JPH03195732A - New polyesterimide - Google Patents
New polyesterimideInfo
- Publication number
- JPH03195732A JPH03195732A JP33599989A JP33599989A JPH03195732A JP H03195732 A JPH03195732 A JP H03195732A JP 33599989 A JP33599989 A JP 33599989A JP 33599989 A JP33599989 A JP 33599989A JP H03195732 A JPH03195732 A JP H03195732A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- general formula
- polyesterimide
- amino
- 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.)
- Pending
Links
- 229920003055 poly(ester-imide) Polymers 0.000 title claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 3
- 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 abstract description 25
- 150000004985 diamines Chemical class 0.000 abstract description 16
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 229920001721 polyimide Polymers 0.000 description 26
- 239000004642 Polyimide Substances 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- -1 and if necessary Chemical compound 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 2
- 240000005220 Bischofia javanica Species 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- MLUKGRBIZZARBA-UHFFFAOYSA-N 1-anilino-1-phenylpropan-1-ol Chemical compound C=1C=CC=CC=1C(O)(CC)NC1=CC=CC=C1 MLUKGRBIZZARBA-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QHDSBTKCTUXBEG-UHFFFAOYSA-N 2-[2-(2-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1N QHDSBTKCTUXBEG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- XBTHNZXADRSYPR-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl)benzene-1,2-diamine Chemical compound NC1=CC=CC(C(C=2C=CC=CC=2)(C(F)(F)F)C(F)(F)F)=C1N XBTHNZXADRSYPR-UHFFFAOYSA-N 0.000 description 1
- NHJNWRVCOATWGF-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenyl)sulfonyl-2-phenoxyaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)=C1OC1=CC=CC=C1 NHJNWRVCOATWGF-UHFFFAOYSA-N 0.000 description 1
- DIRYWKMUDQKIKC-UHFFFAOYSA-N 3-[2-(3-amino-2-phenoxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-phenoxyaniline Chemical compound NC1=CC=CC(C(C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)(C(F)(F)F)C(F)(F)F)=C1OC1=CC=CC=C1 DIRYWKMUDQKIKC-UHFFFAOYSA-N 0.000 description 1
- ULPWATNJVBJKGM-UHFFFAOYSA-N 3-[2-(3-amino-2-phenoxyphenyl)propan-2-yl]-2-phenoxyaniline Chemical compound C=1C=CC(N)=C(OC=2C=CC=CC=2)C=1C(C)(C)C1=CC=CC(N)=C1OC1=CC=CC=C1 ULPWATNJVBJKGM-UHFFFAOYSA-N 0.000 description 1
- COPUOMGHQGSBQO-UHFFFAOYSA-N 3-[2-(4-aminophenyl)propan-2-yl]phenol Chemical compound C=1C=CC(O)=CC=1C(C)(C)C1=CC=C(N)C=C1 COPUOMGHQGSBQO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-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
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 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
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- FZDHAWDOLRMLCD-UHFFFAOYSA-N bis(3-amino-2-phenoxyphenyl)methanone Chemical compound C=1C=CC=CC=1OC=1C(N)=CC=CC=1C(=O)C1=CC=CC(N)=C1OC1=CC=CC=C1 FZDHAWDOLRMLCD-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AVHCASCNGYLWLG-UHFFFAOYSA-N n-[2-[6-(1-anilinopropan-2-ylidene)cyclohexa-2,4-dien-1-ylidene]propyl]aniline Chemical compound C1=CC=CC(=C(C)CNC=2C=CC=CC=2)C1=C(C)CNC1=CC=CC=C1 AVHCASCNGYLWLG-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は溶解性、低温成形性に優れた新規なポリエステ
ルイミドに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyesterimide with excellent solubility and low-temperature moldability.
ポリイミド樹脂は耐熱性が優れているが、多くのものは
、不溶、不融であるため成形性が劣っている。そのため
、フィルムなどに成形するには前駆体であるポリアミド
酸の状態で有機溶媒に溶解したワニスを用いていた。し
かし、ポリアミド酸ワニスは加水分解によって分子量が
低下するため、低温で保存しなければならなかった。ま
た溶媒が吸湿しやすいため、吸湿により樹脂が析出する
等の問題があった。さらにフィルム等に成形した後、イ
ミド化する際に縮合水が発生するため成形物中にボイド
が残るという問題があった。Polyimide resins have excellent heat resistance, but many have poor moldability because they are insoluble and infusible. Therefore, in order to form a film or the like, a varnish prepared by dissolving the precursor polyamic acid in an organic solvent was used. However, polyamic acid varnishes have to be stored at low temperatures because their molecular weight decreases due to hydrolysis. Furthermore, since the solvent easily absorbs moisture, there were problems such as resin precipitation due to moisture absorption. Furthermore, after being molded into a film or the like, condensed water is generated during imidization, resulting in the problem that voids remain in the molded product.
また、イミド化する際に300℃以上の高温にする必要
があるため、熱に弱い基材には用いられないという問題
があった。Furthermore, since it is necessary to raise the temperature to a high temperature of 300° C. or higher during imidization, there is a problem that it cannot be used for heat-sensitive base materials.
この問題点を解決するために、軟化点を有し、成形加工
が可能なポリイミドが開発されている。In order to solve this problem, polyimides that have a softening point and can be molded have been developed.
例えば、特開昭62−10051号公報には、−成人(
)
%式%()
(ただり、X’は C=O又は S02を示す)で表わ
されるジアミンとピロメリット酸からなるポリイミドが
開示されるが、このポリイミドは軟化点を有し、成形加
工が可能である。For example, in Japanese Patent Application Laid-Open No. 62-10051, -Adult (
) A polyimide consisting of a diamine and pyromellitic acid represented by the formula % () (where X' represents C=O or S02) is disclosed, but this polyimide has a softening point and is difficult to mold. It is possible.
また、上記の問題点を解決するために、有機溶剤に可溶
なポリエステルイミドが開発されている。Furthermore, in order to solve the above problems, polyester imides soluble in organic solvents have been developed.
例えば、特公昭43−22120号公報に示されるアル
キレンビストリメリテートとジイソシアネートからなる
ポリエステルイミド及び特公昭47−30437号公報
に示される芳香族ビストリメリテートとジアミンからな
るポリエステルイミドはクレゾールに可溶である。For example, the polyesterimide made of alkylene bistrimelitate and diisocyanate shown in Japanese Patent Publication No. 43-22120 and the polyesterimide made of aromatic bistrimelitate and diamine shown in Japanese Patent Publication No. 47-30437 are soluble in cresol. be.
特開昭62−10051号公報に示されるポリイミドは
軟化点を有し、成形加工が可能であるが、軟化点が高す
ぎ、300℃を超える温度で成形しなければならない。The polyimide disclosed in JP-A-62-10051 has a softening point and can be molded, but the softening point is too high and must be molded at a temperature exceeding 300°C.
また、該ポリイミドは有機溶剤に難溶性であるため、フ
ィルムに成形するためにはその前駒体であるポリアミド
酸を有機溶剤に溶解したワニスを用いてフィルム化し、
これを高温に加熱してイミド化しなければならず、前記
したような問題点がある。In addition, since the polyimide is poorly soluble in organic solvents, in order to form it into a film, it is formed into a film using a varnish in which polyamic acid, which is the front piece, is dissolved in an organic solvent.
This must be heated to a high temperature to be imidized, which poses the problems described above.
特公昭43−22120号公報に示されるポリエステル
イミドは、主鎖にアルキレン鎖を有するため耐熱性が著
しく劣り、特公昭47−30437号公報に示されるポ
リエステルイミドは軟化点が高すぎるため300℃を超
える温度で成形する必要がある。The polyesterimide disclosed in Japanese Patent Publication No. 43-22120 has an alkylene chain in its main chain, so it has extremely poor heat resistance. It is necessary to mold at temperatures exceeding
本発明は、−成人(1)
(ただし、式中、Arは二価の芳香族基を示す)で表わ
される二価の基を表し、Zは一般式(3)%式%(3)
を示す)で表わされる二価の基を示す)〕で表される構
成単位を含んでなるポリエステルイミドに関する。The present invention represents a divalent group represented by -adult (1) (in the formula, Ar represents a divalent aromatic group), and Z represents the general formula (3) % formula % (3) The present invention relates to a polyesterimide comprising a divalent group represented by the following formula)].
上記ポリエステルイミドは、−成人(1)(ただし、式
中、Arは二価の芳香族基を示す)で表わされる酸二無
水物及び−成人(II)・・・(II)
示し、Yはアミノ基又はイソシアナート基を示す)で表
わされる化合物を反応させることにより製造することが
できる。The above-mentioned polyesterimide is an acid dianhydride represented by -adult (1) (wherein Ar represents a divalent aromatic group) and -adult (II)...(II), and Y is It can be produced by reacting a compound represented by (representing an amino group or an isocyanate group).
一般式(1)で表わされる酸二無水物について次に説明
する。The acid dianhydride represented by general formula (1) will be explained next.
一般式(1)中、Arとしては、例えば、下記(a)又
は(b)で示される二価の基などがある。In general formula (1), examples of Ar include divalent groups represented by (a) or (b) below.
(a)
(ただし、式中、Rはメチル基、エチル基、プロピル基
等の低級アルキル基、塩素、臭素、フッ素等のハロゲン
、メトキシ基、エトキシ基等のアルコキシ基、トリフル
オロメチル基、ペンタフルオロエチル基、パーフルオロ
ブチル基、パーフルオロヘキシル基、パーフルオロオク
チル基等のフッ素置換アルキル基等を示し、pはベンゼ
ン環tこ結合しているRの数であって0又は1〜3の整
数を示し、pが2以上のとき、複数のRは同一でも異な
っていてもよい。(a) (In the formula, R is a lower alkyl group such as a methyl group, an ethyl group, or a propyl group, a halogen such as chlorine, bromine, or fluorine, an alkoxy group such as a methoxy group or an ethoxy group, a trifluoromethyl group, or a penta It represents a fluorine-substituted alkyl group such as a fluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc., where p is the number of R bonded to the benzene ring and is 0 or 1 to 3. When p is an integer and is 2 or more, the plurality of R's may be the same or different.
で、mは1以上の整数 RL及びR2はそれぞれ独立に
、メチル基、エチル基、イソプロピル基等の低級アルキ
ル基、塩素、臭素、フッ素等のハロゲン、メトキシ基、
エトキシ基等のアルコキシ基。and m is an integer of 1 or more. RL and R2 each independently represent a lower alkyl group such as a methyl group, an ethyl group, or an isopropyl group, a halogen such as chlorine, bromine, or fluorine, a methoxy group,
Alkoxy groups such as ethoxy groups.
トリフルオロメチル、ペンタフルオロエチル、パーフル
オロブチル、パーフルオロヘキシル、パーフルオロオク
チル基等のフッ素置換アルキル基等を示し、q及びrは
それぞれ、R1及びR2のベンゼン環への結合数であっ
てO又は1〜4の整数を示し、nは1以上の整数を示し
、R”、 Y及びR2がそれぞれ複数個ある場合、複数
個のR1,Y及びR2はそれぞれの場合に同一でも異な
っていてもよい)
一般式(1)で表わされる酸二無水物の具体例としては
カテコールビストリメリテートニ無水物。It represents a fluorine-substituted alkyl group such as trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl group, etc., and q and r are the number of bonds of R1 and R2 to the benzene ring, respectively, and O or represents an integer from 1 to 4, n represents an integer of 1 or more, and when there are multiple R'', Y, and R2, the multiple R1, Y, and R2 may be the same or different in each case. A specific example of the acid dianhydride represented by the general formula (1) is catechol bistrimelitate dianhydride.
レゾルシノールビストリメリテートニ無水物、ジヒドロ
キシベンゼンビストリメリテートニ無水物。Resorcinol bistrimelitate dianhydride, dihydroxybenzene bistrimelitate dianhydride.
ビスフェノールAビストリメリテートニ無水物。Bisphenol A bistrimelitate dianhydride.
テトラクロロビスフェノールAビストリメリテートニ無
水物、テトラブロモビスフェノールAビストリメリテー
トニ無水物、ビフェニルビストリメリテートニ無水物、
下記−成人(m)で表わされるビストリメリテートニ無
水物等が挙げられる。Tetrachlorobisphenol A bistrimelitate dianhydride, tetrabromobisphenol A bistrimelitate dianhydride, biphenyl bistrimelitate dianhydride,
Examples include bistrimelitate dianhydride represented by the following adult (m).
−成人(III)
υ
本発明において、酸二無水物の反応の相手は、−成人(
II)で表わされる化合物を必須成分とする。-adult (III) υ In the present invention, the reaction partner of the acid dianhydride is -adult (III)
The compound represented by II) is an essential component.
一般式(n)で表わされる化合物としては、−成人(I
I)中、イソプロピリデン基に対してアミノ基及び酸素
がパラ位又はメタ位に結合しているものが好ましく、特
に、2個のアミノ基及び2個の酸素のうち少なくとも1
個がイソプロピリデン基に対してメタ位であるのが好ま
しい。The compound represented by the general formula (n) includes -adult (I
Among I), those in which an amino group and oxygen are bonded to the isopropylidene group at the para or meta position are preferred, and in particular, at least one of the two amino groups and the two oxygens is bonded to the isopropylidene group.
Preferably, the isopropylidene group is meta to the isopropylidene group.
−成人(II)において、イソプロピリデン基に対する
アミノ基及び酸素の結合位置のうち、メタ位の割合が増
える程、得られるポリイミドの軟化点は低く、有機溶剤
に対する溶解性が良好になるが、軟化点があまり低くな
りすぎるとポリイミド成形物の高温時における強度が低
下しやすくなるので、目的に応じ、上記メタ位の割合を
決定するのが好ましい。このような観点から、本発明に
おけるジアミン成分は、一般式(IV)
・・・(IV)
(ただし、X及びYは一般式(n)に同じ)で表わされ
る化合物が特に好ましい。- In adult (II), the higher the proportion of the meta-position among the bonding positions of the amino group and oxygen to the isopropylidene group, the lower the softening point of the obtained polyimide and the better the solubility in organic solvents, but the softening If the point becomes too low, the strength of the polyimide molded product at high temperatures tends to decrease, so it is preferable to determine the ratio of the meta position according to the purpose. From this viewpoint, the diamine component in the present invention is particularly preferably a compound represented by the general formula (IV) (IV) (where X and Y are the same as the general formula (n)).
一般式(II)で表わされる化合物は、酸二無水物の反
応の相手として、好ましくは50モル%以上、特に好ま
しくは75モル%以上使用される。The compound represented by the general formula (II) is preferably used in an amount of 50 mol% or more, particularly preferably 75 mol% or more, as a reaction partner for the acid dianhydride.
一般式(II)で表わされる化合物が少なすぎると得ら
れるポリエステルイミドの軟化点が高くなりやすく、ま
た、有機溶剤に難溶性になりやすい。If the amount of the compound represented by the general formula (II) is too small, the resulting polyesterimide tends to have a high softening point and is likely to be poorly soluble in organic solvents.
一般式(II)で表わされる化合物のうち、基Yがアミ
ノ基であるジアミンとしては、4.4′ビスC3−(4
−アミノ−α、α′−ジメチルベンジル)フェノキシュ
ジフェニルスルホン、4゜4′−ビス(3−(4−アミ
ノ−α、α′−ジメチルベンジル)フェノキシフベンゾ
フェノン、4゜4′−ビス[4−(4−アミノ−α、α
′−ジメチルベンジル)フェノキシ]ジフェニルスルホ
ン、4.4′−ビス(4−(4−アミノ−α、α′ジメ
チルベンジル)フェノキシフベンゾフェノン、4− (
3−(4−アミノ−α、α −ジメチルベンジル)フェ
ノキシ) −4’ −(4−(4−アミノ−α、α′−
ジメチルベンジル)フェノキシュジフェニルスルホン、
4− (3−(4−アミノ−α、α′−ジメチルベンジ
ル)フェノキシ〕−4’ −(4−アミノ−α、α′−
ジメチルベンジル)フェノキシフベンゾフェノン、4,
4′−ビス(3−(3−アミノ−α、α −ジメチルベ
ンジル)フェノキシュジフェニルスルホン、4゜4′−
ビス(3−(3−アミノ−α、α′−ジメチルベンジル
)フェノキシフベンゾフェノン、4゜4′−ビス(2−
(4−アミノ−α、α′−ジメチルベンジル)フェノキ
シ〕ジフェニルスルホン。Among the compounds represented by the general formula (II), diamines in which the group Y is an amino group include 4.4'bisC3-(4
-amino-α,α′-dimethylbenzyl)phenoxydiphenylsulfone, 4゜4′-bis(3-(4-amino-α,α′-dimethylbenzyl)phenoxybenzophenone, 4゜4′-bis[4 -(4-amino-α, α
'-Dimethylbenzyl)phenoxy]diphenylsulfone, 4,4'-bis(4-(4-amino-α,α'dimethylbenzyl)phenoxybenzophenone, 4-(
3-(4-amino-α,α-dimethylbenzyl)phenoxy)-4′-(4-(4-amino-α,α′-
dimethylbenzyl) phenoxydiphenyl sulfone,
4-(3-(4-amino-α,α′-dimethylbenzyl)phenoxy]-4′-(4-amino-α,α′-
dimethylbenzyl)phenoxifbenzophenone, 4,
4'-bis(3-(3-amino-α,α-dimethylbenzyl)phenoxydiphenylsulfone, 4°4’-
Bis(3-(3-amino-α,α′-dimethylbenzyl)phenoxifbenzophenone, 4゜4′-bis(2-
(4-amino-α,α′-dimethylbenzyl)phenoxy]diphenylsulfone.
4.4′−ビス(2−(4−アミノ−α、αジメチルベ
ンジル)フェノキシフベンゾフェノン。4.4'-bis(2-(4-amino-α,αdimethylbenzyl)phenoxifbenzophenone.
3.3′−ビス(3−(4−アミノ−α、αジメチルベ
ンジル)フェノキシュジフェニルスルホン、3,3′−
ビス(3−(4−アミノ−α。3.3'-bis(3-(4-amino-α,αdimethylbenzyl)phenoxydiphenylsulfone, 3,3'-
Bis(3-(4-amino-α.
α′−ジメチルベンジル)フェノキシフベンゾフェノン
等が挙げられ、これらを混合して用いても良い。Examples include α'-dimethylbenzyl)phenoxifbenzophenone, and a mixture of these may be used.
一般式(U)で表わされる化合物がジアミンである場合
、酸二無水物の反応の相手として併用してもよい他のジ
アミンとしては、ジアミノジフェニルメタン、ジアミノ
ジフェニルエーテル、ジアミノジフェニルスルホン、ジ
アミノジフェニルケトン、ジアミノジフェニルプロパン
、フェニレンジアミン、トルエンジアミン、ビス(アニ
リノイソプロピリデン)ベンゼン、ビス(アミノフェノ
キシ)ベンゼン、ジアミノジフェニルスルフィド。When the compound represented by the general formula (U) is a diamine, examples of other diamines that may be used in combination as a reaction partner with the acid dianhydride include diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenyl ketone, and diaminodiphenyl methane. Diphenylpropane, phenylenediamine, toluenediamine, bis(anilinoisopropylidene)benzene, bis(aminophenoxy)benzene, diaminodiphenyl sulfide.
ビス(アミノフェノキシフェニル)プロパン、ビス(ア
ミノフェノキシフェニル)スルホン、ビス(アミノフェ
ノキシフェニル)ケトン、ビス(アミノフェノキシフェ
ニル)へキサフルオロプロパン、ジアミノジフェニルへ
キサフルオロプロパン。Bis(aminophenoxyphenyl)propane, bis(aminophenoxyphenyl)sulfone, bis(aminophenoxyphenyl)ketone, bis(aminophenoxyphenyl)hexafluoropropane, diaminodiphenylhexafluoropropane.
ジアミノジアルキルジフェニルメタン等があり、これら
は二種以上併用してもよい。Examples include diaminodialkyldiphenylmethane, and two or more of these may be used in combination.
一般式(II)で表わされる化合物のうち、基Yがイソ
シアナート基であるジイソシアナートとしては、4,4
′−ビス(3−(4−イソシアナート−α、α′−ジメ
チルベンジル)フェノキシュジフェニルケトン、4,4
′−ビス(3−(4−イソシアナート−α、α −ジメ
チルベンジル)フェノキシュジフェニルスルホン等があ
り、その他、一般式(I)で表わされる化合物のうち、
基Yがアミノ基であるジアミンにおいては、アミノ基を
イソシアナート基に代えたものがある。このようなジイ
ソシアナートと併用してもよいジイソシアナートとして
は、ジフェニルメタンジイソシアナート、トルイレンジ
イソシアナート等の前記した他のジアミンのアミノ基を
イソシアナート基にかえたものがある。Among the compounds represented by general formula (II), the diisocyanate in which group Y is an isocyanate group includes 4,4
'-Bis(3-(4-isocyanato-α,α'-dimethylbenzyl)phenoxydiphenylketone, 4,4
'-bis(3-(4-isocyanato-α,α-dimethylbenzyl)phenoxydiphenylsulfone), and other compounds represented by general formula (I),
Among diamines in which the group Y is an amino group, there are diamines in which the amino group is replaced with an isocyanate group. Examples of diisocyanates that may be used in combination with such diisocyanates include those in which the amino groups of the other diamines described above are replaced with isocyanate groups, such as diphenylmethane diisocyanate and tolylene diisocyanate.
本発明において、ポリエステルイミドは1次のようにし
て製造することができる。In the present invention, polyesterimide can be produced in the following manner.
酸二無水物の反応の相手としてジアミンを使用する場合
、これらを有機溶媒中、必要に応じてトリブチルアミン
、トリエチルアミン、亜リン酸トリフェニル等の触媒の
存在下、100℃以上、好ましくは180℃以上に加熱
して、イミド化までを行なわせて、直接ポリエステルイ
ミドを得る方法(触媒は、反応成分の総量に対して0〜
15重量%使用するのが好ましく、特に0.01〜15
重量%使用するのが好ましい)、酸二無水物及びジアミ
ンを有機溶媒中100℃未満で反応させてポリエステル
イミドの前駆体であるポリアミド酸のワニスをいったん
製造し、この後、このワニスを加熱してイミド化するか
、無水酢酸、無水プロピオン酸、無水安息香酸等の酸無
水物、ジシクロへキシルカルボジイミド等のカルボジイ
ミド等の閉環剤、必要に応じてピリジン、イソキノリン
。When diamines are used as reaction partners with acid dianhydrides, they are heated at 100°C or higher, preferably at 180°C, in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite. A method of directly obtaining polyester imide by heating to above temperature and imidization (the catalyst is 0 to 10% based on the total amount of reaction components
It is preferable to use 15% by weight, especially 0.01 to 15% by weight.
A varnish of polyamic acid, which is a precursor of polyesterimide, is produced once by reacting an acid dianhydride and a diamine at less than 100°C in an organic solvent (preferably used in % by weight), and then heating this varnish. or imidize with a ring-closing agent such as an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, or a carbodiimide such as dicyclohexylcarbodiimide, and if necessary, pyridine or isoquinoline.
トリメチルアミン、アミノピリジン、イミダゾール等の
閉環触媒を添加して化学閉環(イミド化)させる方法(
閉環剤及び閉環触媒は、それぞれ、酸無水物1モルに対
して1〜8モルの範囲内で使用するのが好ましい)等が
ある。A method of chemically closing the ring (imidization) by adding a ring-closing catalyst such as trimethylamine, aminopyridine, or imidazole (
The ring-closing agent and the ring-closing catalyst are each preferably used in an amount of 1 to 8 mol per 1 mol of the acid anhydride.
前記有機溶剤としては、N−メチル−ピロリドン(NM
P) 、N、N−ジメチルアセトアミド、N、N−ジメ
チルホルムアミド(DMF) 、ジメチルスルホキシド
、スルホラン、ヘキサメチルリン酸トリアミド、1,3
−ジメチル−2−イミダゾリトン等の非プロトン性極性
溶媒、フェノール、クレゾール、キシレノール、P−ク
ロルフェノール等のフェノール系溶媒等が挙げられる。As the organic solvent, N-methyl-pyrrolidone (NM
P), N, N-dimethylacetamide, N, N-dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, hexamethyl phosphoric acid triamide, 1,3
Examples include aprotic polar solvents such as -dimethyl-2-imidazolitone, phenolic solvents such as phenol, cresol, xylenol, and P-chlorophenol.
これらの溶媒にベンゼン、トルエン、キシレン。These solvents include benzene, toluene, and xylene.
メチルエチルケトン、アセトン、テトラヒドロフラン、
ジオキサン、モノグライム、ジグライム。Methyl ethyl ketone, acetone, tetrahydrofuran,
Dioxane, monoglyme, diglyme.
メチルセロソルブ、セロソルブアセテート、メタノール
、エタノール、インプロパツール、塩化メチレン、クロ
ロホルム、トリクレン、テトラクロロエタン等の溶媒を
ポリイミド又はポリアミド酸の溶解性をそこなわない範
囲で混合して用いることができる。Solvents such as methyl cellosolve, cellosolve acetate, methanol, ethanol, inpropatol, methylene chloride, chloroform, trichlene, and tetrachloroethane can be mixed and used within a range that does not impair the solubility of the polyimide or polyamic acid.
前記したポリイミド及びその前駆体であるポリアミド酸
の製造に際し、場合により、同相反応、300℃以下で
の溶融反応等を利用することができる。When producing the polyimide described above and the polyamic acid that is its precursor, in-phase reaction, melt reaction at 300° C. or lower, etc. can be used depending on the case.
また、酸二無水物の反応の相手としてジイソシアナート
を使用する場合は、前記した直接ポリエステルイミドを
得る方法に準じて行なうことができる。ただし1反応温
度は室温、特に60’C以上であれば充分である。Further, when a diisocyanate is used as a reaction partner of the acid dianhydride, it can be carried out according to the method for directly obtaining polyesterimide described above. However, it is sufficient that the reaction temperature is room temperature, particularly 60'C or higher.
本発明において、酸二無水物とその反応の相手は、はぼ
等モルで用いるのが好ましいが、いずれか一方の過剰量
が10モル%、特に好ましくは5モル%までは許容され
る。In the present invention, the acid dianhydride and its reaction partner are preferably used in approximately equimolar amounts, but an excess of either one of them is allowed up to 10 mol%, particularly preferably up to 5 mol%.
本発明で得られるポリエステルイミドは、N。The polyesterimide obtained in the present invention has N.
N−ジメチルホルムアミド等の非プロトン性極性溶媒、
ジオキサン、テトラヒドロフラン等のエーテル系溶媒、
塩化メチレン等のハロゲン化炭化水素等に可溶であり、
これらの溶液からフィルム等に成形することができる。aprotic polar solvents such as N-dimethylformamide;
Ether solvents such as dioxane and tetrahydrofuran,
It is soluble in halogenated hydrocarbons such as methylene chloride,
These solutions can be formed into films and the like.
また、軟化点は、1o。Moreover, the softening point is 1o.
〜250℃に容品に調整することができる。The temperature can be adjusted to ~250°C.
本発明におけるポリエステルイミドは成形品。The polyesterimide in the present invention is a molded product.
接着剤、構造材料等として用いることができる。It can be used as an adhesive, a structural material, etc.
本発明で得られるポリエステルイミドは、その前駆体か
ら適宜、製造し、使用に供することができる。The polyesterimide obtained in the present invention can be appropriately produced from its precursor and used.
なお、一般式(1)で表わされる化合物の基Yがアミノ
基であるジアミンは、対応するヒドロキシフェニルアミ
ノフェニルプロパン2モルに対し、4.4′−ジフルオ
ロベンゾフェノン又は4゜4′−ジクロロジフェニルス
ルホン1モルを水酸化カリウム、無水炭酸カリウム等の
塩基の存在下。In addition, for the diamine in which the group Y of the compound represented by the general formula (1) is an amino group, 4.4'-difluorobenzophenone or 4.4'-dichlorodiphenylsulfone is added to 2 moles of the corresponding hydroxyphenylaminophenylpropane. 1 mol in the presence of a base such as potassium hydroxide or anhydrous potassium carbonate.
極性有機溶剤中で、100’C以上に加熱することによ
って製造することができる。It can be produced by heating to 100'C or higher in a polar organic solvent.
また、一般式(1)で表わされる化合物の基Yがイソシ
アナート基であるジイソシアナートは、上記のようにし
て得られたジアミンを常法に従いホスゲンと反応させる
ことによって製造することができる。Further, a diisocyanate in which the group Y of the compound represented by general formula (1) is an isocyanate group can be produced by reacting the diamine obtained as described above with phosgene according to a conventional method.
前記したポリエステルイミドの前駆体であるアミド酸は
、一般式(4)
であり、同一ベンゼン環に結合しているアミド基とカル
ボキシル基はAに対してメタ位又はパラ位に結合してい
る〕で表される構成単位を有する。The amic acid that is the precursor of the polyesterimide described above has the general formula (4), and the amide group and carboxyl group bonded to the same benzene ring are bonded to the meta or para position with respect to A.] It has the structural unit represented by .
以下、実施例により本発明の詳細な説明するが、本発明
はこれらの範囲に限定されるものではない。Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these scopes.
製造例1
冷却管、温度計、撹拌機、窒素ガス導入管を備えた4つ
目フラスコに、2− (3−ヒドロキシフェニル) −
2−(4’−アミノフェニル)プロパン45.4g、ジ
メチルスルホキシド100mQ、クロルベンゼン120
mQを加え室温で溶解した後、水酸化カリウム13gを
同様の水に溶解した水溶液を加えた。窒素ガスを流しな
がら加熱撹拌し、水を演出させた。水の演出がとまった
後、温度を100”Cに下げ、4,4′−ジフルオロベ
ンゾフェノン21.8 g を加え、165℃で4時
間反応させた。室温まで冷却し、沈殿をろ過して除いた
後、水中に注ぎ粗生成物を得た。粗生成物をトルエン−
ヘキサン混合溶媒より再結晶し、目的の化合物4,4′
−ビス(3−(4−アミノ−α。Production Example 1 In a fourth flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube, 2-(3-hydroxyphenyl)-
2-(4'-aminophenyl)propane 45.4g, dimethyl sulfoxide 100mQ, chlorobenzene 120
After mQ was added and dissolved at room temperature, an aqueous solution of 13 g of potassium hydroxide dissolved in the same water was added. Water was produced by heating and stirring while flowing nitrogen gas. After the water production stopped, the temperature was lowered to 100"C, 21.8 g of 4,4'-difluorobenzophenone was added, and the mixture was reacted at 165°C for 4 hours. It was cooled to room temperature and the precipitate was removed by filtration. After that, the crude product was obtained by pouring it into water.
Recrystallize from a hexane mixed solvent to obtain the desired compound 4,4'
-bis(3-(4-amino-α).
α′−ジメチルベンジル)フェノキンフジフェニルケト
ンを得た。収量45.5g 、融点107〜111℃液
体クロマトグラフィー(カラム:東ソー(株)TSK
Gel G2000H及びG3000Hを連結、溶離液
テトラヒドロフラン)による純度99.0%(面積比)
であった。α'-dimethylbenzyl)phenoquine fudiphenyl ketone was obtained. Yield 45.5g, melting point 107-111℃ Liquid chromatography (column: Tosoh Corporation TSK)
Connecting Gel G2000H and G3000H, purity 99.0% (area ratio) using eluent tetrahydrofuran
Met.
このジアミンの分析結果は次のとおりである。The analysis results of this diamine are as follows.
(1)元素分析値(%)C43H4゜N、O。(1) Elemental analysis value (%) C43H4°N,O.
CHN
計算値 81,65 6.33 4.43実測値
81,57 6.41 4.32(2)赤外線吸収スペ
クトルエRの吸収位置(KBr錠剤法、C!l−1)
3460.3390 (アミノ基)
2970.2870 (メチル基)
1600 (カルボニル基)1250
(エーテル基)(3)核磁気共鳴スペクトル
NMRのスペクトル位置(DMSO−dct ppm)
1.57 (12H−重線)
4.86 (4H−重線)
6.4〜7.8 (24H多重線)
注)DMSOはジメチルスルホキシドの意味である。CHN Calculated value 81,65 6.33 4.43 Actual value
81,57 6.41 4.32 (2) Absorption position of infrared absorption spectrum E (KBr tablet method, C!l-1) 3460.3390 (Amino group) 2970.2870 (Methyl group) 1600 (Carbonyl group) 1250
(Ether group) (3) Nuclear magnetic resonance spectrum NMR spectral position (DMSO-dct ppm) 1.57 (12H-multiplet) 4.86 (4H-multiplet) 6.4-7.8 (24H-multiplet ) Note) DMSO means dimethyl sulfoxide.
製造例2
冷却管、温度計、撹拌機、窒素ガス導入管を備えた4つ
ロフラスコに、2−(3−ヒドロキシフェニル)−2−
(4’−アミノフェニル)フロパン68.1g、ジメチ
ルスルホキシド150mM、クロルベンゼン180mQ
、4.4’ −ジクロルジフェニルスルホン40.75
g 、無水炭酸カリウム20.5 g を仕込み、窒
素ガス通気下に加熱撹拌し、水を演出させた。165℃
で4時間反応させた後、室温まで冷却した。反応液を水
中に注いで粗生成物を得た。ベンゼン−ヘキサン混合溶
媒で再結晶して目的の化合物4,4′−ビス〔3−(4
−アミノ−α、α′−ジメチルベンジル)フェノキシ〕
ジフェニルスルホン71.1 g を得た。融点67
〜70℃、液体クロマトグラフィーによる純度は99.
4%であった。Production Example 2 2-(3-hydroxyphenyl)-2- was placed in a four-bottle flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube.
(4'-aminophenyl)furopane 68.1g, dimethyl sulfoxide 150mM, chlorobenzene 180mQ
, 4.4'-dichlorodiphenylsulfone 40.75
g and 20.5 g of anhydrous potassium carbonate were added, and the mixture was heated and stirred under nitrogen gas flow to produce water. 165℃
After reacting for 4 hours, the mixture was cooled to room temperature. The reaction solution was poured into water to obtain a crude product. The target compound 4,4'-bis[3-(4
-amino-α,α′-dimethylbenzyl)phenoxy]
71.1 g of diphenyl sulfone was obtained. Melting point 67
~70°C, purity determined by liquid chromatography is 99.
It was 4%.
このジアミンの分析結果は次のとおりである。The analysis results of this diamine are as follows.
(1)元素分析値(%)C42H4゜N20.SCHN
計算値 75.45 5,99 4,19 4゜9
実測値 75.18 6.03 4.02 .4゜6
(2)IRの吸収位置(KBrBr法、Ql−’)34
50.3390 (アミノ基)
2970.2870 (メチル基)
1290.1110 (スルホニル基)1250
(エーテル基)(3)NMRのスペクトル位置
(DMSO−dsyPPl)1.55 (12H
−重線)
4.87 (4H−重線)
6.4〜8.0 (24H多重線)
実施例1
撹拌機、温度計、窒素ガス導入管、下向き冷却管を備え
た4つロフラスコに製造例1で得られた4、4′−ビス
(3−(4−アミノ−α、α′ジメチルベンジル)フェ
ノキシ〕ベンゾフェノン3.16 g とビスフェノ
ールAビストリメリテート二無水物2.88g、N−メ
チルピロリドン15mQ、亜リン酸トリフェニル0.2
g を入れ、窒素ガスを流しながら200℃で5時
間反応させてポリイミドワニスを得た。このワニスを水
に注いで再沈し、粉砕、乾燥してポリイミド粉末を得た
。DMF中、濃度0−1g/dQ 、温度30℃で測定
した還元粘度は0.47dQ/g 、荷重10kg/a
Jで高化式フローテスターで測定した軟化点は165℃
、5%重量減少温度は、437℃であった。また、溶解
性試験(ポリイミド粉末を有機溶剤に、5重量%の濃度
になるように添加し、室温で溶解状態を観察)において
、上記ポリイミド粉末は、DMF、NMP、ジオキサン
、テトラヒドロフラン(THF)及び塩化メチレンにそ
れぞれ可溶であった。上記ポリイミドの赤外線吸収スペ
クトルを第1図に示す。(1) Elemental analysis value (%) C42H4°N20. SCHN Calculated value 75.45 5,99 4,19 4°9 Actual value 75.18 6.03 4.02. 4゜6 (2) IR absorption position (KBrBr method, Ql-') 34
50.3390 (amino group) 2970.2870 (methyl group) 1290.1110 (sulfonyl group) 1250
(ether group) (3) NMR spectral position (DMSO-dsyPPl) 1.55 (12H
- doublet) 4.87 (4H-multiplet) 6.4 to 8.0 (24H multiplet) Example 1 Manufactured in a four-loop flask equipped with a stirrer, thermometer, nitrogen gas introduction tube, and downward cooling tube. 3.16 g of 4,4'-bis(3-(4-amino-α,α'dimethylbenzyl)phenoxy)benzophenone obtained in Example 1 and 2.88 g of bisphenol A bistrimelitate dianhydride, N-methyl Pyrrolidone 15mQ, triphenyl phosphite 0.2
g and reacted at 200° C. for 5 hours while flowing nitrogen gas to obtain a polyimide varnish. This varnish was poured into water and reprecipitated, ground and dried to obtain polyimide powder. The reduced viscosity measured in DMF at a concentration of 0-1 g/dQ and a temperature of 30°C is 0.47 dQ/g, and a load of 10 kg/a.
The softening point measured with a Koka type flow tester at J is 165℃
, the 5% weight loss temperature was 437°C. In addition, in a solubility test (polyimide powder was added to an organic solvent at a concentration of 5% by weight and the state of dissolution was observed at room temperature), the polyimide powder was found to contain DMF, NMP, dioxane, tetrahydrofuran (THF) and Each was soluble in methylene chloride. The infrared absorption spectrum of the above polyimide is shown in FIG.
実施例2
撹拌機、温度計、塩化カルシウム管、窒素ガス導入管の
ついた4つロフラスコに製造例2で得られた4、4′−
ビス(3−(4−アミノ−α。Example 2 4,4'- obtained in Production Example 2 was placed in a four-loaf flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas introduction tube.
Bis(3-(4-amino-α.
α′−ジメチルベンジル)フェノキシフジフェニルスル
ホン3.34g とN、N−ジメチルホルムアミド(
DMF)20mAを入れ溶解する。5℃以下に冷却しな
がらビスフェノールAビストリメリテート二無水物2.
88 g を少しずつ加えた後。3.34 g of α'-dimethylbenzyl)phenoxyfudiphenylsulfone and N,N-dimethylformamide (
Add 20 mA of DMF and dissolve. Bisphenol A bistrimelitate dianhydride while cooling to below 5°C2.
After adding 88 g little by little.
5℃以下で3時間、室温で1時間反応させてポリイミド
の前睨体であるポリアミド酸のワニスを得た。このワニ
スに無水酢酸1.3g、ピリジン1.0 g を加え
室温で3時間反応させてポリイミドワニスを得た。この
ワニスを水に注いで再沈し、粉砕、乾燥してポリイミド
粉末を得た。DMF中、濃度0.1g/dQ 、温度3
0℃で測定した還元粘度は0.33dQ/g、荷重10
kg/ajで高化式フローテスタで測定した軟化点は、
162℃であった。The mixture was reacted for 3 hours at 5°C or lower and for 1 hour at room temperature to obtain a polyamic acid varnish, which is a polyimide precursor. To this varnish, 1.3 g of acetic anhydride and 1.0 g of pyridine were added and reacted at room temperature for 3 hours to obtain a polyimide varnish. This varnish was poured into water and reprecipitated, ground and dried to obtain polyimide powder. In DMF, concentration 0.1 g/dQ, temperature 3
Reduced viscosity measured at 0°C is 0.33 dQ/g, load 10
The softening point measured with a Koka type flow tester in kg/aj is
The temperature was 162°C.
このポリイミド粉末は、溶解性試験においてDMF、ジ
オキサン、テトラヒドロフラン、塩化メチレンに可溶で
あった。5%重量減少温度は432℃であった。上記ポ
リイミドの赤外線吸収スペクトルを第2図に示す。This polyimide powder was soluble in DMF, dioxane, tetrahydrofuran, and methylene chloride in a solubility test. The 5% weight loss temperature was 432°C. FIG. 2 shows the infrared absorption spectrum of the polyimide.
実施例3
実施例1において、ビスフェノールAビストリメリテー
ト二無水物のかわりに0,0′−ビスフェノールビスト
リメリテートニ無水物2.67 gを使用する以外は同
様にしてポリイミド粉末を得た。このポリイミドの還元
粘度は0.52dj2/g、軟化点は140T:、5%
重量減少温度は445℃であり、溶解性試験においてD
MF、NMP。Example 3 A polyimide powder was obtained in the same manner as in Example 1 except that 2.67 g of 0,0'-bisphenol bistrimelitate dianhydride was used instead of bisphenol A bistrimelitate dianhydride. The reduced viscosity of this polyimide is 0.52dj2/g, and the softening point is 140T:, 5%.
The weight loss temperature was 445°C and D in the solubility test.
MF, NMP.
ジオキサン、THF、塩化メチレンに可溶であった。上
記ポリイミドの赤外線吸収スペクトルを第3図に示す。It was soluble in dioxane, THF, and methylene chloride. FIG. 3 shows the infrared absorption spectrum of the polyimide.
実施例4
実施例2において、ビスフェノールAビストリメリテー
ト二無水物のかわりに、下記(V)式で表わされる二無
水物3.47 g を使用する以外は同様にしてポリ
イミド粉末を得た。このポリイミドの還元粘度は0.3
5dQ/g、軟化点は165℃、5%重量減少温度は4
50”Cであり、溶解性試験においてDMF、NMP、
ジオキサン、THF。Example 4 Polyimide powder was obtained in the same manner as in Example 2, except that 3.47 g of dianhydride represented by the following formula (V) was used instead of bisphenol A bistrimelitate dianhydride. The reduced viscosity of this polyimide is 0.3
5dQ/g, softening point is 165℃, 5% weight loss temperature is 4
50"C, and in the solubility test, DMF, NMP,
Dioxane, THF.
塩化メチレンに可溶であった。上記ポリイミドの赤外線
吸収スペクトルを第4図に示す。It was soluble in methylene chloride. FIG. 4 shows the infrared absorption spectrum of the polyimide.
本発明に係るポリエステルイミドは、有機溶剤に対する
溶解性が優れ、比較的低軟化点を示す。The polyesterimide according to the present invention has excellent solubility in organic solvents and exhibits a relatively low softening point.
Claims (1)
される二価の基を表し、Zは一般式(3)▲数式、化学
式、表等があります▼…(3) (ただし、式中、Xは■C=Oまたは■SO_2を示す
)で表わされる二価の基を示す)〕で表される構成単位
を含んでなるポリエステルイミド。 2、一般式(3)で表わされる二価の基が、一般式(3
)中、イソプロピリデン基に対して、結合及び酸素がそ
れぞれパラ位又はメタ位に結合しているものである請求
項1記載のポリエステルイミド。 3、一般式(3)で表わされる二価の基が、請求項2に
記載のものであつて、かつ、一般式(3)中、2個の結
合及び2個の酸素のうち、少なくとも1個がイソプロピ
リデン基に対してメタ位に結合しているものである請求
項2記載のポリエステルイミド。 4、一般式(3)で表わされる二価の基が、請求項3に
記載のものであつて、かつ、一般式(3)中、イソプロ
ピリデン基に対して、結合がパラ位に及び酸素がメタ位
に結合しているものである請求項3記載のポリエステル
イミド。[Claims] 1. General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (1) [However, in the formula, A is general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ …(2) (However, in the formula, Ar represents a divalent aromatic group) represents a divalent group represented by the general formula (3) ▲ Numerical formula, chemical formula, table, etc. ▼…( 3) A polyesterimide comprising a structural unit represented by (wherein, X represents a divalent group represented by ■C=O or ■SO_2). 2. The divalent group represented by the general formula (3) is represented by the general formula (3)
2. The polyesterimide according to claim 1, wherein the bond and oxygen are bonded to the isopropylidene group at the para-position or meta-position, respectively. 3. The divalent group represented by general formula (3) is the one according to claim 2, and in general formula (3), at least one of two bonds and two oxygen 3. The polyesterimide according to claim 2, wherein the isopropylidene group is bonded to the meta position of the isopropylidene group. 4. The divalent group represented by the general formula (3) is the one according to claim 3, and in the general formula (3), the bond is in the para position with respect to the isopropylidene group and the oxygen The polyesterimide according to claim 3, wherein is bonded to the meta position.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33599989A JPH03195732A (en) | 1989-12-25 | 1989-12-25 | New polyesterimide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33599989A JPH03195732A (en) | 1989-12-25 | 1989-12-25 | New polyesterimide |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03195732A true JPH03195732A (en) | 1991-08-27 |
Family
ID=18294651
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP33599989A Pending JPH03195732A (en) | 1989-12-25 | 1989-12-25 | New polyesterimide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03195732A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000061658A1 (en) * | 1999-04-09 | 2000-10-19 | Kaneka Corporation | Polyimide resin, resin composition with improved moisture resistance comprising the same, adhesive solution, filmy bonding member, layered adhesive film, and processes for producing these |
JP2005298623A (en) * | 2004-04-09 | 2005-10-27 | Manac Inc | Polyimide combining high organic solvent dissolvability, high thermoplasticity, high toughness and high glass transition temperature, and its manufacturing method |
JP2006306990A (en) * | 2005-04-28 | 2006-11-09 | Manac Inc | Ester imide oligomer, thermally cured product thereof and method for producing the oligomer and the product |
JP2009001793A (en) * | 2008-06-06 | 2009-01-08 | Kaneka Corp | Adhesive |
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JPH07119281A (en) * | 1993-10-22 | 1995-05-09 | Dainippon Printing Co Ltd | Pattern synchronous decorative sheet |
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JPH07119281A (en) * | 1993-10-22 | 1995-05-09 | Dainippon Printing Co Ltd | Pattern synchronous decorative sheet |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000061658A1 (en) * | 1999-04-09 | 2000-10-19 | Kaneka Corporation | Polyimide resin, resin composition with improved moisture resistance comprising the same, adhesive solution, filmy bonding member, layered adhesive film, and processes for producing these |
US6693162B2 (en) | 1999-04-09 | 2004-02-17 | Kaneka Japan Corporation | Polyimide resin and resin composition, adhesive solution, film-state joining component,and adhesive laminate film improved in moisture resistance using it, and production methods therefor |
JP2005298623A (en) * | 2004-04-09 | 2005-10-27 | Manac Inc | Polyimide combining high organic solvent dissolvability, high thermoplasticity, high toughness and high glass transition temperature, and its manufacturing method |
JP2006306990A (en) * | 2005-04-28 | 2006-11-09 | Manac Inc | Ester imide oligomer, thermally cured product thereof and method for producing the oligomer and the product |
JP4603929B2 (en) * | 2005-04-28 | 2010-12-22 | マナック株式会社 | Esterimide oligomer, thermoset thereof, and production method thereof |
JP2009001793A (en) * | 2008-06-06 | 2009-01-08 | Kaneka Corp | Adhesive |
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