JPH0463865A - Polyaniline composite - Google Patents
Polyaniline compositeInfo
- Publication number
- JPH0463865A JPH0463865A JP20798990A JP20798990A JPH0463865A JP H0463865 A JPH0463865 A JP H0463865A JP 20798990 A JP20798990 A JP 20798990A JP 20798990 A JP20798990 A JP 20798990A JP H0463865 A JPH0463865 A JP H0463865A
- Authority
- JP
- Japan
- Prior art keywords
- polyaniline
- film
- molding
- resin
- mixed solution
- 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
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000002019 doping agent Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 5
- 239000005060 rubber Substances 0.000 claims abstract description 5
- -1 amine compound Chemical class 0.000 claims description 39
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 52
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 1
- BBNQSYUZYQBRAO-UHFFFAOYSA-N 2,3,5-trimethoxyaniline Chemical compound COC1=CC(N)=C(OC)C(OC)=C1 BBNQSYUZYQBRAO-UHFFFAOYSA-N 0.000 description 1
- PLMYBZTUBCRLHI-UHFFFAOYSA-N 2,3,6-trimethoxyaniline Chemical compound COC1=CC=C(OC)C(OC)=C1N PLMYBZTUBCRLHI-UHFFFAOYSA-N 0.000 description 1
- HEZIOZBMPKPOER-UHFFFAOYSA-N 2,3-dimethoxyaniline Chemical compound COC1=CC=CC(N)=C1OC HEZIOZBMPKPOER-UHFFFAOYSA-N 0.000 description 1
- OBSLLHNATPQFMJ-UHFFFAOYSA-N 2,4-Dimethylthiazole Chemical compound CC1=CSC(C)=N1 OBSLLHNATPQFMJ-UHFFFAOYSA-N 0.000 description 1
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 description 1
- HQBJSEKQNRSDAZ-UHFFFAOYSA-N 2,6-dimethoxyaniline Chemical compound COC1=CC=CC(OC)=C1N HQBJSEKQNRSDAZ-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- MCFSNYMQISXQTF-UHFFFAOYSA-N 2-chlorosulfonylacetyl chloride Chemical compound ClC(=O)CS(Cl)(=O)=O MCFSNYMQISXQTF-UHFFFAOYSA-N 0.000 description 1
- JRMAQQQTXDJDNC-UHFFFAOYSA-M 2-ethoxy-2-oxoacetate Chemical compound CCOC(=O)C([O-])=O JRMAQQQTXDJDNC-UHFFFAOYSA-M 0.000 description 1
- GNDQGCHFQDKFDG-UHFFFAOYSA-N 2-ethoxy-3-methoxyaniline Chemical compound CCOC1=C(N)C=CC=C1OC GNDQGCHFQDKFDG-UHFFFAOYSA-N 0.000 description 1
- IRRIDSMXMHAYOV-UHFFFAOYSA-N 2-ethoxy-5-methoxyaniline Chemical compound CCOC1=CC=C(OC)C=C1N IRRIDSMXMHAYOV-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- GUGQQGROXHPINL-UHFFFAOYSA-N 2-oxobutanoyl chloride Chemical compound CCC(=O)C(Cl)=O GUGQQGROXHPINL-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- KGUOCLZDKIBCFN-UHFFFAOYSA-N 3-ethoxy-2-methoxyaniline Chemical compound CCOC1=CC=CC(N)=C1OC KGUOCLZDKIBCFN-UHFFFAOYSA-N 0.000 description 1
- WEZAHYDFZNTGKE-UHFFFAOYSA-N 3-ethoxyaniline Chemical compound CCOC1=CC=CC(N)=C1 WEZAHYDFZNTGKE-UHFFFAOYSA-N 0.000 description 1
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 1
- OPXLVWLFDKRYRB-UHFFFAOYSA-N 3-methoxy-2-methylaniline Chemical compound COC1=CC=CC(N)=C1C OPXLVWLFDKRYRB-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- QAXMCYJNFHCJFB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol;hydrobromide Chemical compound Br.CCCN(CCC)CCC1=CC=C(O)C(O)=C1 QAXMCYJNFHCJFB-UHFFFAOYSA-N 0.000 description 1
- RPJXLEZOFUNGNZ-UHFFFAOYSA-N 5-methoxy-2-methylaniline Chemical compound COC1=CC=C(C)C(N)=C1 RPJXLEZOFUNGNZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-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
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 101150099564 amiF gene Proteins 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- JFCHSQDLLFJHOA-UHFFFAOYSA-N n,n-dimethylsulfamoyl chloride Chemical compound CN(C)S(Cl)(=O)=O JFCHSQDLLFJHOA-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリアニリン複合物に関し、さらに詳しくは
、プラスチック電池の電極材料、コンデンサー、電磁シ
ールド材、静電吸着用フィルム、導電ペースト材、帯電
防止材、表示素子、電子デバイス等において有用なポリ
アニリン複合物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polyaniline composites, and more specifically to electrode materials for plastic batteries, capacitors, electromagnetic shielding materials, electrostatic adsorption films, conductive paste materials, and charging materials. The present invention relates to polyaniline composites useful in preventive materials, display elements, electronic devices, etc.
〔従来の技術及び発明か解決しようとする課題〕従来、
ドーパントをドーピングした導電性ポリアニリンは、皮
膜、フィルムあるいはシート状の形態で、種々の用途に
用いることか提案されている。この様な用途に用いるポ
リアニリン成形体を製造する方法としては、化学重合法
を利用する方法、或いは電解酸化重合法を利用する方法
等が知られている。[Prior art and invention or problem to be solved] Conventionally,
Conductive polyaniline doped with a dopant has been proposed for use in a variety of applications in the form of films, films, or sheets. As methods for producing polyaniline molded bodies for use in such applications, methods using chemical polymerization methods, methods using electrolytic oxidation polymerization methods, etc. are known.
化学重合法を利用する方法によれば、ポリアニリンは、
塩酸水溶液中にアニリンを加え、それに酸化剤として、
例えば、過硫酸アンモニウムを添加して合成される。こ
の方法で得られるポリアニリンは、アンモニア水等のア
ルカリ溶液で脱ドーピングすることによって、Ｎ−メチ
ル−２−ピロリドン（ＮＭＰ）等の有機溶剤に可溶にな
り、そして、そのＮＭＰ溶液からは、膜厚５〜１００
ａｎの自立性ポリアニリンフィルムを得ることができる
。このフィルムは、絶縁性（ａ −１０−” ｓ／ｃｍ
）であり、プロトン酸をドーピングすることにより、導
電性ポリアニリンフィルム（ＬＯ°Ｓ／ｃｍ）にするこ
とができる（例えば、ｒＰｏｌｙｆｆｌｅｒ Ｐｒｅｐ
ｒｉｎｔｓ、 Ｊａｐａｎ、３８（７）、２１３９．（
１９８９）参照）。しかしながら、この方法で形成され
たポリアニリンフィルムは、機械的強度が劣り、−度成
膜した後は、不溶性になるために加工性が劣り、また、
環境の影響を受けやすいという問題があった。また、ベ
ンゼン核の置換基の種類によっては、フィルムが形成で
きない場合がある。According to the method using chemical polymerization method, polyaniline is
Add aniline to an aqueous hydrochloric acid solution and use it as an oxidizing agent.
For example, it is synthesized by adding ammonium persulfate. The polyaniline obtained by this method becomes soluble in organic solvents such as N-methyl-2-pyrrolidone (NMP) by dedoping with an alkaline solution such as aqueous ammonia, and from the NMP solution, a film can be obtained. Thickness 5-100
An free-standing polyaniline film can be obtained. This film has an insulating property (a −10−” s/cm
) and can be made into a conductive polyaniline film (LO°S/cm) by doping with protic acid (for example, rPolyffler Prep
rints, Japan, 38(7), 2139. (
(1989)). However, the polyaniline film formed by this method has poor mechanical strength and becomes insoluble after being formed, resulting in poor processability.
The problem was that it was easily influenced by the environment. Furthermore, depending on the type of substituent on the benzene nucleus, it may not be possible to form a film.
また、電解酸化重合法を利用する方法では、電解質水溶
液にアニリンを溶解し、これに電極を陽極として浸漬し
、電圧を印加することによって電極上にポリアニリンを
析出させる。この方法では、電気量が小さい場合には薄
膜が形成されるが、電気量が大きくなると、粉末が凝集
した状態の析出物が生成し、電極から脱落してしまうた
め、厚膜を得ることか難しいという問題がある。In addition, in a method using electrolytic oxidation polymerization, aniline is dissolved in an aqueous electrolyte solution, an electrode is immersed therein as an anode, and a voltage is applied to deposit polyaniline on the electrode. In this method, a thin film is formed when the amount of electricity is small, but when the amount of electricity is large, a precipitate in the form of agglomerated powder is generated and falls off the electrode, making it difficult to obtain a thick film. The problem is that it is difficult.
上記の問題点を改善する目的で、溶融性の熱可塑性合成
樹脂をパイングーとし、ポリアニリン粉末を分散させた
ポリアニリン複合物か提案されている（特開昭６４−６
９６８２号公報）。このポリアニリン複合物は、機械的
強度に関しては改善が見られるが、ポリアニリンの粉砕
条件によってはポリアニリン粒子の分散状態が不均一に
なる為、導電性にムラが生しやすいこと、耐溶剤性、耐
熱性、耐摩耗性に劣り、また、導電性が劣るため導電性
を高める必要かあり、その為には、ポリアニリンを多量
にドープしたものを使用しなければならないこと等の問
題を有している。In order to improve the above-mentioned problems, a polyaniline composite has been proposed in which polyaniline powder is dispersed in a meltable thermoplastic synthetic resin (Paingu) (Japanese Patent Laid-Open No. 64-6
9682). This polyaniline composite shows improvement in mechanical strength, but depending on the grinding conditions of polyaniline, the dispersion state of polyaniline particles becomes uneven, which tends to cause unevenness in conductivity, solvent resistance, and heat resistance. It has problems such as poor performance and abrasion resistance, and poor conductivity, so it is necessary to increase the conductivity, and for that purpose, it is necessary to use a material doped with a large amount of polyaniline. .
本発明は、従来の技術における上記のような問題を解決
することを目的とするものである。The present invention aims to solve the above-mentioned problems in the conventional technology.
即ち、本発明の目的は、任意の形状に成形され、電極材
料等として有用なポリアニリン複合物を提供することに
ある。That is, an object of the present invention is to provide a polyaniline composite that can be molded into any shape and is useful as an electrode material.
本発明の他の目的は、機械的強度、柔軟性に優れ、或い
は耐摩耗性、耐熱性、耐溶剤性に優れ、工業的に大量生
産可能なポリアニリン複合物を提供することにある。Another object of the present invention is to provide a polyaniline composite that has excellent mechanical strength, flexibility, abrasion resistance, heat resistance, and solvent resistance, and can be industrially mass-produced.
本発明のポリアニリン複合物は、脱トープしたポリアニ
リンを、ゴム、熱可塑性樹脂及び熱硬化性樹脂から選択
された少なくとも１種の高分子材料と共に有機溶剤に溶
解して得た混合溶液を用いて成形された成形体からなり
、そしてその成形体が成形後にドーパントを用いてドー
プされたことを特徴とする。The polyaniline composite of the present invention is molded using a mixed solution obtained by dissolving detoped polyaniline in an organic solvent together with at least one polymeric material selected from rubber, thermoplastic resin, and thermosetting resin. The molded body is characterized in that the molded body is doped with a dopant after molding.
本発明において用いるポリアニリンは、アニリン又はそ
の誘導体を酸化重合した後、得られる酸化重合体をアン
モニア水や水酸化ナトリウム等のアルカリ水溶液により
、或いは電気化学的方法により脱ドーピングすることに
よって得られるもので、下記−数式（Ｉ）で示される単
量体単位より構成される。アニリン又はアニリン誘導体
の酸化重合は、上記した従来公知の化学重合法及び電解
酸化重合法のいずれの方法を用いてもよい。The polyaniline used in the present invention is obtained by oxidative polymerization of aniline or a derivative thereof, and then dedoping the resulting oxidized polymer with an aqueous alkali solution such as aqueous ammonia or sodium hydroxide, or by an electrochemical method. , is composed of a monomer unit represented by the following formula (I). For the oxidative polymerization of aniline or aniline derivatives, any of the conventionally known chemical polymerization methods and electrolytic oxidative polymerization methods described above may be used.
（式中、Ｒ３−Ｒ５は、同−或いは異なっていてもよく
、それぞれ水素原子、炭素数１〜２０のアルキル基また
はアルコキシ基を示す。）
上記−数式（Ｉ）で示される単量体単位を構成するアニ
リン誘導体の具体例としては、２−メトキシアニリン、
３−メトキンアニリン、２，３−ジメトキシアニリン、
２，５−ジメトキシアニリン、３．５−ジメトキシアニ
リン、２，６−ジメトキシアニリン、２−エトキシアニ
リン、２−エトキシ−３−メトキシアニリン、３−エト
キシアニリン、２．３−ジェトキシアニリン、２．５−
ジェトキシアニリン、３，５−ジェトキシアニリン、２
．６−ジェトキシアニリン、２−メトキシ−３−エトキ
シアニリン、２−エトキシ−５−メトキシアニリン、２
，３．５−トリメトキシアニリン、２，３．６−トリメ
トキシアニリン、２．３．５．６−チトラメトキシアニ
リン、２，３，５．６−チトラエトキシアニリン、２，
３−ジメチルアニリン、２−メチル−３−メトキシアニ
リン、２．３，５．６−チトラメチルアニリン、２−メ
チル−５メトキシアニリン、２，５−ジメチルアニリン
等をあげることかできるか、必ずしもこれらに限定され
るものではない。上記アニリン誘導体のうちでも、２つ
以上の置換基を有するものが好ましく、特に２つ以上の
アルコキシ基またはアルキル基を有するアルコキシアニ
リン誘導体またはアルキルアニリン誘導体の酸化重合体
が、有機溶剤に対する溶解性が良好であり、かつ電気伝
導性もよいので好ましい。(In the formula, R3-R5 may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group.) Monomer unit represented by the above-mentioned formula (I) Specific examples of aniline derivatives constituting include 2-methoxyaniline,
3-methquinaniline, 2,3-dimethoxyaniline,
2,5-dimethoxyaniline, 3.5-dimethoxyaniline, 2,6-dimethoxyaniline, 2-ethoxyaniline, 2-ethoxy-3-methoxyaniline, 3-ethoxyaniline, 2.3-jethoxyaniline, 2. 5-
Jetoxyaniline, 3,5-jethoxyaniline, 2
．． 6-jethoxyaniline, 2-methoxy-3-ethoxyaniline, 2-ethoxy-5-methoxyaniline, 2
, 3.5-trimethoxyaniline, 2,3.6-trimethoxyaniline, 2.3.5.6-titramethoxyaniline, 2,3,5.6-titraethoxyaniline, 2,
Can I mention 3-dimethylaniline, 2-methyl-3-methoxyaniline, 2.3,5.6-titramethylaniline, 2-methyl-5methoxyaniline, 2,5-dimethylaniline, etc.? It is not limited to. Among the above aniline derivatives, those having two or more substituents are preferable, and in particular, oxidized polymers of alkoxyaniline derivatives or alkylaniline derivatives having two or more alkoxy groups or alkyl groups are preferred because they have solubility in organic solvents. It is preferable because it has good electrical conductivity.
本発明において上記ポリアニリンと併用して用いられる
高分子材料としては、ゴム、熱可塑性樹脂及び硬化性樹
脂より選択されたものが使用される。ゴムとしては、天
然ゴム、スチレン−ブタジェンゴム、ニトリルゴム、エ
チレン−プロピレンゴム、ブチルゴム、ウレタンゴム、
シリコンゴム等の各種合成ゴムかあげられる。In the present invention, the polymer material used in combination with the above-mentioned polyaniline is selected from rubber, thermoplastic resin, and curable resin. Rubbers include natural rubber, styrene-butadiene rubber, nitrile rubber, ethylene-propylene rubber, butyl rubber, urethane rubber,
Examples include various synthetic rubbers such as silicone rubber.
熱可塑性樹脂としては、ポリ塩化ビニル、ポリスチレン
、エチレン−酢酸ビニル共重合体、ポリエチレン、ポリ
プロピレン、ポリビニルアルコル、ＡＢＳ樹脂、ポリイ
ミド、ポリカーボネート、熱可塑性エラストマー等各種
のものをあげることができる。Examples of the thermoplastic resin include polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyvinyl alcohol, ABS resin, polyimide, polycarbonate, and thermoplastic elastomer.
また、熱硬化性樹脂としては、エポキシ樹脂、フェノー
ル樹脂、メラミン樹脂、ポリエステル樹脂、ポリウレタ
ン樹脂等各種のものがあげられる。Further, examples of the thermosetting resin include various resins such as epoxy resin, phenol resin, melamine resin, polyester resin, and polyurethane resin.
これらのなかでも、特にエポキシ樹脂が好ましい。Among these, epoxy resins are particularly preferred.
本発明において使用できるエポキシ樹脂としては、例え
ば、ビスフェノールＡ１ビスフエノールＦ１フエノール
ノボラツク、ポリグリコールとエピクロルヒドリンとの
反応で得られる常温で液状のジクリンジルエーテル、臭
素化エポキシ樹脂、ビフェニル型エポキシ樹脂、ビニル
シクロヘキセンジオキシド、ジシクロペンタジェンジオ
キシド、アリサイクリックジェポキシ−アジベートのよ
うな脂環式エポキシ化合物、さらにはｎ−ブチルグリシ
ジルエーテル、パーサティック酸グリシジルエーテル、
スチレンオキサイド、フェニルグリシジルエーテル、ク
レジルグリシジルエーテル、ジシクロペンタジェンジオ
キシドのような通常のエポキシ樹脂の希釈剤として用い
られるものかあげられる。Epoxy resins that can be used in the present invention include, for example, bisphenol A1 bisphenol F1 phenol novolac, diclinyl ether which is liquid at room temperature obtained by the reaction of polyglycol and epichlorohydrin, brominated epoxy resin, biphenyl type epoxy resin, vinyl cycloaliphatic epoxy compounds such as cyclohexene dioxide, dicyclopentadiene dioxide, alicyclic gepoxy-adivate, as well as n-butyl glycidyl ether, persatic acid glycidyl ether,
Examples include those commonly used as diluents for epoxy resins, such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, and dicyclopentadiene dioxide.
本発明において、上記エポキシ樹脂か使用される場合に
は、さらに、硬化剤として、アミン系化合物をポリアニ
リンと併用することかできる。ポリアニリンと併用して
使用することかできるアミン系化合物としては、脂肪族
ポリアミン（例えば、ＤＴＡ （ジエチレントリアミン
）、ＴＴＡ（トリエチレンテトラミン） 、ＴＥＰＡ
（テトラエチレンペンタミン） 、ＤＥＡＰＡ （ジエ
チルアミノプロピルアミン） 、ＤＰＤＡ （ジプロピ
レンシアミン）等）、芳香脂肪族ポリアミン（例えば、
ｍ−ＸＤＡ（ａ＋−キシレンジアミン） 、ＤＤＭ （
ジアミノジフェニルメタン）、等）、芳香族ポリアミン
（例えば、ＭＰＤＡ （メタフェニレンジアミン）、Ｄ
ＤＳ （ジアミノジフェニルスルホン、アニリンブラッ
ク）、等）、脂環式ポリアミン（例えば、ＭＰＤＡ （
メンセンジアミン）、ＩＰＤＡ（イソホロンジアミン）
、Ｎ−ＡＥＰ （Ｎ−アミノエチルピペラジン）等）
、ポリアミンのプロピレンオキサイドまたはエチレンオ
キサイド付加物、ポリアミドアミン、変性ポリアミン、
イミダゾール化合物（例えば、２−メチルイミダゾール
、２−エチル−４−メチルイミダゾール、１−シアノエ
チル−２−エチル−４−メチルイミダゾール等）等かあ
げられる。In the present invention, when the above-mentioned epoxy resin is used, an amine compound can be used in combination with polyaniline as a curing agent. Examples of amine compounds that can be used in combination with polyaniline include aliphatic polyamines (for example, DTA (diethylenetriamine), TTA (triethylenetetramine), TEPA
(tetraethylenepentamine), DEAPA (diethylaminopropylamine), DPDA (dipropylenecyamine), etc.), aromatic aliphatic polyamines (e.g.
m-XDA (a+-xylene diamine), DDM (
diaminodiphenylmethane), etc.), aromatic polyamines (e.g. MPDA (metaphenylenediamine), D
DS (diaminodiphenylsulfone, aniline black), etc.), alicyclic polyamines (e.g. MPDA (
menthendiamine), IPDA (isophoronediamine)
, N-AEP (N-aminoethylpiperazine), etc.)
, propylene oxide or ethylene oxide adducts of polyamines, polyamidoamines, modified polyamines,
Examples include imidazole compounds (eg, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc.).
これらのアミン系化合物は、ポリアニリンに対して１０
０：１〜１００：５０の重量比で使用される。These amine compounds have a 10%
A weight ratio of 0:1 to 100:50 is used.
本発明において、複合物におけるポリアニリンまたはポ
リアニリンとアミン系化合物の配合量は、上記高分子材
料に対して、ｔｉｔ−ｉｏ：ｔの重量比の範囲に設定す
るのか好ましい。In the present invention, the blending amount of polyaniline or polyaniline and amine compound in the composite is preferably set within a weight ratio of tit-io:t with respect to the polymer material.
ポリアニリン、場合により併用されるアミン系化合物、
及び上記高分子材料を溶解するのに用いる有機溶剤は、
それらのものを溶解するものであれば如何なるものでも
よく、例えば、脂肪族及び芳香族のケトン類、エーテル
類、エステル類、アミＦ類、ニトリル類、カーボネート
類、カルボン酸類、ハロゲン化物、スルホラン系化合物
、ニトロ化合物、スルホキシド類、ラクタム類、ラクト
ン類、飽和及び不飽和の複素環式化′合物をあげること
ができる。Polyaniline, amine compound used in combination,
and the organic solvent used to dissolve the polymeric material,
Any substance that dissolves these substances may be used, such as aliphatic and aromatic ketones, ethers, esters, amiFs, nitriles, carbonates, carboxylic acids, halides, and sulfolane. Mention may be made of compounds, nitro compounds, sulfoxides, lactams, lactones, saturated and unsaturated heterocyclic compounds.
それらの具体例として、脂肪族及び芳香族のケトン類と
しては、アセトン、ジエチルケトン、２−ブタノン、メ
チルプロピルケトン、ヒドロキシアセトン、メトキシア
セトン、フェニルアセトン、４−フェニル−２−ブタノ
ン等；エーテル類としては、テトラヒドロフラン、ジオ
キサン、ジメチルエーテル、ジエチルエーテル、メチル
エチルエーテル、ジメトキシエタン、ジェトキシエタン
、メチルグリコール、アニソール、１．２−ジメトキシ
ベンゼン、１．４−ジメトキシベンゼン、ｌ、３−ジオ
キソラン：エステル類としては、酢酸メチル、酢酸エチ
ル、トリメチルオルトホルメート、しゆう酸エチル、ト
リメチルリン酸エステル等；アミド類としては、ホルム
アミド、Ｎ−メチルホルムアミド、ジメチルホルムアミ
ド、Ｎ−メチルアセトアミド、ジメチルアセトアミド、
Ｎ−メチルプロピオンアミド、ヘキサメチルホスホルア
ミド等：ニトリル類としては、アセトニトリル、バレロ
ニトリル、ベンゾニトリル等；カーボネート類としては
、プロピレンカーボネート、エチレンカーボネート、ジ
メチルカポネート等、ハロゲン化合物としては、クロロ
ホルム、四塩化炭素、クロロベンゼン、ジクロロベンゼ
ン、塩化ヘンジイル、ペンセンスルホニルクロライド、
ペンセンスルホニルジクロライド、ベンゼンチオホスホ
ニルジクロライト、メタンスルホニルクロライド、塩化
アセチル、ジメチルスルファミルクロライド、エチルオ
キサリルクロライド、クロロスルホニルアセチルクロラ
イド等：スルホラン系化合物としては、スルホラン、３
−メチルスルホラン等；ニトロ化合物としては、ニトロ
メタン、ニトロヘンゼン等；スルホキシド類としては、
ジメチルスルホキシＦ等：ラクタム類としては、Ｎ−メ
チルピロリドン等、ラクトン類としては、γ−ブチロラ
クトン等；飽和及び不飽和複素環式化合物としては、テ
トラヒドロチオフェン、３−メチル−２−オキサゾリド
ン、ピロール、■−メチルピロール、２．４−ジメチル
チアゾール、フラン等がそれぞれあげられる。As specific examples thereof, aliphatic and aromatic ketones include acetone, diethyl ketone, 2-butanone, methylpropyl ketone, hydroxyacetone, methoxyacetone, phenylacetone, 4-phenyl-2-butanone, etc.; ethers; Examples of esters include tetrahydrofuran, dioxane, dimethyl ether, diethyl ether, methyl ethyl ether, dimethoxyethane, jetoxyethane, methyl glycol, anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, l,3-dioxolane. , methyl acetate, ethyl acetate, trimethyl orthoformate, ethyl oxalate, trimethyl phosphate, etc. Amides include formamide, N-methylformamide, dimethylformamide, N-methylacetamide, dimethylacetamide,
N-methylpropionamide, hexamethylphosphoramide, etc. Nitriles include acetonitrile, valeronitrile, benzonitrile, etc. Carbonates include propylene carbonate, ethylene carbonate, dimethyl caponate, etc. Halogen compounds include chloroform, Carbon tetrachloride, chlorobenzene, dichlorobenzene, hendiyl chloride, pencenesulfonyl chloride,
Pencenesulfonyl dichloride, benzenethiophosphonyl dichlorite, methanesulfonyl chloride, acetyl chloride, dimethylsulfamyl chloride, ethyloxalyl chloride, chlorosulfonylacetyl chloride, etc. Sulfolane compounds include sulfolane, 3
- Methylsulfolane, etc.; Nitro compounds include nitromethane, nitrohenzene, etc.; Sulfoxides include:
Dimethylsulfoxy F etc.: Lactams include N-methylpyrrolidone etc. Lactones include γ-butyrolactone etc. Saturated and unsaturated heterocyclic compounds include tetrahydrothiophene, 3-methyl-2-oxazolidone, pyrrole , -methylpyrrole, 2,4-dimethylthiazole, furan, etc., respectively.
本発明のポリアニリン複合物は、′使用目的に応して各
種の形態の成形体として使用される。成形体を製造する
為の成形法としては、種々のものが利用できる。The polyaniline composite of the present invention can be used as molded articles in various forms depending on the purpose of use. Various molding methods can be used to produce the molded body.
例えば、上記高分子材料を有機溶剤に溶解し、得られた
溶液に、ポリアニリン粉末を混合して溶解し、得られた
混合溶液をフィルム状等、所望の形状に成形し、その後
、溶剤を除去して所望の形状のポリアニリン複合物を得
ることができる。For example, the above polymer material is dissolved in an organic solvent, polyaniline powder is mixed and dissolved in the resulting solution, the resulting mixed solution is formed into a desired shape such as a film, and then the solvent is removed. A polyaniline composite having a desired shape can be obtained by doing this.
例えば、ポリアニリンと高分子材料との混合溶液を、金
属、半導体、合成樹脂、セラミック、紙、繊維等、種々
の固体の表面に塗布、吹き付け、浸漬等によって、表面
コーティングを行い、次いて、有機溶剤を除去すること
によって、上記固体表面に導電性皮膜が形成された導電
性物品を製造することができる。また、高分子材料とし
て、エポキシ樹脂等の熱硬化性樹脂を使用した場合には
、表面コーティングを行った後、例えば、８０〜１５０
℃で加熱硬化させながら、有機溶剤を除去すればよい。For example, a mixed solution of polyaniline and a polymer material is coated on the surface of various solids such as metals, semiconductors, synthetic resins, ceramics, paper, and fibers by applying, spraying, or dipping, and then an organic By removing the solvent, a conductive article having a conductive film formed on the solid surface can be manufactured. In addition, when a thermosetting resin such as an epoxy resin is used as the polymer material, after surface coating, for example, 80 to 150
The organic solvent may be removed while heating and curing at °C.
また、ポリアニリンと高分子材料との混合溶液を、ハツ
チ式又は連続的に流延し、乾燥して、所望の厚さの導電
性フィルムを形成することができる。Further, a mixed solution of polyaniline and a polymeric material can be cast in a hatch type or continuously and dried to form a conductive film of a desired thickness.
さらに、ポリアニリンと高分子材料との混合溶液を、ダ
イから押出すことによって、導電性繊維又はフィルム状
物を形成することもてきる。Furthermore, a conductive fiber or film-like material can be formed by extruding a mixed solution of polyaniline and a polymeric material through a die.
同様に、ポリアニリンと高分子材料との混合溶液を、種
々の形のモールドに注型して、モールド内の溶液から有
機溶剤を除去することにより、モルトの形状の導電性注
型品を製造することもてきる。Similarly, a malt-shaped conductive cast product is manufactured by casting a mixed solution of polyaniline and a polymer material into molds of various shapes and removing the organic solvent from the solution in the mold. It can also happen.
なお、上記成形に使用する混合溶液中の固形分濃度は、
特に制限はないが、通常００１〜９０重量％の範囲で設
定される。In addition, the solid content concentration in the mixed solution used for the above molding is
Although there is no particular restriction, it is usually set within a range of 0.001 to 90% by weight.
上記のようにして成形されたポリアニリン複合物の成形
体は、次いてドーピング処理を施す。ドーピングは、例
えば、ポリアニリン複合物の成形体を、塩酸、臭化水素
酸、硫酸、硝酸、過塩素酸、テトラフルオロ硼酸、ヘキ
サフルオロリン酸等のプロトン酸水溶液中に浸漬したり
、或いは、よう素、臭素、塩素等のハロケンの蒸気にさ
らすことによる化学的処理方法、或いは、成形体に無機
酸の塩、第４級アンモニウム塩等のドーパントを電気化
学的に吸着させる方法等によって行うことができる。The polyaniline composite molded article molded as described above is then subjected to a doping treatment. Doping can be carried out, for example, by immersing a polyaniline composite molded body in an aqueous protonic acid solution such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, etc. This can be carried out by a chemical treatment method by exposing the molded body to the vapor of halokenes such as chlorine, bromine, or chlorine, or by a method in which a dopant such as an inorganic acid salt or a quaternary ammonium salt is electrochemically adsorbed onto the molded body. can.
ポリアニリン複合物中に含ませることができるドーパン
トとしては、上記の他に、塩化第２鉄、四塩化錫、二環
化銅等のルイス酸、ピクリン酸やｐ−トルエンスルホン
酸等の有機酸等をあげることができる。In addition to the above, examples of dopants that can be included in the polyaniline composite include Lewis acids such as ferric chloride, tin tetrachloride, and copper dicyclide, and organic acids such as picric acid and p-toluenesulfonic acid. can be given.
本発明において、高分子材料として熱硬化性エポキシ樹
脂を使用する場合には、硬化剤として、ポリアニリンに
上記アミン系化合物を併用し、適正な配合を行うことに
より、生成するアニリン複合体の機械的特性を損なうほ
ど架橋度を高めなくても、導電性を付与させることがで
き、抵抗安定性が良好で、かつ機械的特性に優れた成形
体を得ることができる。そして、上記アミン系化合物の
種類及び配合量を適宜調整することによって、半導電性
領域から導電性領域までの抵抗値を有する成形体を製造
することが可能になる。In the present invention, when a thermosetting epoxy resin is used as a polymer material, the above-mentioned amine compound is used in combination with polyaniline as a curing agent, and by proper blending, the mechanical Even if the degree of crosslinking is not increased so much as to impair the properties, conductivity can be imparted, and a molded article with good resistance stability and excellent mechanical properties can be obtained. By appropriately adjusting the type and amount of the amine compound, it is possible to produce a molded article having a resistance value ranging from a semiconductive region to a conductive region.
以下、本発明を実施例によって詳記するか、本発明はこ
れらによって限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
実施例１
ポリアニリンの合成
水２００ １Ｉ１９に１．２ Ｎ塩酸１０−を入れ、ア
ニリン９．３ ｇを溶解させた。この溶液に３８Ｎ硫酸
９．８ｇを加え、攪拌した。一方、酸化剤溶液として、
（ＮＨ４） ２Ｓ２０８２２．７ｇを水２００ｇに溶解
した溶液を用意した。これら２つの溶液を混合し、０〜
５℃で数時間攪拌した。得られた酸化重合体を濾別し、
アンモニア水て処理した。赤外スペクトル及びＮＭＲか
ら、この酸化重合体は、−数式（Ｉ）におけるＲ Ｉ
−Ｒ５−Ｈの構造の繰り返し単位を含んでいることが確
認された。Example 1 Synthesis of polyaniline 1.2 N hydrochloric acid 10- was added to 200 1I19 water, and 9.3 g of aniline was dissolved therein. 9.8 g of 38N sulfuric acid was added to this solution and stirred. On the other hand, as an oxidizing agent solution,
A solution was prepared in which 22.7 g of (NH4) 2S208 was dissolved in 200 g of water. Mix these two solutions and
The mixture was stirred at 5°C for several hours. The obtained oxidized polymer was separated by filtration,
Treated with ammonia water. From the infrared spectrum and NMR, this oxidized polymer has -RI in formula (I)
It was confirmed that it contained a repeating unit of the structure -R5-H.
ポリアニリン複合フィルムの製造
次いて、ポリメチルメタクリレート５重量部に対して、
脱ドーピングされたポリアニリン０．５重量部及びＮ−
メチル−２−ピロリドン１００重量部を加え、混合溶液
を作成した。得られた混合溶液をドクターブレードを用
いてテフロン基板上に約［５０加の厚さに塗布した。塗
布物を１００℃で乾燥して溶剤を除去し、テフロン基板
から取り外して、膜厚２５節のポリアニリン複合フィル
ムを得た。得られたポリアニリン複合フィルムをＩＮ過
塩素酸水溶液に、１時間浸漬してドーピングを施した後
、純水で洗浄して、乾燥して目的のポリアニリン複合フ
ィルムを得た。電導度の変化を調べたところ、造膜直後
のポリアニリン複合フィルムは１．０×ｌＯ〜１２Ｓ／
ＣＩｉてあり、ドーピング後のポリアニリン複合フィル
ムは２．Ｏｘ １０−’Ｓ／ｃｍてあった。この結果は
、再ドーピング後のポリアニリン複合フィルムは、プロ
トン酸によってドーピングされていることを示している
。Production of polyaniline composite film Next, for 5 parts by weight of polymethyl methacrylate,
0.5 parts by weight of dedoped polyaniline and N-
100 parts by weight of methyl-2-pyrrolidone was added to prepare a mixed solution. The resulting mixed solution was coated on a Teflon substrate to a thickness of about 50 mm using a doctor blade. The coated product was dried at 100° C. to remove the solvent and removed from the Teflon substrate to obtain a polyaniline composite film with a thickness of 25 knots. The obtained polyaniline composite film was doped by immersing it in an IN perchloric acid aqueous solution for 1 hour, and then washed with pure water and dried to obtain the desired polyaniline composite film. When we investigated the change in conductivity, we found that the polyaniline composite film immediately after film formation had a conductivity of 1.0×lO to 12S/
CIi, and the polyaniline composite film after doping is 2. Ox 10-'S/cm. This result indicates that the polyaniline composite film after redoping is doped with protonic acid.
実施例２
実施例１て用いたアニリンの代わりに、ｍ−エチルアニ
リンを用いた以外は、実施例１と全く同様にして重合を
行い、脱ドーピングされた酸化重合物、ポリ（ＩＩ−エ
チルアニリン）を得た。Example 2 Polymerization was carried out in exactly the same manner as in Example 1, except that m-ethylaniline was used instead of the aniline used in Example 1, and the dedoped oxidized polymer, poly(II-ethylaniline) ) was obtained.
次いて、ＡＢＳ樹脂５重量部に対して、脱ドビングされ
たポリ（ｍ−エチルアニリン）１重量部及びメチルエチ
ルケトン１００重量部を加え、実施例１と同様な方法で
均一溶液を調製し、キャスティングによりフィルムを得
た。このフィルムによう素の蒸気中に１時間さらしてド
ーピングを施し、目的の複合フィルムを得た。この複合
フィルムの電導度は、５．６ Ｘ １０−’Ｓ／ｃｎ＋
であった。Next, 1 part by weight of dedoped poly(m-ethylaniline) and 100 parts by weight of methyl ethyl ketone were added to 5 parts by weight of ABS resin, a homogeneous solution was prepared in the same manner as in Example 1, and the solution was cast. Got the film. This film was doped by exposing it to iodine vapor for 1 hour to obtain the desired composite film. The electrical conductivity of this composite film is 5.6 x 10-'S/cn+
Met.
実施例３
実施例１て用いたアニリンの代わりに、Ｎ−メチルアニ
リンを用いた以外は、実施例１と全く同様にして重合を
行ってポリ（Ｎ−メチルアニリン）を合成し、苛性ソー
ダ水溶液で脱ドーピングした。Example 3 Poly(N-methylaniline) was synthesized by polymerization in exactly the same manner as in Example 1, except that N-methylaniline was used in place of the aniline used in Example 1, and then treated with an aqueous solution of caustic soda. De-doped.
次いて、エポキシ樹脂５重量部に対して、脱ドビングさ
れたポリ（Ｎ−メチルアニリン）１重量部及びジメチル
ホルムアミド１００重量部を加え、実施例１と同様な方
法で均一溶液を調製し、キャスティングによりフィルム
を得た。このフィルムにホウフッ化水素水溶液に１時間
浸漬してドーピングを施し、目的の複合フィルムを得た
。この複合フィルムの電導度は、７．８ Ｘ １０−’
Ｓ／ｃａ＋てあった。Next, 1 part by weight of dedoped poly(N-methylaniline) and 100 parts by weight of dimethylformamide were added to 5 parts by weight of the epoxy resin, a homogeneous solution was prepared in the same manner as in Example 1, and casting was performed. A film was obtained. This film was doped by immersing it in an aqueous borohydrogen fluoride solution for 1 hour to obtain the desired composite film. The conductivity of this composite film is 7.8 x 10-'
It was S/ca+.
実施例４
第１表に示すポリアニリン及び高分子材料を用い、実施
例１と同様にして第１表に示す膜厚のフィルムを作成し
、濃度６ＮのＨＣｌＯ４水溶液に１日間浸漬してドーピ
ング処理を行った。得られたフィルムの体積抵抗率を測
定した。結果を第１表に示す。Example 4 Using the polyaniline and polymer materials shown in Table 1, films with the thickness shown in Table 1 were prepared in the same manner as in Example 1, and doped by immersing them in an aqueous HClO4 solution with a concentration of 6N for one day. went. The volume resistivity of the obtained film was measured. The results are shown in Table 1.
以下余白
第１表
実施例５
第２表に示すポリアニリン及び高分子材料を８０゜２０
の混合比で用い、実施例１と同様にして第２表に示す膜
厚のフィルムを作成し、濃度６ＮのＨＣｌＯ４水溶液に
１時間浸漬してドーピング処理を行った。得られたフィ
ルムの体積抵抗率を測定した。Table 1 Example 5 The polyaniline and polymer materials shown in Table 2 were heated at 80°20
A film having the thickness shown in Table 2 was prepared in the same manner as in Example 1 using a mixing ratio of 1, and was doped by immersing it in an aqueous HClO4 solution with a concentration of 6N for 1 hour. The volume resistivity of the obtained film was measured.
結果を第２表に示す。The results are shown in Table 2.
第２表
以下余白
実施例６
ポリアニリン硬化型複合フィルムの製造エピコート８２
８（油化シェルエポキシ■製）２０重量部に対して、実
施例１において用いたと同一のポリアニリン１０重量部
及びジメチルスルホキシド１００重量部を加えて混合溶
液を作製した。得られたこの号溶液を、ドクターブレー
ドを用いて、テフロン基板上に約２５０節の厚さに塗布
した。塗布物を１５０℃において６時間乾燥して、加熱
硬化及び溶剤の除去を行なった。Table 2 and below margins Example 6 Production of polyaniline curable composite film Epikote 82
10 parts by weight of the same polyaniline used in Example 1 and 100 parts by weight of dimethyl sulfoxide were added to 20 parts by weight of 8 (manufactured by Yuka Shell Epoxy ■) to prepare a mixed solution. The obtained solution of this issue was applied to a thickness of about 250 knots on a Teflon substrate using a doctor blade. The coated material was dried at 150° C. for 6 hours to heat cure and remove the solvent.
得られたポリアニリン硬化型複合フィルム（膜厚２００
節）を、ＩＮ過塩素酸水溶液に１時間浸漬してドーピン
グを施した後、純水で洗浄して乾燥し、目的のポリアニ
リン硬化型複合フィルムを得た。電導度の変化を調べた
ところ、製膜直後のポリアニリン硬化型複合フィルムは
、ｉ、ｏ ｘｔｏ−１２Ｓ／Ｃｓであり、ドーピング後
のポリアニリン複合フィルムは３ Ｘ １Ｏ−６Ｓ／ｅ
ｓてあった。この結果は、再ドーピング後のポリアニリ
ン硬化型複合フィルムは、プロトン酸によってドーピン
グされていることを示している。The obtained polyaniline curable composite film (thickness: 200
After doping was performed by immersing the sample in an IN perchloric acid aqueous solution for 1 hour, the sample was washed with pure water and dried to obtain the desired polyaniline cured composite film. When the change in electrical conductivity was investigated, the polyaniline cured composite film immediately after film formation was i,oxto-12S/Cs, and the polyaniline composite film after doping was 3X1O-6S/e.
There was s. This result shows that the polyaniline cured composite film after redoping is doped with protonic acid.
実施例７
実施例１て用いたアニリンの代わりに、０っプロピルア
ニリンを用いた以外は、実施例１とまったく同様にして
重合を行ない、脱ドーピングされた酸化重合物：ポリ（
０−プロピルアニリン）を得た。Example 7 Polymerization was carried out in exactly the same manner as in Example 1, except that 0-propylaniline was used instead of the aniline used in Example 1, and the dedoped oxidized polymer: poly(
0-propylaniline) was obtained.
次いで、エポキシノボラック樹脂（ＤＥＮ４３１、ダウ
ケミカル日本■製）２０重量部に対して、エビキュア１
１３り変性脂環式アミン、油化ンエルエポキシ■製）５
重量部及びポリ（０−プロピルアニリン）５重量部に対
して、２−ブタノン１００重量部を加えて混合溶液を作
製した。この混合溶液を用い、実施例６と同様な方法で
、膜厚１１４節のキャスティングフィルムを得た。この
フィルムを２Ｎ硫酸水溶液に１時間浸漬して、フィルム
にドーピングを施し、目的の硬化型複合フィルムを得た
。この硬化型複合フィルムの電導度は、ｌ ｘｌＯ−５
Ｓ／ｃｎ＋であった。Next, Ebicure 1 was added to 20 parts by weight of epoxy novolac resin (DEN431, manufactured by Dow Chemical Japan).
13-modified alicyclic amine, manufactured by Yuka L Epoxy ■) 5
A mixed solution was prepared by adding 100 parts by weight of 2-butanone to 5 parts by weight of poly(0-propylaniline). Using this mixed solution, a casting film having a thickness of 114 knots was obtained in the same manner as in Example 6. This film was immersed in a 2N sulfuric acid aqueous solution for 1 hour to dope the film to obtain the desired cured composite film. The electrical conductivity of this cured composite film is l xlO-5
It was S/cn+.
実施例８
実施例１で用いたアニリンの代わりに、Ｎ−メチルアニ
リンを用いた以外は、実施例］とまったく同様にして重
合を行なってポリ（Ｎ−メチルアニリン）を合成し、そ
れを苛性ソーダで脱ドーピングした。Example 8 Poly(N-methylaniline) was synthesized by polymerization in exactly the same manner as in Example except that N-methylaniline was used instead of the aniline used in Example 1, and it was added to caustic soda. I was de-doped.
次いで、臭素化エポキシ樹脂（ＤＥＲ５００、ダウケミ
カル日本鞠製）２０重量部に対して、エピキュアＺ（変
性芳香族アミン、油化シェルエポキシ■製）２重量部及
びポリ（Ｎ−メチルアニリン）５重量部に対して、２−
ブタノン１００重量部を加え、実施例６と同様な方法で
均一溶液を調製し、キャスティングにより膜厚９８−の
キャスティングフィルムを得た。このフィルムをＩＮホ
ウフッ化水素水溶液に１時間浸漬して、フィルムにドー
ピングを施し、目的の硬化型複合フィルムを得た。この
硬化型複合フィルムの電導度は、１．４ ｘｌＯ−’Ｓ
／ｃｍてあった。Next, to 20 parts by weight of brominated epoxy resin (DER500, manufactured by Dow Chemical Nippon Mari), 2 parts by weight of Epicure Z (modified aromatic amine, manufactured by Yuka Shell Epoxy ■) and 5 parts by weight of poly(N-methylaniline) were added. 2-
A homogeneous solution was prepared in the same manner as in Example 6 by adding 100 parts by weight of butanone, and a cast film with a thickness of 98 mm was obtained by casting. This film was immersed in an IN aqueous borohydrogen fluoride solution for 1 hour to dope the film to obtain the desired cured composite film. The electrical conductivity of this cured composite film is 1.4 xlO-'S
/cm.
本発明のポリアニリン複合体は、上記の構成を有するか
ら、次のような効果を生じる。Since the polyaniline composite of the present invention has the above structure, it produces the following effects.
（１）脱ドーピング状態の絶縁性のものを、成形後にド
ーピング剤を用いて再ドーピングすることから、ドーパ
ントの濃度、トーピンク時間及び雰囲気（気相、液相）
等を選択することにより、適宜の導電性を持つものとす
ることが可能である。(1) Since the undoped insulating material is redoped using a doping agent after molding, the dopant concentration, toe pink time and atmosphere (gas phase, liquid phase)
By selecting the above, it is possible to obtain appropriate conductivity.
（２）ゴム９．熱可塑性樹脂、熱硬化性樹脂等をポリア
ニリンと共に複合することにより、ポリアニリンのみよ
りなる自己支持性フィルムに比べて、機械的強度、柔軟
性、成形性に優れている。また、熱硬化性樹脂としてエ
ポキシ樹脂を使用した場合には、耐溶剤性及び抵抗安定
性の点で特に優れたものとなる。(2) Rubber9. By combining thermoplastic resin, thermosetting resin, etc. with polyaniline, it has superior mechanical strength, flexibility, and moldability compared to a self-supporting film made only of polyaniline. Furthermore, when an epoxy resin is used as the thermosetting resin, it is particularly excellent in terms of solvent resistance and resistance stability.
（３）出発原料として、ポリアニリン粉末が使用でき、
しかも脱ドーピングして可溶性の状態にして使用するこ
とから、それを単に高分子材料と溶解、複合化させるた
けの操作で、フィルム或いはシート状物及びそれ以外の
任意の形状のものを得ることが可能である。したがって
、成形体の作成が容易であり、工業的に大量生産が可能
である。(3) Polyaniline powder can be used as a starting material,
Moreover, since it is dedoped and used in a soluble state, it is possible to obtain films, sheets, and other arbitrary shapes by simply dissolving and compounding it with a polymeric material. It is. Therefore, it is easy to create a molded body, and industrial mass production is possible.
（４）使用目的に応じた電気伝導度を付与することがで
きるから、プラスチック電池の電極材料、コンデンサー
、電磁シールド材、静電吸着シート、導電性ペースト材
、表示素子等、多岐の分野に適用かできる。(4) It is possible to impart electrical conductivity according to the purpose of use, so it can be applied to a wide variety of fields such as electrode materials for plastic batteries, capacitors, electromagnetic shielding materials, electrostatic adsorption sheets, conductive paste materials, display elements, etc. I can do it.
出願人 富士ゼロックス株式会社Applicant: Fuji Xerox Co., Ltd.
Claims (3)
脂及び熱硬化性樹脂から選択された少なくとも１種の高
分子材料と共に有機溶剤に溶解して得た混合溶液を用い
て成形された成形体からなり、該成形体が、成形後にド
ーパントを用いてドープされたことを特徴とするポリア
ニリン複合物。(1) From a molded body formed using a mixed solution obtained by dissolving dedoped polyaniline in an organic solvent together with at least one polymeric material selected from rubber, thermoplastic resin, and thermosetting resin. A polyaniline composite, characterized in that the molded body is doped with a dopant after molding.
に記載のポリアニリン複合物。(2) Claim (1) wherein the thermosetting resin is an epoxy resin.
The polyaniline composite described in.
脂を添加してなる請求項（２）に記載のポリアニリン複
合物。(3) The polyaniline composite according to claim (2), which contains an amine compound and a polyamide resin as a curing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10044790 | 1990-04-18 | ||
| JP2-100447 | 1990-04-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0463865A true JPH0463865A (en) | 1992-02-28 |
Family
ID=14274175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20798990A Pending JPH0463865A (en) | 1990-04-18 | 1990-08-08 | Polyaniline composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0463865A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04331226A (en) * | 1991-05-01 | 1992-11-19 | Tomoegawa Paper Co Ltd | Polyaniline derivative and its production |
| US6160087A (en) * | 1993-09-28 | 2000-12-12 | Meito Sangyo Kabushiki Kaisha | Peptides having an amino acid sequence from the fimbrial protein of porphyromonas gingivalis and their uses |
| JP2002363300A (en) * | 2001-06-04 | 2002-12-18 | Sumitomo Electric Ind Ltd | Semiconductive belt or roller, and method for producing them |
| US8182580B2 (en) | 2006-05-18 | 2012-05-22 | Valtion Teknillinen Tutkimuskeskus | Filter structure for filtering a particle-containing gas, method of its manufacture and use of porous paper |
-
1990
- 1990-08-08 JP JP20798990A patent/JPH0463865A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04331226A (en) * | 1991-05-01 | 1992-11-19 | Tomoegawa Paper Co Ltd | Polyaniline derivative and its production |
| US6160087A (en) * | 1993-09-28 | 2000-12-12 | Meito Sangyo Kabushiki Kaisha | Peptides having an amino acid sequence from the fimbrial protein of porphyromonas gingivalis and their uses |
| JP2002363300A (en) * | 2001-06-04 | 2002-12-18 | Sumitomo Electric Ind Ltd | Semiconductive belt or roller, and method for producing them |
| US8182580B2 (en) | 2006-05-18 | 2012-05-22 | Valtion Teknillinen Tutkimuskeskus | Filter structure for filtering a particle-containing gas, method of its manufacture and use of porous paper |
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