JP7320334B1 - Novel diamine, method for producing the same, and polyamic acid and polyimide produced from the diamine - Google Patents
Novel diamine, method for producing the same, and polyamic acid and polyimide produced from the diamine Download PDFInfo
- Publication number
- JP7320334B1 JP7320334B1 JP2023046456A JP2023046456A JP7320334B1 JP 7320334 B1 JP7320334 B1 JP 7320334B1 JP 2023046456 A JP2023046456 A JP 2023046456A JP 2023046456 A JP2023046456 A JP 2023046456A JP 7320334 B1 JP7320334 B1 JP 7320334B1
- Authority
- JP
- Japan
- Prior art keywords
- diamine
- polyimide
- polyamic acid
- formula
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 66
- 150000004985 diamines Chemical class 0.000 title claims abstract description 63
- 239000004642 Polyimide Substances 0.000 title claims abstract description 47
- 229920005575 poly(amic acid) Polymers 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002904 solvent Substances 0.000 claims abstract description 79
- -1 dinitro compound Chemical class 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012787 coverlay film Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 9
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 3
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 3
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 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 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 150000005339 4-nitrobenzoic acids Chemical class 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SFVSTECQIQQHHL-UHFFFAOYSA-N 1,2-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C1=C(N)C=C2S(=O)(=O)C3=CC(N)=C(C)C(C)=C3C2=C1 SFVSTECQIQQHHL-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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- SPJXZYLLLWOSLQ-UHFFFAOYSA-N 1-[(1-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CCCCC1(N)CC1(N)CCCCC1 SPJXZYLLLWOSLQ-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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- DXBNPCQFURHJGT-UHFFFAOYSA-N 2-(4-aminophenoxy)-5-[4-(4-aminophenoxy)-3-sulfophenyl]benzenesulfonic acid Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C=2C=C(C(OC=3C=CC(N)=CC=3)=CC=2)S(O)(=O)=O)C=C1S(O)(=O)=O DXBNPCQFURHJGT-UHFFFAOYSA-N 0.000 description 1
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 description 1
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- UOQSEWMPXARXID-UHFFFAOYSA-N 3-[5-amino-2-[4-amino-2-(3-sulfopropoxy)phenyl]phenoxy]propane-1-sulfonic acid Chemical group OS(=O)(=O)CCCOC1=CC(N)=CC=C1C1=CC=C(N)C=C1OCCCS(O)(=O)=O UOQSEWMPXARXID-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-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
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- YARZEPAVWOMMHZ-UHFFFAOYSA-N 4-(3,4-dicarboxy-4-phenylcyclohexa-1,5-dien-1-yl)phthalic acid Chemical compound OC(=O)C1C=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC1(C(O)=O)C1=CC=CC=C1 YARZEPAVWOMMHZ-UHFFFAOYSA-N 0.000 description 1
- QNLCDRXVEPWSBQ-UHFFFAOYSA-N 4-(4,5-dicarboxy-5-phenylcyclohexa-1,3-dien-1-yl)phthalic acid Chemical compound OC(=O)C1=CC=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)CC1(C(O)=O)C1=CC=CC=C1 QNLCDRXVEPWSBQ-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QVMOHNTZLKZWNT-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]ethoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCOCCOCCOC1=CC=C(N)C=C1 QVMOHNTZLKZWNT-UHFFFAOYSA-N 0.000 description 1
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 description 1
- HPUJEBAZZTZOFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)-2,2-dimethylpropoxy]aniline Chemical compound C=1C=C(N)C=CC=1OCC(C)(C)COC1=CC=C(N)C=C1 HPUJEBAZZTZOFL-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- KWFFEQXPFFDJER-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)propoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCOC1=CC=C(N)C=C1 KWFFEQXPFFDJER-UHFFFAOYSA-N 0.000 description 1
- LAFZPVANKKJENB-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)butoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCOC1=CC=C(N)C=C1 LAFZPVANKKJENB-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- AUPIFOPXTAGGSW-UHFFFAOYSA-N 4-[4-[9-[4-(4-aminophenoxy)phenyl]fluoren-9-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 AUPIFOPXTAGGSW-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- KXLZZEPFQYGUPZ-UHFFFAOYSA-N 4-nitrobenzoyl bromide Chemical compound [O-][N+](=O)C1=CC=C(C(Br)=O)C=C1 KXLZZEPFQYGUPZ-UHFFFAOYSA-N 0.000 description 1
- VOTRYGPPYSQQNY-UHFFFAOYSA-N 4-nitrobenzoyl iodide Chemical compound [O-][N+](=O)C1=CC=C(C(I)=O)C=C1 VOTRYGPPYSQQNY-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- UPGRRPUXXWPEMV-UHFFFAOYSA-N 5-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C#CC1=CC=CC=C1 UPGRRPUXXWPEMV-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- ABPUBUORTRHHDZ-UHFFFAOYSA-N [4-(aminomethyl)-3-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2(CN)C(CN)CC1C2 ABPUBUORTRHHDZ-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 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
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- GTTPIBRPFDHJHU-UHFFFAOYSA-N decane-1,3-diamine Chemical compound CCCCCCCC(N)CCN GTTPIBRPFDHJHU-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
【課題】下記式（８）で表されるジアミンと類似の構造を有し、且つ溶媒溶解性に優れる、新規なジアミンの提供。TIFF0007320334000019.tif15116【解決手段】鋭意研究を重ねた結果、下記式（１）で表されるジアミンが、上記式（８）で表されるジアミンと類似の構造を有するにも拘わらず優れた溶媒溶解性を示し、前記課題が解決可能であることを見出した。また、本発明のジアミンより製造される本発明のポリイミドは、高Ｔｇ、低ＣＴＥ、低誘電特性（低誘電率、低誘電正接）に優れ、特に高周波ＦＰＣ基板材料（例えば、フレキシブル銅張積層板やカバーレイフィルム等の積層体における樹脂基板等）として好適に使用することができる。TIFF0007320334000020.tif20121【選択図】なしA novel diamine having a structure similar to that of the diamine represented by the following formula (8) and having excellent solvent solubility is provided. TIFF0007320334000019.tif15116 [Solution] As a result of intensive research, it was found that the diamine represented by the following formula (1) has excellent solvent solubility despite having a structure similar to that of the diamine represented by the above formula (8). The inventors have found that the above problems can be solved. In addition, the polyimide of the present invention produced from the diamine of the present invention is excellent in high Tg, low CTE, low dielectric properties (low dielectric constant, low dielectric loss tangent), especially high frequency FPC substrate material (for example, flexible copper clad laminate and resin substrates in laminates such as coverlay films). TIFF0007320334000020.tif20121 [Selection] None
Description
本発明は、ポリイミド樹脂等の原料として有用な新規なエステル基含有ジアミン及びその製造方法、並びに該ジアミンより製造されるポリアミック酸及びポリイミドに関する。 TECHNICAL FIELD The present invention relates to a novel ester group-containing diamine useful as a raw material for polyimide resins and the like, a method for producing the same, and a polyamic acid and polyimide produced from the diamine.
ポリイミドは、現存する樹脂の中で最高レベルの耐熱性、耐薬品性、電気絶縁性、耐放射線性などを併せ持ち、原料の組み合わせによって容易に様々な用途に合わせた特性を発現できるため幅広い分野で使用されている。 Among existing resins, polyimide has the highest level of heat resistance, chemical resistance, electrical insulation, and radiation resistance. It is used.
中でもポリイミドの用途として、近年第５世代通信システムの普及に伴い、フレキシブルプリント配線板（ＦＰＣ）に注目が集まっている。ＦＰＣの基板材料であるポリイミドは、実装工程において様々な熱サイクルに曝されて寸法変化が生じるため、これを抑えるために、ポリイミドの耐熱性が高い（例えば、ガラス転移温度（Ｔｇ）が工程温度よりも高い）こと、及び線熱膨張係数（ＣＴＥ）ができるだけ低い（例えば、銅箔のＣＴＥ（約２０ｐｐｍ／Ｋ）と同等かそれより低い）ことが望ましい。 Among them, flexible printed wiring boards (FPC) have attracted attention as an application of polyimide in recent years with the spread of fifth-generation communication systems. Polyimide, which is a substrate material for FPCs, is exposed to various thermal cycles during the mounting process, causing dimensional changes. ), and the coefficient of linear thermal expansion (CTE) should be as low as possible (eg, equal to or lower than the CTE of copper foil (about 20 ppm/K)).
このような高耐熱性かつ低ＣＴＥを有するポリイミドを与えるジアミンとして、下記式（８）で表されるジアミンが知られている（特許文献１）。 A diamine represented by the following formula (8) is known as a diamine that gives a polyimide having such high heat resistance and low CTE (Patent Document 1).
しかしながら、上記式（８）で表されるジアミンは溶媒溶解性が極めて乏しいため、均一系で重合を行うには加熱下に該ジアミンを完溶させ、酸二無水物と混合する必要があり、そのため、製造工程が煩雑になったり、生産効率が低下するといった問題が生じる場合がある。 However, since the diamine represented by the above formula (8) has extremely poor solvent solubility, it is necessary to completely dissolve the diamine under heating and mix it with an acid dianhydride in order to carry out homogeneous polymerization. As a result, problems such as the manufacturing process becoming complicated and the production efficiency decreasing may occur.
本発明は、上記式（８）で表されるジアミンと類似の構造を有し、且つ溶媒溶解性に優れる、新規なジアミンの提供を目的とする。 An object of the present invention is to provide a novel diamine which has a structure similar to that of the diamine represented by the formula (8) and has excellent solvent solubility.
本発明者らは、鋭意研究を重ねた結果、下記式（１）で表されるジアミンが優れた溶媒溶解性を示し、前記課題が解決可能であることを見出した。具体的には、本発明は以下の発明を含む。 As a result of intensive studies, the present inventors have found that the diamine represented by the following formula (1) exhibits excellent solvent solubility and can solve the above problems. Specifically, the present invention includes the following inventions.
〔１〕
下記式（１）：
[1]
Formula (1) below:
〔２〕
下記式（２）：
[2]
Formula (2) below:
〔３〕
下記式（２）：
[3]
Formula (2) below:
〔４〕
下記一般式（３）：
[4]
The following general formula (3):
で表される繰り返し単位を有するポリアミック酸。
Polyamic acid having a repeating unit represented by.
〔５〕
下記一般式（４）：
[5]
The following general formula (4):
で表される繰り返し単位を有するポリイミド。
Polyimide having a repeating unit represented by.
〔６〕
〔４〕に記載のポリアミック酸および溶媒を含有するポリアミック酸溶液。
[6]
A polyamic acid solution containing the polyamic acid according to [4] and a solvent.
〔７〕
〔４〕に記載のポリアミック酸を含有するフィルム。
[7]
A film containing the polyamic acid according to [4].
〔８〕
〔５〕に記載のポリイミドを含有するフィルム。
[8]
A film containing the polyimide according to [5].
〔９〕
〔５〕に記載のポリイミドを含有する層を有する積層体。
[9]
A laminate having a layer containing the polyimide according to [5].
上記した本発明のジアミン（上記式（１）で表されるジアミン）は、上記式（８）で表されるジアミンと類似の構造を有するにも拘わらず、優れた溶媒溶解性を有する。そのため、特に加熱を行わず室温（２５℃）付近でも均一系で反応を行うことが可能であり、ゆえに、室温（２５℃）付近でも十分に重合反応が進行し、また、オリゴマー化やゲル化を抑制して本発明のポリアミック酸（上記一般式（３）で表される繰り返し単位を有するポリアミック酸）の均一な溶液を得ることができる。 The diamine of the present invention described above (the diamine represented by the above formula (1)) has excellent solvent solubility in spite of having a structure similar to that of the diamine represented by the above formula (8). Therefore, it is possible to carry out the reaction in a homogeneous system even at around room temperature (25°C) without any particular heating. can be suppressed to obtain a uniform solution of the polyamic acid of the present invention (polyamic acid having a repeating unit represented by the general formula (3)).
また、本発明のジアミンより製造される本発明のポリイミド（上記一般式（４）で表される繰り返し単位を有するポリイミド）は、高Ｔｇかつ低ＣＴＥであるのみならず、低誘電特性（低誘電率、低誘電正接）にも優れる。近年の５Ｇ用途のＦＰＣ基板材料には、伝送損失（伝送ロス）低減の観点から低誘電特性（低誘電率、低誘電正接）を有することが求められていることから、本発明のポリイミドは、例えばＦＰＣ基板材料、特に高周波ＦＰＣ基板材料（例えば、フレキシブル銅張積層板やカバーレイフィルム等の積層体における樹脂基板等）として好適に使用することができる。 Further, the polyimide of the present invention (polyimide having a repeating unit represented by the general formula (4)) produced from the diamine of the present invention not only has a high Tg and a low CTE, but also has low dielectric properties (low dielectric (low dielectric loss tangent). FPC substrate materials for recent 5G applications are required to have low dielectric properties (low dielectric constant, low dielectric loss tangent) from the viewpoint of reducing transmission loss (transmission loss). Therefore, the polyimide of the present invention is For example, it can be suitably used as an FPC board material, particularly a high-frequency FPC board material (for example, a resin board in a laminate such as a flexible copper-clad laminate or a coverlay film).
本明細書において、数値範囲を「Ａ～Ｂ」で示す場合、Ａ以上Ｂ以下を意味する。 In this specification, when a numerical range is indicated by "A to B", it means A or more and B or less.
＜本発明のジアミン＞
本発明のジアミンは、上記式（１）で表される構造を有する。
<Diamine of the present invention>
The diamine of the present invention has a structure represented by the above formula (1).
本発明のジアミンは、例えば、ｔｅｒｔ－ブチルヒドロキノン又はその誘導体と、４－ニトロ安息香酸またはその誘導体とを反応させて上記式（２）で表されるジニトロ化合物を得（エステル化反応）、該ジニトロ化合物のニトロ基を還元する（アミノ化反応）方法により製造することができる。 The diamine of the present invention can be obtained, for example, by reacting tert-butylhydroquinone or a derivative thereof with 4-nitrobenzoic acid or a derivative thereof to obtain a dinitro compound represented by the above formula (2) (esterification reaction). It can be produced by a method of reducing the nitro group of a dinitro compound (amination reaction).
上記エステル化反応の方法としては、例えば、ｔｅｒｔ－ブチルヒドロキノンと４－ニトロ安息香酸類とを高温で直接脱水反応させる方法；ｔｅｒｔ－ブチルヒドロキノンと４－ニトロ安息香酸類とをＮ，Ｎ’－ジシクロヘキシルカルボジイミド等の脱水試薬を用いて脱水縮合させる方法；ｔｅｒｔ－ブチルヒドロキノンのジアセテート化体と４－ニトロ安息香酸類とを高温で反応させて脱酢酸してエステル化する方法（エステル交換法）；ｔｅｒｔ－ブチルヒドロキノンと４－ニトロ安息香酸ハライドとを脱酸剤の存在下で反応させる方法（酸ハライド法）；トシルクロリド／Ｎ，Ｎ－ジメチルホルムアミド／ピリジン混合物を用いて４－ニトロ安息香酸類のカルボキシル基を活性化しｔｅｒｔ－ブチルヒドロキノンと反応させる方法等が挙げられる。これらの方法の中でも、経済性、反応性の観点から酸ハライド法が好ましい。以下、酸ハライド法について詳述する。 Examples of the esterification method include a method of directly dehydrating tert-butylhydroquinone and 4-nitrobenzoic acids at high temperature; A method of dehydration condensation using a dehydrating reagent such as a method of reacting a diacetate of tert-butylhydroquinone with 4-nitrobenzoic acids at high temperature to deacetic acid and esterify (transesterification method); tert- Method of reacting butyl hydroquinone and 4-nitrobenzoic acid halide in the presence of a deacidifying agent (acid halide method); carboxyl group of 4-nitrobenzoic acid compound using tosyl chloride/N,N-dimethylformamide/pyridine mixture is activated and reacted with tert-butylhydroquinone. Among these methods, the acid halide method is preferred from the viewpoint of economy and reactivity. The acid halide method will be described in detail below.
上記酸ハライド法における４－ニトロ安息香酸ハライドとしては、例えば、４－ニトロ安息香酸クロリド、４－ニトロ安息香酸ブロミド、４－ニトロ安息香酸ヨージド等が挙げられる。これら４－ニトロ安息香酸ハライドの中でも、４－ニトロ安息香酸クロリドが好ましい。また、４－ニトロ安息香酸ハライドの使用量は、例えば、ｔｅｒｔ－ブチルヒドロキノン１モルに対して２モル～４モル、好ましくは２モル～３モルである。使用量が２モル以上であれば十分な反応速度を得られ、また、４モル以下であれば未反応の４－ニトロ安息香酸ハライドが低減でき、得られる本発明のジアミンの純度をより向上させることができる。 Examples of the 4-nitrobenzoic acid halide in the acid halide method include 4-nitrobenzoic acid chloride, 4-nitrobenzoic acid bromide, 4-nitrobenzoic acid iodide and the like. Among these 4-nitrobenzoic acid halides, 4-nitrobenzoic acid chloride is preferred. The amount of 4-nitrobenzoic acid halide to be used is, for example, 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of tert-butylhydroquinone. If the amount used is 2 mol or more, a sufficient reaction rate can be obtained, and if it is 4 mol or less, unreacted 4-nitrobenzoic acid halide can be reduced, and the purity of the obtained diamine of the present invention is further improved. be able to.
上記酸ハライド法における脱酸剤として、例えば、ピリジン、トリエチルアミン、Ｎ，Ｎ－ジメチルアニリン等の有機３級アミン類、プロピレンオキサイド、アリルグリシジルエーテル等のエポキシ類、炭酸カリウム、水酸化ナトリウム等の無機塩基等が挙げられる。これら脱酸剤は単独で用いてもよく、２種以上を併用してもよい。これら脱酸剤の中でも、安価かつ反応後の分離除去が容易であることからピリジンが好ましい。また、脱酸剤の使用量は、例えば、ｔｅｒｔ－ブチルヒドロキノン１モルに対して２モル～４モル、好ましくは２モル～３モルである。使用量が２モル以上であれば十分な反応速度が得られ、また、４モル以下であれば不純物の生成を抑制することができる。 Examples of deoxidizing agents in the acid halide method include organic tertiary amines such as pyridine, triethylamine and N,N-dimethylaniline; epoxies such as propylene oxide and allyl glycidyl ether; and inorganic compounds such as potassium carbonate and sodium hydroxide. A base etc. are mentioned. These deoxidizing agents may be used alone or in combination of two or more. Among these deoxidizing agents, pyridine is preferable because it is inexpensive and easy to separate and remove after the reaction. The deacidifying agent is used in an amount of, for example, 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of tert-butylhydroquinone. When the amount is 2 mol or more, a sufficient reaction rate can be obtained, and when it is 4 mol or less, the generation of impurities can be suppressed.
酸ハライド法は、通常溶媒の存在下に実施される。酸ハライド法で使用可能な溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、アセトフェノン等のケトン系溶媒；１，２－ジメトキシエタン、１，２－ジエトキシエタン、テトラヒドロフラン、ジブチルエーテル、ジエチルエーテル、１，４－ジオキサン、シクロペンチルメチルエーテル、ジグライム、トリグライム等のエーテル系溶媒；トルエン、キシレン等の芳香族炭化水素系溶媒；クロロベンゼン、ジクロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、バレロニトリル、イソバレロニトリル、ベンゾニトリル等のニトリル系溶媒；Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、１，３－ジメチル－２－イミダゾリジノン等のアミド系溶媒などが挙げられる。これら溶媒の中でも、入手性及び取扱性の点から、エーテル系溶媒、芳香族炭化水素系溶媒、ニトリル系溶媒が好ましい。これら溶媒は単独で用いてもよく、２種以上を併用してもよい。また、溶媒を使用する際の使用量は、例えば、ｔｅｒｔ－ブチルヒドロキノン１重量倍に対し１重量倍～３０重量倍、好ましくは１重量倍～５重量倍である。 The acid halide method is usually carried out in the presence of a solvent. Examples of solvents that can be used in the acid halide method include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and acetophenone; 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, Ether solvents such as dibutyl ether, diethyl ether, 1,4-dioxane, cyclopentyl methyl ether, diglyme and triglyme; aromatic hydrocarbon solvents such as toluene and xylene; halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene Solvent; nitrile solvents such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, and benzonitrile; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethyl Amide solvents such as acetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and the like are included. Among these solvents, ether-based solvents, aromatic hydrocarbon-based solvents, and nitrile-based solvents are preferred from the viewpoint of availability and handling. These solvents may be used alone or in combination of two or more. The amount of the solvent used is, for example, 1 to 30 times the weight, preferably 1 to 5 times the weight of tert-butylhydroquinone.
酸ハライド法は、例えば、－１０℃～１２０℃、好ましくは－５℃～１００℃、より好ましくは２０℃～９０℃で実施する。反応温度が１２０℃以下であれば、副生成物がより低減され、また、－１０℃以上であれば十分な反応速度が得られる。 The acid halide method is carried out at, for example, -10°C to 120°C, preferably -5°C to 100°C, more preferably 20°C to 90°C. If the reaction temperature is 120° C. or lower, by-products are further reduced, and if it is -10° C. or higher, a sufficient reaction rate can be obtained.
酸ハライド法は、例えば、撹拌下、４－ニトロ安息香酸ハライドと上記溶媒とを含む溶液に、別途調製したｔｅｒｔ－ブチルヒドロキノン、脱酸剤及び上記溶媒を含む溶液を、上記した温度範囲となるよう間欠的あるいは連続的に添加した後、上記した温度範囲にてさらに反応を継続する方法や、４－ニトロ安息香酸ハライド、ｔｅｒｔ－ブチルヒドロキノン及び上記溶媒を含む溶液に、脱酸剤もしくは脱酸剤と上記溶媒とを含む溶液を上記温度範囲となるよう間欠的あるいは連続的に添加した後、上記温度範囲でさらに反応を継続する方法等が挙げられる。 In the acid halide method, for example, a solution containing 4-nitrobenzoic acid halide and the above solvent is added to a solution containing 4-nitrobenzoic acid halide and the above solvent under stirring, and a solution containing separately prepared tert-butylhydroquinone, a deacidifying agent and the above solvent is added to the above temperature range. After intermittently or continuously adding the A method of intermittently or continuously adding a solution containing the agent and the solvent in the above temperature range and then further continuing the reaction in the above temperature range.
酸ハライド法実施後、得られた反応混合物は、そのまま後述するアミノ化反応に用いてもよく、慣用の精製方法（抽出、洗浄、吸着、水蒸気蒸留、晶析、カラム精製等）により精製してもよい。また、精製は一回のみ、もしくは複数回行ってもよい。 After carrying out the acid halide method, the resulting reaction mixture may be used as it is for the amination reaction described later, or may be purified by a conventional purification method (extraction, washing, adsorption, steam distillation, crystallization, column purification, etc.). good too. Further, purification may be performed only once or multiple times.
アミノ化反応の方法としては、例えば、上記式（２）で表されるジニトロ化合物を不活性な溶媒に溶解させ、水素雰囲気化、パラジウムや白金等の遷移金属原子を活性炭に担持させた触媒を用い還元する方法（接触還元法）等が挙げられる。 As a method for the amination reaction, for example, the dinitro compound represented by the above formula (2) is dissolved in an inert solvent, placed in a hydrogen atmosphere, and a catalyst in which a transition metal atom such as palladium or platinum is supported on activated carbon is used. and a reduction method (catalytic reduction method).
接触還元法における触媒としては、例えば、パラジウムや白金等の遷移金属原子を活性炭に担持させた触媒が挙げられ、この中でもパラジウムを活性炭に担持させた触媒（パラジウム／カーボン）又は白金を活性炭に担持させた触媒（白金／カーボン）が反応速度の観点から好ましい。これら触媒は、単独で用いてもよく、２種以上を併用してもよい。これら触媒の使用量は、例えば、触媒中の遷移金属原子の重量として、上記式（２）で表されるジニトロ化合物１重量倍に対し０．０００１重量倍～０．０１重量倍である。 Examples of the catalyst in the catalytic reduction method include catalysts in which a transition metal atom such as palladium or platinum is supported on activated carbon. The catalyst (platinum/carbon) obtained by the reaction is preferable from the viewpoint of the reaction rate. These catalysts may be used alone or in combination of two or more. The amount of these catalysts used is, for example, 0.0001 to 0.01 times the weight of the dinitro compound represented by the above formula (2) in terms of the weight of the transition metal atom in the catalyst.
接触還元法における溶媒としては、例えば、上記式（２）で表されるジニトロ化合物、あるいは生成物である上記式（１）で表されるジアミンと反応せず、且つ接触還元時に反応を受けないものであればよく、例えば、１，２－ジメトキシエタン、１，２－ジエトキシエタン、テトラヒドロフラン、ジブチルエーテル、ジエチルエーテル、１，４－ジオキサン、シクロペンチルメチルエーテル、ジグライム、トリグライム等のエーテル系溶媒；酢酸エチル、酢酸ブチル、酢酸イソブチル、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、ε－カプロラクトン、α－メチル－γ－ブチロラクトン等のエステル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、アセトフェノン等のケトン系溶媒；クロロホルム、ジクロロメタン、クロロホルム、１，２－ジクロロエタン等のハロゲン化アルキル系溶媒；トルエン、キシレン等の芳香族炭化水素系溶媒；Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、１，３－ジメチル－２－イミダゾリジノン等のアミド系溶媒；ジメチルスルホキシド、スルホラン等のスルホン系溶媒；ピコリン；ピリジン等が挙げられる。これら溶媒の中でも、アミド系溶媒が好ましい。これら溶媒は単独で用いてもよく、２種以上を併用してもよい。これら溶媒の使用量としては、例えば、上記式（２）で表されるジニトロ化合物１重量倍に対し２～１０重量倍である。 As a solvent in the catalytic reduction method, for example, a solvent that does not react with the dinitro compound represented by the above formula (2) or the diamine represented by the above formula (1) that is the product and does not undergo a reaction during the catalytic reduction Ether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, dibutyl ether, diethyl ether, 1,4-dioxane, cyclopentylmethyl ether, diglyme, and triglyme; Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; acetone, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ketone, diisobutyl ketone, cyclohexanone and acetophenone; Halogenated alkyl solvents such as chloroform, dichloromethane, chloroform and 1,2-dichloroethane; Aromatic hydrocarbon solvents such as toluene and xylene; N-methyl-2 - amide solvents such as pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone; sulfone solvents such as dimethylsulfoxide and sulfolane ; picoline; pyridine; Among these solvents, amide solvents are preferred. These solvents may be used alone or in combination of two or more. The amount of these solvents used is, for example, 2 to 10 times the weight of the dinitro compound represented by the above formula (2).
接触還元法は、例えば、２０℃～１６０℃、反応速度の向上及び不純物生成抑制の観点から好ましくは２０℃～１００℃で実施される。 The catalytic reduction method is carried out at, for example, 20° C. to 160° C., preferably 20° C. to 100° C. from the viewpoint of improving the reaction rate and suppressing the formation of impurities.
接触還元法を実施後、例えば、触媒を濾過により除去した後、得られた反応混合物を上記式（１）で表されるジアミンが溶解し難い溶媒（以下、目的物が溶解し難い溶媒を「貧溶媒」と称することがある）に滴下する方法等により、上記式（１）で表されるジアミンを分離することができる。こうして得られた上記式（１）で表されるジアミンは、このまま次工程で使用してもよいが、慣用の精製方法（抽出、洗浄、吸着、水蒸気蒸留、晶析、カラム精製など）により精製してもよい。また、精製は一回のみ、もしくは複数回行ってもよい。 After carrying out the catalytic reduction method, for example, after removing the catalyst by filtration, the resulting reaction mixture is treated with a solvent in which the diamine represented by the above formula (1) is difficult to dissolve (hereinafter, a solvent in which the target substance is difficult to dissolve is referred to as " The diamine represented by the above formula (1) can be separated by a method such as adding dropwise to a poor solvent. The diamine represented by the above formula (1) thus obtained may be used as it is in the next step, but is purified by a conventional purification method (extraction, washing, adsorption, steam distillation, crystallization, column purification, etc.). You may Further, purification may be performed only once or multiple times.
＜本発明のポリアミック酸及びその製造方法＞
本発明のポリアミック酸は、上記一般式（３）で表される繰り返し単位を有する。なお、上記一般式（３）において、構造単位Ａに結合した２つのカルボキシル基は便宜上シス位置として記載されているが、実際はシス位置とトランス位置とが混在したものである。
<Polyamic acid of the present invention and method for producing the same>
The polyamic acid of the present invention has repeating units represented by the general formula (3). In the above general formula (3), the two carboxyl groups bonded to the structural unit A are described as cis-positions for the sake of convenience, but actually, cis-positions and trans-positions are mixed.
上記一般式（３）の構造単位Ａは、４価の芳香族基または４価の脂肪族基を表す。なお、４価の芳香族基は芳香族テトラカルボン酸二無水物に由来し、４価の脂肪族基は脂肪族テトラカルボン酸に由来する。 Structural unit A in the general formula (3) represents a tetravalent aromatic group or a tetravalent aliphatic group. A tetravalent aromatic group is derived from an aromatic tetracarboxylic dianhydride, and a tetravalent aliphatic group is derived from an aliphatic tetracarboxylic acid.
上記一般式（３）における構造単位Ａとしては、下記式（５）～（７）で表される構造のうち少なくとも１つを含むことが好ましい。なお、＊は結合点を表す。 The structural unit A in general formula (3) above preferably contains at least one of the structures represented by the following formulas (5) to (7). In addition, * represents a connecting point.
本発明のポリアミック酸の分子量は、例えば、重量平均分子量で１万～５０万、好ましくは１万～３０万、より好ましくは２万～２０万である。ポリアミック酸の分子量が１万以上であれば、良好な力学特性を維持しやすい。またポリアミック酸の分子量が５０万以下であれば、合成する場合に分子量をコントロールしやすく、また適度な粘度の溶液が得られやすく取扱いが容易である場合が多い。なお、ポリアミック酸の分子量は、例えば、ＧＰＣ（ゲル浸透クロマトグラフィー）法等の常法により測定することができる。 The polyamic acid of the present invention has a weight average molecular weight of, for example, 10,000 to 500,000, preferably 10,000 to 300,000, and more preferably 20,000 to 200,000. If the polyamic acid has a molecular weight of 10,000 or more, it is easy to maintain good mechanical properties. Further, if the molecular weight of the polyamic acid is 500,000 or less, it is easy to control the molecular weight during synthesis, and in many cases, it is easy to obtain a solution with an appropriate viscosity and easy to handle. In addition, the molecular weight of polyamic acid can be measured by conventional methods, such as GPC (gel permeation chromatography) method, for example.
本発明のポリアミック酸は、例えば、上記式（１）で表されるジアミン（以下、「本発明のジアミン」と称することがある）と、必要に応じて本発明のジアミン以外の他のジアミン（以下、「他のジアミン」と称することがある。）とを溶媒（重合溶媒）に溶解後、酸二無水物粉末を添加し重合させる方法等により、重合溶媒の溶液（以下、「ポリアミック酸溶液」と称することもある）として得ることができる。本発明のジアミンは溶媒溶解性に優れることから、特に加熱を行わず室温（２５℃）付近でも均一系で反応を行うことが可能であり、ゆえに、室温（２５℃）付近でも十分に重合反応が進行し、また、オリゴマー化やゲル化を抑制して本発明のポリアミック酸の均一な溶液を得ることができる。そのため、重合させる際の温度として、好ましくは１０℃～３０℃である。 The polyamic acid of the present invention includes, for example, the diamine represented by the above formula (1) (hereinafter sometimes referred to as "the diamine of the present invention"), and optionally other diamines other than the diamine of the present invention ( hereinafter, may be referred to as "other diamines".) is dissolved in a solvent (polymerization solvent), and then a solution of the polymerization solvent (hereinafter referred to as "polyamic acid solution ”) can be obtained. Since the diamine of the present invention has excellent solvent solubility, it is possible to carry out the reaction in a homogeneous system even at around room temperature (25°C) without any particular heating. progresses, and oligomerization and gelation can be suppressed to obtain a uniform solution of the polyamic acid of the present invention. Therefore, the temperature for polymerization is preferably 10°C to 30°C.
他のジアミンとしては、例えば、芳香族ジアミン、脂肪族ジアミン、脂環式ジアミン等が挙げられる。より具体的には、例えば、１，４－ジアミノベンゼン、１，３－ジアミノベンゼン、２，４－ジアミノトルエン、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エーテル、３，４’－ジアミノジフェニルエーテル、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、３，７－ジアミノ－ジメチルジベンゾチオフェン－５，５－ジオキシド、４，４－ジアミノベンゾフェノン，３，３’－ジアミノベンゾフェノン，４，４’－ビス（４－アミノフェノル）スルフィド、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノベンズアニリド、１，３－ビス（４－アミノフェノキシ）プロパン、１，４－ビス（４－アミノフェノキシ）ブタン、１，５－ビス（４－アミノフェノキシ）ペンタン、１，３－ビス（４－アミノフェノキシ）－２，２－ジメチルプロパン、１，２－ビス［２－（４－アミノフェノキシ）エトキシ］エタン、９，９－ビス（４－アミノフェニル）フルオレン、１－（４－アミノフェニル）－２，３－ジヒドロ－１，３，３－トリメチル－１Ｈ－インデン－５－アミン、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、４，４’－ビス（３－アミノフェノキシ）ビフェニル、２，２－ビス（４－アミノフェノキシフェニル）プロパン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、３，３’－ジカルボキシ－４，４’－ジアミノジフェニルメタン、４，６－ジヒドロキシ－１，３－フェニレンジアミン、３，３’－ジヒドロキシ－４，４’－ジアミノビフェニル、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）－ヘキサフルオロプロパン、３，３’，４，４’－テトラアミノビフェニル、１，６－ジアミノヘキサン、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、１－アミノ－３－アミノメチル－３，５，５－トリメチルシクロヘキサン、４，４’－メチレンビス（４－シクロヘキシルアミン）、１，４－ジアミノシクロヘキサン、ビシクロ［２．２．１］ヘプタンビス（メチルアミン）、トリシクロ［３．３．１．１３．７］デカン－１，３－ジアミン、４－アミノ安息香酸－４－アミノフェニルエステル、２－（４－アミノフェニル）－５－アミノベンゾオキサゾール、９，９－ビス［４－（４－アミノフェノキシ）フェニル］フルオレン、２，２’－ビス（３－スルホプロポキシ）－４，４’－ジアミノビフェニル、４，４’－ビス（４－アミノフェノキシ）ビフェニル－３，３’－ジスルホン酸等が挙げられる。これら他のジアミンは、１種又は２種以上併用してもよい。他のジアミンを併用する場合、全ジアミン中の他のジアミンの使用量は、例えば、９０重量％以下、好ましくは７０重量％以下である。 Other diamines include, for example, aromatic diamines, aliphatic diamines, alicyclic diamines, and the like. More specifically, for example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diamino biphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis(4-aminophenol)sulfide, 4,4′ -diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy) ) pentane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl ) fluorene, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1,4-bis(4-aminophenoxy)benzene, 1,3 -bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl , 2,2-bis(4-aminophenoxyphenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4 -(4-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3'-dihydroxy-4 ,4′-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 3,3′,4,4′-tetraaminobiphenyl, 1,6-diaminohexane, 1, 3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4′-methylenebis(4- cyclohexylamine), 1,4-diaminocyclohexane, bicyclo[2.2.1]heptanebis(methylamine), tricyclo[3.3.1.13.7]decane-1,3-diamine, 4-aminobenzoic acid -4-aminophenyl ester, 2-(4-aminophenyl)-5-aminobenzoxazole, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 2,2′-bis(3-sulfo propoxy)-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl-3,3'-disulfonic acid and the like. These other diamines may be used alone or in combination of two or more. When other diamines are used together, the amount of other diamines used in the total diamines is, for example, 90% by weight or less, preferably 70% by weight or less.
酸二無水物としては、例えば、無水ピロメリット酸、オキシジフタル酸二無水物、ビフェニル－３，４，３’，４’－テトラカルボン酸二無水物、ベンゾフェノン－３，４，３’，４’－テトラカルボン酸二無水物、ジフェニルスルホン－３，４，３’，４’－テトラカルボン酸二無水物、４，４’－（２，２－ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、ｍ－タ－フェニル－３，４，３’，４’－テトラカルボン酸二無水物、ｐ－タ－フェニル－３，４，３’，４’－テトラカルボン酸二無水物、シクロブタン－１，２，３，４－テトラカルボン酸二無水物、１－カルボキシメチル－２，３，５－シクロペンタントリカルボン酸－２，６：３，５－二酸無水物、シクロヘキサン－１，２，４，５－テトラカルボン酸二無水物、ブタン－１，２，３，４－テトラカルボン酸二無水物、４－フェニルエチニルフタル酸無水物、ナフタレン－１，４，５，８－テトラカルボン酸二無水物、ビス（１，３－ジオキソ－１，３－ジヒドロイソベンゾフラン－５－カルボン酸）１，４－フェニレン等が挙げられる。これら酸二無水物の中でも、上記一般式（３）における構造単位Ａの好ましい態様に対応する、無水ピロメリット酸、ビフェニル－３，４，３’，４’－テトラカルボン酸二無水物、ビス（１，３－ジオキソ－１，３－ジヒドロイソベンゾフラン－５－カルボン酸）１，４－フェニレンが好ましい。これら酸二無水物は、単独で用いてもよく、２種以上を併用してもよい。酸二無水物の使用量は、例えば、本発明のジアミン、及び他のジアミンを併用する場合は他のジアミンも含めた全ジアミン１モルに対し０．９モル～１．１モル、重合度をより高める観点から好ましくは０．９５モル～１．０５モルである。 Acid dianhydrides include, for example, pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3,4,3′,4′-tetracarboxylic dianhydride, benzophenone-3,4,3′,4′ -tetracarboxylic dianhydride, diphenylsulfone-3,4,3′,4′-tetracarboxylic dianhydride, 4,4′-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, m -ter-phenyl-3,4,3',4'-tetracarboxylic dianhydride, p-ter-phenyl-3,4,3',4'-tetracarboxylic dianhydride, cyclobutane-1,2 ,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6:3,5-dianhydride, cyclohexane-1,2,4,5 -tetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 4-phenylethynylphthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride , bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene and the like. Among these acid dianhydrides, pyromellitic anhydride, biphenyl-3,4,3′,4′-tetracarboxylic dianhydride, bis (1,3-Dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene is preferred. These acid dianhydrides may be used alone or in combination of two or more. The amount of the acid dianhydride used is, for example, when the diamine of the present invention and other diamines are used in combination, 0.9 mol to 1.1 mol with respect to 1 mol of all diamines including other diamines, and the degree of polymerization is It is preferably 0.95 mol to 1.05 mol from the viewpoint of further increasing.
重合溶媒としては、例えば、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、１，３－ジメチル－２－イミダゾリジノン等のアミド系溶媒；酢酸エチル、酢酸ブチル、酢酸イソブチル、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、ε－カプロラクトン、α－メチル－γ－ブチロラクトン等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒；トリエチレングリコール、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールメチルエーテルアセテート、２－メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、ジエチレングリコール等のグリコール系溶媒；フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、３－クロロフェノール、４－クロロフェノール等のフェノール系溶媒；１，２－ジメトキシエタン、１，２－ジエトキシエタン、テトラヒドロフラン、ジブチルエーテル、ジエチルエーテル、１，４－ジオキサン、シクロペンチルメチルエーテル、ジグライム、トリグライム等のエーテル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、アセトフェノン等のケトン系溶媒；トルエン、キシレン等の芳香族炭化水素系溶媒；クロロベンゼン、ジクロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；ジメチルスルホキシド、スルホラン等のスルホン系溶媒等が挙げられる。これら重合溶媒の中でも、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－ピロリドン等のアミド系溶媒が好ましい。これら重合溶媒は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the polymerization solvent include amides such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide and 1,3-dimethyl-2-imidazolidinone. solvent; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; ethylene carbonate, Carbonate solvents such as propylene carbonate; triethylene glycol, ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, glycol solvents such as diethylene glycol; phenol, o-cresol, m - Phenolic solvents such as cresol, p-cresol, 3-chlorophenol, 4-chlorophenol; 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, dibutyl ether, diethyl ether, 1,4-dioxane Ether solvents such as , cyclopentyl methyl ether, diglyme, and triglyme; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and acetophenone; Aromatic hydrocarbon solvents such as toluene and xylene; Chlorobenzene, dichlorobenzene and halogenated aromatic hydrocarbon solvents; dimethyl sulfoxide, sulfolane and other sulfone solvents, and the like. Among these polymerization solvents, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-pyrrolidone are preferred. These polymerization solvents may be used alone or in combination of two or more.
重合溶媒の使用量としては、反応系中のモノマー成分（ジアミン＋酸二無水物）の合計濃度が通常５重量％～４０重量％、好ましくは１０重量％～３０重量％となる量である。５重量％～４０重量％のモノマー濃度範囲で重合を行うことにより、均一で高重合度のポリアミック酸溶液を得ることができる。なお、上記モノマー濃度範囲よりも低濃度で重合を行うと、ポリアミック酸の重合度が十分高くならず、最終的に得られるポリイミド膜が脆弱になる場合があり、上記モノマー濃度範囲よりも高濃度で重合を行うとモノマーが十分溶解しない場合や反応溶液が不均一になりゲル化する場合がある。上記の方法で得られた上記一般式（３）で表されるポリアミック酸溶液は通常、そのまま後述する方法で実施されるポリイミド化工程に使用する。 The amount of the polymerization solvent used is such that the total concentration of the monomer components (diamine+acid dianhydride) in the reaction system is usually 5% to 40% by weight, preferably 10% to 30% by weight. A uniform polyamic acid solution with a high degree of polymerization can be obtained by carrying out the polymerization in the monomer concentration range of 5% by weight to 40% by weight. If polymerization is performed at a concentration lower than the above monomer concentration range, the degree of polymerization of the polyamic acid may not be sufficiently high, and the finally obtained polyimide film may become fragile. If the polymerization is carried out in , the monomer may not dissolve sufficiently or the reaction solution may become non-uniform and gel. The polyamic acid solution represented by the general formula (3) obtained by the above method is usually used as it is in the polyimidation step carried out by the method described later.
＜本発明のポリイミド及びその製造方法＞
本発明のポリイミドは上記一般式（４）で表される繰り返し単位を有する。なお、上記一般式（４）における構造単位Ａは、上記一般式（３）における構造単位Ａと同じであり、好ましい態様についても同じである。
<Polyimide of the present invention and its production method>
The polyimide of the present invention has a repeating unit represented by the general formula (4). The structural unit A in the general formula (4) is the same as the structural unit A in the general formula (3), and preferred embodiments are also the same.
本発明のポリイミドは、上記の方法で得られた本発明のポリアミック酸を脱水閉環反応（イミド化反応）することで製造することができる。イミド化反応の方法としては、例えば、熱イミド化法や化学イミド化法が挙げられる。まず、熱イミド化法について詳述する。 The polyimide of the present invention can be produced by subjecting the polyamic acid of the present invention obtained by the above method to a dehydration ring closure reaction (imidization reaction). The imidization reaction method includes, for example, a thermal imidization method and a chemical imidization method. First, the thermal imidization method will be described in detail.
熱イミド化法としては、例えば、上記の方法で得られた本発明のポリアミック酸溶液をガラス板上に流延し、真空中、あるいは窒素等の不活性ガス中、又は空気中で加熱を行う方法等が挙げられる。より具体的には、例えば、本発明のポリアミック酸溶液をガラス板上に流延し、これをオーブン中で５０℃～１９０℃、好ましくは１００℃～１８０℃で加熱して乾燥させることでポリアミック酸フィルム（薄膜）とし、更に、２００℃～４００℃、好ましくは２３０℃～３５０℃で加熱することでイミド化反応が進行し、ポリイミドフィルム（薄膜）が得られる。なお、イミド化反応は、真空中あるいは不活性ガス中で行うことが好ましい。 As a thermal imidization method, for example, the polyamic acid solution of the present invention obtained by the above method is cast on a glass plate and heated in vacuum, in an inert gas such as nitrogen, or in the air. methods and the like. More specifically, for example, the polyamic acid solution of the present invention is cast on a glass plate and dried by heating in an oven at 50° C. to 190° C., preferably 100° C. to 180° C. to obtain polyamic acid. By forming an acid film (thin film) and further heating at 200° C. to 400° C., preferably 230° C. to 350° C., the imidization reaction proceeds to obtain a polyimide film (thin film). Incidentally, the imidization reaction is preferably carried out in vacuum or in an inert gas.
続いて、化学イミド化法について詳述する。化学イミド化法としては、例えば、上記の方法で得られた本発明のポリアミック酸を、溶液中で、有機酸の無水物および塩基存在下に脱水閉環反応させる方法が挙げられる。より具体的には、例えば、ポリアミック酸溶液に必要に応じて、更に溶媒を加えて撹拌し易い適度な溶液粘度に調整し、撹拌しながら、そこに有機酸の無水物と塩基とからなる脱水閉環剤（化学イミド化剤）を添加し、０℃～１００℃、好ましくは１０℃～５０℃で１時間～７２時間撹拌することで、イミド化反応が進行し、ポリイミドが得られる。使用可能な溶媒としては、例えば、ポリアミック酸の重合溶媒と同じものが挙げられ、好ましい態様についても同じである。使用可能な有機酸の無水物としては、例えば、無水酢酸、無水プロピオン酸等が挙げられ、中でも、取り扱いや分離のし易さから無水酢酸が好ましい。また、塩基としては、例えば、ピリジン、トリエチルアミン、キノリン等の３級アミン等が挙げられ、中でも、取り扱いや分離のし易さからピリジンが好ましい。有機酸の無水物の使用量は、ポリアミック酸の理論脱水量１モルに対し、通常１モル～１０モル、好ましくは２モル～５モルである。また塩基の使用量は、有機酸の無水物１モルに対し、通常０．１モル～２モル、好ましくは０．２モル～１モルである。 Next, the chemical imidization method will be described in detail. The chemical imidization method includes, for example, a method of subjecting the polyamic acid of the present invention obtained by the above method to a dehydration ring closure reaction in a solution in the presence of an anhydride of an organic acid and a base. More specifically, for example, if necessary, a solvent is added to the polyamic acid solution to adjust the solution viscosity to an appropriate level that is easy to stir. By adding a ring-closing agent (chemical imidizing agent) and stirring at 0° C. to 100° C., preferably 10° C. to 50° C. for 1 hour to 72 hours, the imidization reaction proceeds and a polyimide is obtained. Usable solvents include, for example, the same solvents as those used for the polymerization of polyamic acid, and preferred embodiments are also the same. Usable anhydrides of organic acids include, for example, acetic anhydride, propionic anhydride, etc. Among them, acetic anhydride is preferable because of ease of handling and separation. Examples of the base include tertiary amines such as pyridine, triethylamine, and quinoline. Among them, pyridine is preferable because of ease of handling and separation. The amount of the anhydride of the organic acid to be used is generally 1 mol to 10 mol, preferably 2 mol to 5 mol, per 1 mol of the theoretical amount of dehydration of the polyamic acid. The amount of the base to be used is generally 0.1 mol-2 mol, preferably 0.2 mol-1 mol, per 1 mol of the organic acid anhydride.
上記化学イミド化法で得られた反応混合物には、未反応の塩基や有機酸の無水物、副生成物等（以下、これらをまとめて不純物ということがある。）が混入しているため、これらを除去してポリイミドを単離・精製してもよい。精製方法としては公知の方法が利用でき、例えば、イミド化反応後に得られた反応混合物を撹拌しながら大量の貧溶媒中に添加してポリイミドを析出させた後、ポリイミド粉末を回収して不純物が除去されるまで繰返し洗浄し、減圧乾燥して、ポリイミド粉末を得る方法等が適用できる。この時、使用できる貧溶媒としては、ポリイミドを析出させ、不純物を効率よく除去でき、乾燥し易い溶媒であれば良く、例えば、水；メタノール、エタノール、イソプロパノールなどのアルコール類等が挙げられ、また、これらは混合して用いてもよい。貧溶媒中に添加して析出させる際のポリイミド溶液の濃度は、高すぎると析出するポリイミドが粒塊となり、その粗大な粒子中に不純物が残留する場合や、得られたポリイミド粉末を溶媒に再溶解する際に長時間要する場合がある。一方、ポリイミド溶液の濃度を薄くし過ぎると、多量の貧溶媒が必要となり、廃溶剤処理による環境負荷増大や製造コスト高になる場合がある。したがって、貧溶媒中に添加する際のポリイミド溶液の濃度は、２０重量％以下、より好ましくは１０重量％以下である。この時使用する貧溶媒の量はポリイミド溶液と同量（重量基準）以上が好ましく、１．５重量倍～１０重量倍が好適である。得られたポリイミド粉末を回収し、残留溶媒を真空乾燥や熱風乾燥などで除去する。乾燥温度と時間は、ポリイミドが変質しない温度、時間であれば制限はなく、例えば、温度３０℃～１５０℃で３時間～２４時間乾燥させる。 Since the reaction mixture obtained by the chemical imidization method contains unreacted bases, organic acid anhydrides, by-products, etc. (hereinafter collectively referred to as impurities), Polyimide may be isolated and purified by removing these. As a purification method, a known method can be used, for example, the reaction mixture obtained after the imidization reaction is stirred and added to a large amount of poor solvent to precipitate polyimide, and then the polyimide powder is recovered to remove impurities. A method of obtaining polyimide powder by repeatedly washing until it is removed and drying under reduced pressure can be applied. At this time, the poor solvent that can be used may be any solvent that can precipitate polyimide, efficiently remove impurities, and is easy to dry. Examples include water; alcohols such as methanol, ethanol, and isopropanol. , these may be mixed and used. If the concentration of the polyimide solution when it is added to the poor solvent and precipitated is too high, the precipitated polyimide becomes grainy, and impurities may remain in the coarse particles, or the obtained polyimide powder may be recycled into the solvent. It may take a long time to dissolve. On the other hand, if the concentration of the polyimide solution is too low, a large amount of poor solvent is required, which may increase the environmental load and increase the production cost due to disposal of the waste solvent. Therefore, the concentration of the polyimide solution when added to the poor solvent is 20% by weight or less, more preferably 10% by weight or less. The amount of the poor solvent used at this time is preferably equal to or more than the polyimide solution (based on weight), preferably 1.5 to 10 times the weight. The obtained polyimide powder is recovered, and the residual solvent is removed by vacuum drying, hot air drying, or the like. The drying temperature and time are not limited as long as the temperature and time do not degrade the polyimide.
このようにして得られた上記一般式（４）で表されるポリイミド粉末をポリイミドフィルムとする場合、一旦上記一般式（４）で表されるポリイミド粉末を溶媒に溶解させポリイミド溶液とする必要がある。使用可能な溶媒としては、例えば、上記重合溶媒と同じ溶媒の他、ターペン、ミネラルスピリット、石油ナフサ系溶媒等が挙げられる。これら溶媒は単独で用いてもよく、２種以上併用してもよい。ポリイミド粉末の溶解方法は、空気中、または不活性ガス中で室温～溶媒の沸点以下の温度範囲で１時間～４８時間かけて溶解させ、ポリイミド溶液にすることができる。 When the polyimide powder represented by the general formula (4) thus obtained is used as a polyimide film, it is necessary to once dissolve the polyimide powder represented by the general formula (4) in a solvent to obtain a polyimide solution. be. Usable solvents include, for example, the same solvents as the above polymerization solvents, turpentine, mineral spirits, petroleum naphtha solvents, and the like. These solvents may be used alone or in combination of two or more. Polyimide powder can be dissolved in the air or in an inert gas at a temperature ranging from room temperature to the boiling point of the solvent for 1 hour to 48 hours to obtain a polyimide solution.
こうして得られたポリイミド溶液をガラス板上に流延し、真空中、あるいは窒素等の不活性ガス中、または空気中で加熱することによりポリイミドフィルム（薄膜）を得ることができる。例えば、オーブン中、通常２００℃～４００℃、好ましくは２５０℃～３５０℃で乾燥させることにより、ポリイミドフィルムを得ることができる。ポリイミドフィルム作製は、真空中あるいは不活性ガス中で行うことが好ましい。 A polyimide film (thin film) can be obtained by casting the polyimide solution thus obtained on a glass plate and heating in a vacuum, in an inert gas such as nitrogen, or in the air. For example, the polyimide film can be obtained by drying in an oven at usually 200°C to 400°C, preferably 250°C to 350°C. Polyimide film production is preferably carried out in a vacuum or in an inert gas.
化学イミド化反応は、基板上に形成されたポリアミック酸フィルムをピリジンやトリエチルアミン等の３級アミン存在下、無水酢酸等の脱水環化試薬を含有する溶液に浸漬することによって行うことも可能である。これにより、部分的またはほぼ完全にイミド化したポリイミドフィルムを作製することもでき、これを更に上記のように熱処理することでポリイミドフィルムが得られる。 The chemical imidization reaction can also be carried out by immersing the polyamic acid film formed on the substrate in a solution containing a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. . This can also produce a partially or almost completely imidized polyimide film, which is further heat-treated as described above to obtain a polyimide film.
上述した方法によって得られた上記一般式（４）で表されるポリイミドの分子量は、重量平均分子量で１万～５０万であることが好ましく、１万～３０万であることがより好ましく、２万～２０万であることがさらに好ましい。ポリイミドの分子量が１万以上であれば、成型可能であり、また良好な力学特性を維持しやすい。またポリイミドの分子量が５０万以下であれば、合成する場合に分子量をコントロールしやすく、また適度な粘度の溶液が得られやすく取扱いが容易である場合が多い。なお、ポリイミドの分子量は、例えば、ＧＰＣ法等の常法により測定することができる。 The molecular weight of the polyimide represented by the general formula (4) obtained by the above-described method is preferably 10,000 to 500,000, more preferably 10,000 to 300,000 in terms of weight average molecular weight. It is more preferably 10,000 to 200,000. If the polyimide has a molecular weight of 10,000 or more, it can be molded and easily maintains good mechanical properties. Further, if the molecular weight of the polyimide is 500,000 or less, it is easy to control the molecular weight during synthesis, and in many cases, it is easy to obtain a solution with an appropriate viscosity, which is easy to handle. In addition, the molecular weight of polyimide can be measured by conventional methods, such as GPC method, for example.
以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。また、各実施例・比較例で示した値は下記分析方法により分析した値である。 Examples of the present invention are shown below, but the present invention is not limited to these. Further, the values shown in each example and comparative example are values analyzed by the following analysis method.
［ＨＰＬＣ純度］
次の測定条件でＨＰＬＣ測定を行ったときの面積百分率値を、実施例に記載している各化合物の純度とした。
＜液体クロマトグラフィー測定条件＞
装置：島津製作所（株）製ＬＣ－２０ＡＤ
カラム：Ｌ－ｃｏｌｕｍｎ２ ＯＤＳ（３μｍ、４．６ｍｍφ×１５０ｍｍ）
移動相：Ａ液＝５０％アセトニトリル水（０．１体積％ギ酸添加）
Ｂ液＝アセトニトリル（０．１体積％ギ酸添加）
移動相グラジエント：Ｂ液濃度：５０％（０分）→１００％（１５分後）→１００％（２５分後）
流量：１．０ｍｌ／ｍｉｎ
カラム温度：４０℃、検出波長：ＵＶ２５４ｎｍ
[HPLC Purity]
The area percentage value when HPLC measurement was performed under the following measurement conditions was defined as the purity of each compound described in Examples.
<Liquid chromatography measurement conditions>
Apparatus: LC-20AD manufactured by Shimadzu Corporation
Column: L-column2 ODS (3 μm, 4.6 mmφ×150 mm)
Mobile phase: A solution = 50% acetonitrile water (0.1% by volume formic acid added)
B solution = acetonitrile (0.1% by volume formic acid added)
Mobile phase gradient: B solution concentration: 50% (0 minutes) → 100% (15 minutes later) → 100% (25 minutes later)
Flow rate: 1.0ml/min
Column temperature: 40°C, detection wavelength: UV254nm
［ＮＭＲ測定］
１Ｈ－ＮＭＲは、内部標準としてテトラメチルシランを用い、溶媒として重ジメチルスルホオキシド（ＤＭＳＯ）を用いて、ＪＥＯＬ－ＥＳＣ４００分光計によって記録した。
[NMR measurement]
1 H-NMR was recorded by a JEOL-ESC400 spectrometer using tetramethylsilane as internal standard and deuterated dimethylsulfoxide (DMSO) as solvent.
［ＬＣ－ＭＳ測定］
ＬＣ－ＭＳは次の測定条件で分離、質量分析し、目的物を同定した。
＜ＬＣ－ＭＳ測定条件＞
装置：（株）Ｗａｔｅｒｓ製「Ｘｅｖｏ Ｇ２ Ｑ－Ｔｏｆ」
カラム：ＣＥＬＩ製
Ｌ－ｃｏｌｕｍｎ２ ＯＤＳ（２μｍ、２．１ｍｍφ×１００ｍｍ）
カラム温度：４０℃
検出波長：ＵＶ ２２０－５５０ｎｍ
移動相：Ａ液＝１０ｍＭ酢酸アンモニウム水、Ｂ液＝アセトニトリル、
Ｃ液＝イソプロピルアルコール
移動相流量：０．４ｍｌ／ｍｉｎ
移動相グラジエント：Ａ／Ｂ／Ｃ＝４０／５０／１０→０／９０／１０（５．２１分）
検出法：Ｑ－Ｔｏｆ
イオン化法：ＥＳＩ（＋）（－）法
Ｉｏｎ Ｓｏｕｒｃｅ：電圧（＋）２．０ｋＶ、温度１２０℃
Ｓａｍｐｌｉｎｇ Ｃｏｎｅ ：電圧 ３０Ｖ、ガスフロー５０Ｌ／ｈ
Ｄｅｓｏｌｖａｔｉｏｎ Ｃａｓ：温度４００℃、ガスフロー１２００Ｌ／ｈ
[LC-MS measurement]
Separation and mass spectrometry were performed by LC-MS under the following measurement conditions to identify the target product.
<LC-MS measurement conditions>
Apparatus: "Xevo G2 Q-Tof" manufactured by Waters Co., Ltd.
Column: CELI L-column2 ODS (2 μm, 2.1 mmφ×100 mm)
Column temperature: 40°C
Detection wavelength: UV 220-550nm
Mobile phase: A solution = 10 mM ammonium acetate water, B solution = acetonitrile,
C liquid = isopropyl alcohol mobile phase flow rate: 0.4 ml / min
Mobile phase gradient: A/B/C = 40/50/10 → 0/90/10 (5.21 min)
Detection method: Q-Tof
Ionization method: ESI (+) (-) method Ion Source: voltage (+) 2.0 kV, temperature 120 ° C.
Sampling Cone: voltage 30V, gas flow 50L/h
Desolvation Cas: temperature 400°C, gas flow 1200L/h
［融点の測定］
ＴＧ－ＤＴＡ（（株）リガク製 ＴＧ－ＤＴＡ ８１２１／Ｓ）を用いて、窒素気流下、室温から５００℃まで１０℃／分で昇温し、融点（融解吸熱最大ピークにおけるピークトップ温度）を測定した。
[Measurement of melting point]
Using TG-DTA (TG-DTA 8121/S manufactured by Rigaku Co., Ltd.), the temperature was raised from room temperature to 500°C at a rate of 10°C/min under a nitrogen stream, and the melting point (the peak top temperature at the maximum melting endothermic peak) was measured. It was measured.
［溶媒溶解性］
ジアミン化合物１重量部と、下記する溶媒５重量部とを混合し、下記評価基準に基づき溶媒溶解性を評価した。
＜溶媒＞
・ＮＭＰ（Ｎ－メチルピロリドン）
・ＤＭＡｃ（Ｎ，Ｎ－ジメチルアセトアミド）
・ＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）
＜評価基準＞
○：室温で溶解する
△：加温すると溶解し、冷却しても結晶が析出しない
×：加温すると溶解するが、冷却すると結晶が析出する、あるいは、加温しても溶解しない
[Solvent solubility]
1 part by weight of a diamine compound and 5 parts by weight of a solvent described below were mixed, and solvent solubility was evaluated based on the following evaluation criteria.
<Solvent>
・NMP (N-methylpyrrolidone)
・DMAc (N,N-dimethylacetamide)
・DMF (N,N-dimethylformamide)
<Evaluation Criteria>
○: Dissolves at room temperature △: Dissolves when heated, crystals do not precipitate even when cooled ×: Dissolves when heated, but crystals precipitate when cooled, or does not dissolve even when heated
［５％重量減少温度の測定］
ＴＧ－ＤＴＡ（（株）リガク製 ＴＧ－ＤＴＡ ８１２１／Ｓ）を用いて、窒素気流下、室温から５００℃まで１０℃／分で昇温し、５％重量減少温度（Ｔｄ
５ ｉｎ Ｎ２、℃）を測定した。
[Measurement of 5% Weight Loss Temperature]
Using TG-DTA (TG-DTA 8121/S manufactured by Rigaku Co., Ltd.), the temperature was raised from room temperature to 500 ° C. at 10 ° C./min under a nitrogen stream to obtain a 5% weight loss temperature (T d 5 in N 2 , °C) were measured.
［ガラス転移温度の測定］
ＤＭＡ（ＳＩＩ ＤＭＳ－６１００（日立ハイテクサイエンス社製）を用いて、引張モード（昇温速度５℃／分、周波数１Ｈｚ、温度４０℃－３５０℃）で測定し、損失弾性率の極大値からガラス転移温度（Ｔｇ、℃）を求めた。
[Measurement of glass transition temperature]
Using DMA (SII DMS-6100 (manufactured by Hitachi High-Tech Science), measured in tensile mode (heating rate 5 ° C./min, frequency 1 Hz, temperature 40 ° C.-350 ° C.), the maximum value of the loss elastic modulus of the glass A transition temperature (Tg, °C) was determined.
［線熱膨張係数の測定］
５ｍｍ×１０ｍｍのサイズのポリイミドフィルムを熱機械分析装置（（株）日立ハイテクサイエンス製 ＴＭＡ－７１００）を用いて、荷重（静荷重）を膜厚（μｍ）×０．５ｇ重として、１５０℃まで加熱後４０℃まで冷却した。これを４５０℃まで５℃／ｍｉｎでセカンドランして得られたＴＭＡ曲線の、１００℃から２００℃までの傾きの平均を線熱膨張係数（ＣＴＥ、ｐｐｍ／Ｋ）とした。
[Measurement of linear thermal expansion coefficient]
Using a thermomechanical analyzer (TMA-7100, manufactured by Hitachi High-Tech Science Co., Ltd.), a polyimide film with a size of 5 mm × 10 mm is used, and the load (static load) is film thickness (μm) × 0.5 g weight, up to 150 ° C. After heating, it was cooled to 40°C. The linear thermal expansion coefficient (CTE, ppm/K) was defined as the average of the slopes from 100°C to 200°C of the TMA curve obtained by second-running this at 5°C/min up to 450°C.
［比誘電率および誘電正接の測定］
ベクトルネットワークアナライザ（Ａｎｒｉｔｓｕ社製、商品名；ＭＳ４６１２２Ｂ）及びＴＥモードの空洞共振器（ＡＥＴ社製）を用いて、周波数１０ＧＨｚにおけるポリイミドフィルムの比誘電率および誘電正接を測定した。なお、測定に使用した材料は、温度：２４℃～２６℃、相対湿度：２５％未満の条件下で、２４時間放置したものである。
[Measurement of dielectric constant and dielectric loss tangent]
Using a vector network analyzer (manufactured by Anritsu, trade name: MS46122B) and a TE mode cavity resonator (manufactured by AET), the dielectric constant and dielectric loss tangent of the polyimide film at a frequency of 10 GHz were measured. The materials used for the measurement were left for 24 hours under conditions of temperature: 24° C. to 26° C. and relative humidity: less than 25%.
［実施例１］（上記式（２）で表されるジニトロ化合物の製造例）
攪拌機、温度計及び還流冷却管を備えた四つ口フラスコに４－ニトロ安息香酸クロリド２４５．６２ｇ（１．３２ｍｏｌ）、アセトニトリル４００ｇを仕込み、攪拌しながら０℃まで冷却した。その後、攪拌しながらｔｅｒｔ－ブチルヒドロキノン１００．０１ｇ（０．６０ｍｏｌ）、アセトニトリル４００．００ｇ、ピリジン１０４．７１ｇ（１．３２ｍｏｌ）を混合溶解したものを０℃～１５℃で２０分かけて滴下した。その後２０℃まで昇温し、反応温度を２０℃～２５℃に保ちながら１５時間攪拌した。反応終了後、析出していた結晶を濾過、乾燥することにより、上記式（２）で表されるジニトロ化合物の白色粉末２７５．２８ｇ（ＨＰＬＣ純度９８．２８％、有姿収率９８．５１％）を得た。１Ｈ－ＮＭＲのスペクトル値を下記すると共に、図１に測定チャートを示す。
[Example 1] (Production example of the dinitro compound represented by the above formula (2))
A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 245.62 g (1.32 mol) of 4-nitrobenzoyl chloride and 400 g of acetonitrile, and cooled to 0° C. while stirring. Then, while stirring, 100.01 g (0.60 mol) of tert-butylhydroquinone, 400.00 g of acetonitrile, and 104.71 g (1.32 mol) of pyridine were mixed and dissolved and added dropwise at 0° C. to 15° C. over 20 minutes. . After that, the temperature was raised to 20°C, and the mixture was stirred for 15 hours while maintaining the reaction temperature between 20°C and 25°C. After completion of the reaction, the precipitated crystals were filtered and dried to give 275.28 g of a white powder of the dinitro compound represented by the above formula (2) (HPLC purity 98.28%, physical yield 98.51%). ). The spectral values of 1 H-NMR are shown below, and the measurement chart is shown in FIG.
［１Ｈ－ＮＭＲ（ジメチルスルホキシド－ｄ６）］
δ（ｐｐｍ）＝８．４７－８．３７ｐｐｍ（８Ｈ、ｍ）、７．４２－７．３９（２Ｈ、ｍ）、７．３３（１Ｈ、ｄｄ）、１．３２（９Ｈ、ｓ）。
[ 1 H-NMR (dimethylsulfoxide-d6)]
δ (ppm) = 8.47-8.37 ppm (8H, m), 7.42-7.39 (2H, m), 7.33 (1H, dd), 1.32 (9H, s).
［実施例２］（上記式（１）で表されるジアミンの製造例）
水素導入管を有する四つ口フラスコに実施例１で得られた式（２）で表されるジニトロ化合物４０．０１ｇ（０．０９ｍｏｌ）、水を５０重量％含むパラジウム／カーボン粉末（パラジウム含量：乾燥重量換算で５重量％）０．８０ｇ及びＮ，Ｎ－ジメチルホルムアミド４００．０１ｇを仕込み、反応容器を水素で置換した。これを撹拌しながら８０℃まで昇温し、式（２）で表されるジニトロ化合物を溶解させた後、８０℃で２時間攪拌し反応させた。反応終了後、パラジウム／カーボン粉末を濾過により除去し、濾液を室温まで冷却した後、大量の水中に滴下することで結晶を析出させた。析出した結晶を濾別し、メタノールで洗浄した後、９０℃で６時間真空乾燥することで上記式（１）で表されるジアミンの灰色粉末３２．９９ｇ（ＨＰＬＣ純度９９．８１％、有姿収率９４．６８％）を得た。融点（ＴＧ－ＤＴＡ）は２９５．２℃であった。また、１Ｈ－ＮＭＲ及びＬＣ－ＭＳのスペクトル値を下記すると共に、図２及び３にそれぞれの測定チャートを示す。また、上記評価基準に従って溶媒溶解性を評価した結果を表１に示す。
[Example 2] (manufacturing example of the diamine represented by the above formula (1))
40.01 g (0.09 mol) of the dinitro compound represented by the formula (2) obtained in Example 1 and palladium/carbon powder containing 50% by weight of water (palladium content: 0.80 g (5% by weight in terms of dry weight) and 400.01 g of N,N-dimethylformamide were charged, and the reaction vessel was purged with hydrogen. The mixture was heated to 80° C. with stirring to dissolve the dinitro compound represented by the formula (2), and then stirred at 80° C. for 2 hours for reaction. After completion of the reaction, the palladium/carbon powder was removed by filtration, and the filtrate was cooled to room temperature and then dropped into a large amount of water to precipitate crystals. The precipitated crystals were collected by filtration, washed with methanol, and dried in vacuum at 90° C. for 6 hours to give 32.99 g of a gray powder of the diamine represented by the above formula (1) (HPLC purity 99.81%, physical form). Yield 94.68%) was obtained. The melting point (TG-DTA) was 295.2°C. In addition, 1 H-NMR and LC-MS spectrum values are shown below, and respective measurement charts are shown in FIGS. Table 1 shows the results of solvent solubility evaluation according to the evaluation criteria described above.
［１Ｈ－ＮＭＲ（ジメチルスルホキシド－ｄ６）］
δ（ｐｐｍ）＝７．８２－７．７８ｐｐｍ（４Ｈ、ｍ）、７．１４－７．０９（３Ｈ、ｍ）、６．６６－６．６２（４Ｈ、ｍ）、６．１９－６．１５（４Ｈ、ｍ）、１．２９（９Ｈ、ｓ）。
[ 1 H-NMR (dimethylsulfoxide-d6)]
δ (ppm) = 7.82-7.78 ppm (4H, m), 7.14-7.09 (3H, m), 6.66-6.62 (4H, m), 6.19-6. 15 (4H, m), 1.29 (9H, s).
［ＬＣ－ＭＳ］
マススペクトル値（［Ｍ＋Ｈ］＋）：４０５．１８２２
（上記式（１）で表されるジアミンの計算上の分子量（ＥＳＩ＋；［Ｃ２４Ｈ２４Ｎ２Ｏ４＋Ｈ］＋）：４０５．１８０９）。
[LC-MS]
Mass spectral value ([M+H] + ): 405.1822
(Calculated molecular weight of diamine represented by formula (1) above (ESI + ; [C 24 H 24 N 2 O 4 +H] + ): 405.1809).
［比較例１］（上記式（８）で表される化合物）
上記式（８）で表される化合物（ＨＰＬＣ純度：９９．６８％）について、上記評価基準に従って溶媒溶解性を評価した。結果を表１に示す。
[Comparative Example 1] (compound represented by the above formula (8))
The solvent solubility of the compound represented by the above formula (8) (HPLC purity: 99.68%) was evaluated according to the above evaluation criteria. Table 1 shows the results.
［参考例１］（下記式（９）で表される化合物）
下記式（９）で表される化合物（ＨＰＬＣ純度：９９．５１％）について、上記評価基準に従って溶媒溶解性を評価した。結果を表１に示す。
[Reference Example 1] (compound represented by the following formula (9))
Solvent solubility of the compound represented by the following formula (9) (HPLC purity: 99.51%) was evaluated according to the evaluation criteria described above. Table 1 shows the results.
［実施例３］（上記一般式（３）で表される繰り返し単位を有するポリアミック酸及び上記一般式（４）で表される繰り返し単位を有するポリイミドの製造例）
実施例２で得られた上記式（１）で表されるジアミン６．０８ｇ（１５．００ｍｍｏｌ）を脱水Ｎ－メチルピロリドン（以下、「ＮＭＰ」と称することがある）２４．４６ｇ中に溶解した。次いで、ビフェニル－３，４，３’，４’－テトラカルボン酸二無水物（以下「ＢＰＤＡ」と称することがある）４．４１ｇ（１５．００ｍｍｏｌ）をゆっくり加えた後（全溶質濃度：３０重量％）、室温で２４時間撹拌したところ、増粘して撹拌困難になったため、適宜脱水ＮＭＰを加えながら更に４８時間撹拌して上記一般式（３）で表される繰り返し単位を有するポリアミック酸の溶液を得た（最終溶質濃度：１８．５３重量％）。次いで、得られたポリアミック酸溶液をガラス板上に塗布した後、８０℃で３時間加熱してポリアミック酸フィルムを得、更にこれを２５０℃で１時間、３００℃で１時間加熱して熱イミド化を行った。その後、残留応力を取り除くためガラス基板から剥離して３１０℃で１時間加熱し、上記一般式（４）で表される繰り返し単位を有するポリイミドフィルムを得た。得られたポリイミドフィルムについて、ガラス転移温度、５％重量減少温度、線熱膨張係数、比誘電率及び誘電正接を測定した。測定結果を表２に示す。
[Example 3] (Production example of a polyamic acid having a repeating unit represented by the general formula (3) and a polyimide having a repeating unit represented by the general formula (4))
6.08 g (15.00 mmol) of the diamine represented by the formula (1) obtained in Example 2 was dissolved in 24.46 g of dehydrated N-methylpyrrolidone (hereinafter sometimes referred to as "NMP"). . Then, after slowly adding 4.41 g (15.00 mmol) of biphenyl-3,4,3′,4′-tetracarboxylic dianhydride (hereinafter sometimes referred to as “BPDA”) (total solute concentration: 30 %), and when stirred at room temperature for 24 hours, the viscosity increased and stirring became difficult. (final solute concentration: 18.53% by weight). Next, the resulting polyamic acid solution was applied onto a glass plate and heated at 80° C. for 3 hours to obtain a polyamic acid film, which was further heated at 250° C. for 1 hour and 300° C. for 1 hour to obtain a hot imide. changed. After that, in order to remove the residual stress, the film was separated from the glass substrate and heated at 310° C. for 1 hour to obtain a polyimide film having repeating units represented by the general formula (4). The obtained polyimide film was measured for glass transition temperature, 5% weight loss temperature, linear thermal expansion coefficient, dielectric constant and dielectric loss tangent. Table 2 shows the measurement results.
［参考例２］（上記式（８）で表されるジアミンとＢＰＤＡから得られるポリイミド）
上記式（８）で表されるジアミン１．０５ｇ（３．００ｍｍｏｌ）を脱水ＮＭＰ７．７１ｇ中に加え、室温にてしばらく撹拌を行ったが完溶しなかった。そこで、９５℃に加熱してジアミンを溶解し、次いで、９５℃加熱下にＢＰＤＡ０．８８ｇ（３．００ｍｍｏｌ）をゆっくり加えた後（全溶質濃度：３０重量％）、室温まで放冷して２時間反応させたところ、増粘して撹拌が困難になったため、脱水ＮＭＰを使用して１５．１５重量％まで希釈し、さらに撹拌を継続してポリアミック酸溶液を得た（ＢＰＤＡ添加後～ポリアミック酸を得るまで、合計７２時間撹拌を行った）。得られたポリアミック酸溶液をガラス板上に塗布した後、８０℃で３時間加熱してポリアミック酸フィルムとし、更にこれを２５０℃で１時間、３００℃で１時間加熱して熱イミド化を行った。その後、残留応力を取り除くためガラス基板から剥離して３１０℃で１時間加熱してポリイミドフィルムを得た。得られたポリイミドフィルムについて、ガラス転移温度、５％重量減少温度、線熱膨張係数、比誘電率及び誘電正接を測定した。測定結果を表２に示す。
[Reference Example 2] (Polyimide obtained from diamine represented by the above formula (8) and BPDA)
1.05 g (3.00 mmol) of the diamine represented by the above formula (8) was added to 7.71 g of dehydrated NMP and stirred at room temperature for a while, but did not dissolve completely. Therefore, the diamine was dissolved by heating to 95°C, and then 0.88 g (3.00 mmol) of BPDA was slowly added while heating to 95°C (total solute concentration: 30% by weight). When the reaction was allowed to proceed for some time, the viscosity increased and stirring became difficult, so dehydrated NMP was used to dilute the solution to 15.15% by weight, and stirring was continued to obtain a polyamic acid solution (after adding BPDA to polyamic acid Stirring was carried out for a total of 72 hours until the acid was obtained). After coating the obtained polyamic acid solution on a glass plate, it was heated at 80° C. for 3 hours to form a polyamic acid film, which was further heated at 250° C. for 1 hour and at 300° C. for 1 hour for thermal imidization. rice field. After that, in order to remove the residual stress, it was separated from the glass substrate and heated at 310° C. for 1 hour to obtain a polyimide film. The obtained polyimide film was measured for glass transition temperature, 5% weight loss temperature, linear thermal expansion coefficient, dielectric constant and dielectric loss tangent. Table 2 shows the measurement results.
［参考例３］（上記式（９）で表されるジアミンとＢＰＤＡから得られるポリイミド）
上記式（８）で表されるジアミンに変えて上記式（９）で表されるジアミン３．６２ｇ（１０．００ｍｍоｌ）を使用した以外は参考例２と同様にしてポリイミドフィルムを得た。得られたポリイミドフィルムについて、ガラス転移温度、５％重量減少温度、線熱膨張係数、比誘電率及び誘電正接を測定した。測定結果を表２に示す。
[Reference Example 3] (polyimide obtained from the diamine represented by the above formula (9) and BPDA)
A polyimide film was obtained in the same manner as in Reference Example 2 except that 3.62 g (10.00 mmol) of the diamine represented by the above formula (9) was used instead of the diamine represented by the above formula (8). The obtained polyimide film was measured for glass transition temperature, 5% weight loss temperature, linear thermal expansion coefficient, dielectric constant and dielectric loss tangent. Table 2 shows the measurement results.
［参考例４］（下記式（１０）で表されるジアミンとＢＰＤＡから得られるポリイミド）
上記式（８）で表されるジアミンに変えて上記式（１０）で表されるジアミン０．６９ｇ（１．５０ｍｍоｌ）を使用した以外は参考例２と同様にしてポリイミドフィルムを得た。得られたポリイミドフィルムについて、ガラス転移温度、５％重量減少温度、線熱膨張係数、比誘電率及び誘電正接を測定した。測定結果を表２に示す。
[Reference Example 4] (polyimide obtained from a diamine represented by the following formula (10) and BPDA)
A polyimide film was obtained in the same manner as in Reference Example 2, except that 0.69 g (1.50 mmol) of the diamine represented by the above formula (10) was used instead of the diamine represented by the above formula (8). The obtained polyimide film was measured for glass transition temperature, 5% weight loss temperature, linear thermal expansion coefficient, dielectric constant and dielectric loss tangent. Table 2 shows the measurement results.
Claims (9)
で表される繰り返し単位を有するポリアミック酸。 The following general formula (3):
Polyamic acid having a repeating unit represented by.
で表される繰り返し単位を有するポリイミド。 The following general formula (4):
Polyimide having a repeating unit represented by.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022070716 | 2022-04-22 | ||
| JP2022070716 | 2022-04-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP7320334B1 true JP7320334B1 (en) | 2023-08-03 |
| JP2023160742A JP2023160742A (en) | 2023-11-02 |
Family
ID=87469808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023046456A Active JP7320334B1 (en) | 2022-04-22 | 2023-03-23 | Novel diamine, method for producing the same, and polyamic acid and polyimide produced from the diamine |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7320334B1 (en) |
| TW (1) | TW202348597A (en) |
| WO (1) | WO2023203897A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255252A (en) | 2007-04-05 | 2008-10-23 | Asahi Kasei Corp | Polyesterimide precursor and polyesterimide |
| CN114989429A (en) | 2022-05-20 | 2022-09-02 | 广东鸿翔瑞材料科技有限公司 | Polyimide film, graphite sheet, corresponding preparation method and resin composition |
| WO2022239534A1 (en) | 2021-05-14 | 2022-11-17 | セイカ株式会社 | Meta-ester aromatic diamines, method for producing same, and polyimide having said meta-ester aromatic diamines as raw material |
-
2023
- 2023-03-06 WO PCT/JP2023/008307 patent/WO2023203897A1/en unknown
- 2023-03-14 TW TW112109390A patent/TW202348597A/en unknown
- 2023-03-23 JP JP2023046456A patent/JP7320334B1/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255252A (en) | 2007-04-05 | 2008-10-23 | Asahi Kasei Corp | Polyesterimide precursor and polyesterimide |
| WO2022239534A1 (en) | 2021-05-14 | 2022-11-17 | セイカ株式会社 | Meta-ester aromatic diamines, method for producing same, and polyimide having said meta-ester aromatic diamines as raw material |
| CN114989429A (en) | 2022-05-20 | 2022-09-02 | 广东鸿翔瑞材料科技有限公司 | Polyimide film, graphite sheet, corresponding preparation method and resin composition |
Non-Patent Citations (1)
| Title |
|---|
| HASEGAWA Masatoshi and HISHIKI Tomoaki，Poly(ester imide)s Possessing Low Coeffcients of Thermal Expansion and Low Water Absorption (V). Eff，Polymers，2020年04月08日，12, 859，doi:10.3390/polym12040859 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023160742A (en) | 2023-11-02 |
| TW202348597A (en) | 2023-12-16 |
| WO2023203897A1 (en) | 2023-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5727795B2 (en) | Ester group-containing tetracarboxylic dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing them | |
| JP6635506B2 (en) | Diamine having fluorene skeleton, polyamic acid, and polyimide | |
| KR100625504B1 (en) | Novel polyimide compositions and novel acid dianhydrides to be used therein | |
| TWI694989B (en) | Tetracarboxylic dianhydride having cyclic hydrocarbon skeleton and ester group | |
| JP2009286854A (en) | Polyesterimide precursor and polyesterimide | |
| JP4829913B2 (en) | Polyimide and method for producing the same | |
| JP7134584B2 (en) | Polyimide with fluorene skeleton | |
| JP2008163088A (en) | Ester group-containing alicyclic tetracarboxylic acid anhydride and method for producing the same | |
| JP7320334B1 (en) | Novel diamine, method for producing the same, and polyamic acid and polyimide produced from the diamine | |
| JPH08157597A (en) | Copolyimide and its production | |
| JP6793434B2 (en) | Tetracarboxylic dianhydride, polyamic acid and polyimide | |
| JP2008163090A (en) | Tetracarboxylic acid dianhydride, method for producing the same and polymer | |
| WO2016190170A1 (en) | Tetracarboxylic acid dianhydride having cyclic hydrocarbon skeleton and ester group, polyamic acid and polyimide | |
| WO2008056808A1 (en) | Polyimide, diamine compound and method for producing the same | |
| JP3339205B2 (en) | Method for producing polyimide copolymer | |
| JP2011173806A (en) | Phosphorus-containing diamine compound and flame-retardant polyimide | |
| JPH06345868A (en) | Polyimide and its production | |
| JP2724424B2 (en) | New polyimide polymer film | |
| JP2008163089A (en) | Copolymer containing at least alicyclic polyester imide unit and aromatic polyimide unit and polyimide film | |
| JP2019052098A (en) | Tetracarboxylic acid dianhydride, polyamide acid, polyimide and polyimide solution | |
| JPH02235842A (en) | Alicyclic tetracarboxylic acid and derivative thereof | |
| JP2729708B2 (en) | New polyimide polymer film | |
| JP2018070823A (en) | Polyimide having a fluorene skeleton | |
| WO2015151924A1 (en) | Acid dianhydride and use thereof | |
| JP3019704B2 (en) | Method for producing polyamic acid and method for producing polyimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230616 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20230616 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230721 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230721 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7320334 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |