JP6086537B2 - Polyimide resin - Google Patents
Polyimide resin Download PDFInfo
- Publication number
- JP6086537B2 JP6086537B2 JP2013224953A JP2013224953A JP6086537B2 JP 6086537 B2 JP6086537 B2 JP 6086537B2 JP 2013224953 A JP2013224953 A JP 2013224953A JP 2013224953 A JP2013224953 A JP 2013224953A JP 6086537 B2 JP6086537 B2 JP 6086537B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- electrode
- resin composition
- present
- component
- 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.)
- Expired - Fee Related
Links
- 229920001721 polyimide Polymers 0.000 title claims description 20
- 239000009719 polyimide resin Substances 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 claims description 50
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 12
- -1 2,5-dioxotetrahydro-3-furanyl Chemical group 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 description 3
- NMFFUUFPJJOWHK-UHFFFAOYSA-N 2-phenoxyaniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1 NMFFUUFPJJOWHK-UHFFFAOYSA-N 0.000 description 3
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical class NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N xylylenediamine group Chemical group C=1(C(=CC=CC1)CN)CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- UTYHQSKRFPHMQQ-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC(OC=2C=C(N)C(O)=CC=2)=C1 UTYHQSKRFPHMQQ-UHFFFAOYSA-N 0.000 description 1
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 description 1
- UNVRXFDNODGYNP-UHFFFAOYSA-N 2-amino-4-(9h-fluoren-1-yl)phenol Chemical compound C1=C(O)C(N)=CC(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)=C1 UNVRXFDNODGYNP-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- YJOAIOIVLVUPST-UHFFFAOYSA-N 4-(4-amino-2-methoxyphenyl)-3-methoxyaniline Chemical compound COC1=CC(N)=CC=C1C1=CC=C(N)C=C1OC YJOAIOIVLVUPST-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- RYYUUQPLFHRZOY-UHFFFAOYSA-N 4-[2-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1OC1=CC=C(N)C=C1 RYYUUQPLFHRZOY-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- IPEMCIBPDYCJLO-UHFFFAOYSA-N 5-[(3,5,5,8,8-pentamethyl-6,7-dihydronaphthalen-2-yl)methyl]-n-(2,4,6-trimethoxyphenyl)furan-2-carboxamide Chemical compound COC1=CC(OC)=CC(OC)=C1NC(=O)C(O1)=CC=C1CC1=CC(C(CCC2(C)C)(C)C)=C2C=C1C IPEMCIBPDYCJLO-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000202785 Calyptronoma Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013108 LiMY2 Inorganic materials 0.000 description 1
- 229910013884 LiPF3 Inorganic materials 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- MYMCSQDRHUQQDW-UHFFFAOYSA-N bis(4-amino-3-methylphenyl)methanone Chemical compound C1=C(N)C(C)=CC(C(=O)C=2C=C(C)C(N)=CC=2)=C1 MYMCSQDRHUQQDW-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、フェノール性水酸基含有芳香族ポリイミド樹脂、及び非水系電池、特にリチウムイオン電池において粉末電極材料（主として電極活物質及び必要に応じて加えられる導電性助剤）を電極に安定的に固着させるために用いられ、且つ電池特性の向上にも寄与しえる反応性芳香族ポリイミド樹脂組成物、その溶液、そのフィルムに関する。 In the present invention, a phenolic hydroxyl group-containing aromatic polyimide resin, and a non-aqueous battery, particularly a lithium ion battery, stably adheres a powder electrode material (mainly an electrode active material and a conductive auxiliary agent added as necessary) to the electrode. The present invention relates to a reactive aromatic polyimide resin composition, a solution thereof, and a film thereof that can be used to improve battery characteristics.
非水系電池の電極活物質などの粉末電極材料のバインダーとしてはフッ化ビニリデン系重合体が多く用いられている（特許文献１）。しかしながら、フッ化ビニリデン系重合体は粉末電極材料との結着力や集電基体との接着力が比較的弱いため、使用中に活物質などの粉末電極材料の脱落や、これら粉末電極材料を含む電極合剤層の集電基体からの剥離などの現象が見られた。このため非水系電池を長時間使用していると、その放電容量が経時的に低下するという問題があった。 As a binder for powder electrode materials such as electrode active materials for non-aqueous batteries, a vinylidene fluoride polymer is often used (Patent Document 1). However, since the vinylidene fluoride polymer has relatively weak binding force with the powder electrode material and adhesive force with the current collector substrate, the powder electrode material such as the active material may fall off during use or include these powder electrode materials. Phenomena such as peeling of the electrode mixture layer from the current collecting substrate were observed. For this reason, when a non-aqueous battery is used for a long time, there has been a problem that its discharge capacity decreases with time.
上述の問題を解決するためにスルホン化ポリフッ化ビニリデン樹脂を放射線によって架橋する方法（特許文献２）などが提案されている。このような方法は確かに耐溶剤溶解性の向上はもたらすが、架橋反応に手間が掛かり、工業的な使用には適さないという問題があった。また、電池容量のますますの増大に伴い、安全性確保の面からバインダー樹脂にはより高い耐熱性が求められるようになっている。 In order to solve the above-mentioned problems, a method of crosslinking a sulfonated polyvinylidene fluoride resin by radiation (Patent Document 2) has been proposed. Although such a method certainly improves the solvent resistance, there is a problem that the cross-linking reaction takes time and is not suitable for industrial use. Further, as the battery capacity increases, higher heat resistance is required for the binder resin from the viewpoint of ensuring safety.
したがって本発明の主たる目的は、耐熱性、耐溶剤性、並びに粉末電極材料及び集電体に対する良好な接着力を有し、かつ電池特性の向上にも寄与し得る、工業的な使用が容易な非水系電池電極形成用バインダー組成物を提供することにある。 Therefore, the main object of the present invention is to facilitate industrial use, which has heat resistance, solvent resistance, and good adhesion to powder electrode materials and current collectors and can contribute to improvement of battery characteristics. It is providing the binder composition for non-aqueous battery electrode formation.
本発明の更なる目的は、上記バインダー組成物の溶液、バインダー組成物の溶液と粉末電極材料との混合物からなる電極合剤スラリー、該電極合剤スラリーを用いて形成される電極構造体及び非水系電池を提供することにある。 A further object of the present invention is to provide a solution of the binder composition, an electrode mixture slurry composed of a mixture of the binder composition solution and a powder electrode material, an electrode structure formed using the electrode mixture slurry, and a non-electrode structure. It is to provide an aqueous battery.
本発明者らは、上記課題を解決するために、鋭意検討を重ねた結果、特定の構造のポリマー（フェノール性水酸基含有芳香族ポリイミド樹脂）、及び該特定の構造のポリマー、エポキシ樹脂及び硬化促進剤からなる組成物を本用途に用いることが極めて有効であることを見出した。 As a result of intensive investigations to solve the above-mentioned problems, the present inventors have determined that a polymer having a specific structure (phenolic hydroxyl group-containing aromatic polyimide resin), a polymer having the specific structure, an epoxy resin, and curing acceleration. It has been found that it is extremely effective to use a composition comprising an agent for this purpose.
即ち、本発明は、
（１）下記式（１）
That is, the present invention
(1) The following formula (1)
（式中、ｍ及びｎは平均値であり、０．０１＜ｎ／（ｍ＋ｎ）≦０．０４、かつ０＜ｍ＋ｎ≦２００の関係を満たす正数である。Ｒ1は３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物から二個の酸無水物基を除いた残基、Ｒ2は１，３−ビス（３−アミノフェノキシ）ベンゼンから二個のアミノ基を除いた残基、Ｒ3は３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホンから二個のアミノ基を除いた残基を示す）で表される繰り返し単位を構造中に有するフェノール性水酸基含有芳香族ポリイミド樹脂（Ａ）、
（２）前項（１）に記載のポリイミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び硬化促進剤（Ｃ）を含有するポリイミド樹脂組成物、
（３）前項（２）に記載のポリイミド樹脂組成物が有機溶剤に溶解しているポリイミド樹脂組成物溶液
（４）前項（３）に記載のポリイミド樹脂組成物溶液をフィルム上に塗布し、乾燥で溶剤を除去して得られるポリイミド樹脂組成物フィルム、
に関する。
(In the formula, m and n are average values, and 0.01 <n / (m + n) ≦ 0.04 and a positive number satisfying the relationship of 0 <m + n ≦ 200. R 1 is 3, 3 ′, Residue obtained by removing two acid anhydride groups from 4,4′-diphenyl ether tetracarboxylic dianhydride , R 2 is obtained by removing two amino groups from 1,3-bis (3-aminophenoxy) benzene Residue , R 3 is a phenolic hydroxyl group having a repeating unit represented by the following structure: 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, a residue obtained by removing two amino groups ) Aromatic polyimide resin (A),
(2) A polyimide resin composition containing the polyimide resin (A), the epoxy resin (B), and the curing accelerator (C) according to (1) above,
(3) A polyimide resin composition solution in which the polyimide resin composition described in (2) above is dissolved in an organic solvent (4) The polyimide resin composition solution described in (3) above is applied onto a film and dried. Polyimide resin composition film obtained by removing the solvent with
About.
本発明の組成物は１６０〜２００℃の低温で硬化可能であり、しかも該組成物の硬化物は２００℃以上の耐熱性を有すると共に、接着性、耐溶剤溶解性に優れるため非水系電池電極形成用途に好適である。 The composition of the present invention can be cured at a low temperature of 160 to 200 ° C., and the cured product of the composition has a heat resistance of 200 ° C. or more, and is excellent in adhesion and solvent solubility, so that it is a nonaqueous battery electrode. Suitable for forming applications.
以下に、本発明の実施形態について説明する。
本発明のバインダー組成物は、前記式（１）で表されるフェノール性水酸基含有ランダム共重合芳香族ポリイミド樹脂（Ａ）（以下、単に「成分（Ａ）」と記載する）を含有する。
式（１）におけるＲ1は四価の芳香族基、Ｒ2は二価の芳香族基、Ｒ3はフェノール性水酸基を有する二価の芳香族基をそれぞれ表す。尚、本発明において「二価の芳香族基」とは、その構造中に少なくとも一つ以上の芳香族基を有する化合物の芳香環から水素原子を二個除いた構造を意味しており、例えばジフェニルエーテルにおいて酸素を挟んで両側に位置する別々のベンゼン環から、それぞれ一つずつ水素原子を除いた構造も本発明でいう「二価の芳香族基」の範疇に含まれる。四価の芳香族基も同様の考え方で表される構造を意味する。
Hereinafter, embodiments of the present invention will be described.
The binder composition of the present invention contains a phenolic hydroxyl group-containing random copolymerized aromatic polyimide resin (A) represented by the formula (1) (hereinafter simply referred to as “component (A)”).
In the formula (1), R1 represents a tetravalent aromatic group, R2 represents a divalent aromatic group, and R3 represents a divalent aromatic group having a phenolic hydroxyl group. In the present invention, the “divalent aromatic group” means a structure in which two hydrogen atoms are removed from the aromatic ring of a compound having at least one aromatic group in the structure. A structure in which one hydrogen atom is removed from each benzene ring located on both sides of oxygen in diphenyl ether is also included in the category of “divalent aromatic group” in the present invention. A tetravalent aromatic group also means a structure represented by the same concept.
式（１）におけるＲ1の具体例としては、無水ピロメリット酸、エチレングリコール−ビス（アンヒドロトリメリテート）、グリセリン−ビス（アンヒドロトリメリテート）モノアセテート、１，２，３，４，−ブタンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、２，２−ビス（３，４−アンヒドロジカルボキシフェニル）プロパン、２，２−ビス（３，４−アンヒドロジカルボキシフェニル）ヘキサフルオロプロパン、５−（２，５−ジオキソテトラヒドロ−３−フラニル）−３−メチルシクロヘキセン−１，２−ジカルボン酸無水物、３ａ，４，５，９ｂ−テトラヒドロ−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン等の四塩基酸二無水物類から二個の酸無水物基を除いた残基が挙げられ、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物の残基が好ましい。 Specific examples of R1 in the formula (1) include pyromellitic anhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,3,4, -Butanetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ' , 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl Lucyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1, Examples include residues obtained by removing two acid anhydride groups from tetrabasic acid dianhydrides such as 3-dione, and the residue of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride is preferable.
式（１）におけるＲ2の具体例としては、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン及びｍ−トリレンジアミン等のフェニレンジアミン類；４，４’−ジアミノジフェニルエーテル、３，３’−ジメチル−４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル及び４，４’−ジアミノジフェニルチオエーテル等のジアミノジフェニルエーテル類；３，３’−ジメチル−４，４’−ジアミノジフェニルチオエーテル、３，３’−ジエトキシ−４，４’−ジアミノジフェニルチオエーテル、３，３’−ジアミノジフェニルチオエーテル及び３，３’−ジメトキシ−４，４’−ジアミノジフェニルチオエーテル等のジアミノジフェニルチオエーテル類；１，３−ビス（３−アミノフェノキシ）ベンゼン及び１，３−ビス（４−アミノフェノキシ）ベンゼン等のアミノフェノキシベンゼン類；４，４’−ジアミノベンゾフェノン及び３，３’−ジメチル−４，４’−ジアミノベンゾフェノン等のジアミノベンゾフェノン類；４，４’−ジアミノジフェニルスルフォキサイド及び４，４’−ジアミノジフェニルスルホン等のジアミノジフェニルスルホン類；ベンチジン、３，３’−ジメチルベンチジン、２，２’−ジメチルベンチジン、３，３’−ジメトキシベンチジン及び２，２’−ジメトキシベンチジン等のベンチジン類；３，３’−ジアミノビフェニル；ｐ−キシリレンジアミン、ｍ−キシリレンジアミン及びｏ−キシリレンジアミン等のキシリレンジアミン類並びに４，４’−ジアミノジフェニルメタン等のジアミノジフェニルメタン類等のジアミン類から二個のアミノ基を除いた残基が挙げられ、ジアミノジフェニルエーテル類、アミノフェノキシベンゼン類、ジアミノベンゾフェノン類が好ましく、アミノフェノキシベンゼン類がより好ましく、中でも１，３−ビス（３−アミノフェノキシ）ベンゼンが特に好ましい。 Specific examples of R2 in the formula (1) include phenylenediamines such as m-phenylenediamine, p-phenylenediamine and m-tolylenediamine; 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4, Diaminodiphenyl ethers such as 4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl thioether; 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy Diaminodiphenyl thioethers such as -4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether and 3,3'-dimethoxy-4,4'-diaminodiphenyl thioether; 1,3-bis (3-amino Phenoxy) benzene and 1,3 Aminophenoxybenzenes such as bis (4-aminophenoxy) benzene; diaminobenzophenones such as 4,4′-diaminobenzophenone and 3,3′-dimethyl-4,4′-diaminobenzophenone; 4,4′-diamino Diaminodiphenyl sulfones such as diphenyl sulfoxide and 4,4′-diaminodiphenyl sulfone; benzidine, 3,3′-dimethylbenzidine, 2,2′-dimethylbenzidine, 3,3′-dimethoxybenzidine and Bendidines such as 2,2'-dimethoxybenzidine; 3,3'-diaminobiphenyl; xylylenediamines such as p-xylylenediamine, m-xylylenediamine and o-xylylenediamine, and 4,4'- Diaminodiphenylmethanes such as diaminodiphenylmethane Examples include residues obtained by removing two amino groups from the group, and diaminodiphenyl ethers, aminophenoxybenzenes and diaminobenzophenones are preferable, aminophenoxybenzenes are more preferable, and 1,3-bis (3-aminophenoxy is particularly preferable. ) Benzene is particularly preferred.
式（１）におけるＲ3の具体例としては、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホン、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、１，３−ヘキサフルオロ−２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、９，９’−ビス（３−アミノ−４−ヒドロキシフェニル）フルオレン等の一分子中に少なくとも二個のアミノ基と少なくとも一個のフェノール性水酸基を有するアミノフェノール類から二個のアミノ基を除いた残基が挙げられるが、これらに限定されるものではない。これらは１種又は２種以上混合して用いても良い。 Specific examples of R 3 in the formula (1) include 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino- 4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-hexafluoro-2,2 At least two amino groups and at least one phenolic hydroxyl group in one molecule such as bis (3-amino-4-hydroxyphenyl) propane and 9,9′-bis (3-amino-4-hydroxyphenyl) fluorene Although the residue remove | excluding two amino groups from aminophenols which has is mentioned, it is not limited to these. You may use these 1 type or in mixture of 2 or more types.
式（１）におけるｍ並びにｎは、０．０１＜ｎ／（ｍ＋ｎ）＜０．０４および０＜ｍ＋ｎ≦２００の関係を満たす平均繰り返し数を表す。
式（１）におけるｎ／（ｍ＋ｎ）の値が０．０１以下の場合は、エポキシ樹脂（Ｂ）（以下、単に「成分（Ｂ）」と記載する）と成分（Ａ）中のフェノール性水酸基との架橋反応が十分に進行せず、硬化物の耐溶剤溶解性や機械強度等が低下する。
式（１）におけるｎ／（ｍ＋ｎ）が０．５以上の場合、バインダー中の極性が高くなり、リチウムイオンがトラップされる可能性があるため好ましくない。また、ｍ＋ｎが２００よりも大きい場合は、溶剤溶解性が極端に低下するため、成分（Ａ）の生産性やバインダー組成物溶液としての作業性に問題が生じる。
成分（Ａ）は、前記の酸無水物類、ジアミン類、アミノフェノール類を用いて、ＷＯ２００７／０４６４０５号公報に記載の方法に準じて合成することができる。尚、本発明においては、成分（Ａ）を成分（Ｂ）の硬化剤として使用する。
M and n in Formula (1) represent the average number of repetitions satisfying the relationship of 0.01 <n / (m + n) <0.04 and 0 <m + n ≦ 200.
When the value of n / (m + n) in the formula (1) is 0.01 or less, the epoxy resin (B) (hereinafter simply referred to as “component (B)”) and the phenolic hydroxyl group in the component (A) And the crosslinking reaction does not proceed sufficiently, and the solvent resistance and mechanical strength of the cured product are reduced.
When n / (m + n) in the formula (1) is 0.5 or more, the polarity in the binder becomes high and lithium ions may be trapped, which is not preferable. Moreover, when m + n is larger than 200, the solvent solubility is extremely lowered, which causes a problem in productivity of the component (A) and workability as a binder composition solution.
Component (A) can be synthesized according to the method described in WO2007 / 046405 using the above acid anhydrides, diamines, and aminophenols. In the present invention, component (A) is used as a curing agent for component (B).
本発明のバインダー組成物が含有する成分（Ｂ）としては、１分子中にエポキシ基を２個以上有するものであれば特に制限はない。具体的にはノボラック型エポキシ樹脂、ジシクロペンタジエンフェノール縮合型エポキシ樹脂、キシリレン骨格含有フェノールノボラック型エポキシ樹脂、ビフェニル骨格含有ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、テトラメチルビフェノール型エポキシ樹脂、脂環式エポキシ樹脂などが挙げられる。これらのエポキシ樹脂は２種以上を併用することも出来る。 The component (B) contained in the binder composition of the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolak type epoxy resin, dicyclopentadiene phenol condensation type epoxy resin, xylylene skeleton-containing phenol novolak type epoxy resin, biphenyl skeleton containing novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbiphenol Type epoxy resin and alicyclic epoxy resin. Two or more of these epoxy resins can be used in combination.
本発明のバインダー組成物には、成分（Ａ）以外の他のエポキシ樹脂用硬化剤を併用しても良い。併用することのできる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、フェノールノボラック、トリフェニルメタン及びこれらの変性物、イミダゾール、ＢＦ3−アミン錯体、
グアニジン誘導体などが挙げられるがこれらに限定されるものではない。これらを併用する場合、成分（Ａ）が全硬化剤中に占める割合としては通常２０質量％以上、好ましくは３０質量％以上である。
本発明のバインダー組成物中における硬化剤の使用量は、成分（Ｂ）中のエポキシ基１当量に対して、成分（Ａ）を含む全硬化剤の活性水素が通常０．７〜１．３当量、好ましくは０．８〜１．２当量となる量である。
You may use together the hardening | curing agent for epoxy resins other than a component (A) with the binder composition of this invention. Specific examples of curing agents that can be used in combination include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, Trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, triphenylmethane and these Modified product of imidazole, BF3-amine complex,
Examples thereof include, but are not limited to, guanidine derivatives. When these are used in combination, the proportion of the component (A) in the total curing agent is usually 20% by mass or more, preferably 30% by mass or more.
The use amount of the curing agent in the binder composition of the present invention is such that the active hydrogen of the entire curing agent including the component (A) is usually 0.7 to 1.3 per 1 equivalent of the epoxy group in the component (B). The amount is equivalent, preferably 0.8 to 1.2 equivalent.
本発明のバインダー組成物が含有する成分（Ｃ）である硬化促進剤の具体例としては、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤は成分（Ｂ）１００質量部に対して０．１〜５．０質量部が用いられる。 Specific examples of the curing accelerator which is the component (C) contained in the binder composition of the present invention include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- ( Dimethylaminomethyl) phenol, tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. . 0.1-5.0 mass parts is used for a hardening accelerator with respect to 100 mass parts of component (B).
本発明の組成物溶液は、本発明の組成物を各種有機溶剤に溶解して得られる。溶解に用いることのできる有機溶剤としては、例えばγ−ブチロラクトン類、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレンなどの芳香族系溶剤が挙げられる。本発明のバインダー組成物溶液中の有機溶剤の濃度は通常３０〜９５質量％、好ましくは４０〜９０質量％である。 The composition solution of the present invention is obtained by dissolving the composition of the present invention in various organic solvents. Examples of organic solvents that can be used for dissolution include γ-butyrolactones, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone. Amide solvents such as tetramethylene sulfone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, ether solvents such as propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl Examples thereof include ketone solvents such as ketone, cyclopentanone and cyclohexanone, and aromatic solvents such as toluene and xylene. The density | concentration of the organic solvent in the binder composition solution of this invention is 30-95 mass% normally, Preferably it is 40-90 mass%.
上記のようにして得られた本発明のバインダー組成物溶液に、粉末電極材料（電極活物質及び必要に応じて加えられる導電助剤、その他の助剤）を分散混合することにより電極合剤スラリーが得られる。 An electrode mixture slurry by dispersing and mixing a powder electrode material (electrode active material and conductive auxiliary agent and other auxiliary agents added as necessary) to the binder composition solution of the present invention obtained as described above. Is obtained.
本発明の電極合剤は、非水系電池の正極合剤、負極合剤のいずれにも適用可能である。 The electrode mixture of the present invention can be applied to both a positive electrode mixture and a negative electrode mixture of a non-aqueous battery.
リチウムイオン二次電池の活物質としては、正極の場合は、一般式ＬｉＭＹ2（ＭはＣｏ、Ｆｅ、Ｍｎ、Ｃｒ、Ｖなどの遷移金属の少なくとも一種:ＹはＯ、Ｓなどのカルコゲン化合物）で表される複合金属カルコゲン化合物、特にＬｉＮｉxｘＣｏ1−xＯ2（０≦ｘ≦１）をはじめとする複合金属酸化物が好ましい。負極の場合は黒鉛、活性炭、あるいはフェノール樹脂やピッチなどを焼成炭化したものなどの粉末状炭素質材料に加えて、金属酸化物系のＧｅＯ、ＧｅＯ2、ＳｎＯ、ＳｎＯ2、ＰｂＯ、ＰｂＯ2、硝酸チタニウム、シリコン酸化物（ＳｉＯ、ＳｉＯx、０＜ｘ＜２）、シリコン、あるいはこれらの複合金属酸化物などが挙げられる。 As the active material of the lithium ion secondary battery, in the case of the positive electrode, the general formula LiMY2 (M is at least one kind of transition metal such as Co, Fe, Mn, Cr, and V: Y is a chalcogen compound such as O and S). Preferred are composite metal chalcogen compounds represented, particularly composite metal oxides including LiNixxCo1-xO2 (0≤x≤1). In the case of the negative electrode, in addition to powdery carbonaceous materials such as graphite, activated carbon, or a baked carbonized phenol resin or pitch, metal oxides such as GeO, GeO2, SnO2, SnO2, PbO, PbO2, titanium nitrate, Examples thereof include silicon oxide (SiO, SiOx, 0 <x <2), silicon, or a composite metal oxide thereof.
電池における導電助剤は、ＬｉＣｏＯ2などの電子伝導性の小さい活物質を使用する場合に電極合剤層の導電性を向上する目的で添加するもので、カーボンブラック、黒鉛微粉末あるいは繊維などの炭素質物質やニッケル、アルミニウムなどの金属微粉末あるいは繊維が使用される。活物質として導電性の大きい物質を用いる場合はこれらの導電剤は使用する必要がない。 The conductive assistant in the battery is added for the purpose of improving the conductivity of the electrode mixture layer when using an active material having a low electron conductivity such as LiCoO2, and carbon such as carbon black, graphite fine powder or fiber. Fine materials, metal fine powders such as nickel and aluminum, or fibers are used. When a highly conductive material is used as the active material, it is not necessary to use these conductive agents.
本発明の電極合剤スラリーは粉末電極材料１００質量部と、固形分０．１〜２０質量部を含有する本発明のバインダー組成物溶液とを混合して形成することが好ましい。 The electrode mixture slurry of the present invention is preferably formed by mixing 100 parts by mass of the powder electrode material and the binder composition solution of the present invention containing 0.1 to 20 parts by mass of the solid content.
上述のようにして形成された電極合剤スラリーを、例えば鉄、ステンレス鋼、鋼、銅、アルミニウム、ニッケル、チタンなどの金属箔あるいは金属網などからなり厚さが５〜２０μｍとなるような集電基体の少なくとも一面、好ましくは両面に塗布し、例えば５０〜１７０℃で乾燥して、例えば小規模の場合厚さが１０〜１０００μｍの電極合剤層を形成することにより、非水系電池用電極が形成される。 The electrode mixture slurry formed as described above is made of, for example, a metal foil such as iron, stainless steel, steel, copper, aluminum, nickel, titanium, or a metal net, and has a thickness of 5 to 20 μm. An electrode for a non-aqueous battery is applied to at least one surface, preferably both surfaces of an electric substrate, and dried at, for example, 50 to 170 ° C. to form an electrode mixture layer having a thickness of 10 to 1000 μm, for example. Is formed.
二次電池は正極及び負極間に電解液を含浸したポリプロピレン、ポリエチレンなどの高分子物質の微多孔質膜からなるセパレータを配置積層したものを渦巻状に巻いた発電素子が、負極端子を形成する有底の金属ケーシング中に収容された構造を有する。 In a secondary battery, a power generation element in which a separator made of a microporous film of a polymer material such as polypropylene and polyethylene impregnated with an electrolyte is placed between a positive electrode and a negative electrode and wound in a spiral shape forms a negative electrode terminal. It has a structure housed in a bottomed metal casing.
セパレータに含浸される非水電解液としては、例えばリチウム塩などの電解質を非水系溶媒（有機溶媒）に溶解したものを用いることが出来る。 As the nonaqueous electrolytic solution impregnated in the separator, for example, an electrolyte such as a lithium salt dissolved in a nonaqueous solvent (organic solvent) can be used.
ここで電解質としてはＬｉＰＦ3、ＬｉＡｓＦ6、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＣＨ3ＳＯ3、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＯＳＯ2）3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＯＳＯ2）3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3などがある。 Here, the electrolytes include LiPF3, LiAsF6, LiClO4, LiBF4, LiCH3SO3, LiCF3SO3, LiN (CF3OSO2) 3, LiN (CF3SO2) 2, LiC (CF3OSO2) 3, LiN (CF3SO2) 2, LiC (CF3SO2) 3, LiN (CF3SO2) 3 ) 2, LiC (CF3SO2) 3.
また電解質の有機溶媒としてはプロピレンカーボネート、エチレンカーボネート、１，２−ジメトキシエタン、ジメチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、プロピオン酸メチル、プロピオン酸エチル及びこれらの混合物などが用いられるが、必ずしもこれらに限定されるものではない。 Examples of the organic solvent for the electrolyte include propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, methyl propionate, ethyl propionate, and mixtures thereof. It is not limited to.
次に本発明を更に実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
合成例１（成分（Ａ）の合成）
撹拌装置、還流管、水分トラップ、温度計をつけた３Ｌフラスコ中に窒素ガスパージを施し、溶剤としてγ−ブチロラクトン１２５９．７５部、ＯＤＰＡ（３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物マナック製、分子量３１０．２２）を２９３．０５部、ＡＢＰＳ（３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホン日本化薬製、分子量２８０．３０）を１０．８０部、ＡＰＢ−Ｎ（１，３−ビス（３−アミノフェノキシ）ベンゼン三井化学製、分子量２９２．３４）を２７０．４１部、触媒としてピリジン１４．９５部、脱水剤としてトルエンを１７６．４１部仕込み、１８０℃で３時間トルエンを還流しながらポリイミドの閉環に伴う水を水分トラップ装置に追い出し、その後４時間水、トルエン及びピリジンを水分トラップ装置経由で除きながら攪拌を行い、下記式（２）
Synthesis Example 1 (Synthesis of component (A))
A 3 L flask equipped with a stirrer, a reflux tube, a water trap, and a thermometer was purged with nitrogen gas. 293.05 parts of anhydrous manac, molecular weight 310.22), 10.80 parts of ABPS (3,3′-diamino-4,4′-dihydroxydiphenylsulfone Nippon Kayaku, molecular weight 280.30), APB 270.41 parts of -N (1,3-bis (3-aminophenoxy) benzene Mitsui Chemicals, molecular weight 292.34), 14.95 parts of pyridine as a catalyst, and 176.41 parts of toluene as a dehydrating agent, 180 While the toluene was refluxed at 3 ° C., water accompanying the polyimide ring closure was expelled to the moisture trap device, and then the water, toluene and Lysine perform stirring while removing through water trap device, the following formula (2)
で表される繰り返し単位を構造中に有する成分（Ａ）３０質量％を含む樹脂溶液１８００部を得た。また、得られた成分（Ａ）のゲルパーミエイションクロマトグラフィーの測定結果を元にポリスチレン換算で求めた数平均分子量は３８０００であり、合成反応に用いた各成分のモル比から算出した式（２）中のｍの値は９６であり、ｎの値は４であった。 1800 parts of a resin solution containing 30% by mass of the component (A) having a repeating unit represented by the formula: Moreover, the number average molecular weight calculated | required in polystyrene conversion based on the measurement result of the gel permeation chromatography of the obtained component (A) is 38000, and is calculated from the molar ratio of each component used in the synthesis reaction ( The value of m in 2) was 96, and the value of n was 4.
実施例１
得られた成分（Ａ）を３０質量％含む樹脂溶液１００部に対して、エポキシ樹脂としてＮＣ−３０００（日本化薬株式会社製、エポキシ当量２７５ｇ／ｅｑ．）を１．６５部、硬化促進剤として２−フェニル−４，５−ジヒドロキシメチルイミダゾール（２ＰＨＺ）を２部加えることにより本発明の非水系電池電極形成用バインダー組成物溶液を得た。
Example 1
1.100 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 275 g / eq.) As an epoxy resin with respect to 100 parts of a resin solution containing 30% by mass of the obtained component (A), a curing accelerator As a result, 2 parts of 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ) was added to obtain a binder composition solution for forming a nonaqueous battery electrode of the present invention.
得られたバインダー組成物溶液をＰＥＴフィルム上に乾燥後の厚みが２５μｍになるように塗布し、１３０℃で２０分間の乾燥条件で溶剤を除去してＰＥＴフィルムからはがした後、１７０℃で１時間硬化せしめ、試験片を作成した。得られた試験片のガラス転移温度をＤＭＡ（動的粘弾性測定装置)を用いて測定したところ２３６．０℃であった。 The obtained binder composition solution was applied onto a PET film so that the thickness after drying was 25 μm, and after removing the solvent under a drying condition of 130 ° C. for 20 minutes and peeling off from the PET film, at 170 ° C. A test piece was prepared by curing for 1 hour. It was 236.0 degreeC when the glass transition temperature of the obtained test piece was measured using DMA (dynamic viscoelasticity measuring apparatus).
得られたバインダー組成物溶液を１００部用いて負極用電極合剤を作成した。負極用活物質としては呉羽化学株式会社製のカーボトロンＰを用いて、活物質１００質量部に対してバインダー樹脂の固形分が１０質量部になるようにバインダー組成物溶液を10 混合して電極合材スラリーを調製した。この電極合剤スラリーを厚さ１０μｍの銅箔の上に塗布し１７０℃で１時間硬化せしめた。銅箔上に形成された電極合材層の厚みは１００〜１２０μｍの範囲であった。 A negative electrode mixture was prepared using 100 parts of the obtained binder composition solution. Carbotron P manufactured by Kureha Chemical Co., Ltd. is used as the negative electrode active material, and 10 binder compositions are mixed so that the solid content of the binder resin is 10 parts by mass with respect to 100 parts by mass of the active material. A material slurry was prepared. This electrode mixture slurry was applied onto a 10 μm thick copper foil and cured at 170 ° C. for 1 hour. The thickness of the electrode mixture layer formed on the copper foil was in the range of 100 to 120 μm.
この電極構造体を用いて、電極合材層からの銅箔の剥離強度をＪＩＳＫ６８５４に準拠して１８０°剥離試験により測定した。剥離強度は１．７２Ｎ／ｍｍと十分高い値を示した。 Using this electrode structure, the peel strength of the copper foil from the electrode mixture layer was measured by a 180 ° peel test in accordance with JISK6854. The peel strength was a sufficiently high value of 1.72 N / mm.
この電極構造体を９０℃のプロピレンカーボネート溶媒に１４４時間浸漬したが、外観上の異常は見られなかった。 This electrode structure was immersed in a propylene carbonate solvent at 90 ° C. for 144 hours, but no abnormality in appearance was observed.
Claims (4)
（式中、ｍ及びｎは平均値であり、０．０１＜ｎ／（ｍ＋ｎ）＜０．５、かつ０＜ｍ＋ｎ≦２００の関係を満たす正数である。）で表される繰り返し単位を構造中に有する両末端にアミノ基を有するフェノール性水酸基含有芳香族ポリイミド樹脂（Ａ）。 Following formula (2)
(Wherein m and n are average values, 0.01 <n / (m + n) <0.5, and a positive number satisfying the relationship 0 <m + n ≦ 200). A phenolic hydroxyl group-containing aromatic polyimide resin (A) having amino groups at both ends in the structure.
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