JP6913346B2 - Polyamide-imide precursor solution - Google Patents
Polyamide-imide precursor solution Download PDFInfo
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- JP6913346B2 JP6913346B2 JP2017074146A JP2017074146A JP6913346B2 JP 6913346 B2 JP6913346 B2 JP 6913346B2 JP 2017074146 A JP2017074146 A JP 2017074146A JP 2017074146 A JP2017074146 A JP 2017074146A JP 6913346 B2 JP6913346 B2 JP 6913346B2
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- Prior art keywords
- compound
- polyamide
- mol
- precursor solution
- imide precursor
- Prior art date
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- 239000004962 Polyamide-imide Substances 0.000 title claims description 85
- 229920002312 polyamide-imide Polymers 0.000 title claims description 85
- 239000002243 precursor Substances 0.000 title claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 181
- 150000003839 salts Chemical class 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003381 stabilizer Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 110
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 54
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 39
- 238000004458 analytical method Methods 0.000 description 31
- 239000007787 solid Substances 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 18
- -1 aliphatic diamine Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000004566 IR spectroscopy Methods 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 11
- 239000000725 suspension Substances 0.000 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 description 8
- 150000003628 tricarboxylic acids Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000003352 sequestering agent Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 0 OC(C1*(C(N*N(C(*2C(O)=O)=O)C2=O)=O)=C1C(O)=O)O Chemical compound OC(C1*(C(N*N(C(*2C(O)=O)=O)C2=O)=O)=C1C(O)=O)O 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-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
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- OFAHVKOHTFOCKT-UHFFFAOYSA-N 2-[1,1-bis(2-aminophenyl)ethyl]aniline Chemical compound C=1C=CC=C(N)C=1C(C=1C(=CC=CC=1)N)(C)C1=CC=CC=C1N OFAHVKOHTFOCKT-UHFFFAOYSA-N 0.000 description 1
- LQNPGOSCDPHHJU-UHFFFAOYSA-N 2-[1,1-bis(2-aminophenyl)propyl]aniline Chemical compound C=1C=CC=C(N)C=1C(C=1C(=CC=CC=1)N)(CC)C1=CC=CC=C1N LQNPGOSCDPHHJU-UHFFFAOYSA-N 0.000 description 1
- BMALTXIIHBBMPO-UHFFFAOYSA-N 2-[bis(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1C(C=1C(=CC=CC=1)N)C1=CC=CC=C1N BMALTXIIHBBMPO-UHFFFAOYSA-N 0.000 description 1
- KEEJZKZQHBPNFA-UHFFFAOYSA-N 2-[tris(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1C(C=1C(=CC=CC=1)N)(C=1C(=CC=CC=1)N)C1=CC=CC=C1N KEEJZKZQHBPNFA-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- APCTZYNYGGYPMN-UHFFFAOYSA-N 3-[[(3-aminophenoxy)methyl-methyl-trimethylsilyloxysilyl]methoxy]aniline Chemical compound C=1C=CC(N)=CC=1OC[Si](C)(O[Si](C)(C)C)COC1=CC=CC(N)=C1 APCTZYNYGGYPMN-UHFFFAOYSA-N 0.000 description 1
- BIYNCFPBGDWKOG-UHFFFAOYSA-N 3h-naphthalene-2,2-diamine Chemical compound C1=CC=CC2=CC(N)(N)CC=C21 BIYNCFPBGDWKOG-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YLFZBPFYWIFYCP-UHFFFAOYSA-N 4-(4-carboxyphenyl)phthalic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 YLFZBPFYWIFYCP-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 239000005639 Lauric acid Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
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- OIFQXZBVIMTLEF-UHFFFAOYSA-N anthracene-2,3,6-tricarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 OIFQXZBVIMTLEF-UHFFFAOYSA-N 0.000 description 1
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- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-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
- BETZQIHWKFBSIA-UHFFFAOYSA-N butane-1,1,1-triamine Chemical compound CCCC(N)(N)N BETZQIHWKFBSIA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- BTHGHFBUGBTINV-UHFFFAOYSA-N naphthalene-2,3,6-tricarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 BTHGHFBUGBTINV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003973 paint 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BLTPNRTWCHWASU-UHFFFAOYSA-N propane-1,1,1-triamine Chemical compound CCC(N)(N)N BLTPNRTWCHWASU-UHFFFAOYSA-N 0.000 description 1
- PZZICILSCNDOKK-UHFFFAOYSA-N propane-1,2,3-triamine Chemical compound NCC(N)CN PZZICILSCNDOKK-UHFFFAOYSA-N 0.000 description 1
- PZRKPUQWIFJRKZ-UHFFFAOYSA-N pyrimidine-2,4,5,6-tetramine Chemical compound NC1=NC(N)=C(N)C(N)=N1 PZRKPUQWIFJRKZ-UHFFFAOYSA-N 0.000 description 1
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、ポリアミドイミド前駆体溶液に関するものである。 The present invention relates to a polyamide-imide precursor solution.
ポリアミドイミドは、耐熱性や耐薬品性が高いことから、フィルム、電線被覆材、成形材、接着材等の用途に広く用いられている。一般に、ポリアミドイミドは、有機溶媒に溶解した原料を加熱反応させてポリアミド−アミド酸と呼ばれる前駆体を経て、前記有機溶媒を留去させ、重合体を得ている（例えば、特許文献１）。 Polyamide-imide has high heat resistance and chemical resistance, and is widely used in applications such as films, electric wire coating materials, molding materials, and adhesives. Generally, in polyamide-imide, a raw material dissolved in an organic solvent is heated and reacted to obtain a polymer by distilling off the organic solvent via a precursor called polyamide-amide acid (for example, Patent Document 1).
しかしながら、ポリアミド−アミド酸の製造に用いられる原料は、酸クロライドやイソシアネートのように、環境への負荷が大きく、取扱い性が悪いものが多い。さらに、酸クロライドは非常に高価である上に、製造中に塩化水素が副生するため後処理工程が必要でありコストが高くなるという問題がある。また、ポリアミド−アミド酸は、一般に溶媒として溶解力の高い高価な有機溶媒に溶解して用いるが、そのような有機溶媒は環境への負荷が大きいものが多い。さらに、ポリアミド−アミド酸をポリアミドイミドとする場合、高温で熱処理するイミド化工程が必要であるため、経済的に不利であるという問題がある。 However, many of the raw materials used for producing polyamide-amidic acid, such as acid chloride and isocyanate, have a large burden on the environment and are difficult to handle. Further, acid chloride is very expensive, and hydrogen chloride is produced as a by-product during production, which requires a post-treatment step, which increases the cost. Further, polyamide-amidoic acid is generally used as a solvent by dissolving it in an expensive organic solvent having a high dissolving power, and such an organic solvent often has a large burden on the environment. Further, when the polyamide-amide acid is a polyamide-imide, there is a problem that it is economically disadvantageous because an imidization step of heat treatment at a high temperature is required.
本発明は、上記課題を解決するものであって、酸クロライドやイソシアネートを用いずに、水等の環境への負荷の小さい溶媒を用いて製造することが可能であって、イミド化工程を必要としないポリアミドイミド前駆体の溶液を提供することを目的とする。 The present invention solves the above-mentioned problems, and can be produced by using a solvent having a small load on the environment such as water without using acid chloride or isocyanate, and requires an imidization step. It is an object of the present invention to provide a solution of a polyamide-imide precursor which is not used.
本発明者らは上記課題を解決すべく鋭意研究した結果、上記問題を解決できることを見出し、本発明に到達した。 As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved, and arrived at the present invention.
すなわち、本発明の要旨は、下記のとおりである。
（１）構造中に、カルボキシル基と、アミド結合および／またはイミド結合を含有する化合物（Ａ）と、アミノ基を含有する化合物（Ｂ）からなる塩と、溶媒から構成され、化合物（Ａ）が、一般式（１）〜（３）で表される化合物のうち１種以上であること特徴とするポリアミドイミド前駆体溶液。
（２）溶媒が、水であることを特徴とする（１）に記載のポリアミドイミド前駆体溶液。
（３）さらに、分散安定剤を添加することを特徴とする（１）または（２）に記載のポリアミドイミド前駆体溶液。
That is, the gist of the present invention is as follows.
(1) in the structure, and a carboxyl group, compounds containing an amide bond and / or an imide bond and (A), a salt comprising a compound containing an amino group (B), is composed of solvent, Compound (A) but features and to Lupo Riamidoimido precursor solution is at least one of the general formulas (1) to the compound represented by (3).
( 2 ) The polyamide-imide precursor solution according to (1 ), wherein the solvent is water.
( 3 ) The polyamide-imide precursor solution according to (1) or (2) , which further comprises adding a dispersion stabilizer.
本発明によれば、酸クロライドやイソシアネートを用いずに、水等の環境への負荷の小さい溶媒を用いて製造することが可能であって、イミド化工程を必要としないポリアミドイミド前駆体の溶液を提供することができる。 According to the present invention, a solution of a polyamide-imide precursor which can be produced by using a solvent having a small environmental load such as water without using acid chloride or isocyanate and which does not require an imidization step. Can be provided.
本発明のポリアミドイミド前駆体溶液は、構造中に、カルボキシル基と、アミド結合および／またはイミド結合を含有する化合物（Ａ）と、アミノ基を含有する化合物（Ｂ）からなる塩と、溶媒から構成される。 The polyamide-imide precursor solution of the present invention is composed of a salt consisting of a carboxyl group, a compound (A) containing an amide bond and / or an imide bond, a compound (B) containing an amino group, and a solvent in the structure. It is composed.
本発明に用いる化合物（Ａ）としては、構造中に、カルボキシル基と、アミド結合および／またはイミド結合を有し、ポリアミドイミドの前駆体となりえるものであれば特に限定されないが、例えば、一般式（１）〜（３）で表される化合物が挙げられ、中でも一般式（１）で表される化合物を主成分とするものが好ましく、一般式（１）で表される化合物を３５質量％以上含むものがより好ましく、一般式（１）で表される化合物を５０質量％以上含むものがさらに好ましく、一般式（１）で表される化合物を６０質量％以上含むものが特に好ましい。化合物（Ａ）は、単独で用いてもよいし、２種以上を併用してもよい。
一般式（１）〜（３）において、Ｒ１は、２価の基であり、例えば、ジアミンの残基が挙げられる。ジアミン残基を与えるジアミンとしては、芳香族ジアミン、脂肪族ジアミン、脂環式ジアミンいずれであってもよい。前記ジアミンは、構造中に−Ｏ−、−Ｓ−が含まれてもよいし、水素原子の１つ以上がハロゲンに置換されていてもよいし、側鎖を有していてもよい。前記ジアミンとしては、例えば、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、ベンジジン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルエーテル、３，３−ジアミノベンゾフェノン、４，４−ジアミノベンゾフェノン、２，４−トリレンジアミン、２，６−トリレンジアミン、１，５−ジアミノナフタレン、３，３−ジアミノナフタレン、１，４−ジアミノシクロヘキサン、１，１０−ジアミノ−１，１０−ジメチルデカン、１，４−ビス（アミノメチル）シクロヘキサン、４，４−ビス（アミノメチル）シクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）、イソホロンジアミン、α，ω−ビスアミノポリジメチルシロキサン、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン、１，３−ビス（３−アミノプロピル）−１，１，３，３−テトラメチルジシロキサン、ビス（１０−アミノデカメチレン）テトラメチルジシロキサン、ビス（３−アミノフェノキシメチル）テトラメチルジシロキサン、α，ω−ビス（３−アミノプロピル）ポリメチルフェニルシロキサン、α，ω−ビス（３−アミノプロピル）ポリ（ジメチルシロキサン−ジフェニルシロキサン）コポリマー、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、１，３−ビス（４−アミノフェノキシ）ベンゼン、ベンゾグアナミンが挙げられる。中でも、化合物（Ａ）と化合物（Ｂ）からなる塩の水溶性が高くなることから、ｍ−キシリレンジアミンが好ましい。前記ジアミンは、単独で用いてもよいし、２種類以上を併用してもよい。 In the general formulas (1) to (3), R 1 is a divalent group, and examples thereof include diamine residues. The diamine that gives the diamine residue may be an aromatic diamine, an aliphatic diamine, or an alicyclic diamine. The diamine may contain —O—, —S— in its structure, one or more hydrogen atoms may be substituted with halogen, or it may have a side chain. Examples of the diamine include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, m-phenylenediamine, p-phenylenediamine, m-xylylene diamine, p-xylylene diamine, and benzidine. , 4,4'-Diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,3-diaminobenzophenone , 4,4-Diaminobenzophenone, 2,4-tolylene diamine, 2,6-tolylene diamine, 1,5-diaminonaphthalene, 3,3-diaminonaphthalene, 1,4-diaminocyclohexane, 1,10-diamino -1,10-dimethyldecane, 1,4-bis (aminomethyl) cyclohexane, 4,4-bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), isophorone diamine, α, ω-bisamino Polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,1 , 3,3-Tetramethyldisiloxane, bis (10-aminodecamethylene) tetramethyldisiloxane, bis (3-aminophenoxymethyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polymethylphenyl Siloxane, α, ω-bis (3-aminopropyl) poly (dimethylsiloxane-diphenylsiloxane) copolymer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-amino) Phenoxy) benzene, benzoguanamine and the like. Of these, m-xylylenediamine is preferable because the salt composed of the compound (A) and the compound (B) has high water solubility. The diamine may be used alone or in combination of two or more.
一般式（１）〜（３）において、Ｒ２、Ｒ３は、３価の基であり、例えば、トリカルボン酸の残基が挙げられる。トリカルボン酸の残基を与えるトリカルボン酸としては、芳香族トリカルボン酸、脂肪族トリカルボン酸、脂環式トリカルボン酸いずれであってもよい。前記トリカルボン酸としては、例えば、トリメリット酸無水物、２，３，６−ナフタレントリカルボン酸無水物、２，３，６−アントラセントリカルボン酸無水物、３，４，４’−ビフェニルトリカルボン酸無水物、１，２，４−シクロヘキサントリカルボン酸無水物等が挙げられ、中でも、反応性が高いことから、トリメリット酸無水物が好ましい。前記トリカルボン酸は、単独で用いてもよいし、２種類以上を併用してもよい。 In the general formulas (1) to (3), R 2 and R 3 are trivalent groups, and examples thereof include residues of tricarboxylic acids. The tricarboxylic acid that gives the residue of the tricarboxylic acid may be any of aromatic tricarboxylic acid, aliphatic tricarboxylic acid, and alicyclic tricarboxylic acid. Examples of the tricarboxylic acid include trimellitic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 2,3,6-anthracentricarboxylic acid anhydride, and 3,4,4'-biphenyltricarboxylic acid anhydride. , 1,2,4-Cyclohexanetricarboxylic acid anhydride and the like, and among them, trimellitic acid anhydride is preferable because of its high reactivity. The tricarboxylic acid may be used alone or in combination of two or more.
本発明に用いる化合物（Ｂ）としては、アミノ基を有し、ポリアミドイミドの前駆体となりえるものであれば特に限定されないが、例えば、一般式（１）〜（３）の化合物のＲ１を与えるジアミンと同一のジアミンや、３価以上のアミン化合物が挙げられる。化合物（Ｂ）がジアミンの場合、一般式（１）〜（３）の化合物のＲ１を与えるジアミンと同一であっても、異なっていてもよい。３価以上のアミノ化合物としては、例えば、プロパントリアミン、ブタントリアミン、ウンデカントリアミン、ピリミジントリアミン、ベンゼントリアミン、トリ（アミノフェニル）メタン、トリ（アミノフェニル）エタン、トリ（アミノフェニル）プロパン、トリ（アミノフェニル）トリフルオロエタン、テトラ（アミノフェニル）メタン、ベンゼンテトラアミン、ピリミジンテトラアミン、ベンゼンペンタアミン、ベンゼンヘキサアミンが挙げられる。化合物（Ｂ）としては、化合物（Ａ）と化合物（Ｂ）からなる塩の水溶性が高くなることから、ｍ−キシリレンジアミンが好ましい。化合物（Ｂ）は、単独で用いてもよいし、２種類以上を併用してもよい。 The compound (B) used in the present invention is not particularly limited as long as it has an amino group and can be a precursor of polyamide-imide, but for example, R 1 of the compounds of the general formulas (1) to (3) can be used. Examples thereof include the same diamine as the given diamine and an amine compound having a trivalent or higher valence. When the compound (B) is a diamine, it may be the same as or different from the diamine giving R 1 of the compounds of the general formulas (1) to (3). Examples of trivalent or higher amino compounds include propantriamine, butanetriamine, undecantriamine, pyrimidinetriamine, benzenetriamine, tri (aminophenyl) methane, tri (aminophenyl) ethane, tri (aminophenyl) propane, and tri (amino). Examples thereof include phenyl) trifluoroethane, tetra (aminophenyl) methane, benzenetetraamine, pyrimidinetetraamine, benzenepentamine and benzenehexaamine. As the compound (B), m-xylylenediamine is preferable because the water solubility of the salt composed of the compound (A) and the compound (B) becomes high. Compound (B) may be used alone or in combination of two or more.
本発明に用いる溶媒としては、有機溶媒、水いずれであってもよいが、取扱い性や環境に対する影響が小さいことから、水が好ましい。有機溶媒としては、例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，４−ジオキサン、１，３−ジオキソラン、テトラヒドロフラン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、トルエン、キシレン、酢酸エチル、プロピレングリコールモノエチルエーテルアセテートが挙げられる。 The solvent used in the present invention may be either an organic solvent or water, but water is preferable because it has little effect on handleability and the environment. Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, methyl ethyl ketone, cyclopentanone, and cyclohexanone. , Toluene, xylene, ethyl acetate, propylene glycol monoethyl ether acetate.
本発明のポリアミドイミド前駆体溶液は、溶媒中で、化合物（Ａ）と、化合物（Ｂ）を反応させることにより得ることができる。反応温度は、用いる化合物（Ａ）や化合物（Ｂ）に応じて適宜設定されるが、５〜２３０℃とすることが好ましく、２０〜１５０℃とすることがより好ましく、２０〜８５℃とすることがさらに好ましい。化合物（Ａ）と化合物（Ｂ）の反応方法としては特に限定されないが、溶媒に化合物（Ａ）を懸濁させたのち化合物（Ｂ）を添加して反応させてもよいし、溶媒に化合物（Ｂ）を溶解させたのち化合物（Ａ）を添加して反応させてもよいし、溶媒に化合物（Ａ）と化合物（Ｂ）を同時に添加して反応させてもよいし、溶媒に化合物（Ａ）と化合物（Ｂ）を分割して添加して反応させてもよいし、化合物（Ａ）や化合物（Ｂ）をそれぞれ溶媒に溶解または懸濁したのち混合して反応させてもよい。化合物（Ａ）は、溶媒に溶解しにくく、懸濁しかできない場合が多いが、化合物（Ａ）と化合物（Ｂ）が反応し塩が形成されれば、反応液は均一なものとなる。ポリアミドイミド前駆体溶液の作製は、窒素等の不活性ガス気流中でおこなってもよく、加圧下でおこなってもよい。 The polyamide-imide precursor solution of the present invention can be obtained by reacting compound (A) with compound (B) in a solvent. The reaction temperature is appropriately set according to the compound (A) and the compound (B) to be used, but is preferably 5 to 230 ° C, more preferably 20 to 150 ° C, and 20 to 85 ° C. Is even more preferable. The reaction method between the compound (A) and the compound (B) is not particularly limited, but the compound (A) may be suspended in a solvent and then the compound (B) may be added to cause a reaction, or the compound (A) may be reacted with the compound (A). After dissolving B), compound (A) may be added and reacted, compound (A) and compound (B) may be added simultaneously to the solvent and reacted, or compound (A) may be added to the solvent. ) And compound (B) may be added separately and reacted, or compound (A) and compound (B) may be dissolved or suspended in a solvent and then mixed and reacted. Compound (A) is difficult to dissolve in a solvent and can only be suspended in many cases. However, if compound (A) and compound (B) react to form a salt, the reaction solution becomes uniform. The polyamide-imide precursor solution may be prepared in an inert gas stream such as nitrogen, or may be prepared under pressure.
ポリアミドイミド前駆体溶液を作製する際の化合物（Ａ）と化合物（Ｂ）のモル比率[
（Ａ）／（Ｂ）]は、８０／２０〜４０／６０とすることが好ましく、５２／４８〜４８
／５２とすることがより好ましい。化合物（Ａ）と化合物（Ｂ）のモル比率[（Ａ）／（
Ｂ）]が８０／２０〜４０／６０の範囲外である場合、目的とする前駆体が得られない場
合がある。
The molar ratio of compound (A) to compound (B) when preparing a polyamide-imide precursor solution [
(A) / (B)] is preferably 80/20 to 40/60, and is preferably 52/48 to 48.
It is more preferable to set it to / 52. Molar ratio of compound (A) to compound (B) [(A) / (
If B)] is outside the range of 80/20 to 40/60, the desired precursor may not be obtained.
ポリアミドイミド前駆体溶液には、化合物（Ａ）および化合物（Ｂ）の溶解性や保存安定性を向上させる観点から、分散安定剤を添加することが好ましい。分散安定剤は、化合物（Ａ）と化合物（Ｂ）とを混合させる前に添加してもよいし、混合後添加してもよい。分散安定剤としては、非イオン界面活性剤、陰イオン界面活性剤、陽イオン・両性イオン界面活性剤、フッ素系界面活性剤や、原料の溶解性向上、塩生成の促進、ｐＨ調整の観点から、化合物（Ｂ）以外のアミン化合物等が挙げられる。非イオン界面活性剤としては、例えば、ニューコール２３０３、ニューコールＮＴ−３、ニューコールＮＴ−５、ニューコールＮＴ−７、ニューコール１５２５、ニューコール７０４、ニューコール７０６、ニューコール７０７、ニューコール７０８、ニューコール７０９、ニューコール７０７−Ｆ、ニューコール２５、ニューコール８２（日本乳化剤社製）が挙げられる。陰イオン界面活性剤としては、例えば、ニューコール２１０、ニューコール２４０、ニューコールＢ４−ＳＮ、ニューコール１０２０−ＳＮ（日本乳化剤社製）が挙げられる。陽イオン・両性イオン界面活性剤としては、例えば、テクスノールＲ２、テクスノールＩＬ５５、テクスノールＲＳ−８１１（日本乳化剤社製）が挙げられる。フッ素系界面活性剤としては、例えば、メガファックＦ−１１４、メガファックＦ−４１０、メガファックＦ−４４４、メガファックＦ−４７７、メガファックＦ−５５１、メガファックＦ−５５４、メガファックＦ−５５９、メガファックＦ−５６９、メガファックＲ−４３、メガファックＲ−９４（ＤＩＣ社製）が挙げられる。化合物（Ｂ）以外のアミン化合物としては、芳香族アミンや脂肪族アミンが挙げられる。芳香族アミンとしては、例えば、アニリン、ピリジン、オキサゾール、チアゾールが挙げられる。脂肪族アミンとしては、例えば、メチルアミン、エチルアミン、プロピルアミン等の第１級アミンや、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ピロリジン、ピペリジン、ピロール等の第２級アミンや、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエチルアミン、Ｎ，Ｎ−ジイソプロピルエチルアミン、テトラメチルエチレンジアミン等の第３級アミンが挙げられ、中でも、加熱した際にカルボン酸とアミド結合を形成しないという観点から、第３級アミンが好ましい。 It is preferable to add a dispersion stabilizer to the polyamide-imide precursor solution from the viewpoint of improving the solubility and storage stability of the compound (A) and the compound (B). The dispersion stabilizer may be added before the compound (A) and the compound (B) are mixed, or may be added after the mixing. Dispersion stabilizers include nonionic surfactants, anionic surfactants, cationic / amphoteric surfactants, fluorine-based surfactants, and from the viewpoints of improving the solubility of raw materials, promoting salt production, and adjusting pH. , Amine compounds other than compound (B) and the like can be mentioned. Examples of the nonionic surfactant include Newcol 2303, Newcol NT-3, Newcol NT-5, Newcol NT-7, Newcol 1525, Newcol 704, Newcol 706, Newcol 707, and Newcol. Examples thereof include 708, Newcol 709, Newcol 707-F, Newcol 25, and Newcol 82 (manufactured by Nippon Emulsifier Co., Ltd.). Examples of the anionic surfactant include Newcol 210, Newcol 240, Newcol B4-SN, and Newcol 1020-SN (manufactured by Nippon Embroidery Co., Ltd.). Examples of the cationic / amphoteric ion surfactant include Texnol R2, Texnol IL55, and Texnol RS-811 (manufactured by Nippon Embroidery Co., Ltd.). Examples of the fluorine-based surfactant include Megafvck F-114, Megafvck F-410, Megafvck F-444, Megafvck F-477, Megafvck F-551, Megafvck F-554, and Megafvck F-. 559, Mega Fvck F-569, Mega Fvck R-43, Mega Fvck R-94 (manufactured by DIC) can be mentioned. Examples of the amine compound other than the compound (B) include aromatic amines and aliphatic amines. Examples of aromatic amines include aniline, pyridine, oxazole, and thiazole. Examples of the aliphatic amine include primary amines such as methylamine, ethylamine and propylamine, secondary amines such as dimethylamine, diethylamine, dipropylamine, pyrrolidine, piperidine and pyrrol, trimethylamine, triethylamine and tri. Examples thereof include tertiary amines such as propylamine, triethanolamine, N, N-dimethylethylamine, N, N-diisopropylethylamine, and tetramethylethylenediamine. Among them, the viewpoint that an amide bond is not formed with a carboxylic acid when heated. Therefore, a tertiary amine is preferable.
なお、化合物（Ａ）は、対応するトリカルボン酸無水物および対応するジアミンを用いて、両者を溶媒中で加熱撹拌したり、高温下での溶融押出したりすることにより製造することができるが、これらの方法に限定されない。前者の方法としては、例えば、トリカルボン酸無水物とジアミンとを溶媒（脂肪族カルボン酸類、脂肪族カルボン酸類、Ｎ，Ｎ−ジアルキルカルボキシルアミド類、アルコール類、エステル類、ハロゲン化炭化水素類等）中で加熱し反応させて、反応終了後に、反応液から分離精製することにより得ることができる。対応するトリカルボン酸無水物とジアミンのモル比率は、２：１であることが好ましい。 The compound (A) can be produced by using the corresponding tricarboxylic acid anhydride and the corresponding diamine by heating and stirring the two in a solvent or melt-extruding them at a high temperature. It is not limited to the method of. As the former method, for example, a solvent of tricarboxylic acid anhydride and diamine is used (aliphatic carboxylic acids, aliphatic carboxylic acids, N, N-dialkylcarboxyamides, alcohols, esters, halogenated hydrocarbons, etc.). It can be obtained by heating and reacting in the inside, and after completion of the reaction, separating and purifying from the reaction solution. The molar ratio of the corresponding tricarboxylic acid anhydride to diamine is preferably 2: 1.
本発明のポリアミドイミド前駆体の固形分濃度は、１〜８０質量％とすることが好ましく、１〜６０質量％とすることがより好ましく、５〜５０質量％とすることがさらに好ましい。固形分濃度を１〜８０質量％とすることにより、塗布するのに適した溶液粘度とすることができる。なお、固形分濃度とは、溶液中に占める化合物（Ａ）と化合物（Ｂ）の合計量の質量割合を百分率で表した数値である。 The solid content concentration of the polyamide-imide precursor of the present invention is preferably 1 to 80% by mass, more preferably 1 to 60% by mass, and even more preferably 5 to 50% by mass. By setting the solid content concentration to 1 to 80% by mass, the solution viscosity suitable for coating can be obtained. The solid content concentration is a numerical value representing the mass ratio of the total amount of the compound (A) and the compound (B) in the solution as a percentage.
本発明のポリアミドイミド前駆体溶液の作製においては、原料を反応容器に供給する際に、本発明の効果を損なわない範囲において、分子量制御の観点から、末端封鎖剤、重合触媒を加えてもよい。さらに、必要に応じて他の添加剤を加えてもよい。 In the preparation of the polyamide-imide precursor solution of the present invention, when the raw material is supplied to the reaction vessel, a terminal sequestering agent and a polymerization catalyst may be added from the viewpoint of molecular weight control as long as the effects of the present invention are not impaired. .. In addition, other additives may be added as needed.
末端封鎖剤は、高分子の末端官能基を封止するものである。末端封鎖剤としては、例えば、酢酸、ラウリン酸、安息香酸、オクチルアミン、シクロヘキシルアミン、アニリンが挙げられる。末端封鎖剤の含有量は、ポリアミドイミド前駆体の総モル数に対して５モル％以下であることが好ましい。 The terminal sequestering agent seals the terminal functional group of the polymer. Examples of the terminal sequestering agent include acetic acid, lauric acid, benzoic acid, octylamine, cyclohexylamine, and aniline. The content of the terminal sequestering agent is preferably 5 mol% or less based on the total number of moles of the polyamide-imide precursor.
重合触媒としては、例えば、リン酸、亜リン酸、次亜リン酸およびそれらの塩が挙げられる。重合触媒の含有量は、製品の性能や加工性低下の原因となるため、ポリアミドイミド前駆体の総モル数に対して２モル％以下であることが好ましい。 Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid and salts thereof. The content of the polymerization catalyst is preferably 2 mol% or less with respect to the total number of moles of the polyamide-imide precursor because it causes deterioration of product performance and processability.
他の添加剤としては、例えば、架橋剤、硬化剤、硬化促進剤、可塑剤、密着付与剤、レベリング剤、剥離促進剤、消泡剤、酸化防止剤、帯電防止剤、イオン捕捉剤、難燃剤、顔染料、有機粒子、希釈剤、無機充填剤、フィラー、安定剤が挙げられる。添加剤の含有量は、ポリアミドイミド前駆体の反応性の観点から、ポリアミドイミド前駆体の総質量に対して３０質量％以下が好ましい。 Other additives include, for example, cross-linking agents, curing agents, curing accelerators, plasticizers, adhesion-imparting agents, leveling agents, peeling accelerators, defoaming agents, antioxidants, antistatic agents, ion trapping agents, difficulties. Examples include flame retardants, facial dyes, organic particles, diluents, inorganic fillers, fillers and stabilizers. The content of the additive is preferably 30% by mass or less with respect to the total mass of the polyamide-imide precursor from the viewpoint of the reactivity of the polyamide-imide precursor.
本発明のポリアミドイミド前駆体溶液は、流延法、スピンコート法、スプレイコート法等により基材上に塗布し、加熱して重合することによって、ポリアミドイミドの被膜や、ポリアミドイミドの被膜を基材上に有する積層体を得ることができる。加熱温度としては、１６０〜３５０℃とすることが好ましい。基材から被膜を剥離することにより、ポリアミドイミドのフィルムを得ることができる。なお、被膜や積層体やフィルムには、加熱条件によって、一部イミド環が開いてカルボキシル基が存在する場合がある。 The polyamide-imide precursor solution of the present invention is coated on a substrate by a casting method, a spin coating method, a spray coating method, etc., and is heated and polymerized to form a polyamide-imide film or a polyamide-imide film. A laminate to be held on the material can be obtained. The heating temperature is preferably 160 to 350 ° C. A polyamide-imide film can be obtained by peeling the film from the substrate. Depending on the heating conditions, the imide ring may partially open and the carboxyl group may be present in the film, the laminate, or the film.
本発明で得られるポリアミドイミド前駆体溶液は、電気・電子分野、接着・塗料分野、自動車分野等、広範な用途に用いることができる。電気・電子分野としては、例えば、高密度磁気記録ベース、コンデンサー、ＦＰＣ用のフィルム、パワートランジスターの絶縁スペーサ、磁気ヘッドスペーサ、パワーリレーのスペーサ、トランスのスペーサ等積層材、電線・ケーブル絶縁被膜用、端末絶縁用チューブ、太陽電池、集積回路、スロットライナー等のエナメルコーティング材、蓄電素子用セパレータが挙げられる。接着・塗料分野としては、例えば、耐熱絶縁テープ、耐熱粘着テープ、低温貯蔵タンク、宇宙断熱材、限外ろ過膜、逆浸透膜、ガス分離膜の製造が挙げられる。自動車分野としては、例えば、フッ素樹脂やグラファイト等を充填した摺動部材、ガラス繊維や炭素繊維で強化した構造部材、プリプレグのマトリックスが挙げられる。 The polyamide-imide precursor solution obtained in the present invention can be used in a wide range of applications such as electrical / electronic fields, adhesive / paint fields, and automobile fields. In the electrical and electronic fields, for example, high-density magnetic recording bases, capacitors, films for FPCs, insulation spacers for power transistors, magnetic head spacers, spacers for power relays, laminates such as spacers for transformers, and insulation coatings for electric wires and cables. , Terminal insulation tubes, solar cells, integrated circuits, enamel coating materials such as slot liners, and separators for power storage elements. The field of adhesion / coating includes, for example, the production of heat-resistant insulating tape, heat-resistant adhesive tape, low-temperature storage tank, space heat insulating material, ultrafiltration membrane, reverse osmosis membrane, and gas separation membrane. Examples of the automobile field include sliding members filled with fluororesin, graphite, and the like, structural members reinforced with glass fibers and carbon fibers, and prepreg matrices.
以下、本発明を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より限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（１）化合物（Ａ）の同定
以下の条件により、赤外分光分析（ＩＲ）、核磁気共鳴分析（ＮＭＲ）および質量分析（ＬＣ／ＭＳ）をおこない同定した。
なお、ＩＲでは、１７７５ｃｍ−１付近、１７１５ｃｍ−１付近に検出されるイミド結合の有無を確認した。
（１ａ）ＩＲ
装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 Ｓｙｓｔｅｍ ２０００ 赤外分光装置
方法：ＫＢｒ法
積算回数：６４スキャン（分解能４ｃｍ−１）
（１ｂ）ＮＭＲ
装置：日本電子社製ＪＮＭ−ＥＣＡ５００
測定核種：プロトン
溶媒：重水素化ジメチルスルホキシド
温度：２５℃
積算回数：１２８回
（１ｃ）ＬＣ／ＭＳ
試料：ビスイミドジカルボン酸／ＤＭＳＯ溶液（２００μｇ／ｍＬ）
装置：ブルカー・ダルトニクス社製ｍｉｃｒｏＴＯＦ２−ｋｐ
カラム：Ｃａｄｅｎｚａ ＣＤ−Ｃ１８ ３μｍ ２ｍｍ×１５０ｍｍ
移動相：（移動相Ａ）０．１％ ギ酸水溶液、（移動相Ｂ）メタノール
グラジエント（Ｂ Ｃｏｎｃ．）：０ｍｉｎ（５０％）−５，７ｍｉｎ（６０％）−１４．２ｍｉｎ（６０％）−１７ｍｉｎ（１００％）−２１．６ｍｉｎ（１００％）−２７．２ｍｉｎ（５０％）−３４ｍｉｎ（５０％）
イオン化法：ＥＳＩ
検出条件：Ｎｅｇａｔｉｖｅモード
(1) Identification of compound (A) Infrared spectroscopy (IR), nuclear magnetic resonance analysis (NMR) and mass spectrometry (LC / MS) were performed under the following conditions for identification.
In IR, the presence or absence of imide bonds detected near 1775 cm -1 and around 1715 cm -1 was confirmed.
(1a) IR
Equipment: Perkin Elmer System 2000 infrared spectroscope Method: KBr method Accumulation number: 64 scans (resolution 4 cm -1 )
(1b) NMR
Equipment: JNM-ECA500 manufactured by JEOL Ltd.
Measurement nuclide: Proton Solvent: Deuterated dimethyl sulfoxide Temperature: 25 ° C
Number of integrations: 128 times (1c) LC / MS
Sample: Bisimidedicarboxylic acid / DMSO solution (200 μg / mL)
Equipment: microTOF2-kp manufactured by Bruker Daltonix
Column: Cadenza CD-C18 3 μm 2 mm x 150 mm
Mobile phase: (Mobile phase A) 0.1% aqueous formic acid solution, (Mobile phase B) Methanol gradient (B Conc.): 0 min (50%) -5,7 min (60%) -14.2 min (60%)- 17min (100%) -21.6min (100%) -27.2min (50%) -34min (50%)
Ionization method: ESI
Detection condition: Negative mode
（２）化合物（Ａ）の純度
（１ｃ）の質量分析（ＬＣ／ＭＳ）により、得られる質量スペクトル中に検出された一般式（１）〜（３）で表される化合物のイオン強度比のうち、一般式（１）で表される化合物が占めるイオン強度比の割合を求めた。
(2) Purity of compound (A) The ionic strength ratio of the compounds represented by the general formulas (1) to (3) detected in the obtained mass spectrum by mass spectrometry (LC / MS) of (1c). Among them, the ratio of the ionic strength ratio occupied by the compound represented by the general formula (1) was determined.
（３）化合物（Ａ）と化合物(Ｂ)とからなる塩の同定
溶媒を留去させるか、貧溶媒により析出させるかして、塩を分離した。
得られた塩は以下の条件により、ＩＲおよび示差走査熱量分析（ＤＳＣ）をおこない同定した。
なお、ＩＲでは、１６４ｃｍ−１、１５５９ｃｍ−１、１３７４ｃｍ−１付近に検出されるカルボン酸とアミンの塩に由来する吸収の増加の有無を確認し、ＤＳＣでは、化合物（Ｂ）の融点に由来するピークの消失の有無を確認した。
（３ａ）ＩＲ
装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 Ｓｙｓｔｅｍ ２０００ 赤外分光装置
方法：ＫＢｒ法
積算回数：６４スキャン（分解能４ｃｍ−１）
（３ｂ）ＤＳＣ
装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 ＤＳＣ８５００
方法：窒素雰囲気下で２５℃から３５０℃まで２０℃／分で昇温し、観測される結晶融解ピークのピークトップ温度を融点とした。
(3) Identification of a salt composed of the compound (A) and the compound (B) The salt was separated by distilling off the solvent or precipitating with a poor solvent.
The obtained salt was identified by IR and differential scanning calorimetry (DSC) under the following conditions.
Incidentally, from the melting point of the IR, 164cm -1, 1559 cm -1, to confirm the presence or absence of increase in absorption from salts of carboxylic acids and amines which are detected in the vicinity of 1374cm -1, the DSC, the compound (B) It was confirmed whether or not the peak disappeared.
(3a) IR
Equipment: Perkin Elmer System 2000 infrared spectroscope Method: KBr method Accumulation number: 64 scans (resolution 4 cm -1 )
(3b) DSC
Equipment: Perkin Elmer DSC8500
Method: The temperature was raised from 25 ° C. to 350 ° C. at 20 ° C./min under a nitrogen atmosphere, and the peak top temperature of the observed crystal melting peak was taken as the melting point.
（４）ポリアミドイミドの同定
以下の条件により、ＩＲ分析およびＤＳＣをおこない同定した。
なお、ＩＲでは、１５３１ｃｍ−１、１６６３ｃｍ−１付近に検出されるアミド結合に由来する吸収の増加の有無で確認し、ＤＳＣでは、ポリアミドイミドのガラス転移温度（Ｔｇ）の有無で確認した。
（４ａ）ＩＲ
装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 Ｓｙｓｔｅｍ ２０００ 赤外分光装置
方法：ＫＢｒ法
積算回数：６４スキャン（分解能４ｃｍ−１）
（４ｂ）ＤＳＣ
装置：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 ＤＳＣ８５００
方法：窒素雰囲気下で２５℃から３５０℃まで２０℃／分で昇温し、１ｓｔ ｓｃａｎにおいて１２０℃以上で観測される２つの屈曲点の中間点をガラス転移温度（Ｔｇ）とした。
(4) Identification of polyamide-imide Under the following conditions, IR analysis and DSC were performed for identification.
In IR, it was confirmed by the presence or absence of an increase in absorption due to the amide bond detected near 1531 cm-1 and 1663 cm-1, and in DSC, it was confirmed by the presence or absence of the glass transition temperature (Tg) of polyamide-imide.
(4a) IR
Equipment: Perkin Elmer System 2000 Infrared Spectroscopy Method: KBr method
Number of integrations: 64 scans (resolution 4 cm -1 )
(4b) DSC
Equipment: Perkin Elmer DSC8500
Method: The temperature was raised from 25 ° C. to 350 ° C. at 20 ° C./min under a nitrogen atmosphere, and the midpoint between the two bending points observed at 120 ° C. or higher in 1st scan was defined as the glass transition temperature (Tg).
（４）溶液粘度
トキメック社製、ＤＶＬ−ＢＩＩ型デジタル粘度計（Ｂ型粘度計）を用い、３０℃における値を測定した。
(4) Solution Viscosity A value at 30 ° C. was measured using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec.
実施例１
トリメリット酸無水物３８．４２６ｇ（０．２００ｍｏｌ）とｍ−キシリレンジアミン１３．６１９ｇ（０．１００ｍｏｌ）をＮ，Ｎ−ジメチルアセトアミド５００ｍＬに溶解させ、窒素ガスを通じながら８０℃に加熱して１時間撹拌して反応させた。反応液から溶媒を留去させて３００℃で２時間焼成をおこない、化合物（Ａ−１）を得た。
得られた化合物は分析方法の化合物（Ａ）の同定により、下記に示す化合物（Ａ−１）であることが確認でき、純度は９９．１％であった。
化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、９０℃に加熱した水３３．３１ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２８４．２Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 1
Dissolve 38.426 g (0.200 mol) of trimellitic acid anhydride and 13.619 g (0.100 mol) of m-xylylene diamine in 500 mL of N, N-dimethylacetamide and heat to 80 ° C. through nitrogen gas. The reaction was carried out with stirring for a time. The solvent was distilled off from the reaction solution, and the mixture was calcined at 300 ° C. for 2 hours to obtain compound (A-1).
The obtained compound was confirmed to be the compound (A-1) shown below by the identification of the compound (A) of the analysis method, and the purity was 99.1%.
38.995 g (0.0805 mol) of compound (A-1) was suspended in 33.31 g of water heated to 90 ° C., and then 10.963 g (0) of m-xylylenediamine while stirring the suspension. .0805 mol) was added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 284.2 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例２
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１７．０１ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２５０．３Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 2
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 17.01 g of water heated to 80 ° C., and then the suspension was stirred. While doing so, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 250.3 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例３
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン３３．３１ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２４１．７Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 3
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was dissolved in 33.31 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine was added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 241.7 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例４
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン１７．０１ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２０３．６Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 4
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was dissolved in 17.01 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, add 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine to prepare a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. Obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 203.6 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例５
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ，Ｎ−ジメチルアセトアミド１７．０１ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２１０．８Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 5
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was dissolved in 17.01 g of N, N-dimethylacetamide heated to 80 ° C., and then a solution was used. While stirring, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. rice field.
The solution viscosity of the obtained polyamide-imide precursor solution was 210.8 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例６
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水８．５１ｇとＮ−メチル−２−ピロリドン８．５１ｇの混合溶液に懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２３２．１Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 6
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was mixed with 8.51 g of water heated to 80 ° C. and 8.51 g of N-methyl-2-pyrrolidone. After suspending in the mixed solution, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added while stirring the suspension, and the solid content concentration was 60% by mass. , A uniform brown polyamide-imide precursor solution was obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 232.1 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例７
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水９．２９ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエタノールアミン２４．０２０ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、３２５．８Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 7
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 9.29 g of water heated to 80 ° C., and then the suspension was stirred. While adding 10.963 g (0.0805 mol) of m-xylylenediamine and 24.020 g (0.161 mol) of triethanolamine, a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass was obtained. rice field.
The solution viscosity of the obtained polyamide-imide precursor solution was 325.8 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例８
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水２０．５７ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とピリジン１２．７３５ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、７４．０Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 8
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 20.57 g of water heated to 80 ° C., and then the suspension was stirred. While doing so, 10.963 g (0.0805 mol) of m-xylylenediamine and 12.735 g (0.161 mol) of pyridine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 74.0 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例９
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水３３．０６ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とフッ素系界面活性剤０．２５０ｇを加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。なお、フッ素系活性剤としては、メガファックＦ−４７７（ＤＩＣ社製）を用いた。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２６８．３Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 9
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 33.06 g of water heated to 80 ° C., and then the suspension was stirred. While doing so, 10.963 g (0.0805 mol) of m-xylylenediamine and 0.250 g of a fluorine-based surfactant were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. As the fluorine-based activator, Megafuck F-477 (manufactured by DIC Corporation) was used.
The solution viscosity of the obtained polyamide-imide precursor solution was 268.3 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例１０
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１６．８１ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．４１９ｇ（０．０７６５ｍｏｌ）と１，２，３−プロパントリアミン０．２４１ｇ（０．００２７ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、３４８．７Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 10
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 16.81 g of water heated to 80 ° C., and then the suspension was stirred. While adding 10.419 g (0.0765 mol) of m-xylylenediamine, 0.241 g (0.0027 mol) of 1,2,3-propanetriamine and 16.292 g (0.161 mol) of triethylamine, the solid content concentration was increased. A uniform brown polyamide-imide precursor solution of 60% by mass was obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 348.7 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
実施例１１
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１７．０１ｇに懸濁させたのち、懸濁液を攪拌しながら、ｐ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２３．７Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｐ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 11
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was suspended in 17.01 g of water heated to 80 ° C., and then the suspension was stirred. While doing so, 10.963 g (0.0805 mol) of p-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 23.7 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and p-xylylenediamine was produced.
実施例１２
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン３６．７４ｇに溶解させたのち、溶液を攪拌しながら、４，４’−ジアミノジフェニルエーテル１６．１１９ｇ（０．０８０５ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１１８．５Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）と４，４’−ジアミノジフェニルエーテルからなる塩が生成していることが確認できた。
Example 12
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was dissolved in 36.74 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, 16.119 g (0.0805 mol) of 4,4'-diaminodiphenyl ether was added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 118.5 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and 4,4'-diaminodiphenyl ether was produced.
実施例１３
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン２０．４５ｇに溶解させたのち、溶液を攪拌しながら、４，４’−ジアミノジフェニルエーテル１６．１１９ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１０５．７Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）と４，４’−ジアミノジフェニルエーテルからなる塩が生成していることが確認できた。
Example 13
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was dissolved in 20.45 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, 16.119 g (0.0805 mol) of 4,4'-diaminodiphenyl ether and 16.292 g (0.161 mol) of triethylamine were added, and a uniform brown polyamide-imide precursor having a solid content concentration of 60% by mass was added. A solution was obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 105.7 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and 4,4'-diaminodiphenyl ether was produced.
実施例１４
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１０．２２ｇとＮ−メチル−２−ピロリドン１０．２２ｇの混合溶液に懸濁させたのち、懸濁液を攪拌しながら、４，４’−ジアミノジフェニルエーテル１６．１１９ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１３７．３Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）と４，４’−ジアミノジフェニルエーテルからなる塩が生成していることが確認できた。
Example 14
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was mixed with 10.22 g of water heated to 80 ° C. and 10.22 g of N-methyl-2-pyrrolidone. After suspending in the mixed solution, while stirring the suspension, 16.119 g (0.0805 mol) of 4,4'-diaminodiphenyl ether and 16.292 g (0.161 mol) of triethylamine were added, and the solid content concentration was 60. A uniform brown polyamide-imide precursor solution of% by weight was obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 137.3 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and 4,4'-diaminodiphenyl ether was produced.
実施例１５
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン３２．２３ｇに溶解させたのち、溶液を攪拌しながら、ヘキサメチレンジアミン９．３５４ｇ（０．０８０５ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、８９．３Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とヘキサメチレンジアミンからなる塩が生成していることが確認できた。
Example 15
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was dissolved in 32.23 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, 9.354 g (0.0805 mol) of hexamethylenediamine was added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 89.3 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and hexamethylenediamine was produced.
実施例１６
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン１５．９４ｇに溶解させたのち、溶液を攪拌しながら、ヘキサメチレンジアミン９．３５４ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、８３．８Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とヘキサメチレンジアミンからなる塩が生成していることが確認できた。
Example 16
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was dissolved in 15.94 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, 9.354 g (0.0805 mol) of hexamethylenediamine and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. ..
The solution viscosity of the obtained polyamide-imide precursor solution was 83.8 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and hexamethylenediamine was produced.
実施例１７
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水７．９７ｇとＮ−メチル−２−ピロリドン７．９７ｇの混合溶液に懸濁させたのち、懸濁液を攪拌しながら、ヘキサメチレンジアミン９．３５４ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１２１．２Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とヘキサメチレンジアミンからなる塩が生成していることが確認できた。
Example 17
38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 was mixed with 7.97 g of water heated to 80 ° C. and 7.97 g of N-methyl-2-pyrrolidone. After suspending in the mixed solution, 9.354 g (0.0805 mol) of hexamethylenediamine and 16.292 g (0.161 mol) of triethylamine were added while stirring the suspension, and the solid content concentration was 60% by mass and uniform. A brown polyamide-imide precursor solution was obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 121.2 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and hexamethylenediamine was produced.
実施例１８
トリメリット酸無水物３８．４２６ｇ（０．２００ｍｏｌ）とｐ−キシリレンジアミン１３．６１９ｇ（０．１００ｍｏｌ）をＮ，Ｎ−ジメチルアセトアミド５００ｍＬに溶解させ、窒素ガスを通じながら８０℃に加熱して１時間撹拌して反応させた。反応液から溶媒を留去させて３００℃で２時間焼成をおこない、化合物（Ａ−２）を得た。得られた化合物は分析方法の化合物（Ａ）の同定により、下記に示す化合物（Ａ−２）であることが確認でき、純度は９８．５％であった。
得られた化合物（Ａ−２）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１７．０１ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１５５．６Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−２）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 18
Dissolve 38.426 g (0.200 mol) of trimellitic acid anhydride and 13.619 g (0.100 mol) of p-xylylene diamine in 500 mL of N, N-dimethylacetamide and heat to 80 ° C. through nitrogen gas. The reaction was carried out with stirring for a time. The solvent was distilled off from the reaction solution, and the mixture was calcined at 300 ° C. for 2 hours to obtain compound (A-2). The obtained compound was confirmed to be the compound (A-2) shown below by the identification of the compound (A) of the analysis method, and the purity was 98.5%.
38.995 g (0.0805 mol) of the obtained compound (A-2) was suspended in 17.01 g of water heated to 80 ° C., and then m-xylylenediamine 10. 963 g (0.0805 mol) and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 155.6 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-2) and m-xylylenediamine was produced.
実施例１９
実施例１８と同様の操作をおこなって得られた化合物（Ａ−２）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン１７．０１ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１４３．８Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−２）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 19
38.995 g (0.0805 mol) of the compound (A-2) obtained by carrying out the same operation as in Example 18 was dissolved in 17.01 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, add 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine to prepare a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. Obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 143.8 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-2) and m-xylylenediamine was produced.
実施例２０
トリメリット酸無水物３８．４２６ｇ（０．２００ｍｏｌ）と４，４’−ジアミノジフェニルエーテル２０．０２４ｇ（０．１００ｍｏｌ）をＮ，Ｎ−ジメチルアセトアミド５００ｍＬに溶解させ、窒素ガスを通じながら８０℃に加熱して１時間撹拌して反応させた。反応液から溶媒を留去させて３００℃で２時間焼成をおこない、化合物（Ａ−３）を得た。得られた化合物は分析方法の化合物（Ａ）の同定により、下記に示す化合物（Ａ−３）であることが確認でき、純度は９８．９％であった。
得られた化合物（Ａ−３）４４．１５１ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水２０．４５ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１９１．５Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−３）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 20
Dissolve 38.426 g (0.200 mol) of trimellitic acid anhydride and 20.024 g (0.100 mol) of 4,4'-diaminodiphenyl ether in 500 mL of N, N-dimethylacetamide and heat to 80 ° C. through nitrogen gas. The mixture was stirred for 1 hour and reacted. The solvent was distilled off from the reaction solution, and the mixture was calcined at 300 ° C. for 2 hours to obtain compound (A-3). The obtained compound was confirmed to be the compound (A-3) shown below by the identification of the compound (A) of the analysis method, and the purity was 98.9%.
After suspending 44.151 g (0.0805 mol) of the obtained compound (A-3) in 20.45 g of water heated to 80 ° C., m-xylylenediamine 10. 963 g (0.0805 mol) and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 191.5 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-3) and m-xylylenediamine was produced.
実施例２１
実施例２０と同様の操作をおこなって得られた化合物（Ａ−３）４４．１５１ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン２０．４５ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１８２．５Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−３）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 21
44.151 g (0.0805 mol) of the compound (A-3) obtained by carrying out the same operation as in Example 20 was dissolved in 20.45 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, add 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine to prepare a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. Obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 182.5 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-3) and m-xylylenediamine was produced.
実施例２２
１，２，４−シクロヘキサントリカルボン酸無水物３９．６３４ｇ（０．２００ｍｏｌ）とｍ−キシリレンジアミン１３．６１９ｇ（０．１００ｍｏｌ）をＮ，Ｎ−ジメチルアセトアミド５００ｍＬに溶解させ、窒素ガスを通じながら８０℃に加熱して１時間撹拌して反応させた。反応液から溶媒を留去させて３００℃で２時間焼成をおこない、化合物（Ａ−４）を得た。得られた化合物は分析方法の化合物（Ａ）の同定により、下記に示す化合物（Ａ−４）であることが確認でき、純度は９５．７％であった。
得られた化合物（Ａ−４）３９．９６７ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１７．６６ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１２８．８Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−４）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 22
39.634 g (0.200 mol) of 1,2,4-cyclohexanetricarboxylic acid anhydride and 13.619 g (0.100 mol) of m-xylylene diamine were dissolved in 500 mL of N, N-dimethylacetamide, and 80 while passing through nitrogen gas. The mixture was heated to ° C. and stirred for 1 hour for reaction. The solvent was distilled off from the reaction solution, and the mixture was calcined at 300 ° C. for 2 hours to obtain compound (A-4). The obtained compound was confirmed to be the compound (A-4) shown below by the identification of the compound (A) of the analysis method, and the purity was 95.7%.
39.967 g (0.0805 mol) of the obtained compound (A-4) was suspended in 17.66 g of water heated to 80 ° C., and then m-xylylenediamine 10. 963 g (0.0805 mol) and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass.
The solution viscosity of the obtained polyamide-imide precursor solution was 128.8 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-4) and m-xylylenediamine was produced.
実施例２３
実施例２２と同様の操作をおこなって得られた化合物（Ａ−４）３９．９６７ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱したＮ−メチル−２−ピロリドン１７．６６ｇに溶解させたのち、溶液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加え、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、１１１．９Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−４）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 23
39.967 g (0.0805 mol) of the compound (A-4) obtained by carrying out the same operation as in Example 22 was dissolved in 17.66 g of N-methyl-2-pyrrolidone heated to 80 ° C., and then. While stirring the solution, add 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine to prepare a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass. Obtained.
The solution viscosity of the obtained polyamide-imide precursor solution was 111.9 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-4) and m-xylylenediamine was produced.
実施例２４
実施例１と同様の操作をおこなって得られた化合物（Ａ−１）３８．９９５ｇ（０．０８０５ｍｏｌ）を、８０℃に加熱した水１６．３７ｇに懸濁させたのち、懸濁液を攪拌しながら、ｍ−キシリレンジアミン１０．９６３ｇ（０．０８０５ｍｏｌ）とトリエチルアミン１６．２９２ｇ（０．１６１ｍｏｌ）を加えた。さらに、安息香酸０．５９０ｇ（４．８３ｍｍｏｌ）と無水次亜リン酸ナトリウム０．０４８ｇ（０．５４７ｍｍｏｌ）を加えて撹拌し、固形分濃度が６０質量％、均一な褐色のポリアミドイミド前駆体溶液を得た。
得られたポリアミドイミド前駆体溶液の溶液粘度は、２５８．９Ｐａ・ｓであった。
また、分析方法の化合物（Ａ）と化合物(Ｂ)とからなる塩の同定により、化合物（Ａ−１）とｍ−キシリレンジアミンからなる塩が生成していることが確認できた。
Example 24
38.995 g (0.0805 mol) of the compound (A-1) obtained by carrying out the same operation as in Example 1 was suspended in 16.37 g of water heated to 80 ° C., and then the suspension was stirred. While doing so, 10.963 g (0.0805 mol) of m-xylylene diamine and 16.292 g (0.161 mol) of triethylamine were added. Further, 0.590 g (4.83 mmol) of benzoic acid and 0.048 g (0.547 mmol) of sodium anhydrous hypophosphate were added and stirred to stir, and a uniform brown polyamide-imide precursor solution having a solid content concentration of 60% by mass was added. Got
The solution viscosity of the obtained polyamide-imide precursor solution was 258.9 Pa · s.
Further, by identifying the salt composed of the compound (A) and the compound (B) in the analysis method, it was confirmed that the salt composed of the compound (A-1) and m-xylylenediamine was produced.
[ポリアミドイミドの確認]
実施例１〜２４で得られたポリアミドイミド前駆体溶液を、ベーカー式アプリケーターを用いて、金属板上に被膜を形成した。３００℃で２時間加熱して、厚さ１００μｍの被膜を有した積層体を作製し、その後、被膜を剥離してフィルムを得た。
得られたフィルムは分析方法のポリアミドイミドの同定によりポリアミドイミドが生成していることが確認できた。
[Confirmation of polyamide-imide]
The polyamide-imide precursor solution obtained in Examples 1 to 24 was coated on a metal plate using a Baker-type applicator. The mixture was heated at 300 ° C. for 2 hours to prepare a laminate having a film having a thickness of 100 μm, and then the film was peeled off to obtain a film.
It was confirmed that the obtained film produced polyamide-imide by identifying the polyamide-imide in the analysis method.
得られた化合物（Ａ−１）〜（Ａ−４）の化合物を表１に示す。なお、Ｒ１、Ｒ２、Ｒ３は、一般式（１）〜（３）の基である。
表２に、実施例１〜２４で得られたポリアミドイミド前駆体溶液の原料と溶液粘度を示す。 Table 2 shows the raw materials and solution viscosities of the polyamide-imide precursor solutions obtained in Examples 1 to 24.
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