYNAWAAL-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000838335 Homo sapiens Dual specificity protein phosphatase 2 Proteins 0.000 description 1
- 101001080401 Homo sapiens Proteasome assembly chaperone 1 Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229960005552 PAC-1 Drugs 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 102100027583 Proteasome assembly chaperone 1 Human genes 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 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
- 230000002349 favourable effect Effects 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
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
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- 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
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Abstract
The invention provides a blocking agent containing crosslinkable groups, modified polyimide precursor resin, a photosensitive resin composition and application thereof. The end-capping agent containing the crosslinkable group has the function of the crosslinking agent during high-temperature curing, can be applied to synthesis of polyimide precursor resin to obtain modified polyimide precursor resin with a crosslinking function, has a self-crosslinking function, does not need to add the crosslinking agent, and can realize intermolecular crosslinking of the polyimide resin by the crosslinking group of the end-capping agent in the high-temperature curing process to form a network crosslinking structure, so that the overall heat resistance of the photoresist is improved, and meanwhile, the effects of improving the stripping resistance, reducing the amount of micromolecular volatiles, improving the vitrification temperature of the photoresist and the like are achieved. Meanwhile, as the crosslinkable group reacts with the phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material can be reduced, and the stability of the device can be improved.
Description
Technical Field
The invention belongs to the technical field of photoetching, and relates to a blocking agent containing a crosslinkable group, modified polyimide precursor resin, a photosensitive resin composition and application thereof.
Background
Polyimide has a plurality of excellent performances such as high and low temperature resistance, mechanical property, dielectric property, biocompatibility, low thermal expansion coefficient and the like, and is widely used in the fields of electronic appliance industry, aerospace industry, advanced composite materials, fibers, engineering plastics, photoresist and the like. Photosensitive polyimide is mainly applied to photoresist in the field of microelectronics, can simplify a photoetching process to a great extent compared with common polyimide, 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. At present, in order to ensure that a film layer has good performance under a spin coating or slit coating process and avoid the defects of air bubbles and the like, the photoresist viscosity is required to be not too high, and the molecular weight of corresponding polyimide resin is low, so that the resin with high self-thermal and mechanical properties and large molecular weight is poor, and a small molecular cross-linking agent is required to be added subsequently to form a network cross-linking structure so as to improve the thermodynamic property of the resin.
JP2014157297A discloses a photosensitive resin composition of polyimide, which forms a crosslinked network structure during a high temperature curing process by introducing a crosslinking functional group containing a benzyl ether structure into the photosensitive resin composition, so that the 5% heat loss temperature of the photoresist is increased, and the photoresist has good solvent stripping resistance.
CN104730861A discloses a positive photosensitive resin composition comprising: an alkali-soluble resin; a photosensitive diazoquinone compound; a crosslinking agent; a thermal acid generator; a phenol compound; and an organic solvent, wherein the crosslinking agent and the heat acid generator are contained at a weight ratio of 1: 50 to 50: 1, the positive photosensitive resin composition can be cured at a low temperature, maintain a front taper without pattern collapse during thermal curing, generate a small amount of outgas from a coating layer after heating and baking, and have excellent heat resistance and chemical resistance. Further, the photosensitive resin film is free from deterioration in performance due to degassing and also free from light-emitting defects such as black spots, pixel shrinkage, and the like.
However, as described above, the prior art has used a method of introducing a crosslinking agent to increase the molecular weight of the resin and form a network structure to improve the physical properties thereof, but the following problems exist: (1) the added micromolecule cross-linking agent is difficult to react completely and has residue; (2) the crosslinking agent has poor heat resistance, and the crosslinking agent affects the heat stability of the system to cause limited improvement of the thermal property of the material and increase of small molecular volatile matters. Therefore, the problem of difficult improvement of the thermal stability, the peel strength and the mechanical property of the photoresist is also a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cross-linkable group-containing end capping agent, a modified polyimide precursor resin, a photosensitive resin composition and application thereof, wherein the cross-linkable group-containing end capping agent can be used for preparing the modified polyimide precursor resin, so that the polyimide precursor has a cross-linking function, a cross-linking agent is not required to be added, and the cross-linking group of the end capping agent can realize cross-linking among polyimide resin molecules in a high-temperature curing process to form a network cross-linking structure, thereby improving the overall heat resistance of the photoresist, and simultaneously having the effects of improving the stripping resistance, reducing the amount of small molecule volatile matters, improving the vitrification temperature of the photoresist and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a crosslinkable group-containing blocking agent having a structure represented by formula I below:
wherein R is1、R2、R3、R4、R5And R6Independently selected from hydrogen atom, halogen atom, hydroxyl group, CxH2xOH orAnd R is1、R2、R3、R4、R5And R6At least one of which is selected from- - - - - -CxH2xOH or1 ≦ x ≦ 5, 0 ≦ i ≦ 5, e.g., x may be 1,2, 3, 4, or 5, i may be 0, 1,2, 3, 4, or 5; n is an integer from 1 to 5, such as 1,2, 3, 4 or 5;
a is any one of the following groups a-g:
wherein the dotted line represents the position of the group's access.
The end-capping reagent containing the crosslinkable group has the function of a crosslinking agent during high-temperature curing, and can be applied to synthesis of polyimide precursor resin to obtain modified polyimide precursor resin with a crosslinking function.
Preferably, said R is1、R2And R3At least one of them is selected from-CH2OH、-CH2OCH3or-CH2OCH2CH3;
Preferably, the end-capping agent containing a crosslinkable group is any one of the following compounds:
in a second aspect, the present invention provides a modified polyimide precursor resin having a structure represented by formula II below:
wherein R isaIs any one of organic groups containing aryl of C6-C30 or naphthenic groups of C3-C20;
Rbis an aryl-containing organic group of C6-C30, an aliphatic hydrocarbon group of C2-C12, a naphthenic hydrocarbon group of C3-C20, an aliphatic hydrocarbon group of C2-C12 containing Si in a main chain or an aromatic hydrocarbon group of C6-C30 connected by an organic group containing Si;
p and q are each independently an integer of 0 to 4; p and q are not zero, the (OH)pAnd (OH)qAre directly connected with aryl, and p and q are not 0 at the same time;
Rcis a hydrogen atom or an alkyl group of C1-C8; m is ≧ 2, e.g., m is 2, 3, 4,5, 6, 9, 10, 12, 15, 18, or the like.
R isWherein R is1、R2、R3、R4、R5And R6Independently selected from hydrogen atom, halogen atom, hydroxyl group, CxH2xOH orAnd R is1、R2、R3、R4、R5And R6At least one of which is selected from- - - - - -CxH2xOH orX is more than or equal to 1 and less than or equal to 5, i is more than or equal to 0 and less than or equal to 5, and n is an integer of 1-5;
a is any one of the following groups a-g:
dotted line in substituent structural formula of the present inventionRepresents the access position of a substituent.
In the invention, the modified polyimide precursor resin has a crosslinkable group-containing R group at the end, namely contains-CxH2xOH orThe cross-linkable group enables the modified polyimide precursor resin to have a self-crosslinking function, no cross-linking agent is needed to be added, in the high-temperature imidization process, benzyl alcohol and phenolic hydroxyl are subjected to dehydration and ether forming reaction, or benzyl ether and phenolic hydroxyl are subjected to ether exchange reaction, thermal cross-linking reaction is generated between polymer main chains, ether bonds are formed, a compact and stable cross-linked network structure is obtained, the performances of thermal stability, stripping resistance, mechanical strength and the like of the photoresist resin can be greatly improved, meanwhile, the introduction of a micromolecular cross-linking agent is avoided, and the overflow amount of micromolecular volatile matters of the photoresist can be effectively reduced.
Meanwhile, as the crosslinkable group reacts with the phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material can be reduced, and the stability of the device can be improved.
That is, in the present invention, the curing mechanism of the modified polyimide precursor resin is as follows:
a) imidization reaction: the amic acid (ester) group in the main chain of the polyamic acid resin precursor generates cyclization reaction at high temperature to remove small molecular compound (water or alcohol) to generate polyimide compound, and the reaction formula is as follows:
b) and (3) crosslinking reaction: the invention utilizes the ether exchange reaction between benzyl ether and phenolic hydroxyl or the dehydration and ether formation reaction between benzyl alcohol and phenolic hydroxyl to form a cross-linked network structure connected by ether bonds between polyimide main chains, thereby improving the indexes of thermal and mechanical properties, stripping resistance, hygroscopicity and the like of the photoresist resin.
In the structure of formula II of the present invention, R is containedaStructural unit (i.e.) The number of (A) may be one or more, that is, the structure does not solely represent a structural unit containing only one carbonyl group, and R may be different depending on the type of RaAnd RcIn the structure of formula II, a plurality of structural units containing the carbonyl group are contained. In the same way, according to different RbAlternatively, the structure of formula II may also contain a plurality of amino-containing structural units (i.e.)。
In the present invention, the aliphatic hydrocarbon group of C2 to C12 containing Si in the main chain means that Si atom is further present in the aliphatic hydrocarbon group main chain, and may be, for exampleEtc.; the Si-containing organic group in the C6-C30 aromatic hydrocarbon group connected by the Si-containing organic group can be an aliphatic hydrocarbon group containing Si or an aliphatic hydrocarbon group containing-Si-O-, and the C12-C30 aromatic hydrocarbon group connected by the Si-containing organic group can beAnd the like.
In the present invention, the organic group containing an aryl group having at least one of C6 to C30 includes an aryl group and a group in which an aryl group is bonded to another organic group, and the bonding position between the organic group containing an aryl group having at least one of C6 to C30 and another group may or may not be an aryl group, and the bonding position is exemplified byIs composed of And the like.
Preferably, the modified polyimide precursor resin has a weight average molecular weight of 2000-50000, such as 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000, 10000, 12000, 15000, 18000, 20000, 23000, 25000, 28000 or 30000, preferably 5000-30000.
Preferably, said R isa(OH)pAny one selected from the following groups:
wherein the dotted line represents the position of the group's access.
Preferably, said R isb(OH)qAny one selected from the following groups:
wherein the dotted line represents the position of the group's access.
Preferably, R is selected from any one of the following groups:
wherein the dotted line represents the position of the group's access.
In the present invention, C6 to C30 in the aromatic hydrocarbon group of C6 to C30, C6 to C30, and C6 to C30 linked by an Si-containing organic group represent the number of carbon atoms in the group, and may be, for example, 6, 8, 10, 15, 18, 20, 23, 26, 28, 30 carbon atoms; similarly, the number of carbon atoms in the cycloalkyl of C3-C20 can be 3, 4,5, 6, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30 carbon atoms and the like, and C2-C12 in the aliphatic hydrocarbon group of C2-C12 and the aliphatic hydrocarbon group of C2-C12 containing Si in the main chain can be 2, 3, 4,5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms in the group. Also, the definition of other ranges of carbon numbers indicates that the number of carbon atoms in the group may take any integer within the numerical range.
In a third aspect, the present invention provides a photosensitive resin composition comprising the modified polyimide precursor resin according to the second aspect.
Preferably, the photosensitive resin composition comprises the following components in percentage by mass:
in the photosensitive resin composition of the present invention, the mass percentage of the modified polyimide precursor resin is 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.%, etc., preferably 6 wt.% to 20 wt.%.
The mass percent of the diazonaphthoquinone sulfonate ester 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.%, or 7.5 wt.%, and the like.
The mass 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.%, or 0.45 wt.%, etc.
The solvent is present in an amount of 61.5 wt.% to 95 wt.%, such as 62 wt.%, 65 wt.%, 68 wt.%, 70 wt.%, 72 wt.%, 75 wt.%, 78 wt.%, 80 wt.%, 71 wt.%, 86 wt.%, 88 wt.%, 90 wt.%, or 94 wt.%, etc.
Preferably, the solid content of the photosensitive resin composition is 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.%.
In the present invention, the sum of the contents of the components in the photosensitive resin composition is 100 wt.%.
In the present invention, 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 invention, the solid content is preferably 5 wt.% to 38.5 wt.%, and too low solid content can affect the continuity and uniformity of the film when the photosensitive resin composition is formed into a film, while too high solid content can cause too high viscosity and further cause the problems of bubble generation, poor flatness and the like in the film coating process.
Preferably, the diazonaphthoquinone sulfonate is selected from any one or a combination of at least two of the following compounds:
wherein D1、D2And D3Each independently selected from-H or a DNQ group which is r, s, t are each independently selected from integers of 0 to 5, such as 0, 1,2, 3, 4 or 5;
the diazonaphthoquinone sulfonate ester contains at least one DNQ group.
The photolithography mechanism of the photosensitive resin composition of the present invention is as follows: diazonaphthoquinone groups in PAC can form hydrogen bonds with phenolic hydroxyl groups, carboxyl groups and other groups in the main chain of the photoresist resin, so that the solubility of the resin in the photoresist in an alkali solution is inhibited, after exposure, the diazonaphthoquinone groups react with water to generate indene acid, so that the PAC compound is easily dissolved in dilute alkali solution, the alkali dissolution rate of an exposed area is increased, and a positive pattern reserved in an unexposed area is obtained; the reaction process of the diazonaphthoquinone group during photolithography is as follows:
in the present invention, the auxiliary agent includes any one or a combination of at least two of a leveling agent, a coupling agent, and a surfactant.
Preferably, the coupling agent is a siloxane group-containing coupling agent.
Preferably, the surfactant is a fluorine-containing surfactant and/or a surfactant containing a polyethylene glycol structure.
In the present invention, the use of the auxiliary agent contributes to the effects of improving the degree of planarization of the thin film, the adhesion between the resist compound and the substrate, and reducing the residual film after development.
In the present invention, the solvent includes any one or a combination of at least two of γ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, N-methylpyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide.
In a fourth aspect, the present invention provides a use of the photosensitive resin composition according to the third aspect above in an OLED display panel;
preferably, the photosensitive resin composition is used as a device protection material, an interlayer insulating material, a buffer layer material, or a pixel partition layer material in the manufacture of an OLED.
Compared with the prior art, the invention has the following beneficial effects:
the end-capping reagent containing the crosslinkable group has the function of a crosslinking agent during high-temperature curing, and can be applied to synthesis of polyimide precursor resin to obtain modified polyimide precursor resin with a crosslinking function.
The modified polyimide precursor resin has a self-crosslinking function due to the crosslinkable group, a crosslinking agent is not required to be added, dehydration and ether formation reaction are carried out between benzyl alcohol and phenolic hydroxyl groups or ether exchange reaction is carried out between benzyl ether and phenolic hydroxyl groups in the high-temperature imidization process, thermal crosslinking reaction is carried out between polymer main chains, ether bonds are formed, a compact and stable crosslinked network structure is obtained, the performances of the photoresist resin such as thermal stability, stripping resistance, mechanical strength and the like can be greatly improved, meanwhile, the introduction of a micromolecule crosslinking agent is avoided, and the overflow amount of micromolecule volatile matters of the photoresist can be effectively reduced.
Meanwhile, as the crosslinkable group reacts with phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material is reduced, and the stability of the device is improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Synthesis example 1:
synthesis of hydroxyl-containing dianhydride monomer 1:
in a nitrogen atmosphere, 10.8g (0.05mol) of 3,3 '-dihydroxy-4, 4' -benzidine was dissolved in 50mL of γ -butyrolactone, the temperature was reduced to-15 ℃, then 22.1g (0.105mol) of 1,2, 4-trimellitic anhydride acid chloride was dissolved in 50mL of γ -butyrolactone, the latter was added dropwise to the former solution (the reaction was exothermic, the reaction temperature should be kept below-5 ℃ during the dropwise addition), and the reaction was continued for 5h after the dropwise addition was completed. Most of the solvent was removed by a rotary evaporator, and the concentrate was poured into 300mL of toluene to precipitate a corresponding hydroxyl dianhydride-containing monomer 1.
Structural characterization: the method comprises the following steps: fourier transform infrared spectroscopy (instruments used for characterization of Fourier transform infrared spectroscopy in the invention are all Spectrum One infrared spectrometers of Perkin Elmer company, USA), characteristic peaks: 1850cm-1Is shown as a characteristic peak of an acid anhydride group at 3400cm-1Is a-OH characteristic peak at 1650cm-1The peak is characteristic of amide group.
Synthesis example 2:
synthesis of hydroxyl-containing dianhydride monomer 2:
the difference from preparation example 1 was that 5,5' - (1, 4-phenylenedi (oxo)) bis (2-aminophenol) in an amount equivalent to that of 3,3' -dihydroxy-4, 4' -benzidine was replaced with another substance to obtain a hydroxyl-containing dianhydride monomer 2.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 1850cm-1Is shown as a characteristic peak of an acid anhydride group at 3400cm-1Is a-OH characteristic peak at 1650cm-1Is characterized by amide group peak at 1240cm-1The peak is the characteristic peak of aromatic C-O-C.
Synthesis example 3:
synthesis of a blocking agent containing crosslinkable groups 1:
1.39g (10mmol) of m-nitrophenol is taken and dissolved in 20mL of DMMSO solvent, and then 1.18g (5mmol) of p-dibromobenzene and 3.69g (22mmol) of CsOH & H are added2O, reacting for 36 hours in an oil bath at 150 ℃, tracking the reaction by TLC, and after the reaction is completed, purifying the product by a column chromatography method to obtain an intermediate I;
2.94g (10mmol) of intermediate I are taken and dissolved in 20ml of a solvent of DMMSO, after which 1.54g (10mmol) of 3, 5-dimethylolphenol and 3.69g (22mmol) of CsOH. H are added2And O, reacting for 36 hours in an oil bath at 150 ℃, tracking the reaction by TLC, and after the reaction is completed, purifying the product by using a column chromatography method to obtain an intermediate II.
Adding 0.72g (30mmol) of sodium hydride into 20mL of dry anisole solution, adding 30mL of dry anisole solvent into 3.67g (10mmol) of intermediate II, dropwise adding into the former solution, refluxing for 2h after dropwise addition, adding 1.39g (11mmol) of dimethyl sulfate, and refluxing overnight. After the reaction is finished, the solution is washed by water, dried by anhydrous sodium sulfate, decompressed and distilled to remove the solvent, and purified by a column chromatography method to obtain an intermediate III;
adding 3.95g (10mmol) of the intermediate III into 50mL of DMF solvent, adding 2.13g (1mmol) of 5% palladium carbon, stirring and reacting under 0.4MPa of hydrogen pressure for 24h, filtering after the reaction is finished, distilling the filtrate under reduced pressure to remove the solvent, and purifying by a column chromatography method to obtain the amino end-capping reagent 1.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 4:
synthesis of a blocking agent containing crosslinkable groups 2:
the p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into m-dibromobenzene, and m-nitrophenol is changed into p-nitrophenol, and other reaction conditions are kept unchanged, so that the following end-capping agent 2 containing the crosslinkable group is obtained:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 5:
synthesis of a blocking agent containing crosslinkable groups 3:
and (3) converting the p-dibromobenzene used in the step of synthesizing the end-capping agent 1 containing the crosslinkable group into the tribromobenzene, and keeping other reaction conditions unchanged to obtain an amino end-capping agent 3:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 6:
synthesis of a blocking agent containing crosslinkable groups 4:
the p-dibromobenzene obtained in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into the 1,2,4, 5-tetrabromobenzene, and other reaction conditions are kept unchanged to obtain the end-capping agent 4 containing the crosslinkable group as follows:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 7:
synthesis of a blocking agent containing a crosslinkable group 5:
and (3) replacing the p-dibromobenzene used in the step of synthesizing the end-capping agent 1 containing the crosslinkable group with 3,3',5,5' -tetrabromobiphenyl, and keeping other reaction conditions unchanged to obtain an end-capping agent 5 containing the crosslinkable group:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 8:
synthesis of a blocking agent containing crosslinkable groups 6:
and (3) replacing the p-dibromobenzene used in the step of synthesizing the end-capping agent 1 containing the crosslinkable group with 2, 3, 6, 7-tetrabromo naphthalene, and keeping other reaction conditions unchanged to obtain the end-capping agent 6 containing the crosslinkable group.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 9:
synthesis of a blocking agent containing a crosslinkable group 7:
the synthesis method comprises the following steps: 1.39g (10mmol) of m-nitrophenol is taken and dissolved in 20mL of DMMSO solvent, and then 1.18g (5mmol) of m-dibromobenzene and 3.69g (22mmol) of CsOH & H are added2O, reacting for 36 hours in an oil bath at 150 ℃, tracking the reaction by TLC, and after the reaction is completed, purifying the product by a column chromatography method to obtain an intermediate I;
2.94g (10mmol) of intermediate I are taken and dissolved in 20ml of a solvent of DMMSO, after which 1.54g (10mmol) of 3, 5-dimethylolphenol and 3.69g (22mmol) of CsOH. H are added2And O, reacting for 36 hours in an oil bath at 150 ℃, tracking the reaction by TLC, and after the reaction is completed, purifying the product by using a column chromatography method to obtain an intermediate II.
Adding 3.67g (10mmol) of the intermediate II into 50mL of DMF solvent, adding 2.13g (1mmol) of 5% palladium carbon, stirring and reacting under 0.4MPa of hydrogen pressure for 24h, filtering after the reaction is finished, distilling the filtrate under reduced pressure to remove the solvent, and purifying by using a column chromatography method to obtain the amino end-capping reagent 7.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The broad peak is-OH characteristic peak, 3250cm-1Is represented by-NH2Characteristic Peak, 1240cm-1The peak is the characteristic peak of aromatic C-O-C.
Synthesis example 10:
synthesis of a blocking agent 8 containing crosslinkable groups:
the synthesis method comprises the following steps: the p-dibromobenzene used in the synthesis step of the end-capping reagent 1 containing the crosslinkable group is changed into 3,3',4,4',5,5' -hexabromobiphenyl, 3, 5-dimethylolphenol is changed into 4-bromobenzyl alcohol, dimethyl sulfate is changed into diethyl sulfate, and other reaction conditions are kept unchanged to obtain the end-capping reagent 8 containing the crosslinkable group
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3250cm-1Is represented by-NH2Characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1240cm-1Is located at 1155cm and is a characteristic peak of aromatic C-O-C-1The fat C-O-C characteristic peak is shown.
Synthesis example 11:
synthesizing a polyimide precursor 1:
5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 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 ℃. Weighing 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP, mixing, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 7.31g (20mmol) of capping agent 1, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and carrying out vacuum drying on the obtained solid precipitate at 80 ℃ for 24h to obtain a polyimide precursor 1 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 12
Synthesis of modified polyimide precursor 2
The end-capping reagent 1 in synthesis example 12 was replaced with the end-capping reagent 2 in an equivalent amount to give the corresponding polyimide precursor 2 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 13
Synthesis of modified polyimide precursor 3
The end-capping agent 1 in synthesis example 12 was replaced with the end-capping agent 3 in an equivalent amount to give the corresponding polyimide precursor 3 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 14
Synthesis of modified polyimide precursor 4
The end-capping agent 1 in synthesis example 12 was replaced with the end-capping agent 4 in an equivalent amount to give the corresponding polyimide precursor 4 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 15
Synthesis of modified polyimide precursor 5
The end-capping agent 1 in Synthesis example 12 was replaced with the end-capping agent 5 in an equivalent amount to give the corresponding polyimide precursor 5 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 16
Synthesizing a modified polyimide precursor 6:
4.24g (15mmol) of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone 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 ℃. Weighing 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP, mixing, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 14.50g (20mmol) of end-capping agent 4, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and carrying out vacuum drying on the obtained solid precipitate at 80 ℃ for 24h to obtain a polyimide precursor 6 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The peak width is-OH characteristic peak, 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH, 1150cm-1Is treated with-SO2Characteristic peak.
Synthesis example 17
Synthesizing a modified polyimide precursor 7:
8.02g (40mmol) of 4,4' -diaminodiphenyl ether was 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 ℃. Weighing 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP, mixing the mixture with NMP, quickly adding the mixture into a reaction system, stirring the mixture to react for 3 hours, heating the mixture to 40 ℃, adding 14.50g (20mmol) of amino-terminated agent 4, stirring the mixture to react for 4 hours, heating the mixture to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting the mixture for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water to precipitate, and drying the obtained solid precipitate in vacuum at 80 ℃ for 24 hours to obtain a polyimide precursor 7 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The peak width is-OH characteristic peak, 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a characteristic peak of-CO in-CONH.
Synthesis example 18
Synthesizing a modified polyimide precursor 8:
4.24g (15mmol) of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone 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 ℃. Weighing 15.51g (50mmol) of 4,4' -diphenyl ether tetracarboxylic dianhydride and 35mL of NMP, mixing the mixture with NMP, quickly adding the mixture into a reaction system, stirring the mixture for reaction for 3 hours, heating the mixture to 40 ℃, adding 14.50g (20mmol) of amino-terminated agent 4, stirring the mixture for reaction for 4 hours, heating the mixture to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting the mixture for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and drying the obtained solid precipitate in vacuum at 80 ℃ for 24 hours to obtain a polyimide precursor 8 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The peak width is-OH characteristic peak, 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH, 1150cm-1Is treated with-SO2Characteristic peak.
Synthesis example 19
Synthesis of modified polyimide precursor 9
The synthesis method comprises the following steps: 5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 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 ℃. Weighing 35.0g (52mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 17.4g (24mmol) of end-capping agent 4, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 9.91g (83.2mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h 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 polyimide precursor 9 with molecular weight of 5000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 20
Synthesis of modified polyimide precursor 10
The synthesis method comprises the following steps: 5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 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 ℃. Weighing 28.2g (42mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, adding into a reaction system twice, stirring for reaction for 3 hours, heating to 40 ℃, adding 3.1g (4mmol) of end-capping agent 6, stirring for reaction for 4 hours, heating to 50 ℃, slowly dropwise adding 8.0g (67.2mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate for 24 hours at 80 ℃ to obtain polyimide precursor 10 with the molecular weight of 30000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 21
Synthesis of modified polyimide precursor 11
The synthesis method comprises the following steps: 5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 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 ℃. Weighing 53.8g (80mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 27.0g (80mmol) of end-capping agent 7, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 15.2g (128mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and performing vacuum drying on the obtained solid precipitate at 80 ℃ for 24h to obtain polyimide precursor 11 with molecular weight of 2000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 22
Synthesis of polyimide precursor 12
Synthesis method 5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25mmol) of 4,4' -diaminodiphenyl ether were weighed 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 ℃. Weighing 27.1g (40.4mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, adding into a reaction system twice, stirring for reaction for 3 hours, heating to 40 ℃, adding 0.81g (0.8mmol) of end-capping agent 8, stirring for reaction for 4 hours, heating to 50 ℃, slowly dropwise adding 8.0g (67.2mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum-drying the obtained solid precipitate at 80 ℃ for 24 hours to obtain polyimide precursor 12 with molecular weight of 50000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Synthesis example 23
Synthesizing a modified polyimide precursor 13:
4.24g (15mmol) of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone and 2.85g (25mmol) of 1, 4-cyclohexanediamine (TCI, CAS: 3114-70-3) were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) were added under nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. In addition, 11.21g (50mmol) of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (TCI, CAS: 2754-41-8) and 35mL of NMP are weighed and mixed, the mixture is rapidly added into a reaction system, after stirring and reacting for 3h, the temperature is raised to 40 ℃, 14.50g (20mmol) of amino end capping agent 4 is added, stirring and reacting for 4h, the temperature is raised to 50 ℃, 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal is slowly dripped into the reaction system, after reacting for 2h at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, the obtained solid precipitate is dried in vacuum at 80 ℃ for 24h, and a polyimide precursor 13 with the molecular weight of 7000 is obtained.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The peak width is-OH characteristic peak, 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH, 1150cm-1Is treated with-SO2Characteristic peak.
Synthesis example 24
Synthesis of modified polyimide precursor 14:
1.74g (15mmol) of 1, 6-hexanediamine (carbofuran, CAS: 124-09-4), 6.21g (25mmol) of 1, 3-bis (3-aminopropyl) -1,1',3,3' -tetramethyldisiloxane (TCI, CAS: 2469-55-8) were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and dissolved by mechanical stirring at 4 ℃. Weighing 33.6g (50mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 14.50g (20mmol) of amino-terminated agent 4, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h 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 polyimide precursor 14 with molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3200-3400 cm-1The broad peak is-OH characteristic peak, 3400-3500cm-1The characteristic peak is-COOH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH, 1020cm-1Is located at-Si-O characteristic peak of 800cm-1The peak is a characteristic peak of-Si-C.
Synthesis example 25
Synthesis of modified polyimide precursor 15
The synthesis method comprises the following steps: 5.49g (15mmol) of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 6.86g (25mmol) of bis (4-aminophenoxy) dimethylsilane (carbofuran, CAS: 1223-16-1) 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 ℃. Weighing 33.6g (50mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 14.5g (20mmol) of end-capping agent 4, stirring for reaction for 4h, heating to 50 ℃, slowly dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2h at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and carrying out vacuum drying on the obtained solid precipitate at 80 ℃ for 24h to obtain a polyimide precursor 15 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak, 1020cm-1Is located at-Si-O characteristic peak of 800cm-1The peak is a characteristic peak of-Si-C.
Comparative synthesis example 1:
synthesis of an unmodified polyimide precursor 1:
5.49g (15mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 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 ℃. Weighing 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP, mixing the mixture with NMP, quickly adding the mixture into a reaction system, stirring the mixture to react for 3 hours, heating the mixture to 40 ℃, adding 1.86g (20mmol) of aniline, stirring the mixture to react for 4 hours, heating the mixture to 50 ℃, slowly and dropwise adding 9.53g (80mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting the mixture for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water to precipitate, and drying the obtained solid precipitate in vacuum at 80 ℃ for 24 hours to obtain an unmodified polyimide precursor 1 with the molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peak: 3400-3500 cm-1The characteristic peak is-COOH characteristic peak, 3200-3400 cm-1The broad peak is-OH characteristic peak, 2850cm-1~2950cm-1Is characterized by methylene and methyl peaks at 1720cm-1Is a characteristic peak of-CO in carboxyl, 1650cm-1Is a-CO characteristic peak in-CONH of 1350cm-1Is of-CF3Characteristic peak.
Example 1
This example provides a photosensitive resin composition prepared by the following method:
5g of modified polyimide precursor resin 1 is weighed and dissolved in 50mL of mixed solvent consisting of 40% of gamma-butyrolactone, 20% of ethyl lactate and 40% of propylene glycol monomethyl ether, 1g of PAC-1, 0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant are added, and after stirring and dissolution, the mixture is filtered through a 0.45 micron filter to obtain the photosensitive polyimide resin composition 1.
Example 2
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 2 was prepared in the same manner by replacing a modified polyimide precursor 1 with a modified polyimide precursor 2 of equal mass.
Example 3
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 3 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 3.
Example 4
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 4 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 4.
Example 5
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 5 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 5.
Example 6
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 6 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 6.
Example 7
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 7 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 7.
Example 8
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 8 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 8.
Example 9
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 9 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 9.
Example 10
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 10 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 10.
Example 11
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 11 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 11.
Example 12
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 12 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 12.
Example 13
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 13 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 13.
Example 14
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 14 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 12.
Example 15
This example provides a photosensitive resin composition, which is different from example 1 in that a photosensitive polyimide resin composition 15 was prepared in the same manner by replacing the modified polyimide precursor 1 with an equivalent mass of the modified polyimide precursor 12.
Comparative example 1
The difference from example 1 was that the modified polyimide precursor 1 was replaced with an equal mass of an unmodified polyimide precursor 1 to obtain a photosensitive resin composition D1.
Comparative example 2
The difference from example 1 was that the modified polyimide precursor 1 was replaced with an equal mass of an unmodified polyimide precursor 1, and 1.0g of a terminal-blocking agent 4 having a crosslinkable group was added as a crosslinking agent to obtain a photosensitive resin composition D2.
And (3) testing the photoetching performance:
the prepared photosensitive polyimide resin composition is coated on a 5-inch square glass substrate in a rotating mode, prebaked for 180s at 120 ℃ to remove most of solvent, exposed under a 365nm ultraviolet exposure machine, developed by 2.38% tetramethylammonium hydroxide (2.38 wt.% TMAH) for 60-120 s to obtain a photoetching pattern, and the light sensitivity is the minimum exposure amount required for displaying a complete pattern within 60s of development time.
Outgas (small molecule volatilization) test:
preparing a sample: the prepared photosensitive resin composition was coated on a 5-inch square glass substrate by spin coating (note: wherein the samples of examples 10 and 12 and comparative example 2 were coated at a coating speed of 1000rpm due to their large molecular weight and high viscosity, the sample of example 11 was small molecular weight and low viscosity, and the coating speed was adjusted to 200rpm, and the other examples and comparative examples were coated at a coating speed of 250 rpm), pre-baked at 120 ℃ for 180 seconds to remove most of the solvent, and then the coated glass substrate was cured in a 250 ℃ clean oven under nitrogen protection (oxygen concentration <500ppm) for 1 hour, and the film was scraped off and vacuum-sealed and stored for use.
Thermogravimetric analysis test: testing atmosphere: nitrogen, temperature rising program: keeping the temperature at 40 ℃ for 30min, then heating to 250 ℃ at the speed of 5K/min, keeping the temperature for 30min, and calculating the mass loss in the heat preservation process at 250 ℃.
And (3) testing the peeling resistance:
the prepared photosensitive polyimide resin composition was spin-coated (rotation speed, 250 rpm) on a 5-inch square glass substrate, prebaked at 120 ℃ for 180 seconds to remove most of the solvent, and the film thickness t was measured, followed by placing in a 250 ℃ nitrogen purge oven (oxygen concentration)<500ppm) for 1h, and the film thickness t is measured with an ellipsometer1. Soaking the coated glass substrate in 6Etching in 5 deg.C TOK106 stripping solution for 150s, taking out, washing with deionized water, and cleaning in 230 deg.C nitrogen oven (oxygen concentration)<500ppm) for 30min, and testing the film thickness t with an ellipsometer2Calculating the film thickness change delta t before and after etching2-t1。
The results of the above performance tests are shown in table 1.
TABLE 1
And (3) testing mechanical properties:
pouring the photosensitive resin composition into a mold with the length of 150mm x 10mm x 0.5mm (length x width x depth), placing on a horizontal table, airing to be semi-dry at room temperature, placing in a nitrogen oven, curing according to the temperature program of 100 ℃ (30min) -130 ℃ (30min) -150 ℃ (30min) -200 ℃ (30min) -250 ℃ (60min) -natural cooling to room temperature to obtain a test standard sample strip, wherein the thickness of the test standard sample strip is 20 mu m, and the mechanical property is tested by a universal material testing machine, the displacement rate is 5mm/min, the environment temperature is 23 ℃, and the humidity is 50 +/-5%.
The mechanical properties test results are shown in table 2.
TABLE 2
Tensile Strength (MPa) | Elongation at Break (%) | |
Example 1 | 100 | 10 |
Example 2 | 100 | 10 |
Example 3 | 110 | 12 |
Example 4 | 150 | 15 |
Example 5 | 150 | 15 |
Example 6 | 150 | 15 |
Example 7 | 95 | 9 |
Example 8 | 95 | 9 |
Example 9 | 92 | 8 |
Example 10 | 150 | 20 |
Example 11 | 90 | 6 |
Example 12 | 180 | 25 |
Example 13 | 85 | 6 |
Example 14 | 65 | 5 |
Example 15 | 100 | 10 |
Comparative example 1 | 20 | 2 |
Comparative example 2 | 80 | 5 |
The data in tables 1 and 2 show that compared with comparative example 1 without crosslinking, the polyimide precursor photosensitive resin composition with crosslinking function prepared by the invention has good comprehensive properties such as photoetching property, heat resistance, mechanical property, low-molecular-weight volatile matter (outgas) and the like, and has excellent application potential. Comparing the examples in the table, it can be seen that the density and content of the crosslinking groups have a greater influence on the overall performance of the photoresist, and the higher the density of the crosslinking sites (hydroxyl groups) in the resin, the more favorable the polyimide resin forms a body-type crosslinking structure during curing, the higher the peel resistance of the resin, and the lower the resin outgas.
If the blocking agent containing a crosslinkable group is added as a small molecular component to the photosensitive resin composition (i.e., comparative example 2), the peeling resistance can be also remarkably improved and outgas can be reduced, but the effect is inferior to that of a resin synthesized directly using an amino blocking agent of a corresponding structure. However, the comparative example 2 can greatly improve the comprehensive properties of the resin, such as heat resistance, mechanical properties, low-molecular-weight volatile matters (outgas) and the like, compared with the comparative example 1 without crosslinking.
The applicant states that the present invention is illustrated by the above examples of the crosslinkable group-containing terminal-blocking agent, the modified polyimide precursor resin, the photosensitive resin composition and the use thereof of the present invention, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be practiced by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An end-capping agent containing a crosslinkable group, wherein the end-capping agent containing a crosslinkable group has a structure represented by the following formula I:
wherein R is1、R2、R3、R4、R5And R6Independently selected from a hydrogen atom, a halogen atom, a hydroxyl group,And R is1、R2、R3、R4、R5And R6At least one of them is selected fromX is more than or equal to 1 and less than or equal to 5, and i is more than or equal to 0 and less than or equal to 5; n is an integer of 1 to 5;
a is any one of the following groups a-g:
wherein the dotted line represents the position of the group's access.
2. The blocking agent containing a crosslinkable group according to claim 1, wherein R is1、R2And R3At least one of them is selected from-CH2OH、-CH2OCH3or-CH2OCH2CH3。
4. a modified polyimide precursor resin, wherein the modified polyimide precursor resin has a structure represented by formula II below:
wherein R isaIs any one of organic groups containing aryl of C6-C30 or naphthenic groups of C3-C20;
Rbis an aryl-containing organic group of C6-C30, an aliphatic hydrocarbon group of C2-C12, a naphthenic group of C3-C20, an aliphatic hydrocarbon group of C2-C12 containing Si in the main chain or an aromatic hydrocarbon group of C6-C30 connected by an organic group containing Si;
p and q are each independently an integer of 0 to 4; p and q are not zero, the (OH)pAnd (OH)qAre directly connected with aryl, and p and q are not 0 at the same time;
Rcis a hydrogen atom or an alkyl group of C1-C8; m is more than or equal to 2;
r isWherein R is1、R2、R3、R4、R5And R6Independently selected from a hydrogen atom, a halogen atom, a hydroxyl group,And R is1、R2、R3、R4、R5And R6At least one of them is selected fromX is more than or equal to 1 and less than or equal to 5, i is more than or equal to 0 and less than or equal to 5, and n is an integer of 1-5;
a is any one of the following groups a-g:
wherein the dotted line represents the position of the group's access.
5. The modified polyimide precursor resin as claimed in claim 4, wherein the modified polyimide precursor resin has a weight average molecular weight of 2000-50000, preferably 5000-30000.
9. A photosensitive resin composition, characterized in that it comprises the modified polyimide precursor resin according to any one of claims 4 to 8;
preferably, the solid content of the photosensitive resin composition is 5 wt.% to 38.5 wt.%, preferably 8 wt.% to 30 wt.%.
10. Use of the photosensitive resin composition according to claim 9 in an OLED display panel;
preferably, the photosensitive resin composition is used as a device protection material, an interlayer insulating material, a buffer layer material, or a pixel partition layer material in the manufacture of an OLED.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114539524A (en) * | 2022-01-11 | 2022-05-27 | 吉林奥来德光电材料股份有限公司 | Photosensitive resin precursor polymer, photosensitive resin composition paste and use thereof |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07145282A (en) * | 1993-10-01 | 1995-06-06 | Asahi Chem Ind Co Ltd | Modified polyphenylene ether resin composition |
JP2007133377A (en) * | 2005-10-12 | 2007-05-31 | Toray Ind Inc | Photosensitive resin composition |
US20080108723A1 (en) * | 2005-03-15 | 2008-05-08 | Toray Industries, Inc. | Photosensitive Resin Composition |
JP2009009107A (en) * | 2007-05-25 | 2009-01-15 | Toray Ind Inc | Photosensitive resin composition |
JP2014157297A (en) * | 2013-02-18 | 2014-08-28 | Toray Ind Inc | Positive photosensitive resin composition |
CN104584297A (en) * | 2012-08-23 | 2015-04-29 | 株式会社可乐丽 | Polyelectrolyte film |
CN105367976A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | Highly-wear-resistant TPE foaming shoe material and preparation method thereof |
CN108059722A (en) * | 2017-12-22 | 2018-05-22 | 杭州师范大学 | A kind of polyarylether-polysiloxane copolymer and preparation method thereof |
WO2018173840A1 (en) * | 2017-03-21 | 2018-09-27 | 東レ株式会社 | Photosensitive resin composition, photosensitive resin composition film, insulating film and electronic component |
US20190086800A1 (en) * | 2016-05-25 | 2019-03-21 | Toray Industries, Inc. | Resin composition |
-
2019
- 2019-05-09 CN CN201910384714.XA patent/CN111909045B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07145282A (en) * | 1993-10-01 | 1995-06-06 | Asahi Chem Ind Co Ltd | Modified polyphenylene ether resin composition |
US20080108723A1 (en) * | 2005-03-15 | 2008-05-08 | Toray Industries, Inc. | Photosensitive Resin Composition |
JP2007133377A (en) * | 2005-10-12 | 2007-05-31 | Toray Ind Inc | Photosensitive resin composition |
JP2009009107A (en) * | 2007-05-25 | 2009-01-15 | Toray Ind Inc | Photosensitive resin composition |
CN104584297A (en) * | 2012-08-23 | 2015-04-29 | 株式会社可乐丽 | Polyelectrolyte film |
JP2014157297A (en) * | 2013-02-18 | 2014-08-28 | Toray Ind Inc | Positive photosensitive resin composition |
CN105367976A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | Highly-wear-resistant TPE foaming shoe material and preparation method thereof |
US20190086800A1 (en) * | 2016-05-25 | 2019-03-21 | Toray Industries, Inc. | Resin composition |
WO2018173840A1 (en) * | 2017-03-21 | 2018-09-27 | 東レ株式会社 | Photosensitive resin composition, photosensitive resin composition film, insulating film and electronic component |
CN108059722A (en) * | 2017-12-22 | 2018-05-22 | 杭州师范大学 | A kind of polyarylether-polysiloxane copolymer and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
孙自淑,马家举,江棂: "光敏聚酰亚胺的发展现状", 化工新型材料, no. 10 * |
魏文康;虞鑫海;王凯;吕伦春;: "光敏聚酰亚胺的研究与应用进展", 合成技术及应用, no. 03 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114539524A (en) * | 2022-01-11 | 2022-05-27 | 吉林奥来德光电材料股份有限公司 | Photosensitive resin precursor polymer, photosensitive resin composition paste and use thereof |
CN114539524B (en) * | 2022-01-11 | 2023-12-26 | 吉林奥来德光电材料股份有限公司 | Photosensitive resin precursor polymer, photosensitive resin composition slurry and application thereof |
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