CN104478932B - Phosphorous polyimides and manufacture method thereof - Google Patents
Phosphorous polyimides and manufacture method thereof Download PDFInfo
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- CN104478932B CN104478932B CN201410643564.7A CN201410643564A CN104478932B CN 104478932 B CN104478932 B CN 104478932B CN 201410643564 A CN201410643564 A CN 201410643564A CN 104478932 B CN104478932 B CN 104478932B
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- CN
- China
- Prior art keywords
- phosphorous
- polyimides
- formula
- tetracarboxylic dianhydride
- phenyl
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract description 102
- 229920001721 Polyimide Polymers 0.000 title abstract description 83
- 239000004642 Polyimide Substances 0.000 title abstract description 77
- 238000004519 manufacturing process Methods 0.000 title abstract description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 61
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 11
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000003252 repetitive Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 5
- -1 phosphorus compound Chemical class 0.000 description 58
- 229920005575 poly(amic acid) Polymers 0.000 description 55
- 239000000243 solution Substances 0.000 description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 35
- 229910052698 phosphorus Inorganic materials 0.000 description 31
- 239000011574 phosphorus Substances 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 239000002904 solvent Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 21
- 238000007792 addition Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 235000010290 biphenyl Nutrition 0.000 description 14
- 239000004305 biphenyl Substances 0.000 description 14
- 150000004985 diamines Chemical class 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N Benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical group 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N Anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- YFPJFKYCVYXDJK-UHFFFAOYSA-N oxo(diphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4,4'-Oxydianiline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 150000004984 aromatic diamines Chemical class 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 125000006159 dianhydride group Chemical group 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 230000000051 modifying Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000011068 load Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000006267 biphenyl group Chemical group 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000004816 dichlorobenzenes Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- UAKNFLCLKRYKFO-UHFFFAOYSA-N C#C.NC=1C=CC=CC1 Chemical group C#C.NC=1C=CC=CC1 UAKNFLCLKRYKFO-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N Diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N Triethylene glycol dimethyl ether Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N Trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive Effects 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-Methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N Diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000005712 crystallization Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-Aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- 229940018563 3-aminophenol Drugs 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N Diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- LJJQENSFXLXPIV-UHFFFAOYSA-N Fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920000539 Poly[1,4-benzenedicarbonyl-alt-bis(4-phenoxyphenyl)methanone] Polymers 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N Tolidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 125000004419 alkynylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005842 heteroatoms Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Inorganic materials [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- RXCOGDYOZQGGMK-UHFFFAOYSA-N (3,4-diaminophenyl)-phenylmethanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=CC=C1 RXCOGDYOZQGGMK-UHFFFAOYSA-N 0.000 description 1
- FUADXEJBHCKVBN-UHFFFAOYSA-N (3-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 FUADXEJBHCKVBN-UHFFFAOYSA-N 0.000 description 1
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N 1,3-Diaminopropane Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- HIYRIYOUSQLJHP-UHFFFAOYSA-N 3-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=C(N)C=C1 HIYRIYOUSQLJHP-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical class 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
- HFACYLZERDEVSX-UHFFFAOYSA-N Benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N Cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N Carbohydrazide Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LXCIHXPVYQKJAG-UHFFFAOYSA-N N-[aziridin-1-yl-(2-methylaziridin-1-yl)phosphoryl]-N-prop-2-enylprop-2-en-1-amine Chemical compound CC1CN1P(=O)(N(CC=C)CC=C)N1CC1 LXCIHXPVYQKJAG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N O-Phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 210000002356 Skeleton Anatomy 0.000 description 1
- IVGBGCPUDUTSHT-UHFFFAOYSA-N [3-(3-aminobenzoyl)phenyl]-(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(C=CC=2)C(=O)C=2C=C(N)C=CC=2)=C1 IVGBGCPUDUTSHT-UHFFFAOYSA-N 0.000 description 1
- UVXIFYUJZWURAR-UHFFFAOYSA-N [3-(4-aminobenzoyl)phenyl]-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(N)=CC=2)=C1 UVXIFYUJZWURAR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay method Methods 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical group [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- NHOWLEZFTHYCTP-UHFFFAOYSA-N benzylhydrazine Chemical compound NNCC1=CC=CC=C1 NHOWLEZFTHYCTP-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical class NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000004437 phosphorous atoms Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 239000003229 sclerosing agent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
The present invention provides has following logical formula (II) (R in formula1、R2And R3As described in specification and claims) the phosphorous polyimides of repetitive that represents, as the phosphorous tetracarboxylic dianhydride of its raw material, and the manufacture method of phosphorous polyimides.The phosphorous polyimides of the present invention plays excellent flame-retarding characteristic.
Description
The application is the patent of invention of entitled " phosphorous polyimides and the manufacture method thereof " of December in 2010 submission on the 3rd
The divisional application of application 201080054983.7.
Technical field
The present invention relates to a kind of phosphorous tetracarboxylic dianhydride, the phosphorous polyimides manufactured with it and manufacture method thereof.Enter
And, the invention still further relates to use various duplexers that these phosphorous polyimides or the polyamic acid as its precursor manufacture and
Use the circuit such as the flexible printing patch panel that these duplexers manufacture.
Background technology
Generally polyimides is excellent at aspects such as anti-flammability, thermostability, mechanical property, electrical characteristics, prints accordingly, as flexibility
The protecting film of the baseplate material of brush distributing board, distribution and semiconductor element, heat resistant adhesive, interlayer dielectic etc. and by extensively
General use.
In recent years, for meeting the demand of compactization of electric power, e-machine etc., it is desirable to for electric power, e-machine
Deng Kapton.But, along with the filming of polyimides, the anti-flammability of polyimides has the tendency of reduction.
It addition, along with the parts used in e-machine in recent years and element, the high performance of CPU, there is its thermal discharge and significantly increase
Add, mean temperature also rises in machine tendency, it is therefore desirable for higher flame-retarded technology.On the other hand, from the sight of environmental problem
From the point of view of Dian, when giving the anti-flammability required by electric power, electronic product, it is desirable to consider natural environment and the safety of human body
, the higher method of safety.
As the technology giving polyimides anti-flammability, it is proposed that by silicone-modified polyimides and magnesium hydroxide etc.
Metal hydrate mixing method (such as, referenced patent document 1).But, in the method, it is necessary to additionally by phosphoric acid class
Surfactant carries out surface process to magnesium hydroxide, and operation becomes complicated.Further, in the method, as poly-for basis
The diamine component of compound, it is recommended that intramolecular has the diamidogen of two or more hydroxyl, but such diamidogen may be not readily available.
It addition, propose by using the specific polyimide resin containing silicon unit and the specific ring containing P elements
Epoxy resins and manifest the method (such as, referenced patent document 2) of anti-flammability.In the method, phosphorus compound and epoxy resin are made
Reaction, can obtain object phosphorous epoxy resin, but in order to make it have the function as epoxy resin, preferably must react
To two epoxy radicals of residue, the higher limit of phosphorous rate only has 5 weight %.Have owing to having imported the polyimide resin of silicon unit
Inflammability, thus the anti-flammability enough for giving the polyimide resin composition obtained in the method, it is necessary to polyhybird is resistance to
Hot low epoxy resin.
It addition, as give resin combination anti-flammability method, it is known that have in resin combination add phosphatization close
The method (such as, non-patent literature 1) of thing.But, in order to manifest anti-flammability with existing known technology, need a large amount of interpolation
Phosphorus compound.
Prior art literature
Patent documentation:
Patent documentation 1: JP 2008-63459 publication
Patent documentation 2: JP 2009-29982 publication
Non-patent literature:
Non-patent literature 1: ノ Application Ha ロ ゲ Application system combustible material To I Ru burning skill (エ ヌ テ イ mono-エ
ス), p.28 (calendar year 2001 distribution)
Summary of the invention
The problem that invention is to be solved
The present invention provides a kind of phosphorous tetracarboxylic dianhydride, plays the phosphorous poly-of excellent flame characteristic with it for what raw material manufactured
Acid imide and manufacture method thereof.
Technological means
The present inventor etc. find the phosphorus compound with ad hoc structure and have the reaction of dianhydride of ad hoc structure and make
The lossless existing polyamides of phosphorous polyimides manufactured with the phosphorous tetracarboxylic dianhydride with ad hoc structure obtained by this reaction
The character of imines and have excellent flame retardancy further, completes the present invention.First embodiment of the invention relates to following logical
The phosphorous tetracarboxylic dianhydride that formula (I) represents,
[changing 1]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein R1And R2Each on phenyl ring extremely
A few hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each carbon atom on phenyl ring
Can be mutually with singly bound).
Second embodiment of the invention relates to having following logical formula (II) table with what these phosphorous tetracarboxylic dianhydrides manufactured
The phosphorous polyimides of the repetitive shown,
[changing 2]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein R1And R2Each on phenyl ring extremely
A few hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each carbon atom on phenyl ring
Can be mutually with singly bound, R3For divalent organic group).
Third embodiment of the invention relates to the phosphorous polyimides with the repetitive that following logical formula (II) represents
Manufacture method, it is characterised in that the phosphorous polyamic acid with the repetitive that following logical formula (III) represents is carried out heat
And/or chemistry closed loop,
[changing 3]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein R1And R2Each on phenyl ring extremely
A few hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each carbon atom on phenyl ring
Can be mutually with singly bound, R3For divalent organic group),
[changing 4]
(in formula, R1、R2And R3With above-mentioned synonym).
And then, the inventors discovered that by having in the presence of the phosphorus compound of ad hoc structure, to having benzophenone
The polyamic acid of skeleton carries out imidizate, can obtain phosphorous polyimides, thus complete the present invention.Therefore, the present invention
The 4th embodiment relate to the manufacture method of phosphorous polyimides, it is characterised in that the polyamides that following formula (I ') is represented
Amino acid,
[changing 5]
(in formula, R3For divalent organic group), in the presence of the phosphorus compound that following formula (1) represents, carry out acyl sub-
Amination,
[changing 6]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein R1And R2Each on phenyl ring extremely
A few hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each carbon atom on phenyl ring
Can be mutually with singly bound).
Invention effect
The phosphorous tetracarboxylic dianhydride of first embodiment of the invention can be used as having the phosphorous polyimides of anti-flammability
Raw material or as the sclerosing agent of epoxy resin, modifying agent.It addition, use containing of the anti-flammability that this phosphorous tetracarboxylic dianhydride manufactures
Phosphorus polyimides demonstrates the flame-retarding characteristic of excellence, can be used as having the heat resistant adhesive of anti-flammability, have the electricity of anti-flammability
The insulant of base board.
It addition, the manufacture method of the phosphorous polyimides of fourth embodiment of the invention, it is in the presence of phosphorus compound,
The polyamic acid with benzophenone skeletal is carried out the short-cut method of imidizate, is in polyimide backbone, to import phosphorus
The excellent method of compound.It addition, the phosphorous polyimides obtained by this manufacture method also shows that the flame-retarding characteristic of excellence,
Can be used as there is the heat resistant adhesive of anti-flammability, there is the insulant etc. of the circuit substrate of anti-flammability.
Accompanying drawing explanation
Fig. 1 represents that the compound obtained in embodiment 1 (leads in formula (I), R1And R2It is phenyl)1H-NMR schemes.
Fig. 2 represents that the compound obtained in embodiment 1 (leads in formula (I), R1And R2It is phenyl)13C-NMR schemes.
Fig. 3 represents that the compound obtained in embodiment 1 (leads in formula (I), R1And R2Be phenyl) FT-IR figure.
Detailed description of the invention
Hereinafter embodiment of the present invention are described in detail.
The most phosphorous tetracarboxylic dianhydride
First, containing the raw material as the phosphorous polyimides of the present invention of first embodiment of the invention (acid composition)
Phosphorus tetracarboxylic dianhydride and manufacture method thereof illustrate.
(phosphorous tetracarboxylic dianhydride and manufacture method thereof)
Phosphorous tetracarboxylic dianhydride represented by the logical formula (I) of the present invention can be by benzophenone tetracarboxylic dianhydride and following formula
(1) phosphorus compound represented reacts and obtains,
[changing 7]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein, R1And R2Each on phenyl ring
At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon on phenyl ring is former
Son can be mutually with singly bound).
As the concrete example of benzophenone tetracarboxylic dianhydride used herein, 3,3 ', 4 can be enumerated, 4 '-benzophenone four
Carboxylic acid dianhydride, 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride.
The phosphorus compound represented as formula (1), preferably R1And R2(wherein, at least one hydrogen on phenyl ring is former to be phenyl
Son can be substituted by the alkyl of carbon number 1-6 or alkoxyl) phosphorus compound, as object lesson, following formula (1a) can be enumerated
The diphenyl phosphine oxide (DPO) represented.
[changing 8]
Similarly, the phosphorus compound represented as formula (1), preferably R1And R2In one be phenyl, another is benzene oxygen
Base, on respective phenyl ring, with singly bound, (wherein, at least one hydrogen atom on phenyl ring can be by carbon number 1-mutually for a carbon atom
The alkyl of 6 or alkoxyl substitute) phosphorus compound, as concrete example, can enumerate that following formula (1b) represents 9,10-dihydro-
9-oxa--10-phospho hetero phenanthrene-10-oxide (HCA (registered trade mark)).
[changing 9]
By the reaction of the phosphorus compound that benzophenone tetracarboxylic dianhydride and formula (1) represent, can obtain the present invention's
The phosphorous tetracarboxylic dianhydride that logical formula (I) represents:
[changing 10]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein, R1And R2Each on phenyl ring
At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon on phenyl ring is former
Son can also be mutually with singly bound).As concrete example, following formula (Ia) can be enumerated:
[changing 11]
Or the phosphorous tetracarboxylic dianhydride represented by following formula (Ib),
[changing 12]
(in formula, R1' and R2' can be the same or different, for hydrogen, the alkyl of carbon number 1-6 or alkoxyl).
This reaction can heat 1 point-12 little at 40-250 DEG C at a temperature of preferably 50-200 DEG C, more preferably 70-180 DEG C
Time, preferably 5 points-6 hours, more preferably 10 points-3 hours and carry out.
In the reaction, it is possible to use solvent.The solvent used, as long as special to the solvent just nothing that reaction is inert
Limit, suitably can select according to desired reaction temperature.Can be used alone or two or more solvent is with arbitrary proportion
It is used in mixed way.It is, for example possible to use the such aromatic hydrocarbon of toluene, dimethylbenzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, dichloro-benzenes, trichloro-benzenes,
The such ether solvent of oxolane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether., DMF, N, N-dimethyl
Acetamide, METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) such aprotic polar solvent etc..Making of solvent
Consumption is 50-1000 weight % relative to benzophenone tetracarboxylic dianhydride, preferably 100-500 weight %.
After reaction terminates, thick product can be obtained by concentration of reaction solution.With polar solvent, such as acetonitrile, ethyl acetate,
The thick product of the such solvent clean of methyl iso-butyl ketone (MIBK) can be purified.Cleaned crystallization is filtered, decompression or
Under normal pressure 40-250 DEG C, make at a temperature of preferred 80-200 DEG C it be dried and obtain object.
The most phosphorous polyimides and manufacture method thereof
Then, to the second of the present invention and the 3rd embodiment phosphorous polyimides and manufacture method illustrate.
(phosphorous polyamic acid and manufacture method thereof)
For the manufacture of the phosphorous polyimides of the present invention, first, be manufactured as its precursor has following logical formula (III)
The phosphorous polyamic acid of the repetitive represented:
[changing 13]
(in formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein, R1And R2Each on phenyl ring
At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon on phenyl ring is former
Son can be mutually with singly bound, R3Organic group for bivalence.)
The manufacture of phosphorous polyamic acid can be by the phosphorous tetracarboxylic dianhydride that will obtain in said method and Shi H2N-R3-
NH2The diamine component represented known method polymerization is carried out.Generally, polyreaction is in a solvent in 5-80 weight %, excellent
Select and carry out under the solute concentration of 10-50 weight %.After reaction terminates, reaction solution can be directly as phosphorous polyamic acid solution
(varnish), continues to use in imidization reaction.Alternatively, it is also possible to phosphorous polyamic acid is separated from reaction solution, so
After be re-dissolved in suitable solvent, modulate phosphorous polyamic acid solution.
Formula H2N-R3-NH2The diamine component represented can be aromatic diamine, aliphatic diamine or ester ring type diamidogen, because of
This, as R3Example, monocyclic or the divalent group (example of condensation polycyclic formula aromatic compound of carbon number 6-14 can be enumerated
As, phenylene, sub indenyl, naphthylene, fluorenylidene), divalent group (such as, the carbon number 2-of the aliphatic compound of carbon number 2-12
Alkylidene, alkenylene or the alkynylene of 12) or divalent group (such as, the carbon number 3-10 of ester ring type compound of carbon number 3-10
Cycloalkylidene or sub-cycloalkenyl group), or two the above-mentioned divalent groups that can be the same or different are directly or by bridge joint group
(wherein, bridge joint group is selected from-O-,-CO-,-COO-,-OCO-,-SO2-、-S-、-CH2-、-C(CH3)2-and-C (CF3)2-) phase
The group that links mutually (such as, biphenyl-4,4 '-diyl, diphenyl ether-4,4 '-diyl, diphenyl ether-3,4 '-diyl, benzophenone-
4,4 '-diyl).These aromatic diamines, aliphatic diamine or ester ring type diamidogen can have more than one selected from carbon number 1-6's
Alkyl, thiazolinyl, alkynyl or alkoxyl or the substituent group of halogen atom.
As the example of aromatic diamine composition used herein, the diamidogen with an aromatic series base can be enumerated: right
Phenylenediamine, m-diaminobenzene., p-benzylamine, an amino-benzylamine, diaminotoluene class, diaminourea xylene, diaminourea naphthalenes,
Diaminoanthraquinone-class etc.；There is the diamidogen of two aromatic series bases: 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-diamino
Base biphenyl, o-tolidine, a tolidine, dianisidine, 4,4 '-MDA, 3,4 '-diaminourea hexichol first
Alkane, 3,3 '-MDA, 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether,
DDS, 3,4 '-DADPS, 3,3 '-DADPS, 4,4 '-diaminourea benzophenone, 3,4 '-
Diaminourea benzophenone, 3,3 '-diaminourea benzophenone, 3,4-diaminobenzophenone, 2,2-bis-(4-amino-benzene oxygen) propane, 2,
2-bis-(3-amino-benzene oxygen) propane, 2-(3-aminophenyl)-2-(4-aminophenyl) propane etc.；There are three aromatic series bases
Diamidogen: Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-two (3-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,
3-bis-(3-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-two (4-amino benzoyl) benzene, Isosorbide-5-Nitrae-two (3-amino benzoyl) benzene, 1,3-bis-
(4-amino benzoyl) benzene, 1,3-bis-(3-amino benzoyl) benzene, 9,9-bis-(4-aminophenyl) fluorenes etc.；Have four with
The diamidogen of upper aromatic series base: 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 4,4 '-two (4-amino-benzene oxygen) biphenyl,
4,4 '-two (3-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl]
Sulfone, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, 4,4 '-two (4-aminobenzene oxygen
Base) benzophenone, 4,4 '-two (3-amino-benzene oxygen) benzophenone, Isosorbide-5-Nitrae-two [4-(2-, 3-or 4-amino-benzene oxygen) benzene first
Acyl group) benzene, 1,3-bis-[4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] benzene, Isosorbide-5-Nitrae-two [3-(2-, 3-or 4-aminobenzene oxygen
Base) benzoyl] benzene, 1,3-bis-[3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] benzene, 4,4 '-two [4-(2-, 3-or 4-
Amino-benzene oxygen) benzoyl] diphenyl ether, 4,4 '-two [3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] diphenyl ether, 4,
4 '-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] biphenyl, 4,4 '-two [3-(2-, 3-or 4-amino-benzene oxygen) benzene
Formoxyl] biphenyl, 4,4 '-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] diphenyl sulphone (DPS), 4,4 '-two [3-(2-, 3-or
4-amino-benzene oxygen) benzoyl] diphenyl sulphone (DPS) etc..It addition, the hydrogen atom on the aromatic ring of these materials can also be by one
The substituent group of the above alkyl selected from carbon number 1-6, thiazolinyl, alkynyl or alkoxyl or halogen atom substitutes.If it is considered that obtain
Easiness, be specifically preferably used 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, Isosorbide-5-Nitrae-two (4-aminobenzene
Epoxide) benzene, Isosorbide-5-Nitrae-two (3-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene,
2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-aminobenzene oxygen
Base) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 9,9-bis-(4-aminobenzene
Base) fluorenes.
As aliphatic used herein or the example of ester ring type diamine component, can enumerate 1，2-diaminoethane, 1,2-third
Diamidogen, 1,3-propane diamine, Putriscine, 1,3-pentanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-is pungent
Diamidogen, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-hendecane diamidogen, 1,12-dodecamethylene diamine, 2-methyl isophthalic acid, 5-penta 2
Amine, 1,3-bis-(aminomethyl) hexamethylene, Isosorbide-5-Nitrae-two (aminomethyl) hexamethylene, 1,3-diamino-cyclohexane, Isosorbide-5-Nitrae-diaminourea hexamethylene
Alkane, 4,4 '-diamino-dicyclohexyl methane, isophorone diamine etc..In view of the easiness obtained, and specifically, it is preferable to use
1,6-hexamethylene diamine, 1,3-bis-(aminomethyl) hexamethylene, Isosorbide-5-Nitrae-two (aminomethyl) hexamethylene, Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-two
Amino bicyclic hexyl methane, isophorone diamine.
Above-mentioned diamine component can be used in mixed way alone or in any combination.And then, it is also possible to rub at diamine component 1-50
The siloxane diamine using following logical formula (IV) to represent in the range of your % carries out combined polymerization:
[changing 14]
(in formula, m is the mixed number of the integer of 0-20, R4Represent methyl, isopropyl, phenyl, vinyl, R5Represent carbon number 1-
The bivalent hydrocarbon radical of 7, such as trimethylene, tetramethylene, phenylene etc.).
And then, for adjusting molecular weight, mono-amine compound or dicarboxylic anhydride can be added.The mono-amine compound used is
Aniline, PAP, 3-amino-phenol, 4-aminobphenyl, 4-phenoxybenzamine, 3-aminobenzene acetylene, 4-aminobenzene acetylene
Deng, dicarboxylic anhydride is maleic anhydride, phthalic anhydride, 4-phenylene-ethynylene phthalic anhydride, 4-acetenyl O-phthalic
Anhydride, trimellitic acid etc..The addition of mono-amine compound or dicarboxylic anhydride is according to the molecular weight of the phosphorous polyimides of object
Difference and different, but several times of the 1.0-of the difference of the molal quantity of the whole dianhydrides usually used and diamine compound mole
Number, preferably 1.5-4.0 times.Add mono-amine compound when dianhydride is many, when diamine compound is many, add dicarboxylic anhydride.
Manufacture the solvent that the phosphorous polyamic acid of the present invention is used, as long as the most special to the solvent that reaction is inert
Limit, for example, it is possible to individually or use DMF, N,N-dimethylacetamide, N-methyl pyrrole with mixed style
Pyrrolidone, dimethyl sulfoxide, tetramethylurea, oxolane etc..Particularly preferably N,N-dimethylacetamide, N-crassitude
Ketone.Alternatively, it is also possible to by these solvents and toluene, dimethylbenzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, dichloro-benzenes, trichloro-benzenes, diethylene glycol two
Methyl ether, triethylene glycol dimethyl ether. equal solvent are used in mixed way with arbitrary proportion.It addition, these solvents also can be by separated phosphorous poly-
Use the when that amic acid re-dissolved being to modulate phosphorous polyamic acid solution.
The phosphorous polyamic acid with repetitive represented by logical formula (III) of the present invention and there is logical formula (II) institute table
The phosphorous polyimides of the repetitive shown, the phosphorous polyamide that the repetitive referring not only to only be represented by logical formula (III) is constituted
The phosphorous polyimides that acid and the repetitive only represented by logical formula (II) are constituted, also includes containing with the most described repetition list
Unit is the material of main composition unit.Therefore, in the purpose of phosphorous polyimides of the lossless present invention or containing as its precursor
In the reactive scope of phosphorus polyamic acid, when manufacturing phosphorous polyamic acid, can partly use represented by above-mentioned logical formula (I)
Phosphorous tetracarboxylic dianhydride beyond tetracarboxylic dianhydride.
As such tetracarboxylic dianhydride, can enumerate pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,
3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 4, the double O-phthalic acid dianhydride of 4 '-oxygen, 3,4 '-
The double O-phthalic acid dianhydride of oxygen, 3, the double O-phthalic acid dianhydride of 3 '-oxygen, 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-hexichol
Base sulfone tetracarboxylic dianhydride, 2,2-bis-(3,4-dicarboxyphenyi) propane dianhydride, 2,2-bis-(3,4-dicarboxyphenyi) HFC-236fa
Dianhydride, 1,2,7,8-naphthalene tetracarboxylic acid dianhydrides etc..In order to provide the phosphorous of excellent flame characteristic that have as the object of the invention to gather
Acid imide, in tetracarboxylic dianhydride's composition of use, logical phosphorous tetracarboxylic dianhydride represented by formula (I) be preferably used 30 moles of % with
On, more preferably use 50 moles of more than %.
And then, the manufacture of phosphorous polyamic acid can also save the separation of above-mentioned corresponding acid dianhydride, purge process.That is,
Can by comprise the phosphorus compound represented by benzophenone tetracarboxylic dianhydride and formula (1) in a solvent in 40-250 DEG C, excellent
Heating 1 point at 50-200 DEG C, more preferably 70-180 DEG C is selected to obtain to 3 hours for-12 hours, preferably 5 points-6 hours, more preferably 10 points
After the solution cooling of the phosphorous tetracarboxylic dianhydride arrived, add desired diamine compound (diamine compound is as previously mentioned) and must
Will time add N,N-dimethylacetamide, the such solvent of METHYLPYRROLIDONE, make solute concentration be 5-80 weight %,
More preferably 10-50 weight % is carried out.
(manufacture method of phosphorous polyimides)
By making the phosphorous polyamic acid with the repetitive that following logical formula (III) represents obtained as described above enter
Capable hot and/or chemical closed loop,
[changing 15]
(in formula, R1And R2Can be identical, it is also possible to different, for phenyl or phenoxy group, wherein, R1And R2Each on phenyl ring
At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon on phenyl ring is former
Son can be mutually with singly bound, R3For divalent organic group), can obtain the present invention has what following logical formula (II) represented
The phosphorous polyimides of repetitive,
[changing 16]
(in formula, R1、R2And R3With above-mentioned synonym.)
The phosphorous polyimides of the present invention can utilize known method to make phosphorous polyamide acid heat and/or chemistry closed loop
(that is, dehydration) manufactures.For example, it is possible at metal forming or polyethylene terephthalates such as glass plate, copper, aluminum or rustless steels
The resins such as ester (PET), PEN (PEN), polyphenylene sulfide (PPS), polyimides, silicones or fluororesin
Being coated with phosphorous polyamic acid solution on the base materials such as thin film makes its dried thickness be 0.1-250 μm, more preferably 1.0-100 μm,
At 40-500 DEG C, more preferably 70-350 DEG C, it is dried 1 point-5 hours, more preferably 3 points-3 hours, thus obtains phosphorous polyamides sub-
Amine.The polyimides obtained can be peeled off from base material and use as film morphology or directly as duplexer.
Furthermore it is possible to add toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichloro-benzenes, trichloro-benzenes in phosphorous polyamic acid solution
The solvent of such azeotrope with water, heats at 100-300 DEG C, more preferably 150-250 DEG C, will be along with imidizate institute
The water produced is discharged and is carried out hot-imide outside system, thus obtains phosphorous polyimides.At this point it is possible to use pyridine, first
The such nitrogen-containing heterocycle compound of yl pyridines, imidazoles or such three low-grade alkylamines of triethylamine etc..Or, interpolation acetic anhydride,
Trifluoroacetic anhydride, N, the such dehydrant of N-dicyclohexylcarbodiimide and pyridine, picoline, the such nitrogen heterocyclic ring of imidazoles
Compound or such three low-grade alkylamines of triethylamine etc., at 0-200 DEG C, dehydration carries out chemical imidization for 1-24 hour,
Thus obtaining phosphorous polyimides can also.The above-mentioned solution so completing heat or chemical imidization can be injected water,
The such single solvent of methanol, ethanol, isopropanol, acetone, toluene, dimethylbenzene or their mixed solution, separate out crystallization also
Filter, be dried, pulverize and obtain the form of powdery.The polyimides obtained, is used directly for injection moulding or compression forming.
It addition, as other purposes, it can be made to be dissolved in solvent, use as varnish, it is also possible to be coated in aforementioned substrates,
It is made to be dried to obtain film morphology.
The manufacture method of the most phosphorous polyimides
The manufacture method of polyimides phosphorous to fourth embodiment of the invention illustrates.
(manufacture method of polyamic acid)
For the manufacture of the phosphorous polyimides of the present invention, first it is manufactured as the polyamides that the formula (I ') of its raw material represents
Amino acid,
[changing 17]
(in formula, R3Represent the organic group of bivalence).
The polyamic acid that formula (I ') represents, can be by benzophenone tetracarboxylic dianhydride and formula H2N-R3-NH2Two represented
Amine component reacts and obtains.This manufacture method is not particularly limited, available known method the most in a solvent 5-80 weight %,
Carry out under the solute concentration of preferably 10-50 weight %.After reaction terminates, reaction solution can be directly as polyamic acid solution
(varnish) then uses in imidization reaction.Alternatively, it is also possible to make polyamic acid separate from reaction solution, the most molten
Solution, in suitable solvent, thus modulates phosphorous polyamic acid solution.
The solvent used in the manufacture of polyamic acid, as long as be just not particularly limited reacting inert solvent,
For example, it is possible to by DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, dimethyl sulfoxide, tetramethyl
Base urea, oxolane etc. use under independent or mixed style.Particularly preferably N,N-dimethylacetamide, N-methyl-2-pyrroles
Alkanone.Alternatively, it is also possible in these solvents with arbitrary proportion be used in mixed way toluene, dimethylbenzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, two
Chlorobenzene, trichloro-benzenes, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether. equal solvent.It addition, these solvents can also be separated in re-dissolved
Polyamic acid thus use when modulating polyamic acid solution.
As the object lesson of the benzophenone tetracarboxylic dianhydride wherein used, 3,3 ', 4 can be enumerated, 4 '-benzophenone
Tetracarboxylic dianhydride, 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride.
Formula H wherein used2N-R3-NH2The diamine component represented, can be aromatic diamine, aliphatic diamine or alicyclic ring
Formula diamidogen, accordingly, as the example of R3, can enumerate the monocyclic or the two of condensation polycyclic formula aromatic compound of carbon number 6-14
Valency group (such as, phenylene, sub indenyl, naphthylene, fluorenylidene), the divalent group (example of aliphatic compound of carbon number 2-12
As, the alkylidene of carbon number 2-12, alkenylene or alkynylene) or divalent group (such as, the carbon of ester ring type compound of carbon number 3-10
The cycloalkylidene of number 3-10 or sub-cycloalkenyl group) or two above-mentioned divalent groups can be the same or different directly or by
(wherein bridge joint group is selected from-O-,-CO-,-COO-,-OCO-,-SO for bridge joint group2-、-S-、-CH2-、-C(CH3)2-and-C
(CF3)2-) interconnected group (such as, biphenyl-4,4 '-diyl, diphenyl ether-4,4 '-diyl, diphenyl ether-3,4 '-diyl,
UVINUL MS 40,4 '-diyl).These aromatic diamines, aliphatic diamine or ester ring type diamidogen can have more than one and be selected from
The alkyl of carbon number 1-6, thiazolinyl, alkynyl or alkoxyl or the substituent group of halogen atom.
Aromatic diamine composition, aliphatic or the example of ester ring type diamine component, and at above-mentioned (the phosphorous polyimides of II.
And manufacture method) entry in, the example as aromatic diamine composition, aliphatic or ester ring type diamine component is specifically enumerated
Each diamine compound be identical.
Above-mentioned diamine component can also be used in mixed way alone or in any combination.And then, it is also possible at diamine component 1-
The siloxane diamine using following logical formula (IV) to represent in the range of 50 moles of % carries out combined polymerization,
[changing 18]
(in formula, m is the mixed number of the integer of 0-20, R4Represent methyl, isopropyl, phenyl, vinyl, R5Represent carbon number 1-
The divalent group of the hydrocarbon of 7, such as trimethylene, tetramethylene, phenylene etc.).
Utilize benzophenone tetracarboxylic dianhydride and the diamine component of the present invention react the polyamic acid obtained, refer not only to only by
The polyamic acid that the repetitive that formula (I ') represents is constituted, also included containing gathering of being main composition unit with this repetitive
Amic acid.Therefore, the lossless present invention phosphorous polyimides purpose or as polyamic acid reactive of its precursor
In the range of, when manufacturing polyamic acid, can partly use the tetracarboxylic dianhydride beyond benzophenone tetracarboxylic dianhydride.
As such tetracarboxylic dianhydride, can enumerate PMA, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,
3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 4, the double O-phthalic acid dianhydride of 4 '-oxygen, 3,4 '-
The double O-phthalic acid dianhydride of oxygen, 3, the double O-phthalic acid dianhydride of 3 '-oxygen, 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 2,2-bis-(3,
4-dicarboxyphenyi) propane dianhydride, 2,2-bis-(3,4-dicarboxyphenyi) hexafluoropropane dianhydride, 1,2,7,8-naphthalene tetracarboxylic acid dianhydrides
Deng.In order to provide as the object of the invention, the phosphorous polyimides with excellent flame characteristic, the tetracarboxylic dianhydride of use becomes
In Fen, the benzophenone tetracarboxylic dianhydride being preferably used at 30 moles of more than %, more preferably 50 moles more than %.
And then, for adjusting molecular weight, mono-amine compound or dicarboxylic anhydride can be added.The mono-amine compound used is
Aniline, PAP, 3-amino-phenol, 4-aminobphenyl, 4-phenoxybenzamine, 3-aminobenzene acetylene, 4-aminobenzene acetylene
Deng, dicarboxylic anhydride is maleic anhydride, phthalic anhydride, 4-phenylene-ethynylene phthalic anhydride, 4-acetenyl O-phthalic
Anhydride, trimellitic acid etc..The addition of mono-amine compound or dicarboxylic anhydride is according to the molecular weight of object polyimides not
Different together, but the molal quantity of several times of the 1.0-of the difference of the molal quantity of the whole dianhydrides usually used and diamine compound, excellent
Select 1.5-4.0 times.Add mono-amine compound when dianhydride is many, when diamine compound is many, add dicarboxylic anhydride.
(manufacture method of phosphorous polyimides)
The polyamic acid represented with following formula (I ') obtained as described above,
[changing 19]
(in formula, R3Represent divalent organic group), by carrying out in the presence of the phosphorus compound that following formula (1) represents
Imidizate and manufacture,
[changing 20]
(in formula, R1And R2Can be identical, it is also possible to different, for phenyl or phenoxy group, wherein, R1And R2Each on phenyl ring
At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon on phenyl ring is former
Son can be mutually with singly bound).In polyimide backbone, the phosphatization conjunction that formula (1) represents is imported while imidizate
Thing, manufactures phosphorous polyimides.
The phosphorus compound represented as formula (1), preferably R1And R2(wherein, at least one hydrogen on phenyl ring is former to be phenyl
Son can be substituted by the alkyl of carbon number 1-6 or alkoxyl), as its concrete example, the hexichol that following formula (1a) represents can be enumerated
Base phosphine oxide (DPO).
[changing 21]
Preferably, also, the phosphorus compound represented as formula (1), R1And R2One of them is phenyl, and another is benzene
Epoxide, with singly bound, (wherein, at least one hydrogen atom on phenyl ring can be by carbon mutually for a carbon atom on respective phenyl ring
The number alkyl of 1-6 or alkoxyl substitute), as concrete example, can enumerate that following formula (1b) represents 9,10-dihydro-9-oxy is miscellaneous-
10-phospho hetero phenanthrene-10-oxide (HCA (registered trade mark)).
[changing 22]
The usage amount of the phosphorus compound that formula (1) represents, the molal quantity of the benzophenone tetracarboxylic dianhydride for using
The molal quantity that 0.5-is several times, preferably 0.8-4.0 times mole.
In the presence of the phosphorus compound that formula (1) represents, the above-mentioned polyamic acid obtained is carried out imidizate,
Thus can manufacture phosphorous polyimides.For example, it is possible to add formula (1) table in the above-mentioned polyamic acid solution obtained
After the phosphorus compound shown, implement imidizate.Or, it is also possible to the addition of phosphorus compound that formula (1) represents in advance
In solvent, benzophenone tetracarboxylic dianhydride and diamine component manufacture polyamic acid as described above, be then carried out imidizate.
The phosphorus compound that formula (1) represents directly can be made an addition in polyamic acid solution or reaction dissolvent, but also may be used
With in the inert solvent of reaction, such as DMF, N,N-dimethylacetamide, N-methyl-2-pyrroles
Alkanone, dimethyl sulfoxide, tetramethylurea, oxolane, toluene, dimethylbenzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, dichloro-benzenes, trichloro-benzenes, two
In glyme, triethylene glycol dimethyl ether. equal solvent, after dissolving with the solute concentration of 5-90 weight %, preferred 10-80 weight %
Add.
Then, can the metal formings such as glass plate, copper, aluminum or rustless steel or polyethylene terephthalate (PET),
The bases such as resin film such as PEN (PEN), polyphenylene sulfide (PPS), polyimides, silicones or fluororesin
The mixed solution being coated with this polyamic acid and phosphorus compound on material makes dried thickness be 0.1-250 μm, more preferably 1.0-
100 μm, are dried 1 point-5 hours, more preferably 3 points-3 hours at 40-500 DEG C, more preferably 70-350 DEG C, thus obtain phosphorous poly-
Acid imide.The phosphorous polyimides obtained can be peeled off from base material and use as film morphology or directly as duplexer.
Furthermore it is possible in the mixed solution of this polyamic acid and phosphorus compound, add toluene, dimethylbenzene, ethylbenzene, chlorine
The solvent of the such azeotrope with water of benzene, dichloro-benzenes, trichloro-benzenes, heats at 100-300 DEG C, more preferably 150-250 DEG C, will companion
The water produced along with imidizate is discharged outside system and carries out hot-imide, thus obtains phosphorous polyimides.Now, it is possible to
To use pyridine, picoline, the such nitrogen-containing heterocycle compound of imidazoles or such three low-grade alkylamines of triethylamine etc..Or
Person, adds acetic anhydride, trifluoroacetic anhydride, N, the such dehydrant of N-dicyclohexylcarbodiimide and pyridine, picoline, imidazoles
Such nitrogen-containing heterocycle compound or such three low-grade alkylamines of triethylamine etc., be dehydrated 1-24 hour at 0-200 DEG C, and enter
Row chemical imidization, the most also can obtain phosphorous polyimides.Can will complete above-mentioned such heat or chemical imidization
Solution inject water, methanol, ethanol, isopropanol, acetone, toluene, the such single solution of dimethylbenzene or their mixing molten
Liquid, separates out crystallization and filters, and is dried, pulverizes and obtain powder form.The phosphorous polyimides obtained, is used directly for injection
Molding or compression forming.It addition, as other purposes, it is possible to so that it is dissolved in solvent, use as varnish, it is also possible to by it
It is coated in aforementioned substrates so that it is be dried to obtain film morphology.
The most various duplexers, circuit
The metal laminate of the present invention, such as can be by according to above-mentioned (the phosphorous polyimides of II. and manufacture method thereof) bar
Purpose record and the phosphorous polyamic acid solution that manufactures coat thickness 0.5-400 μm, the copper of more preferably 1.0-200 μm, aluminum or
On at least side of the metal formings such as rustless steel so that it is dried thickness is 0.1-250 μm, more preferably 1.0-100 μm, at 40-
It is dried 1 point at 500 DEG C, more preferably 70-350 DEG C-5 hours, more preferably 3 points-3 hours, thus manufactures.
Or, can be according to above-mentioned (the phosphorous polyimides of II. and manufacture method thereof) or (the phosphorous polyimides of III.
Manufacture method) record of entry and at least side of phosphorous Kapton that obtains, via epoxy resin, acrylic acid
The binding agents such as resinae, polyimide resin class, with thickness 0.5-400 μm, copper, aluminum or the rustless steel of more preferably 1.0-200 μm
Etc. metal foil laminated, under normal pressure or pressurized conditions, 100-500 DEG C, process at preferred 150-350 DEG C and manufacture.
The aromatic polymer duplexer of the present invention, for example, it is possible to will be according to above-mentioned (the phosphorous polyimides of II. and system thereof
Make method) record of entry and the phosphorous polyamic acid solution that manufactures, being coated on thickness is 0.5-400 μm, more preferably 1.0-200
The aromatic polyester of μm, polyphenylene sulfide, aromatic polyimide, PAEK, aromatic copolycarbonate, aromatic liquid-crystal are poly-
Making its dried thickness on the aromatic polymer such as compound or polybenzoxazole is 0.1-250 μm, more preferably 1.0-100 μm,
At 40-500 DEG C, more preferably 70-350 DEG C, it is dried 1 point-5 hours, more preferably 3 points-3 hours, manufactures therefrom.
It addition, be 0.5-400 μm, the aromatic polyester of more preferably 1.0-200 μm, polyphenylene sulfide, fragrance adoption at thickness
The aromatic polymers such as acid imide, PAEK, aromatic copolycarbonate, aromatic liquid crystal polymer or polybenzoxazole,
Or on any one side of the metal forming such as copper, aluminum or the rustless steel that thickness is 0.5-400 μm, more preferably 1.0-200 μm, such as
The phosphorous polyamic acid solution that coating manufactures according to the record of above-mentioned (the phosphorous polyimides of II. and manufacture method thereof) entry,
After making another one overlapping with coated face, by lamination or heat pressurization, can be situated between manufacturing and to have the phosphorous polyimides of the present invention
Aromatic polymer metal composite layer stack.
Can be with known on the above-mentioned metal laminate manufactured and aromatic polymer metal composite layer stack
Method makes circuit pattern, and uses as circuit.The circuit using the phosphorous polyimides of the present invention to make has excellence
Anti-flammability, is thus provided that safe electric power, e-machine.
Embodiment
Below in order to make embodiment of the present invention distinct, it is shown that embodiment and comparative example, but the present invention should not be only
It is limited to embodiment shown herein.
The solution viscosity of the compound obtained in embodiment, purity, fusing point or glass transition temperature, NMR and infrared suction
Assay method and the anti-flammability evaluation methodology of receiving spectrum are as follows.
Solution viscosity: use Brookfield viscometer (Tokyo gauge system), measures at a temperature of 25 DEG C.
Purity: use HPLC (Shimadzu Seisakusho Ltd.'s system) and post (east ソ mono-society TSKgel ODS-80TM) to be measured.Sample
This solution by dissolved samples in the mixed liquor of acetonitrile/water or after making it disperse, solution is heated 15 minutes at 60 DEG C and
Modulation.Eluent uses acetonitrile/water/Phosphoric Acid, and purity utilizes area percentage to calculate.
Fusing point or glass transition temperature: utilize differential scanning calorimetry (DSC) (Shimadzu Seisakusho Ltd. DSC-60), with every point 10
DEG C it is warming up to 40-400 DEG C, and is measured.Utilize and resolve software, calculate fusing point or vitrification from the extrapolation point of DSCDSC curve
Transition temperature.
NMR: modulation is mixed with compound, and (Cambrige Isotope Laboratories, Inc. system, contain with weight DMSO
There is the DMSO-d of 0.05%TMS6) solution, utilize NMR (NEC society system, JNM-AL400) to carry out1H-NMR measure and13C-NMR measures.
Infrared absorption spectroscopy: use IR determinator (パ mono-キ Application エ Le マ mono-society Spectrum 100 FT-IR
Spectrometer), utilize KBr method, or use IR determinator (Shimadzu Seisakusho Ltd. Prestage 21), utilize ATR method to survey
Determine infrared absorption spectroscopy.
The evaluation of anti-flammability: thin film is cut into the test film of 200mm × 50mm size.Test film is rolled into cylindrical shape, hangs down
Directly being fixed in clip, and carry out burnings in 3 seconds of twice at sample bottom burner, burning time was within 10 seconds
Zero, more than 10 seconds be ×.
Embodiment 1
Logical formula (I) (R
1
And R
2
It is phenyl) synthesis of phosphorous tetracarboxylic dianhydride that represents
Diphenyl phosphine oxide is loaded in the four-hole boiling flask possessing blender, thermometer, nitrogen ingress pipe and cooling tube
(Aldrich) 2.8g (0.014mol), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (ダ イ セ Le chemistry society system) 3.5g
(0.011mol) and toluene 25g, under nitrogen flowing, stir 4 hours at 110 DEG C.After reaction terminates, toluene is all distilled and removes
Go, after being cooled to 80 DEG C, add acetonitrile 10g.After being cooled to room temperature, leach the solid of precipitation, clean with toluene and acetonitrile.Will
The solid arrived is drying over night at 60 DEG C, obtains the thick purified 2.8g of purity 94.2%.With acetonitrile, this thick purified is carried out
Heated wash, obtains purity 97.5%, fusing point is the purification product of 151 DEG C.By purification product1H-NMR represents in FIG,13C-
NMR represents in fig. 2, and FT-IR schemes (based on パ mono-キ Application エ Le マ mono-society Spectrum 100 FT-IR
The KBr method of Spectrometer) represent in figure 3.
1H-NMR (400MHz, DMSO-d6): δ (ppm)=7.08 (d, J=10Hz, 1H), 7.48 (ddd, J=7.6,7.6,
3.6Hz, 4H), 7.59 (ddd, J=7.6,7.6,1.2Hz, 2H), 7.76 (ddd, J=12.4,7.5,1.2Hz, 4H), 8.06
(d, J=8.0Hz, 2H), 8.23 (dd, J=8.0,1.2Hz, 2H), 8.29 (s, 2H).
13C-NMR (400MHz, DMSO-d6): δ (ppm)=75.0 (d, J=16.4Hz), 123.1,125.8,128.7 (d,
J=52.8Hz), 130.7 (d, J=537.6Hz), 131.0,131.2 (d, J=39.6Hz), 131.9,132.5 (d, J=
13.2Hz), 133.9,148.3 (d, J=16.8Hz), 162.5,162.6.
Embodiment 2
Logical formula (II) (R
1
And R
2
It is phenyl, R
3
For diphenyl ether-4,4 '-diyl) conjunction of phosphorous polyimides that represents
Become
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, load 4,4 '-diamino-diphenyl ether (Wakayama essence
Change society system) 10.0118g (0.05mol), the phosphorous tetracarboxylic dianhydride 26.2207g (0.05mol) of synthesis in embodiment 1,
NMP205g, under nitrogen flowing, stirs 12 hours under room temperature, synthesizes phosphorous polyamic acid.By reaction solution (solute concentration 15%,
Viscosity (Brookfield viscometer: Tokyo gauge system) 5,500mPa s) use directly as phosphorous polyamic acid solution.By containing of obtaining
Phosphorus polyamic acid solution is coated with on a glass so that dried thickness is 25 μm, 90 DEG C, 130 DEG C, 180 DEG C of each temperature
Under be dried 30 minutes after, peel off from glass plate and be fixed in metal frame, carrying out at each temperature 1 hour at 200 DEG C, 250 DEG C
Heat treatment.Obtain the phosphorous polyimides of the film morphology that thickness is 25 μm.
Embodiment 3
Logical formula (II) (R
1
And R
2
It is phenyl, R
3
For Isosorbide-5-Nitrae-phenylene epoxide biphenyl-4,4 '-diyl Oxy-1,4-Asia benzene
Base) synthesis of phosphorous polyimides that represents
3,3 ', 4 are loaded, 4 '-benzophenone tetracarboxylic dianhydride in the four-hole boiling flask possessing thermometer, nitrogen ingress pipe
8.5602g (0.027mol), diphenyl phosphine oxide (DPO) 5.3713g (0.027mol), diethylene glycol dimethyl ether 47.4g, 160
Heat 3 hours at DEG C, synthesize phosphorous tetracarboxylic dianhydride.The solution comprising this dianhydride is cooled to room temperature, loads 4,4 '-two (4-
Amino-benzene oxygen) biphenyl (BAPB) 9.7876g (0.027mol), NMP47.4g, it is stirred at room temperature under nitrogen flowing 12 hours,
Synthesize phosphorous polyamic acid.By reaction solution (solute concentration 20%, viscosity (Brookfield viscometer: Tokyo gauge system) 8,000mPa
S) use directly as phosphorous polyamic acid solution.It is applied to glass plate similarly to Example 2 and is dried He Rechu
Reason, obtains the phosphorous polyimides of the film morphology that thickness is 20 μm.
Comparative example 1
3,3 ', 4 are loaded, 4 '-benzophenone tetracarboxylic dianhydride in the four-hole boiling flask possessing thermometer, nitrogen ingress pipe
16.1113g (0.05mol), 4,4 '-diaminodiphenyl ether 10.0118g (0.05mol), NMP148g, under nitrogen flowing in room temperature
Lower stirring 12 hours, synthesizes phosphorous polyamic acid.By reaction solution (solute concentration 15%, viscosity (Brookfield viscometer: Tokyo gauge
System) 12,000mPa s) use directly as polyamic acid solution.It is applied to similarly to Example 2 on glass plate and carries out
It is dried and heat treatment, obtains the most phosphorous polyimides of the film morphology that thickness is 20 μm.
Comparative example 2
Except diamine compound being changed into 4,4 '-two (4-amino-benzene oxygen) biphenyl (BAPB) 18.4214g (0.05mol)
Outside, carry out the operation as comparative example 1, obtain the most phosphorous polyimides of the film morphology that thickness is 20 μm.
Anti-flammability is evaluated
The polyimides obtained in embodiment 2 and 3 and comparative example 1 and 2 is evaluated.The results are shown in table 1
In.
[table 1]
Embodiment 4
The manufacture of metal laminate
By in embodiment 2 manufacture phosphorous polyamic acid solution be coated on thickness 18 μm Copper Foil (Mitsui Metal Co., Ltd.'s (strain) system,
On 3EC-VLP) so that the thickness of dried resin is 25 μm, it is dried 30 minutes at each temperature at 90 DEG C, 130 DEG C, 180 DEG C
After, vacuum drier carries out at 250 DEG C the heat treatment of 1 hour, obtains phosphorous polyimides/metal laminate.
Embodiment 5
The manufacture of aromatic polymer duplexer
Phosphorous polyamic acid solution embodiment 2 manufactured is coated on the aromatic polyimide film (デ of thickness 25 μm
ュ Port Application (strain) system, カ プ ト Application (registered trade mark) H) on so that dried resin thickness is 25 μm, 90 DEG C, 130 DEG C,
After 180 DEG C are dried 30 minutes at each temperature, drying machine carries out at 250 DEG C the heat treatment of 1 hour, obtain phosphorous polyamides sub-
Amine/aromatic polymer duplexer.
Embodiment 6
The manufacture of aromatic polymer metal composite layer stack
By in embodiment 2 manufacture phosphorous polyamic acid solution be coated on thickness 18 μm Copper Foil (Mitsui Metal Co., Ltd.'s (strain) system,
On 3EC-VLP) so that dried resin thickness is 5 μm, it is dried 3 minutes at a temperature of 160 DEG C.Then, on coated face
The aromatic polyimide film (デ ュ Port Application (strain) system, カ プ ト Application (registered trade mark) EN) of superposition thickness 40 μm, at 200 DEG C
At a temperature of be laminated.The duplexer obtained is carried out heat treatment at a temperature of 350 DEG C, obtains metal/phosphorous polyamides sub-
Amine/aromatic polymer compound stack body.
Embodiment 7
The synthesis (according to the manufacture method of fourth embodiment of the invention) of phosphorous polyimides
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, nitrogen stream loads 4,4 '-diamino-diphenyl ether
(4-ODA) (Wakayama refine society's system) 10.0118g (0.05mol), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
(HCA (registered trade mark)) (Sanko Co., Ltd.'s system) 10.8086g (0.05mol), METHYLPYRROLIDONE (NMP)
148.0g so that it is dissolve.Thereafter, load 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) (ダ イ セ Le chemistry society system)
16.1113g (0.05mol), is stirred at room temperature 12 hours, obtains solution viscosity 5,000mPa s, solute concentration 20% poly-
Amic acid and the mixed solution of phosphorus compound.The mixed solution obtained is coated with on a glass so that dried thickness is
20 μm, after being dried 30 minutes at each temperature at 90 DEG C, 130 DEG C, 180 DEG C, peel off from glass plate and are fixed on metal frame,
200 DEG C, the 250 DEG C heat treatments carrying out 1 hour at each temperature, obtain repetitive and are contained within the phosphorus atoms of 4.4% (theoretical value)
Kapton.When measuring IR (based on Shimadzu Seisakusho Ltd. Prestage 21, the ATR method) of Kapton,
1670cm-1Benzophenone carbonylic stretching vibration absorption disappear.The glass transition temperature of thin film is 255 DEG C, anti-flammability
It is evaluated as zero.
Comparative example 3
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, in nitrogen stream, load 4,4 '-diamino-diphenyl
Ether (4-ODA) (Wakayama refine society's system) 10.0118g (0.05mol), METHYLPYRROLIDONE (NMP) 148.0g so that it is
Dissolve.Thereafter, load 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BTDA) (ダ イ セ Le chemistry society system) 16.1113g
(0.05mol), it is stirred at room temperature 12 hours, obtains solution viscosity 12,500mPa s, the polyamic acid of solute concentration 15%
Solution.The polyamic acid solution that obtains is coated with on a glass so that dried thickness is 20 μm, 90 DEG C, 130 DEG C,
After 180 DEG C are dried 30 minutes at each temperature, peel off from glass plate and be fixed on metal frame, 200 DEG C, 250 DEG C at each temperature
Carry out the heat treatment of 1 hour, obtain the most phosphorous Kapton.The glass transition temperature of thin film is 263 DEG C, anti-flammability
Be evaluated as ×.
Comparative example 4
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, in nitrogen stream, load 4,4 '-diamino-diphenyl
Ether (4-ODA) 10.0118g (0.05mol), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registrar
Mark)) (Sanko Co., Ltd.'s system) 21.6172g (0.10mol), METHYLPYRROLIDONE (NMP) 188.6g so that it is dissolve.
Thereafter, loading 4, double O-phthalic acid dianhydride 15.5107g (0.05mol) of 4 '-oxygen (マ ナツ Network Co., Ltd. system), in room temperature
Lower stirring 12 hours, obtains solution viscosity 7, mixing of 800mPa s, the polyamic acid solution of solute concentration 20% and phosphorus compound
Compound.The mixture that obtains is coated with on a glass so that dried thickness is 20 μm, 90 DEG C, 130 DEG C, 180 DEG C each
At a temperature of be dried after 30 minutes, peel off from glass plate and be fixed on metal frame, carrying out 1 at each temperature at 200 DEG C, 250 DEG C little
Time heat treatment, obtain Kapton.Measure the IR of Kapton (based on Shimadzu Seisakusho Ltd. Prestage 21
ATR method) time, do not find the existence of phosphorus.The glass transition temperature of thin film is 228 DEG C, anti-flammability is evaluated as ×.
Embodiment 8-10, comparative example 5
Similarly to Example 7, change various composition and make Kapton.Its composition and result are shown in Table 2.
[table 2]
Writing a Chinese character in simplified form in table is expressed as follows.
BTDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
DSDA:3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride
APB:1,3-bis-(3-amino-benzene oxygen) benzene
BAPP:2,2-2 [4-(4-amino-benzene oxygen) phenyl] propane
BAPS:2 [4-(4-amino-benzene oxygen) phenyl] sulfone
HCA (registered trade mark): 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
DPO: diphenyl phosphine oxide (Aldrich)
Industrial utilization probability
The phosphorous polyimides using the phosphorous tetracarboxylic dianhydride of the present invention to manufacture has identical with existing polyimides
Physical property, demonstrate simultaneously excellence flame-retarding characteristic, i.e. become thin film and also show good thermostability, therefore can meet electricity
The demand of compactization such as power, e-machine.It addition, use the phosphorous polyimides of anti-flammability of the present invention, be avoided that or
Reduce and additionally add fire retardant, be therefore the flame-retarded technology safer for natural environment or human body.
Especially by using the manufacture method of the phosphorous polyimides of narration in fourth embodiment of the invention, it is not necessary to
Special device, step can manufacture phosphorous polyimides with easy method.Use the phosphorous polyamides that this manufacture method manufactures
Imines is highly useful as insulant requiring filming and flame-retarded heat resistant adhesive or circuit substrate etc..
Claims (3)
- The most phosphorous tetracarboxylic dianhydride, is represented by following logical formula (I),[changing 24]In formula, R1And R2Can be the same or different, for phenyl or phenoxy group, wherein R1And R2Each at least one on phenyl ring Hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl, and/or R1And R2Each a carbon atom on phenyl ring can be mutual With singly bound.
- 2. the phosphorous tetracarboxylic dianhydride described in claim 1, in logical formula (I), R1And R2It is phenyl or R1And R2Wherein one Individual for phenyl, another is phenoxy group, and each a carbon atom on phenyl ring is mutually with singly bound, wherein, on phenyl ring for it At least one hydrogen atom can be substituted by the alkyl of carbon number 1-6 or alkoxyl.
- 3. the phosphorous tetracarboxylic dianhydride described in claim 1 or 2, selected from following formula (Ia):[changing 25]With following formula (Ib),[changing 26]In formula, R1And R2Can be the same or different, for hydrogen, the alkyl of carbon number 1-6 or alkoxyl.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-276066 | 2009-12-04 | ||
| JP2009276067A JP5489682B2 (en) | 2009-12-04 | 2009-12-04 | Method for producing phosphorus-containing polyimide |
| JP2009276066A JP5570793B2 (en) | 2009-12-04 | 2009-12-04 | Phosphorus-containing tetracarboxylic dianhydride and flame retardant polyimide |
| JP2009-276067 | 2009-12-04 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080054983.7A Division CN102639547B (en) | 2009-12-04 | 2010-12-03 | Phosphorus-containing polyimide and method for producing same |
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| CN104478932A CN104478932A (en) | 2015-04-01 |
| CN104478932B true CN104478932B (en) | 2017-01-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3222373A (en) * | 1963-06-06 | 1965-12-07 | Union Oil Co | Derivatives of ferrocene |
| CN1136817A (en) * | 1994-10-10 | 1996-11-27 | 托马斯·P·阿本德 | Cross-linking agents for polymers with acid anhydride groups |
| WO2002092654A2 (en) * | 2001-05-17 | 2002-11-21 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Space environmentally durable polyimides and copolyimides |
| JP2006251715A (en) * | 2005-03-14 | 2006-09-21 | Kaneka Corp | Photosensitive resin composition having flame resistance and photosensitive dry film resist |
| CN101291990A (en) * | 2005-10-21 | 2008-10-22 | 日本化药株式会社 | Thermosetting resin composition and use thereof |
| JP2009221309A (en) * | 2008-03-14 | 2009-10-01 | Manac Inc | Tetracarboxylic acid containing phosphorus-containing ester group or its dianhydride and phosphorus-containing polyester imide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3222373A (en) * | 1963-06-06 | 1965-12-07 | Union Oil Co | Derivatives of ferrocene |
| CN1136817A (en) * | 1994-10-10 | 1996-11-27 | 托马斯·P·阿本德 | Cross-linking agents for polymers with acid anhydride groups |
| WO2002092654A2 (en) * | 2001-05-17 | 2002-11-21 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Space environmentally durable polyimides and copolyimides |
| JP2006251715A (en) * | 2005-03-14 | 2006-09-21 | Kaneka Corp | Photosensitive resin composition having flame resistance and photosensitive dry film resist |
| CN101291990A (en) * | 2005-10-21 | 2008-10-22 | 日本化药株式会社 | Thermosetting resin composition and use thereof |
| JP2009221309A (en) * | 2008-03-14 | 2009-10-01 | Manac Inc | Tetracarboxylic acid containing phosphorus-containing ester group or its dianhydride and phosphorus-containing polyester imide |
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