JP2017186560A - Polyamide-imide precursor solution - Google Patents
Polyamide-imide precursor solution Download PDFInfo
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- JP2017186560A JP2017186560A JP2017074146A JP2017074146A JP2017186560A JP 2017186560 A JP2017186560 A JP 2017186560A JP 2017074146 A JP2017074146 A JP 2017074146A JP 2017074146 A JP2017074146 A JP 2017074146A JP 2017186560 A JP2017186560 A JP 2017186560A
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- Prior art keywords
- compound
- mol
- precursor solution
- salt
- solution
- Prior art date
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- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 90
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 90
- 239000002243 precursor Substances 0.000 title claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 181
- 150000003839 salts Chemical class 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims 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 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 109
- 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 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 239000003245 coal Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- -1 aliphatic diamine Chemical class 0.000 description 14
- 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
- 150000004985 diamines Chemical class 0.000 description 11
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- 150000003628 tricarboxylic acids Chemical group 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000010438 heat treatment Methods 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
- 239000011248 coating agent Substances 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 125000006850 spacer group Chemical group 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
- 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
- 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
- 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
- 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
- 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
- 239000002280 amphoteric surfactant Substances 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
- 239000003093 cationic surfactant Substances 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
- 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
- 238000009413 insulation Methods 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
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 238000002360 preparation method Methods 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
- 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
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- 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
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- 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
- 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
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- 238000000752 ionisation method Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 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
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- 239000011146 organic particle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- BLTPNRTWCHWASU-UHFFFAOYSA-N propane-1,1,1-triamine Chemical compound CCC(N)(N)N BLTPNRTWCHWASU-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 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
- 238000000108 ultra-filtration Methods 0.000 description 1
- NSYLACLNZOHRCH-UHFFFAOYSA-N undecane-1,1,1-triamine Chemical compound CCCCCCCCCCC(N)(N)N NSYLACLNZOHRCH-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
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 polyamideimide 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）。 Polyamideimide is widely used for applications such as films, wire coating materials, molding materials, adhesives and the like because of its high heat resistance and chemical resistance. In general, polyamideimide is obtained by heating and reacting a raw material dissolved in an organic solvent to distill off the organic solvent through 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 raw materials used for the production of polyamide-amide acid have a large environmental load and are poor in handleability, such as acid chloride and isocyanate. Furthermore, the acid chloride is very expensive, and hydrogen chloride is produced as a by-product during production, so that there is a problem that a post-treatment step is required and the cost is increased. Polyamide-amic 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 environmental load. Furthermore, when polyamide-amide acid is used as polyamideimide, there is a problem that it is economically disadvantageous because an imidization step in which heat treatment is performed at a high temperature is necessary.
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-described problems, and can be produced using a solvent having a low environmental impact such as water without using an acid chloride or isocyanate, and requires an imidization step. It is an object to provide a solution of a polyamideimide precursor that does not.
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 intensive studies to solve the above problems, the present inventors have found that the above problems can be solved, and have reached 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、溶媒から構成されることを特徴とするポリアミドイミド前駆体溶液。
（２）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）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（１）に記載のポリアミドイミド前駆体溶液。
（３）溶媒が、水であ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。
（４）さらに、分散安定剤を添加することを特徴とする（１）〜（３）いずれか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) It is characterized in that the structure is composed of a salt comprising a compound (A) containing a carboxyl group, an amide bond and / or an imide bond, a compound (B) containing an amino group, and a solvent. A polyamideimide precursor solution.
(2) The compound (A) containing a carboxyl group and an amide bond and / or an imide bond in the structure is at least one of the compounds represented by the general formulas (1) to (3) And the polyamideimide precursor solution according to (1).
(3) The polyamideimide precursor solution according to (1) or (2), wherein the solvent is water.
(4) The polyamideimide precursor solution according to any one of (1) to (3), further comprising 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 polyamidoimide precursor that can be produced using a solvent having a low environmental burden, such as water, without using acid chloride or isocyanate, and 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 polyamideimide precursor solution of the present invention comprises, in its structure, a salt composed of a compound (A) containing a carboxyl group, an amide bond and / or an imide bond, a compound (B) containing an amino group, and a solvent. 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 a diamine residue. As a diamine which gives a diamine residue, any of an aromatic diamine, an aliphatic diamine, and an alicyclic diamine may be used. The diamine may contain —O— or —S— in the structure, one or more hydrogen atoms may be substituted with halogen, or may have a side chain. Examples of the diamine include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and benzidine. 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl ether, 3,3-diaminobenzophenone 4,4-diaminobenzophenone, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,5-diaminonaphthalene, 3,3-diaminonaphthalene, 1,4-diaminocyclohexane, 1,10-diamino -1, 0-dimethyldecane, 1,4-bis (aminomethyl) cyclohexane, 4,4-bis (aminomethyl) cyclohexane, 4,4′-methylenebis (cyclohexylamine), isophoronediamine, α, ω-bisaminopolydimethylsiloxane , 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) polymethylphenylsiloxane, α , Ω-bis (3-aminopropyl) poly (dimethylsiloxane-diphenylsiloxy Down) copolymers, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, benzoguanamine. Among these, m-xylylenediamine is preferable because the water solubility of the salt composed of the compound (A) and the compound (B) is increased. The diamines 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 tricarboxylic acid residues. The tricarboxylic acid that gives the residue of 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, 3,4,4′-biphenyltricarboxylic acid anhydride. 1,2,4-cyclohexanetricarboxylic acid anhydride and the like. Among them, trimellitic acid anhydride is preferable because of its high reactivity. The said tricarboxylic acid may be used independently and may use 2 or more types together.
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 polyamideimide. For example, R 1 of the compounds of the general formulas (1) to (3) Examples thereof include the same diamine as the diamine to be provided and trivalent or higher amine compounds. When the compound (B) is a diamine, it may be the same as or different from the diamine that gives R 1 of the compounds of the general formulas (1) to (3). Examples of the trivalent or higher valent amino compound include propanetriamine, butanetriamine, undecanetriamine, pyrimidinetriamine, benzenetriamine, tri (aminophenyl) methane, tri (aminophenyl) ethane, tri (aminophenyl) propane, and tri (amino). Phenyl) trifluoroethane, tetra (aminophenyl) methane, benzenetetraamine, pyrimidinetetraamine, benzenepentamine, and benzenehexamine. As the compound (B), m-xylylenediamine is preferable because the water solubility of the salt composed of the compound (A) and the compound (B) is increased. A compound (B) may be used independently and may use 2 or more types together.
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。 As the solvent used in the present invention, either an organic solvent or water may be used, but water is preferred because it has a small effect on handling 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 polyamideimide precursor solution of the present invention can be obtained by reacting compound (A) with compound (B) in a solvent. Although reaction temperature is suitably set according to the compound (A) and compound (B) to be used, it is preferable to set it as 5-230 degreeC, it is more preferable to set it as 20-150 degreeC, and it is set as 20-85 degreeC. More preferably. The reaction method of the compound (A) and the compound (B) is not particularly limited, but after suspending the compound (A) in a solvent, the compound (B) may be added and reacted, or the compound (A After dissolving B), the compound (A) may be added and reacted, or the compound (A) and the compound (B) may be simultaneously added to the solvent and reacted, or the compound (A) may be reacted with 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 preparation of the polyamideimide precursor solution may be performed in an inert gas stream such as nitrogen, or may be performed 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。
Molar ratio of compound (A) and compound (B) when preparing a polyamideimide precursor solution [
(A) / (B)] is preferably 80/20 to 40/60, and 52/48 to 48.
/ 52 is more preferable. Molar ratio of compound (A) to compound (B) [(A) / (
B)] is outside the range of 80/20 to 40/60, the target 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。 A dispersion stabilizer is preferably added to the polyamideimide 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 mixing the compound (A) and the compound (B), or may be added after mixing. As dispersion stabilizers, nonionic surfactants, anionic surfactants, cationic and amphoteric surfactants, fluorosurfactants, from the viewpoint of improving the solubility of raw materials, promoting salt formation, and adjusting pH And amine compounds other than the compound (B). Nonionic surfactants include, for example, New Coal 2303, New Coal NT-3, New Coal NT-5, New Coal NT-7, New Coal 1525, New Coal 704, New Coal 706, New Coal 707, New Coal 708, New Coal 709, New Coal 707-F, New Coal 25, New Coal 82 (manufactured by Nippon Emulsifier Co., Ltd.). Examples of the anionic surfactant include New Coal 210, New Coal 240, New Coal B4-SN, New Coal 1020-SN (manufactured by Nippon Emulsifier Co., Ltd.). Examples of the cation / amphoteric surfactant include Texnol R2, Texnol IL55, Texnol RS-811 (manufactured by Nippon Emulsifier Co., Ltd.). Examples of the fluorosurfactant include Mega-Fuck F-114, Mega-Fuck F-410, Mega-Fuck F-444, Mega-Fuck F-477, Mega-Fuck F-551, Mega-Fuck F-554, Mega-Fuck F- 559, Megafuck F-569, Megafuck R-43, Megafuck R-94 (manufactured by DIC). Examples of amine compounds other than the compound (B) include aromatic amines and aliphatic amines. Examples of the aromatic amine 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 pyrrole, trimethylamine, triethylamine, and triamine. Tertiary amines such as propylamine, triethanolamine, N, N-dimethylethylamine, N, N-diisopropylethylamine, and tetramethylethylenediamine can be mentioned. Among them, a 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 both in a solvent or by melt extrusion at a high temperature. It is not limited to this method. As the former method, for example, a tricarboxylic acid anhydride and a diamine are used as a solvent (aliphatic carboxylic acids, aliphatic carboxylic acids, N, N-dialkylcarboxylamides, alcohols, esters, halogenated hydrocarbons, etc.) It can be obtained by heating in the reaction and separating and purifying from the reaction solution after completion of the reaction. The corresponding tricarboxylic acid anhydride to diamine molar ratio 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 polyamideimide 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, it is possible to obtain a solution viscosity suitable for coating. In addition, solid content concentration is the numerical value which represented the mass ratio of the total amount of the compound (A) and compound (B) which occupies in a solution with 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 polyamideimide precursor solution of the present invention, a terminal blocking agent and a polymerization catalyst may be added from the viewpoint of molecular weight control within the range where the effects of the present invention are not impaired when the raw materials are supplied to the reaction vessel. . Furthermore, you may add another additive 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 blocking agent seals the terminal functional group of the polymer. Examples of the terminal blocking agent include acetic acid, lauric acid, benzoic acid, octylamine, cyclohexylamine, and aniline. The content of the terminal blocking agent is preferably 5 mol% or less with respect to the total number of moles of the polyamideimide 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. Since the content of the polymerization catalyst is a cause of product performance and processability deterioration, it is preferably 2 mol% or less with respect to the total number of moles of the polyamideimide precursor.
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。 Examples of other additives include a crosslinking agent, a curing agent, a curing accelerator, a plasticizer, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antifoaming agent, an antioxidant, an antistatic agent, an ion scavenger, and a difficult agent. Examples include flame retardants, facial dyes, organic particles, diluents, inorganic fillers, fillers, and stabilizers. From the viewpoint of the reactivity of the polyamideimide precursor, the content of the additive is preferably 30% by mass or less with respect to the total mass of the polyamideimide 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 polyamideimide precursor solution of the present invention is coated on a substrate by a casting method, spin coating method, spray coating method, or the like, and polymerized by heating to form a polyamideimide coating or a polyamideimide coating. The laminated body which has on a material can be obtained. The heating temperature is preferably 160 to 350 ° C. A film of polyamideimide can be obtained by peeling the coating from the substrate. In addition, in a coating film, a laminated body, or a film, a imide ring may partly open and a carboxyl group may exist depending on heating conditions.
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 polyamideimide precursor solution obtained in the present invention can be used in a wide range of applications such as the electric / electronic field, the adhesion / painting field, and the automobile field. In the electric / electronic field, for example, for high-density magnetic recording bases, capacitors, FPC films, power transistor insulation spacers, magnetic head spacers, power relay spacers, transformer spacers, laminated materials, and wire / cable insulation coatings , Terminal insulating tubes, solar cells, integrated circuits, enamel coating materials such as slot liners, and storage element separators. Examples of the adhesive / paint field include production of heat-resistant insulating tapes, heat-resistant adhesive tapes, low-temperature storage tanks, space heat insulating materials, ultrafiltration membranes, reverse osmosis membranes, and gas separation membranes. Examples of the automobile field include sliding members filled with fluororesin and graphite, 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。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by 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 spectroscopic analysis (IR), nuclear magnetic resonance analysis (NMR), and mass spectrometry (LC / MS) were identified under the following conditions.
In IR, to confirm the presence or absence of the imide bond to be detected 1775cm around -1, around 1715 cm -1.
(1a) IR
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Integration count: 64 scans (resolution: 4 cm −1 )
(1b) NMR
Apparatus: JNM-ECA500 manufactured by JEOL Ltd.
Measurement nuclide: Proton Solvent: Deuterated dimethyl sulfoxide Temperature: 25 ° C
Integration count: 128 times (1c) LC / MS
Sample: Bisimide dicarboxylic acid / DMSO solution (200 μg / mL)
Equipment: microTOF2-kp manufactured by Bruker Daltonics
Column: Cadenza CD-C18 3 μm 2 mm × 150 mm
Mobile phase: (Mobile phase A) 0.1% formic acid aqueous solution, (Mobile phase B) Methanol gradient (B Conc.): 0 min (50%)-5, 7 min (60%)-14.2 min (60%)- 17 min (100%)-21.6 min (100%)-27.2 min (50%)-34 min (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 the 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 salt comprising compound (A) and 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) The presence or absence of disappearing peaks was confirmed.
(3a) IR
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Integration count: 64 scans (resolution: 4 cm −1 )
(3b) DSC
Device: DSC8500 manufactured by Perkin Elmer
Method: The temperature was raised from 25 ° C. to 350 ° C. at 20 ° C./min in 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 Polyamideimide Identification was performed by IR analysis and DSC under the following conditions.
In addition, in IR, it confirmed by the presence or absence of the increase in the absorption derived from the amide bond detected in 1531 cm <-1> and 1663 cm <-1> vicinity, and in DSC, it confirmed by the presence or absence of the glass transition temperature (Tg) of polyamideimide.
(4a) IR
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method
Integration count: 64 scans (resolution 4cm -1 )
(4b) DSC
Device: DSC8500 manufactured by Perkin Elmer
Method: The temperature was raised from 25 ° C. to 350 ° C. at a rate of 20 ° C./min in a nitrogen atmosphere, and the midpoint between 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 The value in 30 degreeC was measured using the Tokimec company make and DVL-BII type digital viscometer (B type viscometer).
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
38.426 g (0.200 mol) of trimellitic anhydride and 13.619 g (0.100 mol) of m-xylylenediamine were dissolved in 500 mL of N, N-dimethylacetamide and heated to 80 ° C. while passing nitrogen gas. The reaction was stirred for an hour. The solvent was distilled off from the reaction solution, followed by baking 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) in the analytical method, and the purity was 99.1%.
After 38.995 g (0.0805 mol) of the compound (A-1) was suspended in 33.31 g of water heated to 90 ° C., 10.963 g of m-xylylenediamine (0 0.0805 mol) was added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 284.2 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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 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. Then, 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 polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 250.3 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 in 33.31 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine was added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 241.7 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 in 17.01 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added, and a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass was added. Obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 203.6 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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
The compound (A-1) 38.995 g (0.0805 mol) obtained by the same operation as in Example 1 was dissolved in 17.01 g of N, N-dimethylacetamide heated to 80 ° C. While stirring the mixture, 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 polyamideimide precursor solution having a solid concentration of 60% by mass. It was.
The solution viscosity of the obtained polyamideimide precursor solution was 210.8 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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 carrying out the same operation as in Example 1, 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 polyamideimide precursor solution was obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 232.1 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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 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 solid brown polyamideimide precursor solution having a solid concentration of 60% by mass was obtained. It was.
The solution viscosity of the obtained polyamideimide precursor solution was 325.8 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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. Then, 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 polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 74.0 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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. Then, 10.963 g (0.0805 mol) of m-xylylenediamine and 0.250 g of a fluorosurfactant were added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass. In addition, Megafac F-477 (made by DIC) was used as a fluorine-type activator.
The solution viscosity of the obtained polyamideimide precursor solution was 268.3 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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 the same operation as in Example 1 was suspended in 16.81 g of water heated to 80 ° C., and 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 60% by weight, uniform brown polyamideimide precursor solution was obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 348.7 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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 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. Then, 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 polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 23.7 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and p-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by the same operation as in Example 1 in 36.74 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 16.119 g (0.0805 mol) of 4,4′-diaminodiphenyl ether was added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 118.5 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and 4,4'- diamino diphenyl ether was producing | generating by identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 in 20.45 g of N-methyl-2-pyrrolidone heated to 80 ° C., 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 the solid content concentration was 60% by mass, and a uniform brown polyamideimide precursor. A solution was obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 105.7 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and 4,4'- diamino diphenyl ether was producing | generating by identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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
The compound (A-1) 38.995 g (0.0805 mol) obtained by carrying out 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 mass%, uniform brown polyamideimide precursor solution was obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 137.3 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and 4,4'- diamino diphenyl ether was producing | generating by identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by the same operation as in Example 1 in 32.23 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 9.354 g (0.0805 mol) of hexamethylenediamine was added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 89.3 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and hexamethylenediamine was producing | generating by identification of the salt which consists of the compound (A) and compound (B) of an analytical method.
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-1) obtained by the same operation as in Example 1 in 15.94 g of N-methyl-2-pyrrolidone heated to 80 ° C., 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 polyamideimide precursor solution having a solid content concentration of 60% by mass. .
The solution viscosity of the obtained polyamideimide precursor solution was 83.8 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and hexamethylenediamine was producing | generating by identification of the salt which consists of the compound (A) and compound (B) of an analytical method.
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
The compound (A-1) 38.995 g (0.0805 mol) obtained by carrying out the same operation as in Example 1 was prepared by adding 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 uniform to 60% by mass. A brown polyamideimide precursor solution was obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 121.2 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and hexamethylenediamine was producing | generating by identification of the salt which consists of the compound (A) and compound (B) of an analytical method.
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
Trimellitic anhydride (38.426 g, 0.200 mol) and p-xylylenediamine (13.619 g, 0.100 mol) were dissolved in N, N-dimethylacetamide (500 mL) and heated to 80 ° C. while passing nitrogen gas. The reaction was stirred for an hour. The solvent was distilled off from the reaction solution, followed by baking 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) in the analytical 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 m-xylylenediamine 10. 963 g (0.0805 mol) and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 155.6 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-2) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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
After dissolving 38.995 g (0.0805 mol) of the compound (A-2) obtained by performing the same operation as in Example 18, in 17.01 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added, and a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass was added. Obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 143.8 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-2) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
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
38.426 g (0.200 mol) of trimellitic anhydride and 20.024 g (0.100 mol) of 4,4′-diaminodiphenyl ether were dissolved in 500 mL of N, N-dimethylacetamide and heated to 80 ° C. while passing nitrogen gas. The reaction was allowed to stir for 1 hour. The solvent was distilled off from the reaction solution, followed by baking 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 identification of the compound (A) in the analytical method, and the purity was 98.9%.
44.151 g (0.0805 mol) of the obtained compound (A-3) was suspended in 20.45 g of water heated to 80 ° C., and m-xylylenediamine 10. 963 g (0.0805 mol) and 16.292 g (0.161 mol) of triethylamine were added to obtain a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 191.5 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-3) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) and compound (B) of an analytical method.
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
After dissolving 44.151 g (0.0805 mol) of the compound (A-3) obtained by carrying out the same operation as in Example 20, in 20.45 g of N-methyl-2-pyrrolidone heated to 80 ° C., While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added, and a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass was added. Obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 182.5 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-3) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) and compound (B) of an analytical method.
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-xylylenediamine are dissolved in 500 mL of N, N-dimethylacetamide, and 80% while passing nitrogen gas. The mixture was heated to ° C and stirred for 1 hour to react. The solvent was distilled off from the reaction solution, and calcination was performed at 300 ° C. for 2 hours to obtain a compound (A-4). The obtained compound was confirmed to be the compound (A-4) shown below by the identification of the compound (A) in the analytical method, and the purity was 95.7%.
After 39.967 g (0.0805 mol) of the obtained compound (A-4) was suspended in 17.66 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 polyamideimide precursor solution having a solid concentration of 60% by mass.
The solution viscosity of the obtained polyamideimide precursor solution was 128.8 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-4) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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. While stirring the solution, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added, and a uniform brown polyamideimide precursor solution having a solid concentration of 60% by mass was added. Obtained.
The solution viscosity of the obtained polyamideimide precursor solution was 111.9 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-4) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) and the compound (B) of an analytical method.
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
After suspending 38.995 g (0.0805 mol) of the compound (A-1) obtained by performing the same operation as in Example 1 in 16.37 g of water heated to 80 ° C., the suspension was stirred. Then, 10.963 g (0.0805 mol) of m-xylylenediamine and 16.292 g (0.161 mol) of triethylamine were added. Furthermore, 0.590 g (4.83 mmol) of benzoic acid and 0.048 g (0.547 mmol) of anhydrous sodium hypophosphite were added and stirred, and the solid content concentration was 60% by mass and the uniform brown polyamideimide precursor solution Got.
The solution viscosity of the obtained polyamideimide precursor solution was 258.9 Pa · s.
Moreover, it has confirmed that the salt which consists of a compound (A-1) and m-xylylenediamine was produced | generated by the identification of the salt which consists of the compound (A) of an analytical method, and a compound (B).
[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 polyamideimide]
A film was formed on the metal plate from the polyamideimide precursor solution obtained in Examples 1 to 24 using a Baker type applicator. It heated at 300 degreeC for 2 hours, the laminated body which has a 100 micrometer-thick film was produced, and the film was peeled after that and the film was obtained.
It was confirmed that polyamideimide was produced from the obtained film by identification of polyamideimide 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 polyamideimide precursor solutions obtained in Examples 1 to 24.
Claims (4)
求項１に記載のポリアミドイミド前駆体溶液。
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| CN112321829A (en) * | 2020-10-29 | 2021-02-05 | 宜兴市泽润高分子新材料有限公司 | Method for aqueous phase synthesis of polyamide-imide resin |
| WO2021048074A1 (en) | 2019-09-09 | 2021-03-18 | Solvay Specialty Polymers Usa, Llc | Polyamide-imide polymer and process for its manufacture |
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| JPS63117035A (en) * | 1986-11-05 | 1988-05-21 | Toray Ind Inc | Thermosplastic polyether-imide-amide |
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| WO2021048074A1 (en) | 2019-09-09 | 2021-03-18 | Solvay Specialty Polymers Usa, Llc | Polyamide-imide polymer and process for its manufacture |
| CN112321829A (en) * | 2020-10-29 | 2021-02-05 | 宜兴市泽润高分子新材料有限公司 | Method for aqueous phase synthesis of polyamide-imide resin |
| CN112321829B (en) * | 2020-10-29 | 2023-01-06 | 山东君昊高性能聚合物有限公司 | Method for aqueous phase synthesis of polyamide-imide resin |
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