CN115232017A - Compound, resin, and preparation method and application thereof - Google Patents
Compound, resin, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115232017A CN115232017A CN202210249190.5A CN202210249190A CN115232017A CN 115232017 A CN115232017 A CN 115232017A CN 202210249190 A CN202210249190 A CN 202210249190A CN 115232017 A CN115232017 A CN 115232017A
- Authority
- CN
- China
- Prior art keywords
- bis
- diamine
- dianhydride
- compound
- diaminobiphenyl
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000004305 biphenyl Substances 0.000 claims abstract description 10
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- -1 cyano, hydroxyl Chemical group 0.000 claims description 211
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 72
- 238000000059 patterning Methods 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 31
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 18
- 238000011161 development Methods 0.000 claims description 13
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 12
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 12
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 12
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 239000012024 dehydrating agents Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- UTYHQSKRFPHMQQ-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC(OC=2C=C(N)C(O)=CC=2)=C1 UTYHQSKRFPHMQQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- KCFVSHSJPIVGCG-UHFFFAOYSA-N 2-amino-4-[(3-amino-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC(CC=2C=C(N)C(O)=CC=2)=C1 KCFVSHSJPIVGCG-UHFFFAOYSA-N 0.000 claims description 6
- NLGOBIIKXFNGQR-UHFFFAOYSA-N 2-amino-4-[9-(3-amino-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(N)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(N)C(O)=CC=2)=C1 NLGOBIIKXFNGQR-UHFFFAOYSA-N 0.000 claims description 6
- VXTJVMWIVSZHNI-UHFFFAOYSA-N 2-amino-4-propylphenol Chemical compound CCCC1=CC=C(O)C(N)=C1 VXTJVMWIVSZHNI-UHFFFAOYSA-N 0.000 claims description 6
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 6
- QMAQHCMFKOQWML-UHFFFAOYSA-N 3-[2-[2-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)S(=O)(=O)C=2C(=CC=CC=2)OC=2C=C(N)C=CC=2)=C1 QMAQHCMFKOQWML-UHFFFAOYSA-N 0.000 claims description 6
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 6
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 claims description 6
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 claims description 6
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims description 6
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 6
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 6
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 6
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims description 6
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 claims description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- 239000007868 Raney catalyst Substances 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 150000004984 aromatic diamines Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 3
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 description 81
- 239000009719 polyimide resin Substances 0.000 description 80
- 238000006243 chemical reaction Methods 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 239000002313 adhesive film Substances 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 229920005575 poly(amic acid) Polymers 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 150000005690 diesters Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- 102100026735 Coagulation factor VIII Human genes 0.000 description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- GWGZFNRFNIXCGH-UHFFFAOYSA-N 4-nitro-2-(trifluoromethyl)benzenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C(F)(F)F GWGZFNRFNIXCGH-UHFFFAOYSA-N 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- AYVGBNGTBQLJBG-UHFFFAOYSA-N [3-(hydroxymethyl)cyclopentyl]methanol Chemical compound OCC1CCC(CO)C1 AYVGBNGTBQLJBG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BBYQSYQIKWRMOE-UHFFFAOYSA-N naphthalene-1,2,6,7-tetracarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 BBYQSYQIKWRMOE-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/34—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups and esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
-
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The application discloses a compound, a resin, and a preparation method and application thereof. The chemical structural formula of the compound is shown as follows:
R 1 is composed of
Or
R 2 Is one of the following groups: single bond, -NH-, -NCH 3 ‑、‑O‑、‑S‑、‑S‑S‑、‑SO 2 ‑、‑CO‑、‑COO‑、‑CONH‑、‑CONCH 3 ‑、‑O‑(CH2) m′ -O-, and substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12; the amino, trifluoromethyl and carboxyl connected with the benzene ring of the compound can replace hydrogen at any position on the benzene ring.
Description
Technical Field
The application relates to the technical field of patterned chip manufacturing, and discloses a compound, a resin, and a preparation method and application thereof.
Background
Photosensitive polyimide (PSPI) is a photosensitive resin having an imide ring and a photosensitive group, has excellent thermal stability and good mechanical, electrical, chemical and photosensitive properties, and is widely used in the fields of microelectronics, optoelectronics, aerospace and the like. Photosensitive polyimide resins are classified into positive polyimide resins and negative polyimide resins according to the difference in the pattern to be retained after the patterned development, and in the case of the negative polyimide resins, the exposed portions of the negative photosensitive polyimide resins are crosslinked and cured, while the unexposed portions are soluble in a developing solution and removed.
In the negative photosensitive polyimide resin provided by the related art, an alkali-soluble group is introduced at the end of the main chain of the polyimide resin, so that the negative polyimide resin can be dissolved in an environmentally-friendly aqueous alkaline developer. However, the negative photosensitive polyimide resin provided at present absorbs part of the exposure light, so that the bottom of the patterned adhesive film cannot be crosslinked sufficiently, and is finally dissolved in an alkaline developer, resulting in distortion of the patterned pattern.
Disclosure of Invention
In view of this, the present application provides a diamine compound, a polyimide resin, a preparation method thereof, a patterned coating, and a patterning process, which can solve the above technical problems.
Specifically, the method comprises the following technical scheme:
in one aspect, the present application provides a diamine compound, wherein the chemical structural formula of the diamine compound is as follows:
wherein R is 1 Is composed of
R 2 Is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、 -CONH-、-CONCH 3 -、-O-(CH 2 ) m′ -O-, and substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12;
the amino, trifluoromethyl and carboxyl connected with the benzene ring of the diamine compound can replace hydrogen at any position on the benzene ring.
As mentioned above, R 2 And may be substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, each of which includes substituents for substituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, exemplary substituents include: C1-C6 linear or branched (e.g., linear or branched alkyl, etc.), cyano, hydroxy, hydroxymethyl, trifluoromethyl, trifluoromethoxy, carboxy, mercapto, C1-C4 alkoxy, and the like.
As an example, the diamine compound has the following chemical formula:
the diamine compound provided by the embodiment of the application has a carboxyl group as an acid group and has alkali solubility, so that when the diamine compound is introduced into a polyimide resin as a monomer, the solubility of the polyimide resin in a water-based developing solution can be increased, and water-based development is realized; the diamine compound provided by the embodiment of the application also introduces a trifluoromethyl group in the molecular structure, wherein the trifluoromethyl group is a strong electron-withdrawing group with large volume steric hindrance, and can weaken the charge transfer effect in molecules and the tight accumulation among molecules. When the diamine compound with the chemical structure is introduced into the polyimide resin as a monomer, the polyimide resin not only has aqueous development characteristics, but also has higher transparency and stronger solubility, and the transparency is improved, so that exposure light is not easily absorbed by the polyimide resin, the bottom of a patterned adhesive film can be easily reached, and a high-precision patterned graph is obtained; the increase of the solubility allows the patterning glue comprising the polyimide resin to use higher solid content, avoids the viscosity increase caused by the increase of the solid content of the patterning glue, and is beneficial to obtaining a thick film with good quality.
The thick film has a thickness in the range of 10 microns to 100 microns, including, by way of example and not limitation: 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 35 microns, 40 microns, 50 microns, 55 microns, 60 microns, 65 microns, 70 microns, 75 microns, 80 microns, 85 microns, 90 microns, 95 microns, 100 microns, etc.
In the embodiment of the present application, after the diamine compound is introduced as a monomer into the polyimide resin, the polyimide resin can be developed using an aqueous alkaline developer: tetramethylammonium hydroxide (TMAH) aqueous solution (concentration is 2wt% to 5wt%, for example, 2.38 wt%), and the like.
In some possible implementations, the substituted aryl, the naphthyl, the biphenyl, the 5-to 7-membered aromatic heterocycle include substituents comprising: C1-C6 straight chain or branched chain, cyano, hydroxyl, hydroxymethyl, trifluoromethyl, trifluoromethoxy, carboxyl, sulfydryl and C1-C4 alkoxy.
On the other hand, the embodiment of the present application also provides a polyimide resin, which includes a structural unit formed by the diamine compound as a polymerization monomer.
In some possible implementations, the polyimide resin has a chemical structural formula as follows:
wherein R is a (meth) acrylate residue;
Ar 1 is an aromatic or alicyclic tetracarboxylic acid residue;
x is the residue of a diamine compound according to claim 1 or 2;
y is an aromatic diamine residue or an alicyclic diamine residue;
m is 0.1-1, n is an integer of 10-100.
According to the polyimide resin provided by the embodiment of the application, a carboxyl group is introduced into a molecular structure of the diamine compound based on the used diamine compound, and the diamine compound is used as an acid group and has alkali solubility, so that when the diamine compound is introduced into the polyimide resin as a monomer, the solubility of the polyimide resin in a water-based developing solution can be increased, and water-based development can be realized. In addition, the molecular structure of the diamine compound also introduces a trifluoromethyl group which is a strong electron-withdrawing group with large volume steric hindrance and can weaken the charge transfer effect in molecules and the close packing between molecules. When the diamine compound with the chemical structure is introduced into the polyimide resin as a monomer, the polyimide resin not only has aqueous development characteristics, but also has higher transparency and stronger solubility, and the transparency is improved, so that exposure light is not easily absorbed by the polyimide resin, the bottom of a patterned adhesive film can be easily reached, and a high-precision patterned graph is obtained; the increase of the solubility allows the patterning glue comprising the polyimide resin to use higher solid content, avoids viscosity increase caused by the increase of the solid content of the patterning glue, and is beneficial to obtaining a thick film with good quality.
In some possible implementations, the Ar 1 The group is derived from one of the following compounds: pyromellitic dianhydride, 3,3',4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 2,3,5, 6-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2, 6-dichloronaphthalene-1, 4,5, 8-tetracarboxylic dianhydride, 2, 7-dichloronaphthalene-1, 4,5, 8-tetracarboxylic dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic dianhydride, thiophene-2, 3,4, 5-tetracarboxylic dianhydride2,3,5, 6-pyridinetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, norbornane-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2] bicyclo]Oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4' -benzophenonetetracarboxylic dianhydride, 2,2', 3' -benzophenonetetracarboxylic dianhydride, 2,3,3',4' -benzophenonetetracarboxylic dianhydride, 3,3',4' -diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3' -diphenylsulfone tetracarboxylic dianhydride, 2, 3',4' -diphenylsulfone tetracarboxylic dianhydride, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2',3,3' -Diphenyl ether tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl)]Hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In some possible implementations, the Y group is from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds and alicyclic diamine compounds.
In some possible implementations, the hydroxyl-containing diamine compound includes: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene;
the diamine compound containing sulfonic acid group includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether;
the diamine compound containing a thiol group includes: dimercapto-phenylene diamine;
the organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenylethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane;
the aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl;
the nitrogen-containing aromatic heterocyclic diamine compound comprises: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine);
the alicyclic diamine compound comprises: cyclohexanediamine, or diaminodicyclohexylmethane.
In another aspect, an embodiment of the present application provides a method for preparing a diamine compound, where the method for preparing a diamine compound includes:
in the presence of a dehydrating agent and a first catalyst, carrying out esterification reaction on a carboxyl-containing compound and a phenolic hydroxyl-containing compound to obtain an intermediate compound;
in the presence of a second catalyst, carrying out reduction reaction on the intermediate compound and a reducing agent to obtain the diamine compound;
wherein the chemical structural formula of the carboxyl-containing compound is shown as follows:
R 2 is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、 -CONH-、-CONCH 3 -、-O-(CH 2 ) m′ -O-, and substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12;
the trifluoromethyl and carboxyl connected with the benzene ring of the carboxyl-containing compound can substitute hydrogen at any position on the benzene ring;
the chemical structural formula of the phenolic hydroxyl group-containing compound is as follows:
the hydroxyl, trifluoromethyl and nitro connected with the benzene ring of the phenolic hydroxyl-containing compound can replace hydrogen at any position on the benzene ring.
In some possible implementations, the first catalyst is 4-dimethylaminopyridine, pyridine or triethylamine, for example, 4-dimethylaminopyridine is used as the first catalyst in the examples of the present application, so as to obtain a good catalytic effect.
In some possible implementations, the dehydrating agent used is Dicyclohexylcarbodiimide (DCC), and Dicyclohexylcarbodiimide is used to cooperate with 4-dimethylaminopyridine to ensure the reaction rate and also to reduce side reactions.
In some possible implementations, the reducing agent is selected from hydrazine hydrate, hydrogen gas, iron powder, stannous chloride, or zinc powder;
the second catalyst is selected from palladium carbon or Raney nickel.
In some possible implementations, the diamine compound is synthesized by the following steps:
adding a carboxyl-group-containing compound and a phenolic hydroxyl-group-containing compound into a reaction vessel containing a first solvent at a molar ratio of 1. Among these, the first solvents used include, but are not limited to: dimethyl sulfoxide (DMSO), and the like.
In another aspect, an embodiment of the present invention provides a method for preparing a polyimide resin, where the method for preparing a polyimide resin includes: performing esterification reaction on a (methyl) acrylic compound and a dianhydride monomer to obtain an esterification product;
carrying out acyl chlorination treatment on the esterification product to obtain diacyl chloride diester;
and carrying out condensation reaction on the diacid chloride diester, the diamine compound and an optional diamine monomer to obtain the polyimide resin.
In the step of esterification reaction, pyridine can be added into the reaction system, and the pyridine not only can play a certain catalytic role, but also can be used as an acid-binding agent in the subsequent acyl chlorination reaction process.
In some possible implementations, the dianhydride-based monomer is selected from one of the following compounds: <xnotran> ,3,3',4,4' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In some possible implementations, the esterification product is subjected to an acid chlorination treatment by thionyl chloride, oxalyl chloride, or phosphorus pentachloride.
In some possible implementations, the diamine-based monomer is selected from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds, and alicyclic diamine compounds.
In some possible implementations, the hydroxyl group-containing diamine compound includes: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene;
the sulfonic acid group-containing diamine compound includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether;
the diamine compound containing a thiol group includes: dimercapto-phenylene diamine;
the organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenyl ethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane;
the aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl;
the nitrogen-containing aromatic heterocyclic diamine compound comprises: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine);
the alicyclic diamine compound comprises: cyclohexanediamine, or diaminodicyclohexylmethane.
In some possible implementations, the polyimide resin is synthesized by the following steps:
dissolving the dianhydride-based compound and the (meth) acrylic compound in a third solvent at a molar ratio of 1. Wherein the third solvent includes, but is not limited to: n-methylpyrrolidone, and the like.
Then, controlling the reaction temperature to be 0-5 ℃, continuously adding thionyl chloride (the molar ratio of the thionyl chloride to the dianhydride compound is 2.
In another large-capacity three-neck flask connected with a nitrogen inlet and a nitrogen outlet, the diamine compound obtained by the preparation and an optional diamine monomer are added into a fourth solvent according to a certain molar ratio, the reaction temperature is controlled to be 0-5 ℃, then the prepared diacid chloride diester solution is slowly dripped into a reaction system, and the reaction is carried out for a certain time, for example, 10-20 hours, so as to synthesize the polyimide resin.
After the reaction is finished, pouring the reaction product system into a large amount of deionized water, separating out a large amount of solids, and separating to obtain the polyimide resin after filtering, washing and drying.
In still another aspect, embodiments of the present application further provide a patterned coating material, where the patterned coating material includes any one of the polyimide resins described above.
When the polyimide resin provided by the embodiment of the application is used as a photosensitive resin, the coating for patterning can be cured during exposure, and an uncured coating part is removed by using an alkaline developing solution. The coating for patterning is suitable for preparing a coating film having a large thickness, for example, in the range of 10 to 100 μm.
In addition to the polyimide resin, the patterning coating provided by the embodiments of the present application may include, but is not limited to: solvents, and optionally photoinitiators and auxiliaries, and the like.
The polyimide resin and the coating for patterning provided in the embodiments of the present application can be used as at least the following functional materials: the radiation shielding layer material, the insulating layer material, the buffer layer material, the flat layer material, the liquid crystal orientation layer material, the nonlinear optical material, the optical waveguide material, the ion implantation mask, the high temperature resistant gas-liquid separation membrane, the flexible printed circuit and the like, and is particularly suitable for being used in the fields of microelectronics, photoelectrons, aerospace and the like.
In another aspect, an embodiment of the present application further provides a patterning process, where the patterning process includes a film forming step, an exposure step, and a developing step, which are performed in sequence;
the film forming step adopts the coating for patterning;
the developing step employs an alkaline developer.
As for the film forming step, the film forming step uses the patterned coating material provided in the embodiment of the present application, and forms a patterned liquid film on the surface of the substrate by applying the coating solution for patterning on the substrate surface. After the formation of the patterned liquid film, the liquid film may be subjected to a pre-bake treatment to enhance adhesion, release stress in the patterned adhesive film, and the like. Wherein the substrate includes but is not limited to: and the silicon chip is provided with a dielectric layer, and the liquid film is coated on the surface of the dielectric layer.
In the exposure step, under the masking action of a mask plate, exposure treatment is carried out on the patterned film by utilizing irradiation light, the part irradiated by the irradiation light in the patterned adhesive film is subjected to crosslinking curing, and the part masked by the mask plate is not subjected to crosslinking curing.
In the developing step, the uncured patterned adhesive film is dissolved by using an aqueous alkaline developing solution to remove the part of the patterned adhesive film, so as to form a patterned cured film layer.
Detailed Description
In order to make the technical solutions and advantages of the present application more clear, the following will describe the embodiments of the present application in further detail.
The photosensitive polyimide resin can be used as a photosensitive resin for preparing a patterning paste (also referred to as a coating for patterning), and a patterning process using the patterning paste includes a film formation step, an exposure step, and a development step, which are sequentially performed. For example, after the patterned photoresist is formed on a substrate, the patterned photoresist is exposed by light under the action of a mask plate, so that the exposed part of the negative photosensitive polyimide resin is crosslinked and cured, and the unexposed part is dissolved in a developing solution and removed (i.e., a developing step).
At present, the common negative photosensitive polyimide resin at least has the following technical problems: only the organic developer can be used for development, and the organic developer has high pollution. Currently available polyimide resins generally contain a large number of aromatic heterocyclic rings in the resin structure, which form intramolecular and intermolecular Charge Transfer Complexes (CTCs) and cause absorption of light having a wavelength of 300nm to 500 nm. The wavelength of the ultraviolet light used for exposure is generally 365nm, so that the polyimide resin can absorb part of the ultraviolet light used for exposure, the bottom of the patterned adhesive film cannot be fully crosslinked, and finally the patterned adhesive film is dissolved in an alkaline developing solution, so that the patterned graph is distorted. In addition, in order to increase the film thickness and obtain a thick film with uniform thickness, the solid content of the patterning glue needs to be increased, and because the solubility of the polyimide resin is poor, when the solid content of the patterning glue is increased, the viscosity of the patterning glue is also correspondingly increased, which affects the film quality, and thus, the currently provided negative photosensitive polyimide resin is not suitable for preparing a thicker patterning glue film (called thick film for short).
In one aspect, the embodiments of the present application provide a diamine compound, and a chemical structural formula of the diamine compound is as follows:
wherein R is 1 Is composed of
Wherein, two R in the chemical structural formula are 1 May be the same or different, e.g. one of them is
And the other is
R 2 Is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、 -CONH-、-CONCH 3 -、-O-(CH 2 ) m′ -O-, and substituted or unsubstituted aromatic, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle. m' is an integer of 1 to 12;
the amino, trifluoromethyl and carboxyl connected with the benzene ring of the diamine compound can substitute hydrogen at any position on the benzene ring, that is, the positions of the amino, trifluoromethyl and carboxyl on the benzene ring can be selected in various ways.
As mentioned above, R 2 The aromatic group, naphthyl group, biphenyl group, 5-to 7-membered aromatic heterocycle which may be substituted or unsubstituted, and for the substituted aromatic group, naphthyl group, biphenyl group, 5-to 7-membered aromatic heterocycle, each of them includes a substituent, and exemplary substituents include: C1-C6 straight chain or branched chain (for example, straight chain alkyl or branched chain alkyl, etc.), cyano, hydroxy, hydroxymethyl, trifluoromethyl, trifluoromethoxy, carboxyl, mercapto, C1-C4 alkoxy.
The diamine compound provided by the embodiment of the application has a carboxyl group as an acid group and has alkali solubility, so that when the diamine compound is introduced into a polyimide resin as a monomer, the solubility of the polyimide resin in a water-based developing solution can be increased, and water-based development is realized; according to the diamine compound provided by the embodiment of the application, a trifluoromethyl group is introduced into a molecular structure of the diamine compound, and the diamine compound is a strong electron-withdrawing group with large volume steric hindrance and can weaken the charge transfer effect in molecules and the close packing between molecules. When the diamine compound with the chemical structure is introduced into the polyimide resin as a monomer, the polyimide resin not only has aqueous development characteristics, but also has higher transparency and stronger solubility, and the transparency is improved, so that exposure light is not easily absorbed by the polyimide resin, the bottom of a patterned adhesive film can be easily reached, and a high-precision patterned graph is obtained; the increase of the solubility allows the patterning glue comprising the polyimide resin to use higher solid content, avoids the viscosity increase caused by the increase of the solid content of the patterning glue, and is beneficial to obtaining a thick film with good quality.
For example, the thick film has a thickness in the range of 10 microns to 100 microns, including, but not limited to: 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 35 microns, 40 microns, 50 microns, 55 microns, 60 microns, 65 microns, 70 microns, 75 microns, 80 microns, 85 microns, 90 microns, 95 microns, 100 microns, etc.
In the embodiment of the present application, after the diamine compound is introduced as a monomer into a polyimide resin, development can be performed using an aqueous alkaline developer: tetramethylammonium hydroxide (TMAH) aqueous solution (concentration is 2wt% to 5wt%, for example, 2.38 wt%), and the like.
As an example, the diamine compound has the following chemical formula:
on the other hand, the embodiment of the present application further provides a preparation method of the diamine compound, and the preparation method of the diamine compound includes:
step 101, in the presence of a dehydrating agent and a first catalyst, subjecting a carboxyl group-containing compound and a phenolic hydroxyl group-containing compound to an esterification reaction to obtain an intermediate compound.
Wherein, the chemical structural formula of the carboxyl-containing compound is shown as follows:
R 2 is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、 -CONH-、-CONCH 3 -、-O-(CH2) m′ -O-, and substituted or unsubstituted aromatic, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12. The trifluoromethyl and carboxyl groups attached to the phenyl ring of the carboxy-containing compound can replace hydrogen at any position on the phenyl ring.
The chemical structural formula of the compound containing the phenolic hydroxyl group is as follows:
wherein, the hydroxyl, trifluoromethyl and nitro connected with the benzene ring of the phenolic hydroxyl group-containing compound can replace hydrogen at any position on the benzene ring.
In some possible implementations, the first catalyst used includes, but is not limited to: 4-Dimethylaminopyridine (DMAP), pyridine or triethylamine, for example, 4-Dimethylaminopyridine is used as the first catalyst in the examples of the present application, so as to obtain a good catalytic effect.
In some possible implementations, the dehydrating agent used is Dicyclohexylcarbodiimide (DCC), and Dicyclohexylcarbodiimide is used to cooperate with 4-dimethylaminopyridine to ensure the reaction rate and also to reduce side reactions.
The preparation principle of the intermediate compound can be seen in the following chemical reaction equation:
and 102, carrying out reduction reaction on the intermediate compound and a reducing agent in the presence of a second catalyst to obtain a diamine compound.
In some possible implementations, the reducing agent is selected from hydrazine hydrate, hydrogen gas, iron powder, stannous chloride, or zinc powder; the second catalyst is selected from palladium carbon or Raney nickel.
A specific reducing agent acts synergistically with a specific second catalyst to achieve a better reducing effect, and for example, the following combination of a reducing agent and a second catalyst may be used: hydrazine hydrate + palladium on carbon, hydrogen + palladium on carbon, or hydrogen + raney nickel, etc.
In some possible implementations, the reducing agent provided in the embodiments of the present application may be combined as follows, and a good reducing effect can also be obtained, and the embodiments of the present application do not exclude the use of the following combinations: iron powder (Fe) + acetic acid; stannous chloride + hydrochloric acid (HCl); zinc powder + ammonium chloride (NH) 4 Cl), and the like.
The principle of obtaining diamines by reduction is shown in the following chemical reaction equation:
under the dehydration action of the dehydrating agent and the catalytic action of the first catalyst, the carboxyl-containing compound with the chemical structural formula and the phenolic hydroxyl-containing compound with the chemical structural formula are subjected to esterification reaction, and the obtained intermediate compound is substantially an intermediate compound with a nitro group. The nitro group on the intermediate compound is reduced by a reducing agent under the catalytic action of a second catalyst, and the diamine compound expected in the embodiment of the application can be obtained.
In some possible implementations, the first catalyst used is 4-Dimethylaminopyridine (DMAP); the second catalyst is palladium carbon to obtain good catalytic effect.
In some possible implementations, the dehydrating agent used is Dicyclohexylcarbodiimide (DCC), and Dicyclohexylcarbodiimide is used to cooperate with 4-dimethylaminopyridine to ensure the reaction rate and also to reduce side reactions.
In some possible implementations, the diamine compound is synthesized by the following steps:
adding the carboxyl-group-containing compound and the phenolic hydroxyl-group-containing compound to a reaction vessel containing a first solvent at a molar ratio of 1. Among these, the first solvents used include, but are not limited to: dimethyl sulfoxide (DMSO), and the like.
After the esterification reaction is finished, filtering the reaction liquid system, introducing the filtrate into a large amount of water to obtain a crude product, and further separating the crude product by using silica gel column chromatography to obtain the intermediate compound containing the nitro.
In a three-neck flask connected with a nitrogen inlet and a nitrogen outlet, a nitro-containing intermediate compound and a second catalyst are mixed according to the mass ratio of 1: 0.005-0.02, dispersing in the second solvent, blowing with nitrogen and stirring for a certain time, such as 10-20 min, then heating to the reaction temperature and refluxing (the reaction temperature is between 75-80 ℃, such as 78 ℃), and slowly dripping hydrazine hydrate into the reaction system for reaction. The second solvent used includes, but is not limited to: alcohols such as ethanol, methanol, isopropanol and ethylene glycol, N-dimethylformamide and N, N-dimethylacetamide.
Detecting whether the reaction is finished or not by using a thin-layer chromatography in the reaction process, filtering to remove the second catalyst after the reaction is finished, introducing the filtrate into a large amount of water to obtain a precipitate, and sequentially filtering and carrying out silica gel column chromatography on the precipitate to obtain the diamine compound.
In another aspect, an embodiment of the present invention provides a polyimide resin, including a structural unit formed from the diamine compound as a polymerization monomer.
Wherein the diamine compound has the following chemical structural formula:
according to the polyimide resin provided by the embodiment of the application, a carboxyl group is introduced into a molecular structure of the diamine compound based on the used diamine compound, and the diamine compound is used as an acid group and has alkali solubility, so that when the diamine compound is introduced into the polyimide resin as a monomer, the solubility of the polyimide resin in a water-based developing solution can be increased, and water-based development can be realized. In addition, the molecular structure of the diamine compound also introduces a trifluoromethyl group which is a strong electron-withdrawing group with large volume steric hindrance and can weaken the charge transfer effect in molecules and the close packing between molecules. When the diamine compound with the chemical structure is introduced into the polyimide resin as a monomer, the polyimide resin not only has water system development characteristics, but also has higher transparency and stronger solubility, the transparency is improved, exposure light is not easily absorbed by the polyimide resin, the bottom of a patterned adhesive film can be easily reached, and a high-precision patterned graph is obtained; the increase of the solubility allows the patterning paste including the polyimide resin to use a higher solid content, avoids the increase of viscosity caused when the solid content of the patterning paste rises, and is beneficial to obtaining a thick film with good quality.
In some possible implementations, the chemical structural formula of the polyimide resin provided in the embodiments of the present application is as follows:
wherein R is a (meth) acrylate residue;
Ar 1 is an aromatic or alicyclic tetracarboxylic acid residue;
x is residue of diamine compound provided by the embodiment of the application (the diamine compound is formed by reacting amine group on benzene ring with Ar 1 Linking, i.e., allowing the amine group to participate in a condensation reaction);
y is an aromatic diamine residue or an alicyclic diamine residue;
m is 0.1-1, n is an integer of 10-100.
In some possible implementations, ar 1 The group is from one of the following compounds: pyromellitic dianhydride, 3',4' -biphenyltetracarboxylic dianhydride, 2, 3',4' -Biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5-tetracarboxylic dianhydride, 5-norbornane-2,5-tetracarboxylic dianhydride6-tetracarboxylic dianhydrides, bicyclo [2.2.2]Oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4' -benzophenonetetracarboxylic dianhydride, 2,2', 3' -benzophenonetetracarboxylic dianhydride, 2,3,3',4' -benzophenonetetracarboxylic dianhydride, 3,3',4' -diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3' -diphenylsulfone tetracarboxylic dianhydride, 2, 3',4' -diphenylsulfone tetracarboxylic dianhydride, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2',3,3' -Diphenyl ether tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl)]Hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In some possible implementations, the Y group is from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds, and alicyclic diamine compounds.
Exemplary hydroxyl group-containing diamine compounds include: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene.
The sulfonic acid group-containing diamine compound includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether.
Diamine compounds containing thiol groups include: dimercapto-phenylene diamine.
The organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenyl ethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane.
The aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 'bis (trifluoromethyl) -4,4' -diaminobiphenyl. The aromatic diamine compound includes substituted or unsubstituted aromatic diamine compounds, and in the substituted aromatic diamine compounds, the hydrogen atoms of the benzene ring of the aromatic diamine compounds are partially substituted by C1-C10 alkyl, fluoroalkyl, halogen atoms and other substituent groups.
The nitrogen-containing aromatic heterocyclic diamine compound includes: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine).
Alicyclic diamine compounds include: cyclohexanediamine, or diaminodicyclohexylmethane.
In another aspect, an embodiment of the present application further provides a method for preparing a polyimide resin, where the method for preparing a polyimide resin includes:
step 201, performing esterification reaction between a (meth) acrylic compound and a dianhydride monomer to obtain an esterification product.
In the step, pyridine can be added into the reaction system, and the pyridine not only can play a certain catalytic role, but also can be used as an acid-binding agent in the subsequent acyl chlorination reaction process.
For example, the chemical formula of the (meth) acrylic compound is abbreviated as R-OH, and the mechanism of formation of the above-mentioned esterification product can be seen in the following chemical equation:
step 202, performing acyl chlorination on the esterification product to obtain diacyl chloride diester. Illustratively, the esterification product is subjected to an acid chlorination treatment by thionyl chloride, oxalyl chloride or phosphorus pentachloride, during which an acid-binding agent such as pyridine may be used.
For example, the mechanism of formation of the esterification product by the acylchlorination treatment of thionyl chloride can be seen in the following chemical equation:
step 203, performing a condensation reaction on the diacyl chloride diester, the diamine compound provided in the embodiment of the present application, and the optional diamine monomer to obtain the polyimide resin.
Illustratively, the condensation reaction of the diacid chloride diester and the diamine compound provided in the examples of the present application forms the polyimide resin, and the formation mechanism can be seen in the following chemical equation:
wherein H 2 N-R # -NH 2 Is the expression of the diamine compound described above in the examples of the present application, R # Is the residue of the diamine compound.
In some possible implementations, the dianhydride-based monomer is selected from one of the following compounds: <xnotran> ,3,3',4,4' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In some possible implementations, the diamine-based monomer is selected from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds and alicyclic diamine compounds.
Exemplary hydroxyl group-containing diamine compounds include: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene.
The sulfonic acid group-containing diamine compound includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether.
The diamine compound containing a thiol group includes: dimercapto-phenylene diamine.
The organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenylethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane.
The aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl. The aromatic diamine compound includes substituted or unsubstituted aromatic diamine compounds, and in the substituted aromatic diamine compounds, the aromatic diamine compounds are obtained by substituting a part of hydrogen atoms on a benzene ring by a substituent group such as C1-C10 alkyl, fluoroalkyl, halogen atom, etc.
The nitrogen-containing aromatic heterocyclic diamine compound includes: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine).
The alicyclic diamine compound includes: cyclohexanediamine, or diaminodicyclohexylmethane.
In some possible implementations, the polyimide resin is synthesized by the following steps:
dissolving the dianhydride compound and the (meth) acrylic compound in a third solvent at a molar ratio of 1. Wherein the third solvent includes, but is not limited to: n-methylpyrrolidone, and the like.
Then, controlling the reaction temperature to be 0-5 ℃, continuously adding thionyl chloride (the molar ratio of the thionyl chloride to the dianhydride compound is 2.
In another large-capacity three-neck flask connected with a nitrogen inlet and a nitrogen outlet, the diamine compound obtained by the preparation and an optional diamine monomer are added into a fourth solvent according to a certain molar ratio, the reaction temperature is controlled to be 0-5 ℃, then the prepared diacid chloride diester solution is slowly dripped into a reaction system, and the reaction is carried out for a certain time, for example, 10-20 hours, so as to synthesize the polyimide resin.
After the reaction is finished, pouring the reaction product system into a large amount of deionized water, separating out a large amount of solids, and separating to obtain the polyimide resin after filtering, washing and drying.
In still another aspect, embodiments of the present application further provide a patterned coating, where the patterned coating includes any one of the polyimide resins described above.
When the polyimide resin provided by the embodiment of the application is used as the photosensitive resin, the patterned coating can be cured during exposure, and uncured coating parts are removed by using an alkaline developing solution. The patterned coating is suitable for preparing coating films having a substantial thickness, for example, in the range of 10 microns to 100 microns, including, but not limited to: 10 microns, 15 microns, 20 microns, 25 microns, 30 microns, 35 microns, 40 microns, 50 microns, 55 microns, 60 microns, 65 microns, 70 microns, 75 microns, 80 microns, 85 microns, 90 microns, 95 microns, 100 microns, and the like.
In addition to polyimide resins, the patterned coatings provided by embodiments of the present application may include, but are not limited to: solvents, and optionally photoinitiators and auxiliaries, and the like.
The polyimide resin and the patterned coating provided by the embodiment of the application can be at least used as the following functional materials: ray shielding layer materials, insulating layer materials, buffer layer materials, flat layer materials, liquid crystal orientation layer materials, nonlinear optical materials, optical waveguide materials, ion implantation masks, high-temperature-resistant gas-liquid separation membranes, flexible printed circuits and the like, and the preparation method is particularly suitable for being used in the fields of microelectronics, photoelectrons, aerospace and the like.
In another aspect, an embodiment of the present application further provides a patterning process, where the patterning process includes a film formation step, an exposure step, and a development step, which are performed in sequence.
For the film forming step, the film forming step uses the patterned coating provided in the embodiments of the present application, and forms a patterned liquid film on the surface of the substrate by applying the patterned coating solution on the surface of the substrate. After the formation of the patterned liquid film, a pre-baking process may be performed on the liquid film to enhance adhesion, release stress in the patterned adhesive film, and the like. Wherein the substrate includes but is not limited to: and the silicon chip is provided with a dielectric layer, and the liquid film is coated on the surface of the dielectric layer.
In the exposure step, under the masking action of a mask plate, exposure treatment is carried out on the patterned adhesive film by utilizing irradiation light, the part irradiated by the irradiation light in the patterned adhesive film is subjected to crosslinking curing, and the part masked by the mask plate is not subjected to crosslinking curing.
In the developing step, the uncured patterned adhesive film is dissolved by using an aqueous alkaline developing solution to remove the part of the patterned adhesive film, so as to form a patterned cured film layer.
According to the patterning process provided by the embodiment of the application, the coating for patterning provided by the embodiment of the application is adopted in the film forming step, so that highly refined patterns and a film layer with larger thickness can be obtained; an aqueous alkaline developing solution is used in the developing step, so that the patterning process is safer and more environment-friendly.
The present application will be further described below by way of specific examples:
example 1: synthesis of diamine Compound BA-COOH
In a 500mL flask, 2-trifluoromethyl-4-nitrophenol (16.56g, 80mmol), 3',4' -biphenyltetracarboxylic acid (13.22g, 40mmol), 4-dimethylaminopyridine (DMAP, 0.20g,1.6 mmol) and dicyclohexylcarbodiimide (DCC, 16.51g, 80mmol) were dissolved in 300mL of dimethyl sulfoxide (DMSO), and the reaction was stirred at room temperature for 12 hours. After the reaction is finished, the reaction liquid system is filtered, the filtrate is led into a large amount of water to obtain a crude product (yellow solid), and the crude product is further separated by utilizing silica gel column chromatography to obtain the intermediate compound containing the nitro group.
In a 250mL three-neck flask connected with a nitrogen inlet and a nitrogen outlet, 10g of nitro compound and 0.1 g of palladium-carbon with the mass fraction of 10% are dispersed in 120mL of ethanol, nitrogen is used for blowing and stirring for 10min, then the temperature is raised to 78 ℃ for refluxing, and 24mL of hydrazine hydrate (with the mass concentration of 98%) is slowly dripped into a reaction system for reaction. Detecting whether the reaction is complete by using a thin-layer chromatography, filtering to remove palladium carbon after the reaction is finished, introducing the filtrate into a large amount of water to obtain a precipitate, filtering, and performing silica gel column chromatography to obtain the target diamine compound.
The diamine compound has the following chemical structural formula:
example 2: synthesis of polyimide resin 1
Pyromellitic dianhydride (PMDA, 10.91g,0.05 mol), hydroxyethyl methacrylate (HEMA, 13.01g, 0.10mol) and pyridine (9.49g, 0.12mol) were dissolved in 100 mL of N-methylpyrrolidone (NMP) in a 250mL three-necked flask equipped with a nitrogen inlet/outlet, and reacted with stirring at room temperature for 12 hours to obtain the corresponding diacid diester. Controlling the temperature between 0 ℃ and 5 ℃, and adding thionyl chloride (SOCl) into the reaction system 2 11.90g,0.10 mol) was added, and the reaction was stirred for 2 hours to give the corresponding diacyl chloride diester solution.
4,4' -diaminodiphenyl ether (ODA, 8.01g,0.04 mol) and the diamine compound BA-COOH (6.49g, 0.01mol) prepared in example 1 were dissolved in 150mL of N-methylpyrrolidone (NMP) in a 500mL three-necked flask equipped with a nitrogen inlet/outlet, the temperature was controlled to 0 ℃ to 5 ℃, the prepared diacylchloride diester solution was slowly dropped into the reaction system, and the reaction was carried out for 12 hours to synthesize a polyamic acid ester resin 1.
After the reaction is finished, pouring the reaction product system into 2000mL of deionized water, precipitating a large amount of solid, sequentially filtering, washing, drying, and separating to obtain the polyamic acid ester resin 1.
Wherein the polyamic acid ester resin 1 is composed of PMDA/ODA/BA-COOH monomers, and the molar content of BA-COOH is 25% (wherein the molar content of BA-COOH means that the molar content thereof is 25% in terms of the molar content ratio of the whole diamine, hereinafter all referring to this explanation).
The chemical structural formula of the polyamic acid ester resin 1 is shown as follows, wherein x: y is 4.
Example 3: synthesis of polyimide resin 2
In a 250mL three-necked flask equipped with a nitrogen inlet/outlet port, 3',4' -biphenyltetracarboxylic dianhydride (BPDA, 16.51g, 0.05mol), hydroxyethyl methacrylate (HEMA, 13.01g,0.10 mol), and pyridine (9.49g, 0.12mol) were dissolved in 120mL of N-methylpyrrolidone (NMP), and stirred at room temperature for 12 hours to obtain the corresponding diacid diester. Controlling the temperature to be 0-5 ℃, and continuously adding thionyl chloride (SOCl) into the system 2 11.90g,0.10 mol) was added, and the reaction was stirred for 2 hours to give the corresponding diacyl chloride diester solution.
In a 500mL three-necked flask with a nitrogen inlet and outlet, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB, 12.81g, 0.04mol) and diamine BA-COOH (6.49g, 0.01mol) were dissolved in 150mL of NMP, the temperature was controlled to 0 to 5 ℃, the diacylchloride diester solution prepared as described above was slowly added dropwise to the system, and the reaction was carried out for 12 hours to synthesize a polyamic acid ester resin 2.
After the reaction is finished, pouring the reaction product system into 2000mL of deionized water, precipitating a large amount of solid, sequentially filtering, washing, drying, and separating to obtain the polyamic acid ester resin 2.
Wherein the polyamic acid ester resin 2 is composed of BPDA/TFMB/BA-COOH monomers, and the molar content of BA-COOH is 25%.
The chemical structural formula of the polyamic acid ester resin 2 is shown as follows, wherein x: y is 4.
Example 4: synthesis of polyimide resin 3
In a 250mL three-necked flask with nitrogen inlet and outlet, 3',4' -diphenyl ether tetracarboxylic dianhydride (ODPA, 15.51g, 0.05mol) and hydroxyethyl methacrylate (HEMA, 13.01g,0.10 mol), pyridine (9.49g, 0.12 mol) were dissolved in 120mL of N-methylpyrrolidone (NMP) and stirred at room temperature for 12h to give the corresponding diacid diester. Controlling the temperature at 0-5 deg.C, and continuously adding thionyl chloride (SOCl) 2 11.90g, 0.10mol), and stirring to react for 2 hours to obtain a corresponding diacyl chloride diester solution.
4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl (TFMB, 9.61g, 0.03mol) and diamine BA-COOH (12.70g, 0.02mol) are dissolved in 150mL of NMP in a 500mL three-necked flask with a nitrogen inlet and outlet connected thereto, the temperature is controlled to be 0-5 ℃, the prepared diacylchloride diester solution is slowly dripped into the system, and the polyamic acid ester resin 3 is synthesized after 12 hours of reaction.
After the reaction is finished, pouring the reaction product system into 2000mL of deionized water, precipitating a large amount of solid, sequentially filtering, washing and drying, and separating to obtain the polyamic acid ester resin 3.
Wherein the polyamic acid ester resin 3 is composed of ODPA/TFMB/BA-COOH monomers, and the molar content of BA-COOH is 40%.
The chemical structural formula of the polyamic acid ester resin 3 is shown as follows, wherein x: y is 3.
Comparative example: synthesis of polyimide resin 4
In a 250mL three-necked flask with nitrogen inlet and outlet, pyromellitic dianhydride (PMDA, 10.91g,0.05 mol), hydroxyethyl methacrylate (HEMA, 13.01g,0.10 mol), pyridine (9.49g, 0.10 mol) were dissolved in 100 mL of N-methylpyrrolidone (NM, 0.10 mol)P) and stirring for 12 hours at room temperature to obtain the corresponding diacid diester. Controlling the temperature at 0-5 deg.C, and continuously adding thionyl chloride (SOCl) 2 11.90g, 0.10mol), and stirring to react for 2 hours to obtain a corresponding diacyl chloride diester solution.
4,4' -diaminodiphenyl ether (ODA, 10.01g,0.05 mol) was dissolved in 150mL of N-methylpyrrolidone (NMP) in a 500mL three-necked flask equipped with a nitrogen inlet/outlet, and the diacylchloride diester solution prepared as described above was slowly added dropwise to the system at a temperature of 0 to 5 ℃ to react for 12 hours.
After the reaction is finished, pouring the reaction product system into 2000mL of deionized water, precipitating a large amount of solid, sequentially filtering, washing and drying, and separating to obtain the polyamic acid ester resin 4.
Wherein, the polyamide acid ester resin 4 does not contain BA-COOH monomer structure.
Test example
The performance of the polyimide resins provided in examples 2 to 4 and comparative example was tested using the test examples, and the test results showed that: (1) The polyimide resins provided in examples 2 to 4 can be developed with an aqueous alkaline developer (for example, tetramethylammonium hydroxide), whereas the polyimide resins provided in comparative examples cannot be developed with an aqueous alkaline developer but can be developed with only an organic developer.
(2) When the i-line with the wavelength of 365nm is used for exposure, the bottom of the glue film of the polyimide resin provided by the embodiment 2-4 can be fully crosslinked, and finally, a high-fineness pattern is obtained; under the same conditions, the bottom of the polyimide resin provided in the comparative example was only partially crosslinked, and a distorted pattern was obtained.
In the embodiments of the present application, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. The term "plurality" means two or more unless explicitly defined otherwise.
The above description is only for facilitating the understanding of the technical solutions of the present application by those skilled in the art, and is not intended to limit the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (17)
1. A compound having the chemical formula:
wherein R is 1 Is composed of
R 2 Is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、-CONH-、-CONCH 3 -、-O-(CH 2 ) m′ -O-, and substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12;
the amino, trifluoromethyl and carboxyl connected with the benzene ring of the compound can substitute hydrogen at any position on the benzene ring.
2. The compound of claim 1, wherein said substituted aromatic group, said naphthyl group, said biphenyl group, said 5-to 7-membered aromatic heterocycle comprise substituents comprising: C1-C6 straight chain or branched chain, cyano, hydroxyl, hydroxymethyl, trifluoromethyl, trifluoromethoxy, carboxyl, sulfydryl and C1-C4 alkoxy.
3. A resin comprising a structural unit formed from the compound of claim 1 or 2 as a polymerized monomer.
4. The resin of claim 3, wherein the resin has the following chemical formula:
wherein R is a (meth) acrylate residue;
Ar 1 is an aromatic or alicyclic tetracarboxylic acid residue;
x is the residue of a compound of claim 1 or 2;
y is an aromatic diamine residue or an alicyclic diamine residue;
m is 0.1-1, n is an integer of 10-100.
5. The resin of claim 4, wherein Ar is Ar 1 The group is derived from one of the following compounds: pyromellitic dianhydride, 3',4' -biphenyltetracarboxylic dianhydride, 2, 3',4' -Biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [ 2.6.2.6 ] tetracarboxylic dianhydride]Oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4' -benzophenonetetracarboxylic dianhydride, 2,2', 3' -benzophenonetetracarboxylic dianhydride, 2,3,3',4' -benzophenonetetracarboxylic dianhydride, 3,3',4' -diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3' -diphenylsulfone tetracarboxylic dianhydride, 2, 3',4' -diphenylsulfone tetracarboxylic dianhydride, 3',4' -diphenylether tetracarboxylic dianhydride, 2',3,3' -Diphenyl ether tetracarboxylic acid dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic acid dianhydride, 2- [ bis (3, 4-dicarboxyphenyl)]Hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
6. The resin of claim 4, wherein the Y group is derived from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds and alicyclic diamine compounds.
7. The resin of claim 6, wherein the hydroxyl group-containing diamine compound comprises: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene;
the sulfonic acid group-containing diamine compound includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether;
the diamine compound containing a thiol group includes: dimercapto-phenylene diamine;
the organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenyl ethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane;
the aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 'bis (trifluoromethyl) -4,4' -diaminobiphenyl;
the nitrogen-containing aromatic heterocyclic diamine compound comprises the following components: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine);
the alicyclic diamine compound comprises: cyclohexanediamine, or diaminodicyclohexylmethane.
8. A preparation method of diamine compounds is characterized by comprising the following steps:
in the presence of a dehydrating agent and a first catalyst, carrying out esterification reaction on a carboxyl-containing compound and a phenolic hydroxyl-containing compound to obtain an intermediate compound;
in the presence of a second catalyst, carrying out a reduction reaction on the intermediate compound and a reducing agent to obtain the diamine compound;
wherein the chemical structural formula of the carboxyl-containing compound is shown as follows:
R 2 is one of the following groups: single bond, -NH-, -NCH 3 -、-O-、-S-、-S-S-、-SO 2 -、-CO-、-COO-、-CONH-、-CONCH 3 -、-O-(CH 2 ) m′ -O-, and substituted or unsubstituted aryl, naphthyl, biphenyl, 5-to 7-membered aromatic heterocycle, m' is an integer from 1 to 12;
the trifluoromethyl and the carboxyl connected with the benzene ring of the carboxyl-containing compound can replace hydrogen at any position on the benzene ring;
the chemical structural formula of the phenolic hydroxyl group-containing compound is as follows:
the hydroxyl, trifluoromethyl and nitro connected with the benzene ring of the phenolic hydroxyl compound can replace hydrogen at any position on the benzene ring.
9. The method of claim 8, wherein the first catalyst is 4-dimethylaminopyridine, pyridine or triethylamine.
10. The method for preparing diamine compounds according to claim 8, wherein the reducing agent is selected from hydrazine hydrate, hydrogen gas, iron powder, stannous chloride or zinc powder;
the second catalyst is selected from palladium carbon or Raney nickel.
11. A method for preparing a resin, comprising: performing esterification reaction on a (methyl) acrylic compound and a dianhydride monomer to obtain an esterification product;
performing acyl chlorination on the esterification product to obtain diacyl chloride diester;
subjecting the diacid chloride diester, the diamine compound of claim 1 or 2, and optionally a diamine monomer to a condensation reaction to obtain the resin.
12. The method of claim 11, wherein the dianhydride-based monomer is selected from one of the following compounds: <xnotran> ,3,3',4,4' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
13. The method for preparing resin according to claim 11, wherein the esterification product is subjected to acylchlorination treatment by thionyl chloride, oxalyl chloride or phosphorus pentachloride.
14. The method of claim 11, wherein the diamine monomer is selected from one of the following compounds: diamine compounds containing hydroxyl groups, diamine compounds containing sulfonic acid groups, diamine compounds containing thiol groups, diamine compounds containing polyethylene oxide groups, organosilicon diamine compounds, substituted or unsubstituted aromatic diamine compounds, nitrogen-containing aromatic heterocyclic diamine compounds and alicyclic diamine compounds.
15. The method for preparing a resin according to claim 14, wherein the hydroxyl group-containing diamine compound comprises: 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3 '-diamino-4, 4' -biphenol, or 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene;
the diamine compound containing sulfonic acid group includes: 3-sulfonic acid-4, 4' -diaminodiphenyl ether;
the diamine compound containing a thiol group includes: dimercapto-phenylene diamine;
the organosilicon diamine compound comprises: 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (p-aminophenyl) -1, 3-tetramethyldisiloxane 1, 3-bis (p-aminophenylethyl) -1, 3-tetramethyldisiloxane or 1, 7-bis (p-aminophenyl) -1,3,5, 7-octamethyltetrasiloxane;
the aromatic diamine compound includes: 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4 '-diaminobiphenyl, 3',4 '-tetramethyl-4, 4' -diaminobiphenyl, or 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl;
the nitrogen-containing aromatic heterocyclic diamine compound comprises: 2, 4-diamino-1, 3, 5-triazine (guanamine), 2, 4-diamino-6-methyl-1, 3, 5-triazine (methylguanamine), or 2, 4-diamino-6-phenyl-1, 3, 5-triazine (benzoguanamine);
the alicyclic diamine compound comprises: cyclohexanediamine, or diaminodicyclohexylmethane.
16. A patterned coating comprising the resin of any of claims 3-7.
17. A patterning process, comprising: a film forming step, an exposure step and a development step are sequentially carried out;
the film forming step employs the patterning coating material according to claim 16;
the developing step employs an alkaline developer.
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| CN116285863A (en) * | 2023-02-17 | 2023-06-23 | 深圳市聚芯源新材料技术有限公司 | Composite engineering plastic with low dielectric constant and preparation method thereof |
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| CN116178716B (en) * | 2023-05-04 | 2023-08-01 | 广州奥松电子股份有限公司 | Polyisonimide and preparation method and application thereof |
| CN116333303A (en) * | 2023-05-25 | 2023-06-27 | 明士(北京)新材料开发有限公司 | Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof |
| CN116333303B (en) * | 2023-05-25 | 2023-08-04 | 明士(北京)新材料开发有限公司 | Anti-mould-pressing alkaline aqueous development photosensitive adhesive film and application thereof |
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