CN114805805B - Polyimide with high adhesive strength and preparation method and application thereof - Google Patents
Polyimide with high adhesive strength and preparation method and application thereof Download PDFInfo
- Publication number
- CN114805805B CN114805805B CN202210493965.3A CN202210493965A CN114805805B CN 114805805 B CN114805805 B CN 114805805B CN 202210493965 A CN202210493965 A CN 202210493965A CN 114805805 B CN114805805 B CN 114805805B
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- CN
- China
- Prior art keywords
- diamino
- phenylenediamine
- polyimide
- diamine
- diamine monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 179
- 229920001721 polyimide Polymers 0.000 title claims abstract description 179
- 239000000853 adhesive Substances 0.000 title claims abstract description 73
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 claims abstract description 83
- 239000010949 copper Substances 0.000 claims abstract description 83
- 239000000126 substance Substances 0.000 claims abstract description 63
- 230000003993 interaction Effects 0.000 claims abstract description 49
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims description 100
- 239000000178 monomer Substances 0.000 claims description 72
- 229920005575 poly(amic acid) Polymers 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 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 26
- 238000000034 method Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 239000003495 polar organic solvent Substances 0.000 claims description 21
- -1 4-chloro-methyl-phenylenediamine Chemical compound 0.000 claims description 14
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 13
- BXIXXXYDDJVHDL-UHFFFAOYSA-N 4-Chloro-ortho-phenylenediamine Chemical compound NC1=CC=C(Cl)C=C1N BXIXXXYDDJVHDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 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 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- OJSCBKGRGMBEEW-UHFFFAOYSA-N 3-fluorobenzene-1,2-diamine Chemical compound NC1=CC=CC(F)=C1N OJSCBKGRGMBEEW-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-N 0.000 claims description 6
- NGULVTOQNLILMZ-UHFFFAOYSA-N 2-bromobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(Br)=C1 NGULVTOQNLILMZ-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 5
- VWYTZNPMXYCBPK-UHFFFAOYSA-N 3-bromobenzene-1,2-diamine Chemical compound NC1=CC=CC(Br)=C1N VWYTZNPMXYCBPK-UHFFFAOYSA-N 0.000 claims description 5
- ZHMAVICRSKFCFD-UHFFFAOYSA-N 6-(4-chlorophenyl)-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC(Cl)=CC=2)=N1 ZHMAVICRSKFCFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- HMVJXTUUQJUYJI-UHFFFAOYSA-N (3,4-diaminophenyl)methanol Chemical compound NC1=CC=C(CO)C=C1N HMVJXTUUQJUYJI-UHFFFAOYSA-N 0.000 claims description 3
- HYBCFWFWKXJYFT-UHFFFAOYSA-N 1,3-benzothiazole-2,6-diamine Chemical compound C1=C(N)C=C2SC(N)=NC2=C1 HYBCFWFWKXJYFT-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 claims description 3
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 claims description 3
- UONVFNLDGRWLKF-UHFFFAOYSA-N 2,5-diaminobenzoic acid Chemical compound NC1=CC=C(N)C(C(O)=O)=C1 UONVFNLDGRWLKF-UHFFFAOYSA-N 0.000 claims description 3
- XQRUEDXXCQDNOT-UHFFFAOYSA-N 2,5-diaminophenol Chemical compound NC1=CC=C(N)C(O)=C1 XQRUEDXXCQDNOT-UHFFFAOYSA-N 0.000 claims description 3
- MJFBGMMDLNKGNC-UHFFFAOYSA-N 2,5-dibromobenzene-1,4-diamine Chemical compound NC1=CC(Br)=C(N)C=C1Br MJFBGMMDLNKGNC-UHFFFAOYSA-N 0.000 claims description 3
- CIEFZSDJGQKZNS-UHFFFAOYSA-N 2,6-diaminobenzoic acid Chemical compound NC1=CC=CC(N)=C1C(O)=O CIEFZSDJGQKZNS-UHFFFAOYSA-N 0.000 claims description 3
- XBQYRNRIHZDZPK-UHFFFAOYSA-N 2,6-diaminophenol Chemical compound NC1=CC=CC(N)=C1O XBQYRNRIHZDZPK-UHFFFAOYSA-N 0.000 claims description 3
- NIXNGYGWQMXMCA-UHFFFAOYSA-N 2,6-dibromobenzene-1,4-diamine Chemical compound NC1=CC(Br)=C(N)C(Br)=C1 NIXNGYGWQMXMCA-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FFXSDAGPJYALFE-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC=C1OC1=CC=C(N)C(O)=C1 FFXSDAGPJYALFE-UHFFFAOYSA-N 0.000 claims description 3
- DAZJCNWHHPUGCC-UHFFFAOYSA-N 2-benzylsulfanylpyrimidine-4,6-diamine Chemical compound NC1=CC(N)=NC(SCC=2C=CC=CC=2)=N1 DAZJCNWHHPUGCC-UHFFFAOYSA-N 0.000 claims description 3
- UBGJVBQNURZQEV-UHFFFAOYSA-N 2-ethylsulfanylpyrimidine-4,6-diamine Chemical compound CCSC1=NC(N)=CC(N)=N1 UBGJVBQNURZQEV-UHFFFAOYSA-N 0.000 claims description 3
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 claims description 3
- LMKVISRKRWWZIS-UHFFFAOYSA-N 2-methylpyrimidine-4,6-diamine Chemical compound CC1=NC(N)=CC(N)=N1 LMKVISRKRWWZIS-UHFFFAOYSA-N 0.000 claims description 3
- FPXQABNVPCVWQU-UHFFFAOYSA-N 3,4-diaminobenzenethiol Chemical compound NC1=CC=C(S)C=C1N FPXQABNVPCVWQU-UHFFFAOYSA-N 0.000 claims description 3
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 3
- VWLLPPSBBHDXHK-UHFFFAOYSA-N 3,4-diaminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1N VWLLPPSBBHDXHK-UHFFFAOYSA-N 0.000 claims description 3
- QGNXDMSEEPNKCF-UHFFFAOYSA-N 3,5-difluorobenzene-1,2-diamine Chemical compound NC1=CC(F)=CC(F)=C1N QGNXDMSEEPNKCF-UHFFFAOYSA-N 0.000 claims description 3
- VPMJBJSLTPBZLR-UHFFFAOYSA-N 3,6-dibromobenzene-1,2-diamine Chemical compound NC1=C(N)C(Br)=CC=C1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 claims description 3
- FUMWDRKZNGZIJJ-UHFFFAOYSA-N 3,6-dimethoxybenzene-1,2-diamine Chemical compound COC1=CC=C(OC)C(N)=C1N FUMWDRKZNGZIJJ-UHFFFAOYSA-N 0.000 claims description 3
- JCUYNPHEESTECG-UHFFFAOYSA-N 3-amino-6-(4-aminophenyl)benzene-1,2-disulfonic acid Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O JCUYNPHEESTECG-UHFFFAOYSA-N 0.000 claims description 3
- BFLWXPJTAKXXKT-UHFFFAOYSA-N 3-methoxybenzene-1,2-diamine Chemical compound COC1=CC=CC(N)=C1N BFLWXPJTAKXXKT-UHFFFAOYSA-N 0.000 claims description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 3
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 claims description 3
- BTVHLEVGNAQTBN-UHFFFAOYSA-N 4,6-diaminopyrimidine-5-carbonitrile Chemical compound NC1=NC=NC(N)=C1C#N BTVHLEVGNAQTBN-UHFFFAOYSA-N 0.000 claims description 3
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 claims description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 3
- HWKHQQCBFMYAJZ-UHFFFAOYSA-N 4-amino-n-(3-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC(N)=C1 HWKHQQCBFMYAJZ-UHFFFAOYSA-N 0.000 claims description 3
- HQDCQNCMUSAKQU-UHFFFAOYSA-N 4-bromobenzene-1,3-diamine Chemical compound NC1=CC=C(Br)C(N)=C1 HQDCQNCMUSAKQU-UHFFFAOYSA-N 0.000 claims description 3
- CYICLOPCYFOPRK-UHFFFAOYSA-N 4-methoxy-1,3-benzothiazole-2,6-diamine Chemical compound COC1=CC(N)=CC2=C1N=C(N)S2 CYICLOPCYFOPRK-UHFFFAOYSA-N 0.000 claims description 3
- MCGDFFHOFXZDDV-UHFFFAOYSA-N 5-bromobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC(Br)=C1 MCGDFFHOFXZDDV-UHFFFAOYSA-N 0.000 claims description 3
- VZNUCJOYPXKLTA-UHFFFAOYSA-N 5-chlorobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC(Cl)=C1 VZNUCJOYPXKLTA-UHFFFAOYSA-N 0.000 claims description 3
- PWZNTESZSJQVGW-UHFFFAOYSA-N 6-(2-fluorophenyl)-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C(=CC=CC=2)F)=N1 PWZNTESZSJQVGW-UHFFFAOYSA-N 0.000 claims description 3
- IFTSWIQNKJOSLN-UHFFFAOYSA-N 6-(4-bromophenyl)-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC(Br)=CC=2)=N1 IFTSWIQNKJOSLN-UHFFFAOYSA-N 0.000 claims description 3
- WBDWTNWLWBQFJU-UHFFFAOYSA-N 6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diamine Chemical compound C1=CC(OC)=CC=C1C1=NC(N)=NC(N)=N1 WBDWTNWLWBQFJU-UHFFFAOYSA-N 0.000 claims description 3
- YCZUWQOJQGCZKG-UHFFFAOYSA-N 9h-carbazole-3,6-diamine Chemical compound C1=C(N)C=C2C3=CC(N)=CC=C3NC2=C1 YCZUWQOJQGCZKG-UHFFFAOYSA-N 0.000 claims description 3
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 3
- VZPGINJWPPHRLS-UHFFFAOYSA-N phenazine-2,3-diamine Chemical compound C1=CC=C2N=C(C=C(C(N)=C3)N)C3=NC2=C1 VZPGINJWPPHRLS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 4
- HGSZQBRMZNHXJZ-UHFFFAOYSA-N 1,3-benzothiazole-2,5-diamine Chemical compound NC1=CC=C2SC(N)=NC2=C1 HGSZQBRMZNHXJZ-UHFFFAOYSA-N 0.000 claims 2
- AJDXVTCUJNIISK-UHFFFAOYSA-N 1-fluorocyclohexa-3,5-diene-1,2-diamine Chemical compound NC1C=CC=CC1(N)F AJDXVTCUJNIISK-UHFFFAOYSA-N 0.000 claims 2
- HPDUOIDFHRYULE-UHFFFAOYSA-N 1h-indazole-4,7-diamine Chemical compound NC1=CC=C(N)C2=C1C=NN2 HPDUOIDFHRYULE-UHFFFAOYSA-N 0.000 claims 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims 2
- QNDFYLBDUWCFJO-UHFFFAOYSA-N 4-fluorobenzene-1,3-diamine Chemical compound NC1=CC=C(F)C(N)=C1 QNDFYLBDUWCFJO-UHFFFAOYSA-N 0.000 claims 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 238000013461 design Methods 0.000 abstract description 11
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 2
- SVWKIGRDISDRLO-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-9h-carbazole Chemical compound C=1C=CC=2NC3=CC=CC=C3C=2C=1OCC1CO1 SVWKIGRDISDRLO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- OAOBMEMWHJWPNA-UHFFFAOYSA-N (4-aminophenyl)phosphonic acid Chemical compound NC1=CC=C(P(O)(O)=O)C=C1 OAOBMEMWHJWPNA-UHFFFAOYSA-N 0.000 description 1
- YIDVLWDHYNWHMH-UHFFFAOYSA-N (4-hydroxyphenyl)phosphonic acid Chemical compound OC1=CC=C(P(O)(O)=O)C=C1 YIDVLWDHYNWHMH-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- DIPGYZSCGXBTEU-UHFFFAOYSA-N 2,3-difluoro-6-nitroaniline Chemical compound NC1=C(F)C(F)=CC=C1[N+]([O-])=O DIPGYZSCGXBTEU-UHFFFAOYSA-N 0.000 description 1
- RRHRTSXHXQNGEP-UHFFFAOYSA-N 2,4-dichlorocyclohexa-1,5-diene-1,4-diamine Chemical compound NC1=C(Cl)CC(N)(Cl)C=C1 RRHRTSXHXQNGEP-UHFFFAOYSA-N 0.000 description 1
- XKWQAXGDFYIFMB-UHFFFAOYSA-N 2-aminopyridine-3-thiol Chemical compound NC1=NC=CC=C1S XKWQAXGDFYIFMB-UHFFFAOYSA-N 0.000 description 1
- FXFTWEVIIHVHDS-UHFFFAOYSA-N 2-fluorobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(F)=C1 FXFTWEVIIHVHDS-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- RGVHBPPWCQVMDR-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 RGVHBPPWCQVMDR-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- UNAJNYASXFIDJJ-UHFFFAOYSA-N C1=CC(=C(C2=C1C(=O)OC2=O)CCC3=C(C=CC4=C3C(=O)OC4=O)C(=O)O)C(=O)O Chemical compound C1=CC(=C(C2=C1C(=O)OC2=O)CCC3=C(C=CC4=C3C(=O)OC4=O)C(=O)O)C(=O)O UNAJNYASXFIDJJ-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
- 230000006978 adaptation Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 229960001051 dimercaprol Drugs 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CHGSZEWACGNXMT-UHFFFAOYSA-N methyl 2-(3,6-diaminocarbazol-9-yl)acetate Chemical compound NC1=CC=C2N(CC(=O)OC)C3=CC=C(N)C=C3C2=C1 CHGSZEWACGNXMT-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- 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
- C08G2170/00—Compositions for adhesives
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
Abstract
The invention provides polyimide with high adhesive strength, a preparation method and application thereof, wherein the molecular structure of the polyimide is provided with a side chain, the side chain contains a structure with chemical interaction with copper, the polyimide has high adhesive strength with copper, and the structure with chemical interaction with copper is at least one selected from nitrogen heterocycle, thioether, siloxane and phosphate. According to the invention, through molecular chain structure design, a structure with chemical interaction with copper is designed on a side chain of polyimide molecules, so that polyimide with high adhesive strength is prepared, and the preparation method has high selectivity. The polyimide with high adhesive strength is applied to the wafer-level chip packaging rewiring structure, has high adhesive strength with the smooth copper surface, prevents the occurrence of interface failure, and can be used for high-frequency transmission.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to polyimide with high adhesive strength, and a preparation method and application thereof.
Background
Polyimide is a rigid chain polymer with a highly regular chemical structure and containing imide rings on the main chain, has excellent electrical, mechanical and thermal properties, and plays a role in protecting chips and metal circuits in a rewiring process. In the wafer-level chip packaging rewiring structure, copper lines are continuously refined and surface flattened, and the requirements on the adhesive strength of polyimide and a smooth copper surface are increasingly improved, so that the performance requirements of polyimide in the rewiring processing and application processes are met, and the occurrence of interface failure phenomenon is prevented.
In order to solve the problem of interface failure, roughening treatment is generally carried out on the copper surface and a bonding aid is added in the prior art. The roughening treatment of the copper surface has skin effect, the transmission of signals is concentrated on the surface thin layer of the conductor copper, and in order to reduce the loss of high-speed high-frequency signals in transmission, the roughness of the copper must be below 0.1 μm, so that the bonding strength between polyimide and copper cannot be increased by roughening treatment of the copper. The use of the adhesion promoter can improve the adhesion strength between the polyimide and the copper metal layer, but can increase the dielectric constant and dielectric loss tangent of the system, impeding high frequency transportation. Therefore, research and development of polyimide with high adhesive strength for smooth copper surfaces in wafer-level chip package rewiring structures is becoming increasingly important.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present invention is to provide a polyimide with high adhesive strength, in which the side chain of the molecular structure of the polyimide contains a structure having chemical interaction with copper, and has high adhesive strength with copper.
The second object of the present invention is to provide a method for producing polyimide with high adhesive strength, which has a structure having chemical interaction with copper on a side chain of polyimide molecule by molecular chain structure design, and has high selectivity.
The third object of the present invention is to provide an application of polyimide with high adhesive strength in a rewiring structure of a wafer level chip package, so as to prevent the occurrence of interface failure.
The invention aims at realizing the following steps:
the invention provides polyimide with high adhesive strength, which has a repeated structural unit shown in a general formula (1), wherein the repeated structural unit contains a structure with chemical interaction with copper,
in the general formula (1),represents a dianhydride functional group, -/->Represents a diamine functional group +.>Having a side chain and containing therein the structure having a chemical interaction with copper selected from at least one of nitrogen heterocycle, siloxane and phosphate.
The invention also provides a preparation method of the polyimide with high adhesive strength, which comprises the following steps:
s11, synthesizing polyamide acid: dissolving diamine in a polar organic solvent, and adding dianhydride to synthesize a first polyamic acid solution;
s12, grafting polyamide acid: adding a grafting compound into the first polyamic acid solution to perform a grafting reaction to obtain a second polyamic acid solution;
S13, imidization reaction: carrying out thermal imidization on the second polyamic acid solution to obtain polyimide with high adhesive strength; wherein,
the diamine comprises a diamine monomer I, wherein the diamine monomer I is a diamine monomer containing a reactive grafting structure, and the reactive grafting structure is at least one of hydroxyl, carboxyl, sulfhydryl, alkoxy, amido, sulfonic acid group, cyano and halogen atoms;
the graft compound comprises a reactive group capable of reacting with the active graft structure and a structure having a chemical interaction with copper, the reactive group being selected from at least one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and an epoxy group, and the structure having a chemical interaction with copper being selected from at least one of an azacyclic ring, a siloxane, and a phosphate.
Preferably, the diamine further comprises a diamine monomer II and/or a diamine monomer III, wherein the diamine monomer II is a diamine monomer containing a structure with chemical interaction with copper; the diamine monomer III is a diamine monomer without a target structure, and the target structure comprises the structure with chemical interaction with copper and the active grafting structure.
The invention also provides a preparation method of the polyimide with high adhesive strength, which comprises the following steps:
S21, synthesizing polyamide acid: dissolving diamine in a polar organic solvent, and adding dianhydride to synthesize a first polyamic acid solution;
s22, imidization reaction: adding an imidizing agent and an imidizing accelerator into the first polyamic acid solution to perform chemical imidization to obtain a first polyimide solution;
s23, precipitating polyimide pre-solid from the first polyimide solution;
s24, grafting polyimide: dissolving the polyimide pre-solid in a polar organic solvent to obtain a second polyimide solution; adding a dehydrating agent and a grafting compound into the second polyimide solution to carry out a grafting reaction to obtain a third polyimide solution;
s25, precipitating polyimide solids from the third polyimide solution to obtain polyimide with high adhesive strength; wherein,
the diamine comprises a diamine monomer I, wherein the diamine monomer I is a diamine monomer containing a reactive grafting structure, and the reactive grafting structure is at least one of hydroxyl, carboxyl, sulfhydryl, alkoxy, amido, sulfonic acid group, cyano and halogen atoms;
the graft compound comprises a reactive group capable of reacting with the active graft structure and a structure having a chemical interaction with copper, the reactive group being selected from at least one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and an epoxy group, and the structure having a chemical interaction with copper being selected from at least one of an azacyclic ring, a siloxane, and a phosphate.
Preferably, the diamine further comprises a diamine monomer II and/or a diamine monomer III, wherein the diamine monomer II is a diamine monomer containing a structure with chemical interaction with copper; the diamine monomer III is a diamine monomer without a target structure, and the target structure comprises the structure with chemical interaction with copper and the active grafting structure.
The invention also provides an application of the polyimide with high adhesive strength in a wafer-level chip packaging rewiring structure, which comprises the following steps: and coating the polyimide on a copper wire with a smooth surface to form a film.
In the polyimide with high adhesive strength provided by the embodiment of the invention, the side chain of the molecular structure of the polyimide contains a structure with chemical interaction with copper, the structure with chemical interaction with copper is selected from at least one of nitrogen heterocycle, siloxane and phosphate, and the structure with chemical interaction with copper can be in chemical interaction with copper, so that the polyimide with high adhesive strength is provided.
According to the preparation method of polyimide with high adhesive strength, provided by the embodiment of the invention, through the design of the molecular chain structure, the structure with chemical interaction with copper is designed on the side chain of polyimide molecules, and the structure with chemical interaction with copper is selected from at least one of nitrogen heterocycle, siloxane and phosphate, so that the adhesive strength between polyimide and the smooth copper surface can be improved. In addition, the structural design with chemical interaction with copper is arranged in the side chain of the polyimide molecule, so that the adhesive strength can be improved under the condition that the main chain structure of the polyimide and the main properties of good heat, mechanics, electricity and the like are not affected, meanwhile, the flexibility of the structure and grafting regulation of the side chain is high, the structural design of the polyimide molecule is more flexible, and other properties can be synergistically improved while the adhesive strength is improved. The preparation method of polyimide with high adhesive strength provided by the embodiment of the invention can flexibly select the structure of the side chain, and has high selectivity.
The polyimide with high adhesive strength is applied to the wafer-level chip packaging rewiring structure, has high adhesive strength with the smooth copper surface, prevents the occurrence of interface failure, and can be used for high-frequency transmission.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the specific embodiments of the present invention will be provided.
In view of the problem of low adhesion strength between polyimide and copper in the prior art, a first object of the present invention is to provide a polyimide having high adhesion strength, in which a side chain of a molecular structure of the polyimide has a structure having chemical interaction with copper, and has high adhesion strength with copper. The second object of the present invention is to provide a method for producing polyimide with high adhesive strength, which has a structure having chemical interaction with copper on a side chain of polyimide molecule by molecular chain structure design, and has high selectivity. The third object of the present invention is to provide an application of polyimide with high adhesive strength in a rewiring structure of a wafer level chip package, so as to prevent the occurrence of interface failure.
The embodiment of the invention provides polyimide with high adhesive strength, which has a repeated structural unit shown in a general formula (1), wherein the repeated structural unit contains a structure with chemical interaction with copper,
in the general formula (1),represents a dianhydride functional group, -/->Represents a diamine functional group +.>Having a side chain and containing therein the structure having a chemical interaction with copper selected from at least one of nitrogen heterocycle, siloxane and phosphate.
The nitrogen atom in the nitrogen heterocycle can coordinate with copper, so that the adhesive strength between polyimide and copper can be improved; the siloxane has good flexibility and low surface energy, and can have good spreading characteristics on the surface of copper so as to improve the bonding strength between polyimide and copper; the phosphate contains coordination chemical action, and can generate chemical action with copper to improve the adhesive strength of polyimide and copper.
The structural design with the chemical interaction of copper is arranged in the side chain of the polyimide molecule, so that the adhesive strength can be improved under the condition that the main chain structure of the polyimide and the main properties of good heat, mechanics, electricity and the like are not affected, meanwhile, the structure and grafting regulation and control flexibility of the side chain are high, the structural design of the polyimide molecule is more flexible, and other properties can be synergistically improved while the adhesive strength is improved. For example, due to the introduction of nitrogen-containing heterocycles, hydrogen bonds are generated between molecular chains, intermolecular forces are enhanced, the degree of freedom of the molecular chains is reduced, and polyimide exhibits a low Coefficient of Thermal Expansion (CTE) and residual stress. At the same time, the introduction of siloxane enhances the hydrophobicity and dielectric properties of polyimide, so that polyimide exhibits a low dielectric constant.
The polyimide having high adhesive strength as described above can be obtained by the following production method (one) or production method (two).
Wherein the preparation method (I) comprises the following steps:
step S11, synthesizing polyamide acid: diamine is dissolved in a polar organic solvent, and dianhydride is added to synthesize a first polyamic acid solution.
Step S12, grafting polyamide acid: and adding a grafting compound into the first polyamic acid solution to perform a grafting reaction to obtain a second polyamic acid solution.
Step S13, imidization reaction: and (3) carrying out thermal imidization on the second polyamic acid solution to obtain polyimide with high adhesive strength.
Wherein the preparation method (II) comprises the following steps:
step S21, synthesizing polyamide acid: diamine is dissolved in a polar organic solvent, and dianhydride is added to synthesize a first polyamic acid solution.
Step S22, imidization reaction: and adding an imidizing agent and an imidizing accelerator into the first polyamic acid solution to perform chemical imidization to obtain a first polyimide solution.
And S23, precipitating polyimide pre-solid from the first polyimide solution.
Step S24, grafting polyimide: dissolving the polyimide pre-solid in a polar organic solvent to obtain a second polyimide solution; and adding a dehydrating agent and a grafting compound into the second polyimide solution to carry out grafting reaction, so as to obtain a third polyimide solution.
And S25, precipitating polyimide solid from the third polyimide solution to obtain polyimide with high adhesive strength.
Wherein in the production method (one) and the production method (two), the diamine includes a diamine monomer i which is a diamine monomer having a reactive grafting structure selected from at least one of a hydroxyl group, a carboxyl group, a mercapto group, an alkoxy group, an amide group, a sulfonic acid group, a cyano group, and a halogen atom;
the graft compound comprises a reactive group capable of reacting with the active graft structure and a structure having a chemical interaction with copper, the reactive group being selected from at least one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and an epoxy group, and the structure having a chemical interaction with copper being selected from at least one of an azacyclic ring, a siloxane, and a phosphate.
In a preferred embodiment, the diamine of the preparation method (one) and the preparation method (two) further comprises a diamine monomer II and/or a diamine monomer III, wherein the diamine monomer II is a diamine monomer containing a structure having a chemical interaction with copper; the diamine monomer III is a diamine monomer without a target structure, and the target structure comprises the structure with chemical interaction with copper and the active grafting structure.
In particular, the method comprises the steps of, the diamine monomer I is selected from 3, 5-diaminobenzoic acid, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, benzidine disulfonic acid, 3 '-dihydroxybenzidine, 3' -diamino-4, 4 '-biphenyldiol, 2, 3-diaminophenol, 2, 4-diaminophenol, 2, 5-diaminophenol, 2, 6-diaminophenol, 3, 4-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 2, 6-diaminobenzoic acid, 4-methoxym-phenylenediamine, 1, 2-diamino-3-methoxybenzene, 2' -diaminobenzidine 5,5 '-oxybis (2-aminophenol), 3, 6-dimethoxybenzene-1, 2-diamine, 2-methoxy-p-phenylenediamine, 3, 4-diaminobenzenethiol, 4' -diaminodiphenyl sulfide, 2 '-diaminodiphenyl sulfide, 4-amino-N- (3-aminophenyl) benzamide, 4' -diaminoanilide, 3, 4-diaminophenylhydrazide, 3, 5-diaminophenylhydrazide, 3, 4-diaminobenzonitrile, (3, 4-diaminophenyl) methanol, 4 '-diamino- [1,1' -biphenyl ] -3-carbonitrile, 4 '-diamino- [1,1' -biphenyl ] -3,3 '-dicyano-le, 4' -diamino-3 '-3, 5,5' -tetrabromobiphenyl, 3,3' -dichlorobenzidine, 2, 3-diaminofluorobenzene, 2, 3-difluoro-6-nitroaniline, 1, 2-diamino-3, 5-difluorobenzene, 4-methyl-5-bromophthalene diamine, 4-chloro-1, 2-phenylenediamine, 4, 5-dichloro-1, 2-phenylenediamine, 5-chloro-m-phenylenediamine, 5-bromo-1, 3-phenylenediamine, 3-bromo-1, 2-diaminobenzene, 2, 5-dibromo-p-phenylenediamine, 4-bromo-1, 3-phenylenediamine, 2, 6-dibromo-1, 4-phenylenediamine, 2-bromo-1, 4-diaminobenzene, 2, 5-diaminobromobenzene, 3, 6-dibromo-1, 2-phenylenediamine, 2, 3-diamino-4-fluorobenzene, 3-fluoro-1, 2-phenylenediamine, 2-fluoro-1, 4-phenylenediamine, 2-dibromo-1, 4-phenylenediamine, 2, 4-dichloro-1, 4-phenylenediamine, 4-chloro-1, 2-diaminobenzene, 4-chloro-1, 2-phenylenediamine and at least one of the other types.
Specifically, the diamine monomer II is selected from 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, aminopropyl bis-blocked polydimethylsiloxanes, 3, 5-diamino-1, 2, 4-triazole, diaminopyridine, 2- (4-aminophenyl) -5-aminobenzimidazole, 1 hydro-indazole-4, 7-diamine, 2 '-diamino-4, 4' -dithiazole, 3, 6-diaminocarbazole, methyl 2- (3, 6-diamino-9H-carbazol-9-yl) acetate, 2, 5-diaminobenzothiazole, 2, 6-benzothiazole diamine, 4-methoxy-1, 3-benzothiazole-2, 6-diamine, benzomelamine, 2, 4-diamino-6- (2-fluorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-chlorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- [ trifluoromethyl ] -1,3, 6-diamino-phenyl ] -1,3, 5-triazine, 2-methoxy-1, 3-benzothiazole-2, 3-4-diamino-6-diamine, 4-diamino-phenyl ] -1,3, 5-triazine, 2, 4-diamino-6-trifluoro-phenyl ] -1,3, 4-triazine, 4-diamino-6-phenyl ] -3, 6-trifluoro-phenyl-triazine, 1,3, 6-diamino-6-triazine, at least one of 2, 4-diamino-6- (4-bromophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 3-diaminophenazine, methylguanamine, 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine, 4, 6-diaminopyrimidine-5-carbonitrile, 2-benzylthio-4, 6-diaminopyrimidine, 2- (ethylthio) -4, 6-diaminopyrimidine, and 2-methyl-4, 6-pyrimidinediamine.
Specifically, the diamine monomer III is at least one selected from 4,4' -diaminodiphenyl ether, 1, 3-bis (4 ' -aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, biphenyl diamine, 4' -diaminobenzophenone, 4' -diaminodiphenylmethane, 4' -diaminodiphenyl sulfone and 2, 2-bis (4-aminophenyl) hexafluoropropane.
In practice, in the preparation method (one) and the preparation method (two), the dianhydride used in the embodiment of the present invention may be any dianhydride which is commercially available and soluble in the polar organic solvent provided in the embodiment of the present invention. In particular, the dianhydride is selected from pyromellitic dianhydride, maleic anhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -Diphenyl ether tetracarboxylic dianhydride, 4 '-oxydiphthalic anhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, 3', at least one of 4,4' -benzophenone tetracarboxylic dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride, 4 '-terephthaloxybisphthalic anhydride, hexafluorodianhydride, 1, 2-ethylenebis [1, 3-dihydro-1, 3-dioxoisobenzofuran-5-carboxylate ], bisphenol A dianhydride, glycerol bis (dehydrated trimellitate) acetate, 2, 3',4 '-biphenyl tetracarboxylic dianhydride, p-phenylene-bistrimellitate dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride and 4,4' - (acetylene-1, 2-diyl) dicarboxylic anhydride.
Specifically, the polar organic solvent is at least one selected from N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, m-cresol, gamma-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric triamide and chloroform. In practice, the amount of the polar organic solvent used in the embodiments of the present invention may be changed as needed, and it is only necessary to completely dissolve the diamine and the dianhydride.
In the production method (one) and the production method (two), the diamine and the dianhydride used in the step S11 and the step S21 are used in approximately equimolar amounts, but in order to control the polymerization degree of the obtained polyamic acid and obtain a polyimide having high adhesive strength, the molar ratio of the diamine and the dianhydride may be (0.9 to 1.1): 1, for example, 0.9:1, 0.95:1, 1:1. 1.05:1 or 1.1:1.
in addition, in the embodiment of the present invention, in order to obtain polyimide with a higher polymerization degree, the diamine and the dianhydride used in the step S11 and the step S21 are subjected to pretreatment to remove impurities before use, specifically: treating the diamine in a vacuum oven at 60 ℃ for 2-3 hours, and treating the dianhydride in a vacuum oven at 160 ℃ for 4-6 hours.
It should be noted that in the preparation method (one) and the preparation method (two), the operations of the step S11 and the step S21 are preferably performed such that a predetermined amount of the diamine is dissolved in the polar organic solvent, and a predetermined amount of the dianhydride is added while stirring to synthesize the first polyamic acid solution, wherein the dianhydride is added in portions, preferably in two portions, with an interval of 10min to 30min.
In other embodiments, other methods may be used, such as: the dianhydride is dissolved in the polar organic solvent, and the diamine is added while stirring to react to obtain a polyamic acid solution. The following methods may also be employed: alternately charging the diamine and the dianhydride into the polar organic solvent to react and obtain a polyamic acid solution.
The conditions of the steps S11 and S21 are not particularly limited, and in order to reduce the cost and obtain a polyamide acid solution having a higher polymerization degree, the process is preferably performed at 10 to 50 ℃ under an inert atmosphere, more preferably at room temperature under a nitrogen atmosphere.
In particular, in the preparation method (one) and the preparation method (two), the graft compound may be represented by the general formula Representation, wherein->Represents a reactive group which reacts with the reactive grafting structure of the diamine monomer I, the reactive group being selected from at least one of hydroxyl, carboxyl, amino and epoxy groups; />Represents a linking group, which may or may not have a linking group, including but not limited to benzene rings, alkane chains, and the like; />Represents a structure having a chemical interaction with copper selected from at least one of nitrogen heterocycle, siloxane and phosphate.
Specifically, in the preparation method (one), in order to remove impurities and obtain a higher second polyamic acid solution, the step S12 further includes adding acetonitrile to the mixed system after the grafting reaction to wash out polyamic acid solids grafted with a structure having a chemical interaction with copper, and drying the polyamic acid solids grafted with a structure having a chemical interaction with copper and then redissolving the dried polyamic acid solids in the polar organic solvent to obtain a second polyamic acid solution.
In effect, the conversion of polyamic acid to polyimide is a dehydrative ring closure process that involves intramolecular dehydration of the polyamic acid to produce a cyclic polyimide. Imidization is carried out in two ways, namely thermal imidization and chemical imidization.
The thermal imidization method is preferably carried out by adopting a multi-step method programmed temperature rise and maintaining at different temperatures for a certain time to complete thermal imidization under the influence of the thermal mechanical interruption effect, and can be carried out by adopting a continuous or stepped temperature rise mode. The thermal imidization process may be performed in air, but since the vacuum state can sufficiently discharge the generated small molecular water and solvent, the inert atmosphere can effectively reduce the thermal oxidation side reaction, and thus it is preferable to perform the thermal imidization in the vacuum state or the inert atmosphere.
The chemical imidization method requires the use of an imidizing agent selected from at least one of acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, and benzoic anhydride. Meanwhile, in the chemical imidization reaction, aliphatic, aromatic or heterocyclic tertiary amines such as pyridine, picoline, quinoline, isoquinoline, trimethylamine, triethylamine and the like can be used as imidization accelerators, so that the imidization reaction can be efficiently performed at a low temperature.
The equivalent weight of the imidizing agent used is not less than the equivalent weight of the amide bond of the polyamic acid to be subjected to the chemical imidization reaction, preferably 1.1 to 5 times, more preferably 1.5 to 4 times the equivalent weight of the amide bond. By using a small excess of the imidizing agent relative to the amide bond in this manner, the imidization reaction can be efficiently performed even at a relatively low temperature.
In particular, a polar organic solvent is preferably added to dilute the polyamic acid solution prior to chemical imidization so that chemical imidization proceeds more efficiently.
In a preferred embodiment, the preparation method (one) uses a thermal imidization method to imidize the second polyamic acid solution into polyimide, which is convenient to operate. The specific process of the step S13 is as follows: and heating the second polyimide solution in a stepwise heating mode in a nitrogen atmosphere, and cooling to room temperature to obtain polyimide with high adhesive strength. In the step heating, each temperature step is 50-100 ℃, the holding time is 30-120 min, the heating rate is 1-10 ℃/min, the highest temperature at the last heating is 300-400 ℃, and the heating process is not lower than 2h.
It should be noted that, to increase the efficiency of thermal imidization, the second polyamic acid solution is soft baked in a flat mold to remove a part of the polar organic solvent before the thermal imidization is performed. Wherein, the mode of placing the second polyamic acid solution on a flat mold is preferably spin coating or blade coating.
In a preferred embodiment, the preparation method (II) imidizes the first polyamic acid solution into a first polyimide solution using a chemical imidization method so as to improve the solubility of the polyimide after curing to make side group modification. Specifically, in the preferred embodiment of the present invention, acetic anhydride is the preferred imidizing agent in view of the combination of cost and ease of removal after reaction, and triethylamine is selected as the imidizing accelerator to enable the imidization reaction to proceed efficiently at low temperature.
Specifically, the polar organic solvent is preferably added to dilute the first polyamic acid solution before chemical imidization is performed, so that imidization proceeds more efficiently.
In the embodiment of the present invention, the step S22 is not particularly limited, and is preferably performed at room temperature under nitrogen protection.
In the second preparation method (ii), the side chain of the first polyimide in the first polyimide solution obtained in the step S22 does not contain a structure having a chemical interaction with copper, and a grafting reaction is required to obtain a polyimide with high adhesive strength. Step S23 is required to obtain a polyimide pre-solid of high purity before the grafting reaction is performed.
Specifically, the precipitation of the polyimide pre-solid from the first polyimide solution in step S23 may be performed by any method, and a method of precipitating polyimide to form a solid by adding a poor solvent for polyimide is preferable. When polyimide is deposited by adding a poor solvent, any poor solvent that can deposit polyimide may be used as the poor solvent.
Specifically, the poor solvent is selected from any one of water, methanol and ethanol.
In the case of precipitating polyimide with a poor solvent, the amount of the poor solvent to be used is required to be an amount sufficient for precipitating polyimide, and is determined in consideration of the structure of polyimide, the solvent of the polyimide solution, the solution concentration of polyimide, and the like, and is usually 0.5 times or more by weight of the polyimide solution.
In the specific operation of the invention, after the polyimide pre-solid is precipitated by adding the poor solvent, a system containing the polyimide pre-solid is subjected to suction filtration to collect solid phase and is dried in a vacuum oven at 50 ℃ for 6 hours, so that the polyimide pre-solid with high purity is obtained.
Specifically, after obtaining the polyimide pre-solid of high purity obtained in the step S23, the step S24 and the step S25 are required to be performed to obtain a polyimide having a structure having a chemical interaction with copper in a side chain.
Specifically, in the step S24, the dehydrating agent may be specifically selected from at least one of N, N' -dicyclohexylcarbodiimide, diisopropylcarbodiimide, phosphorus pentachloride, phosphorus oxychloride, and thionyl chloride.
Specifically, in the step S25, there are various methods for precipitating polyimide solids from the third polyimide solution to obtain polyimide with high adhesive strength, and in the preferred embodiment of the present invention, it is preferable to add water or methanol to the third polyimide solution to precipitate polyimide, and after precipitating polyimide solids, to remove the dehydrating agent, the polar organic solvent and the graft compound, to obtain polyimide with higher purity, the obtained polyimide solids should be suction-filtered and dried, and the drying condition is preferably oven drying at 50 ℃ for 6 hours under vacuum.
According to the preparation method of polyimide with high adhesive strength, provided by the embodiment of the invention, through the design of the molecular chain structure, the structure with chemical interaction with copper is designed on the side chain of polyimide molecules, and the structure with chemical interaction with copper is selected from at least one of nitrogen heterocycle, siloxane and phosphate, so that the adhesive strength between polyimide and the smooth copper surface can be improved.
In addition, the structural design with chemical interaction with copper is arranged in the side chain of the polyimide molecule, so that the adhesive strength can be improved under the condition that the main chain structure of the polyimide and the main properties of good heat, mechanics, electricity and the like are not affected, meanwhile, the flexibility of the structure and grafting regulation of the side chain is high, the structural design of the polyimide molecule is more flexible, and other properties can be synergistically improved while the adhesive strength is improved. The preparation method of polyimide with high adhesive strength provided by the embodiment of the invention can flexibly select the structure of the side chain, and has high selectivity.
The embodiment of the invention also provides an application of the polyimide with high adhesive strength in a wafer-level chip packaging rewiring structure, which comprises the following steps: the polyimide with high adhesive strength is coated on a copper wire with smooth surface to form a film.
Specifically, in step S13, the second polyamic acid solution is uniformly spread on a copper line with a smooth surface by spin coating or knife coating, and imidized after soft baking to obtain a polyimide copper-clad sample; or, the polyimide with high adhesive strength obtained in the step S25 is dissolved in a polar organic solvent to obtain a polyimide solution, and then the polyimide solution is uniformly spread on a copper circuit with a smooth surface in a spin coating or blade coating mode, and a polyimide copper-clad sample is obtained by curing with nitrogen after soft baking.
After the polyimide copper-clad sample is obtained, the peel force is tested, and the obtained peel strength is the adhesive strength between the polyimide and the copper circuit with smooth surface.
Specifically, in the embodiment of the present invention, the method for testing the peel force is as follows: the adhesion properties between polyimide and smooth-surfaced copper wire, characterized by the change in peel strength of polyimide and smooth-surfaced copper wire during the peel process in a 90 ° peel test, were tested by a fold resistance tester. According to the IPC-TM-650 standard, a sample is cut into test bars with the width of 3mm and the length of not less than 100mm before testing, then the test bars are fixed on a stripping test clamp, 90 DEG stripping test is carried out, the stripping speed is 50mm/min, the change of stripping force in the stripping process is recorded, and finally the average value of three measured values is calculated and expressed as stripping strength, so that the adhesive strength between polyimide and a copper circuit with a smooth surface is obtained, wherein the unit is N/3mm.
In order to further illustrate the present invention, a polyimide having high adhesive strength, a method for preparing the same, and applications thereof, which are provided by the present invention, will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
S11, synthetic Polyamic acid
2- (4-aminophenyl) -5-aminobenzimidazole and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were placed in a vacuum oven at 60℃for 3 hours, and pyromellitic dianhydride was placed in a vacuum oven at 160℃for 4 hours to remove impurities.
1.6019g of 2- (4-aminophenyl) -5-aminobenzimidazole and 1.1212g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were dissolved in 28.1089g of N, N-dimethylacetamide at room temperature, and then 2.2373g of pyromellitic dianhydride was added with stirring twice under a nitrogen atmosphere and stirred for 24 hours to synthesize a first polyamic acid solution.
S12, grafting polyamic acid
Adding 4-glycidoxycarbazole with the same molar quantity of hydroxyl into the first polyamic acid solution for grafting reaction, adding acetonitrile after the reaction is finished to wash out polyamic acid solid grafted with copper with a structure with chemical interaction, drying the polyamic acid solid grafted with copper with the structure with chemical interaction, and then redissolving the polyamic acid solid in N, N-dimethylacetamide to obtain a second polyamic acid solution.
S13, imidization reaction
Uniformly spreading the second polyamic acid solution on a copper line with a smooth surface in a spin coating mode, wherein the rotating speed is 1000rad/s, the time is 30s, and the second polyamic acid solution is soft baked on a hot plate at 80 ℃ for 10min to remove part of organic solvent. The smooth surface copper line roughness is less than 500nm.
Then heating to 100 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and keeping for 1h; raising the temperature to 200 ℃ from 100 ℃ at a speed of 5 ℃/min, and keeping for 1h; raising the temperature from 200 ℃ to 300 ℃ at a speed of 5 ℃/min, and keeping for 1h; raising the temperature from 300 ℃ to 350 ℃ at a speed of 5 ℃/min, and keeping for 1h; and cooling to room temperature after the reaction is finished, and obtaining polyimide with high adhesive strength on a copper circuit with a smooth surface, so as to prepare and obtain a polyimide copper-clad sample.
Example 2
Example 2 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 1:1, 2- (4-aminophenyl) -5-aminobenzimidazole and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 1, and thus will not be described in detail.
Example 3
Example 3 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 3: 7- (4-aminophenyl) -5-aminobenzimidazole and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 1, and thus will not be described in detail.
Example 4
Example 4 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 1, and thus will not be described in detail.
Example 5
Example 5 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 3:7, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 1, and thus will not be described in detail.
Example 6
Example 6 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 1:1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the remaining materials and preparation processes in this example are exactly the same as in example 1, and thus are not described in detail.
Example 7
Example 7 differs from example 1 in that: the diamine monomer used in this example was used in a molar ratio of 1:1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the remaining materials and preparation processes in this example are exactly the same as those in example 1, and thus a detailed description thereof will be omitted.
Example 8
S21, synthesizing polyamide acid: 3, 5-diaminobenzoic acid and 4,4' -diaminodiphenyl ether are placed in a vacuum oven at 60 ℃ for 3h, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride is placed in the vacuum oven at 160 ℃ for 6h, and impurities are removed.
A first polyamic acid solution was synthesized by adding 0.5g of 3, 5-diaminobenzoic acid and 0.381g of a mixed diamine of 4,4' -diaminodiphenyl ether to a flask at room temperature, dissolving 13.781g of N-methylpyrrolidone, and then adding 1.55g of 2, 3',4' -diphenylether tetracarboxylic dianhydride under nitrogen atmosphere with stirring twice and stirring for 6 hours.
S22, imidization reaction: 13.77g of N-methylpyrrolidone was added to the first polyamic acid solution, and after stirring for 5 minutes so that the solution was sufficiently diluted, 1.5606g of acetic anhydride and 1.737g of triethylamine were added, and stirred under a nitrogen atmosphere for 12 hours, to obtain a first polyimide solution.
S23, adding 2L of deionized water into the first polyimide solution, precipitating a first polyimide solid, carrying out suction filtration on a system containing polyimide pre-solid, collecting solid phase, and drying in a vacuum oven at 50 ℃ for 6 hours to obtain the polyimide pre-solid with high purity.
S24, grafting polyimide: 2.2g of polyimide pre-solid is dissolved in 41.8g of N-methylpyrrolidone and stirred for 4 hours to obtain a second polyimide solution;
Adding N, N' -dicyclohexylcarbodiimide into the second polyimide solution, stirring for 2 hours under the conditions of nitrogen atmosphere and ice water bath, then adding 0.205g of 3-amino-1, 2, 4-triazole into the solution, and stirring for 6 hours to obtain a third polyimide solution;
s25, dripping the third polyimide solution into 2L of deionized water, filtering, and then drying the obtained product in a vacuum oven at 50 ℃ for 6 hours to obtain polyimide with high adhesive strength.
And (3) dissolving the polyimide with high adhesive strength obtained in the step (S25) in N-methylpyrrolidone to obtain a polyimide solution, uniformly spreading the polyimide solution on a copper circuit with a smooth surface in a spin coating or blade coating mode, and curing with nitrogen after soft baking to obtain a polyimide copper-clad sample. Wherein the smooth-surfaced copper wire roughness is less than 400nm.
Example 9
Example 9 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 4,4' -diaminodiphenyl ether, the grafting compound used in step S24 being 4-aminotriazole in a molar amount with the carboxyl groups. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 10
Example 10 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 4,4' -diaminodiphenyl ether, the grafting compound used in step S24 being 2-mercaptopyrimidine in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 11
Example 11 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole, the grafting compound used in step S24 being 2-amino-3-mercaptopyridine in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 12
Example 12 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 4,4' -diaminodiphenyl ether, the grafting compound used in step S24 being 3-pyridinesulfonic acid in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 13
Example 13 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 3:7, 2, 3-diaminophenol and m-phenylenediamine, the grafting compound used in step S24 is 4-glycidoxycarbazole in equimolar amount with the hydroxyl groups. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 14
Example 14 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 6:4 and 4,4' -diaminobenzophenone, the grafting compound used in step S24 being 1, 4-butanedithiol in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 15
Example 15 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole, the grafting compound used in step S24 being dimercaprol in a molar amount with the carboxyl groups. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 16
Example 16 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole, the grafting compound used in step S24 being (4-hydroxyphenyl) phosphonic acid in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 17
Example 17 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole, the grafting compound used in step S24 being (4-aminophenyl) phosphonic acid in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 18
Example 18 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole, the grafting compound used in step S24 is 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane in a molar amount with the carboxyl group. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Example 19
Example 19 differs from example 8 in that: the diamine monomer used in this example was used in a molar ratio of 1:1:1 and 2- (4-aminophenyl) -5-aminobenzimidazole and 4,4' -diaminodiphenyl ether, the grafting compound used in step S24 being 4-aminotriazole in a molar amount with the carboxyl groups. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 8, and thus will not be described in detail.
Comparative example 1
Comparative example 1 is different from example 1 in that: the diamine monomer used in this example was 4,4' -diaminodiphenyl ether and step S12 was not required. The rest of the materials and the preparation process in this embodiment are exactly the same as those in embodiment 1, and thus will not be described in detail.
The polyimide copper clad samples prepared in examples 1 to 19 and comparative example 1 above were cut into test bars having a width of 3mm and a length of not less than 100mm before testing according to IPC-TM-650 standard, and then fixed on a peel test jig, subjected to a 90 ° peel test at a peel speed of 50mm/min, the change in peel force during peeling was recorded, and finally the average value of the three measured values was calculated and expressed as peel strength, i.e., the adhesive strength between polyimide and copper wire having a smooth surface in N/3mm. The experimental data are shown in table 1.
TABLE 1
| Examples of the invention | Adhesive strength | Examples of the invention | Adhesive strength |
| Example 1 | 1.0295 | Example 11 | 1.1941 |
| Example 2 | 1.1143 | Example 12 | 1.0059 |
| Example 3 | 1.2674 | Example 13 | 1.0564 |
| Example 4 | 0.9292 | Example 14 | 1.1936 |
| Example 5 | 1.3367 | Example 15 | 1.2652 |
| Example 6 | 1.1853 | Example 16 | 1.1783 |
| Example 7 | 0.9858 | Example 17 | 1.1896 |
| Example 8 | 1.0965 | Example 18 | 1.1377 |
| Example 9 | 1.1374 | Example 19 | 1.0191 |
| Example 10 | 0.9783 | Comparative example 1 | 0.5950 |
As can be seen from Table 1, the adhesion strength between the polyimide and the smooth-surfaced copper wire was improved by at least 55% in example 1-example 19 as compared with comparative example 1. Therefore, the polyimide with high adhesive strength is applied to the wafer level chip packaging rewiring structure, the polyimide and the copper circuit surface with smooth surface have high adhesive strength, the occurrence of interface failure phenomenon is prevented, and the polyimide-copper wire rewiring structure can be used for high-frequency transmission.
The foregoing is merely exemplary of the application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the application and are intended to be comprehended within the scope of the application.
Claims (8)
1. A method for preparing polyimide with high adhesive strength, which is characterized by comprising the following steps:
s11, synthesizing polyamide acid: dissolving diamine in a polar organic solvent, and adding dianhydride to synthesize a first polyamic acid solution;
S12, grafting polyamide acid: adding a grafting compound into the first polyamic acid solution to perform a grafting reaction to obtain a second polyamic acid solution;
s13, imidization reaction: carrying out thermal imidization on the second polyamic acid solution to obtain polyimide with high adhesive strength; wherein,
the diamine comprises a diamine monomer I, wherein the diamine monomer I is a diamine monomer containing a reactive grafting structure, and the reactive grafting structure is at least one of hydroxyl, carboxyl, sulfhydryl, alkoxy, amido, sulfonic acid group, cyano and halogen atoms;
the graft compound comprises a reactive group capable of reacting with the active graft structure and a structure having a chemical interaction with copper, the reactive group being selected from at least one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and an epoxy group, and the structure having a chemical interaction with copper being selected from at least one of an azacyclic ring, a siloxane, and a phosphate.
2. The method for producing a polyimide having high adhesive strength according to claim 1, wherein the diamine further comprises a diamine monomer ii and/or a diamine monomer iii, the diamine monomer ii being a diamine monomer having a structure having a chemical interaction with copper; the diamine monomer III is a diamine monomer without a target structure, and the target structure comprises the structure with chemical interaction with copper and the active grafting structure.
3. The method for producing a polyimide with high adhesive strength according to claim 2, the diamine monomer I is selected from 3, 5-diaminobenzoic acid, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, benzidine disulfonic acid, 3' -dihydroxybenzidine, 3' -diamino-4, 4' -biphenyldiol, 2, 3-diaminophenol, 2, 4-diaminophenol, 2, 5-diaminophenol, 2, 6-diaminophenol, 3, 4-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 2, 6-diaminobenzoic acid, 4-methoxym-phenylenediamine, 1, 2-diamino-3-methoxybenzene, 2' -diaminobenzidine 5,5' -oxybis (2-aminophenol), 3, 6-dimethoxybenzene-1, 2-diamine, 2-methoxy-p-phenylenediamine, 3, 4-diaminobenzenethiol, 4' -diaminodiphenyl sulfide, 2' -diaminodiphenyl sulfide, 4-amino-N- (3-aminophenyl) benzamide, 4' -diaminoanilide, 3, 4-diaminophenylhydrazide, 3, 5-diaminophenylhydrazide, 3, 4-diaminobenzonitrile, (3, 4-diaminophenyl) methanol, 4' -diamino- [1,1' -biphenyl ] -3-carbonitrile, 4' -diamino- [1,1' -biphenyl ] -3,3' -dicyano-le, at least one of 4,4 '-diamino-3, 3',5 '-tetrabromobiphenyl, 3' -dichlorobenzidine, 2, 3-diaminofluorobenzene, 1, 2-diamino-3, 5-difluorobenzene, 4-methyl-5-bromophthalene diamine, 4-chloro-1, 2-phenylenediamine, 4, 5-dichloro-1, 2-phenylenediamine, 5-chloro-m-phenylenediamine, 5-bromo-1, 3-phenylenediamine, 3-bromo-1, 2-diaminobenzene, 2, 5-dibromo-p-phenylenediamine, 4-bromo-1, 3-phenylenediamine, 2, 6-dibromo-1, 4-phenylenediamine, 2-bromo-1, 4-diaminobenzene, 2, 5-diaminobromobenzene, 3, 6-dibromo-1, 2-phenylenediamine, 2, 3-diaminofluorobenzene, 1, 3-diamino-4-fluorobenzene, 3-fluoro-1, 2-phenylenediamine, 2-fluoro-phenylenediamine, 3-bromo-1, 2-phenylenediamine, 4-dibromo-1, 4-phenylenediamine, 2-diaminobenzene, 4-chloro-1, 2-phenylenediamine, 4-chloro-1, 2-diaminobenzene, 4-chloro-1, 2-phenylenediamine, 4-chloro-1, 2-phenylenediamine, 4-chloro-methyl-phenylenediamine, 4-chloro-2-phenylenediamine;
The diamine monomer II is selected from 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, aminopropyl double-end-capped polydimethyl siloxane, 3, 5-diamino-1, 2, 4-triazole, diaminopyridine, 2- (4-aminophenyl) -5-aminobenzimidazole, 1H-indazole-4, 7-diamine, 2 '-diamino-4, 4' -bisthiazole, 3, 6-diamino-carbazole, 2- (3, 6-diamino-9H-carbazole-9-yl) methyl acetate, 2, 5-diaminobenzothiazole, 2, 6-benzothiazole diamine, 4-methoxy-1, 3-benzothiazole-2, 6-diamine, benzomelamine, 2, 4-diamino-6- (2-fluorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-chlorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- [4- (trifluoromethyl) phenyl ] -1,3, 6-diamino-9-yl) methyl 2- (3, 6-diamino-benzothiazole, 2, 5-diamino-6-phenyl) -1,3, 5-triazine, 2-diamino-6- (2-fluorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-chlorophenyl) -1,3, 5-triazine, 2, 4-diamino-6-4-trifluoromethyl-6-phenyl ] -1,3, 5-triazine, 3, 5-diamino-6-triazine, 2, 4-diamino-6- (4-bromophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 3-diaminophenazine, methylguanamine, 2, 4-diamino
-at least one of 6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine, 4, 6-diaminopyrimidine-5-carbonitrile, 2-benzylthio-4, 6-diaminopyrimidine, 2- (ethylthio) -4, 6-diaminopyrimidine and 2-methyl-4, 6-pyrimidinediamine;
The diamine monomer III is at least one selected from 4,4' -diaminodiphenyl ether, 1, 3-bis (4 ' -aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, biphenyl diamine, 4' -diaminodiphenyl ketone, 4' -diaminodiphenyl methane, 4' -diaminodiphenyl sulfone and 2, 2-bis (4-aminophenyl) hexafluoropropane.
4. A method for preparing polyimide with high adhesive strength according to any one of claims 1 to 3, wherein the specific process of thermal imidization is as follows: heating in a step heating mode under nitrogen atmosphere, and cooling to room temperature to obtain polyimide with high adhesive strength; in the step heating, each temperature step is 50-100 ℃, the holding time is 30-120 min, the heating rate is 1-10 ℃/min, the highest temperature at the last heating is 300-400 ℃, and the heating process is not lower than 2h.
5. A method for preparing polyimide with high adhesive strength, which is characterized by comprising the following steps:
s21, synthesizing polyamide acid: dissolving diamine in a polar organic solvent, and adding dianhydride to synthesize a first polyamic acid solution;
s22, imidization reaction: adding an imidizing agent and an imidizing accelerator into the first polyamic acid solution to perform chemical imidization to obtain a first polyimide solution;
S23, precipitating polyimide pre-solid from the first polyimide solution;
s24, grafting polyimide: dissolving the polyimide pre-solid in a polar organic solvent to obtain a second polyimide solution; adding a dehydrating agent and a grafting compound into the second polyimide solution to carry out a grafting reaction to obtain a third polyimide solution;
s25, precipitating polyimide solids from the third polyimide solution to obtain polyimide with high adhesive strength; wherein,
the diamine comprises a diamine monomer I, wherein the diamine monomer I is a diamine monomer containing a reactive grafting structure, and the reactive grafting structure is at least one of hydroxyl, carboxyl, sulfhydryl, alkoxy, amido, sulfonic acid group, cyano and halogen atoms;
the graft compound comprises a reactive group capable of reacting with the active graft structure and a structure having a chemical interaction with copper, the reactive group being selected from at least one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and an epoxy group, and the structure having a chemical interaction with copper being selected from at least one of an azacyclic ring, a siloxane, and a phosphate.
6. The method for producing a polyimide with high adhesive strength according to claim 5, wherein the diamine further comprises a diamine monomer II and/or a diamine monomer III, the diamine monomer II being a diamine monomer having a structure having a chemical interaction with copper; the diamine monomer III is a diamine monomer without a target structure, and the target structure comprises the structure with chemical interaction with copper and the active grafting structure.
7. The method for producing a polyimide with high adhesive strength according to claim 6, the diamine monomer I is selected from 3, 5-diaminobenzoic acid, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, benzidine disulfonic acid, 3' -dihydroxybenzidine, 3' -diamino-4, 4' -biphenyldiol, 2, 3-diaminophenol, 2, 4-diaminophenol, 2, 5-diaminophenol, 2, 6-diaminophenol, 3, 4-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 2, 6-diaminobenzoic acid, 4-methoxym-phenylenediamine, 1, 2-diamino-3-methoxybenzene, 2' -diaminobenzidine 5,5' -oxybis (2-aminophenol), 3, 6-dimethoxybenzene-1, 2-diamine, 2-methoxy-p-phenylenediamine, 3, 4-diaminobenzenethiol, 4' -diaminodiphenyl sulfide, 2' -diaminodiphenyl sulfide, 4-amino-N- (3-aminophenyl) benzamide, 4' -diaminoanilide, 3, 4-diaminophenylhydrazide, 3, 5-diaminophenylhydrazide, 3, 4-diaminobenzonitrile, (3, 4-diaminophenyl) methanol, 4' -diamino- [1,1' -biphenyl ] -3-carbonitrile, 4' -diamino- [1,1' -biphenyl ] -3,3' -dicyano-le, at least one of 4,4 '-diamino-3, 3',5 '-tetrabromobiphenyl, 3' -dichlorobenzidine, 2, 3-diaminofluorobenzene, 1, 2-diamino-3, 5-difluorobenzene, 4-methyl-5-bromophthalene diamine, 4-chloro-1, 2-phenylenediamine, 4, 5-dichloro-1, 2-phenylenediamine, 5-chloro-m-phenylenediamine, 5-bromo-1, 3-phenylenediamine, 3-bromo-1, 2-diaminobenzene, 2, 5-dibromo-p-phenylenediamine, 4-bromo-1, 3-phenylenediamine, 2, 6-dibromo-1, 4-phenylenediamine, 2-bromo-1, 4-diaminobenzene, 2, 5-diaminobromobenzene, 3, 6-dibromo-1, 2-phenylenediamine, 2, 3-diaminofluorobenzene, 1, 3-diamino-4-fluorobenzene, 3-fluoro-1, 2-phenylenediamine, 2-fluoro-phenylenediamine, 3-bromo-1, 2-phenylenediamine, 4-dibromo-1, 4-phenylenediamine, 2-diaminobenzene, 4-chloro-1, 2-phenylenediamine, 4-chloro-1, 2-diaminobenzene, 4-chloro-1, 2-phenylenediamine, 4-chloro-1, 2-phenylenediamine, 4-chloro-methyl-phenylenediamine, 4-chloro-2-phenylenediamine;
The diamine monomer II is selected from 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, aminopropyl double-end-capped polydimethyl siloxane, 3, 5-diamino-1, 2, 4-triazole, diaminopyridine, 2- (4-aminophenyl) -5-aminobenzimidazole, 1H-indazole-4, 7-diamine, 2 '-diamino-4, 4' -bisthiazole, 3, 6-diamino-carbazole, 2- (3, 6-diamino-9H-carbazole-9-yl) methyl acetate, 2, 5-diaminobenzothiazole, 2, 6-benzothiazole diamine, 4-methoxy-1, 3-benzothiazole-2, 6-diamine, benzomelamine, 2, 4-diamino-6- (2-fluorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-chlorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- [4- (trifluoromethyl) phenyl ] -1,3, 6-diamino-9-yl) methyl 2- (3, 6-diamino-benzothiazole, 2, 5-diamino-6-phenyl) -1,3, 5-triazine, 2-diamino-6- (2-fluorophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-chlorophenyl) -1,3, 5-triazine, 2, 4-diamino-6-4-trifluoromethyl-6-phenyl ] -1,3, 5-triazine, 3, 5-diamino-6-triazine, 2, 4-diamino-6- (4-bromophenyl) -1,3, 5-triazine, 2, 4-diamino-6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 3-diaminophenazine, methylguanamine, 2, 4-diamino
-at least one of 6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine, 4, 6-diaminopyrimidine-5-carbonitrile, 2-benzylthio-4, 6-diaminopyrimidine, 2- (ethylthio) -4, 6-diaminopyrimidine and 2-methyl-4, 6-pyrimidinediamine;
The diamine monomer III is at least one selected from 4,4' -diaminodiphenyl ether, 1, 3-bis (4 ' -aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, biphenyl diamine, 4' -diaminodiphenyl ketone, 4' -diaminodiphenyl methane, 4' -diaminodiphenyl sulfone and 2, 2-bis (4-aminophenyl) hexafluoropropane.
8. The method for producing a polyimide with high adhesive strength according to any one of claims 5 to 7, wherein the imidizing agent is at least one selected from acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride and benzoic anhydride;
the imidization accelerator is at least one selected from triethylamine, pyridine, picoline, quinoline, isoquinoline and trimethylamine;
the dehydrating agent is at least one selected from N, N' -dicyclohexylcarbodiimide, diisopropylcarbodiimide, phosphorus pentachloride, phosphorus oxychloride and thionyl chloride.
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