JPH0552658B2 - - Google Patents
Info
- Publication number
- JPH0552658B2 JPH0552658B2 JP21244284A JP21244284A JPH0552658B2 JP H0552658 B2 JPH0552658 B2 JP H0552658B2 JP 21244284 A JP21244284 A JP 21244284A JP 21244284 A JP21244284 A JP 21244284A JP H0552658 B2 JPH0552658 B2 JP H0552658B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- electrolytic capacitor
- solid electrolytic
- conductive
- 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.)
- Expired - Lifetime
Links
- 239000003990 capacitor Substances 0.000 claims description 32
- -1 aniline compound Chemical class 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 26
- 239000002019 doping agent Substances 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 27
- 239000011888 foil Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910017008 AsF 6 Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- ICMGOJSGLIVFHM-UHFFFAOYSA-N 1-n,4-n-bis[4-(dimethylamino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N(C)C)=CC=C1NC(C=C1)=CC=C1NC1=CC=C(N(C)C)C=C1 ICMGOJSGLIVFHM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910016467 AlCl 4 Inorganic materials 0.000 description 3
- 229910020366 ClO 4 Inorganic materials 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IHZJPHSLRAKNDC-UHFFFAOYSA-N 2-propyl-1h-isoquinoline Chemical compound C1=CC=C2C=CN(CCC)CC2=C1 IHZJPHSLRAKNDC-UHFFFAOYSA-N 0.000 description 1
- HDEXQZFQDZGFLQ-UHFFFAOYSA-N 4,5-dibromo-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound BrC1=C(Br)C(=O)C(C#N)=C(C#N)C1=O HDEXQZFQDZGFLQ-UHFFFAOYSA-N 0.000 description 1
- DWJXWSIJKSXJJA-UHFFFAOYSA-N 4-n-[4-(4-aminoanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC(C=C1)=CC=C1NC1=CC=C(N)C=C1 DWJXWSIJKSXJJA-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- ZRZKFGDGIPLXIB-UHFFFAOYSA-N fluoroform;sulfuric acid Chemical compound FC(F)F.OS(O)(=O)=O ZRZKFGDGIPLXIB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001545 sodium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Inorganic materials [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Oscillators With Electromechanical Resonators (AREA)
- Glass Compositions (AREA)
- Conductive Materials (AREA)
Description
本発明は、特定のアニリン系化合物にドーパン
トをドープして得られる電導性アニリン系化合物
を固体電解質として用いた性能の良好な固体電解
コンデンサに関する。
従来の電解コンデンサ、例えばアルミニウム電
解コンデンサは、エツチング処理した比表面積の
大きい多孔質アルミニウム箔の上に誘電体である
酸化アルミニウム層を設け、陰極箔との間の電解
紙に液状の電解液を含浸させた構造からなつてい
るが、この電解液が液状であることは液漏れ等の
問題を惹起し好ましいものではなく、従つて、こ
の電導層を固体電解質で代替する試みがなされて
いる。それらの固体電解コンデンサは、陽極酸化
皮膜を有するアルミニウム、タンタルなどの皮膜
形成金属に固体電解質を付着した構造を有したも
のであり、この種の固体コンデンサの固体電解質
には、主に硫酸マンガンの熱分解により形成され
る二酸化マンガンが用いられている。しかし、こ
の熱分解の際に要する高熱と発生するNOXガス
の酸化作用などによつて、誘電体であるアルミニ
ウム、タンタルなどの金属酸化皮膜の損傷があ
り、そのため耐電圧は低下し、漏れ電流が大きく
なり、誘電特性を劣化させるなど極めて大きな欠
点がある。また、再化成という工程も必要であ
る。
これらの欠点を補うため、高熱を付加せずに固
体電解質層を形成する方法、つまり高電導性の有
機半導体材料を固体電解質とする方法が試みられ
ている。その例としては、特開昭52−79255号公
報に記載されている７，７，８，８−テトラシア
ノキノジメタン（TCNQ）錯塩を含む電導性高
重合体組成物を固体電解質として含む固体電解コ
ンデンサ、特開昭58−17609号公報に記載されて
いるＮ−ｎ−プロピルイソキノリンと７，７，
８，８−テトラシアノキノジメタンからなる錯塩
を固体電解質として含む固体電解コンデンサが知
られている。これらTCNQ錯塩化合物は、陽極
酸化皮膜との付着性に劣り、導電度も
10-310-2S・cm-1と不十分であるため、コンデン
サの容量値は小さく誘電損失も大きい。また熱的
経時的な安定性も劣り信頼性が低い。
本発明の目的は、上述した従来の欠点を解決
し、電導度が高く、誘電体皮膜との付着性のよい
有機半導体を固体電解質に用いた固体電解コンデ
ンサを提供することにある。
この目的は固体電解質として特定の電導性アニ
リン系化合物を用いることにより達成されること
を見出した。
即ち、本発明は、一般式
（式中、R1、R2、R3およびR4は水素または炭素
数が６以下の飽和炭化水素基であり、ｎは２〜６
の整数である。炭素数及び整数ｎを限定するの
は、この範囲において高い電導度が得られるから
である。）
で表わされる系化合物にドーパントをドープして
得られる電導性アニリン系化合物を固体電解質と
することを特徴とする固体電解コンデンサに関す
る。
本発明により得られる固体電解コンデンサは、
従来の無機酸化半導体や有機半導体を用いた固体
電解コンデンサに比して容量、誘電損失、経時安
定性において著しく優れた性能を有している。
また、本発明の固体電解コンデンサは、従来公
知の固体電解コンデンサに比較して下記の利点を
有している。
高温加熱することなしに電解質層を形成でき
るので陽極の酸化被膜の損傷がなく、補修のた
めの陽極酸化（再化成）を行なう必要がない。
そのため、定格電圧を従来の数倍にでき、同容
量、同定格電圧のコンデンサを得るのに、形状
を小型化できる。
漏れ電流が小さい。
高耐圧のコンデンサを作製できる。
電解質の電導度が10-2〜103S・cm-1と十分に
高いため、グラフアイトなどの導電層を設ける
必要がない。そのため工程が簡略化され、コス
ト的にも有利となる。
本発明の固体電解コンデンサに用いられる電解
質は、前記一般式(1)で表わされる固体状のアニリ
ン系化合物である。
一般式(1)で表わされる化合物の代表例として
は、Ｎ，N′−ビス（４−ジメチルアミノフエニ
ル）−ｐ−フエニレンジアミン（一般式(1)におい
てｎは２、R1、R2はCH3、R3はＨ、R4は
The present invention relates to a solid electrolytic capacitor with good performance using a conductive aniline compound obtained by doping a specific aniline compound with a dopant as a solid electrolyte. Conventional electrolytic capacitors, such as aluminum electrolytic capacitors, have an aluminum oxide dielectric layer placed on an etched porous aluminum foil with a large specific surface area, and the electrolytic paper between the cathode foil and the electrolytic paper is impregnated with a liquid electrolyte. However, it is not preferable that the electrolyte is in a liquid state because it causes problems such as leakage, and therefore attempts have been made to replace the conductive layer with a solid electrolyte. These solid electrolytic capacitors have a structure in which a solid electrolyte is attached to a film-forming metal such as aluminum or tantalum that has an anodized film. Manganese dioxide, which is formed by thermal decomposition, is used. However, due to the high heat required during this thermal decomposition and the oxidizing effect of NO This has extremely large drawbacks, such as increased dielectric properties and deterioration of dielectric properties. In addition, a process called reconstitution is also necessary. In order to compensate for these drawbacks, attempts have been made to form a solid electrolyte layer without applying high heat, that is, to use a highly conductive organic semiconductor material as the solid electrolyte. An example of this is a solid electrolyte containing a conductive polymer composition containing a 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex salt as described in JP-A-52-79255. Electrolytic capacitor, N-n-propylisoquinoline and 7,7, described in JP-A-58-17609
Solid electrolytic capacitors containing a complex salt of 8,8-tetracyanoquinodimethane as a solid electrolyte are known. These TCNQ complex salt compounds have poor adhesion to anodic oxide films and low conductivity.
10 -3 10 -2 S cm -1 is insufficient, so the capacitance value of the capacitor is small and the dielectric loss is large. Furthermore, thermal stability over time is poor and reliability is low. An object of the present invention is to solve the above-mentioned conventional drawbacks and to provide a solid electrolytic capacitor in which an organic semiconductor having high conductivity and good adhesion to a dielectric film is used as a solid electrolyte. It has been found that this objective can be achieved by using a specific conductive aniline compound as a solid electrolyte. That is, the present invention provides the general formula (In the formula, R 1 , R 2 , R 3 and R 4 are hydrogen or a saturated hydrocarbon group having 6 or less carbon atoms, and n is 2 to 6
is an integer. The reason why the number of carbon atoms and the integer n are limited is that high electrical conductivity can be obtained within these ranges. The present invention relates to a solid electrolytic capacitor characterized in that the solid electrolyte is a conductive aniline compound obtained by doping a dopant into a compound represented by the following formula. The solid electrolytic capacitor obtained by the present invention is
It has significantly superior performance in terms of capacity, dielectric loss, and stability over time compared to conventional solid electrolytic capacitors using inorganic oxide semiconductors or organic semiconductors. Furthermore, the solid electrolytic capacitor of the present invention has the following advantages compared to conventionally known solid electrolytic capacitors. Since the electrolyte layer can be formed without high-temperature heating, there is no damage to the oxide film of the anode, and there is no need to perform anodization (reformation) for repair.
Therefore, the rated voltage can be increased several times compared to conventional capacitors, and the shape can be made smaller to obtain a capacitor with the same capacity and rated voltage. Leakage current is small. Capacitors with high withstand voltage can be manufactured. Since the electrolyte has a sufficiently high conductivity of 10 −2 to 10 3 S·cm −1 , there is no need to provide a conductive layer such as graphite. This simplifies the process and is advantageous in terms of cost. The electrolyte used in the solid electrolytic capacitor of the present invention is a solid aniline compound represented by the above general formula (1). A representative example of the compound represented by the general formula (1) is N,N'-bis(4-dimethylaminophenyl)-p-phenylenediamine (in the general formula (1), n is 2, R 1 , R 2 is CH3 , R3 is H, R4 is
【式】）、Ｎ，N′−ビス（４−
アミノフエニル）−ｐ−フエニレンジアミン（一
般式(1)においてｎは２、R1、R2、R3はＨ、R4は
[Formula]), N,N'-bis(4-aminophenyl)-p-phenylenediamine (in general formula (1), n is 2, R 1 , R 2 , R 3 are H, and R 4 is
【式】）、Ｎ，N′−ビス（４−ジメチ
ルアミノフエニル）−Ｎ，N′−ジメチル−ｐ−フ
エニレンジアミン（一般式(1)においてｎは２、
R1、R2、R3はCH3、R4は
[Formula]), N,N'-bis(4-dimethylaminophenyl)-N,N'-dimethyl-p-phenylenediamine (in general formula (1), n is 2,
R 1 , R 2 , R 3 are CH 3 , R 4 is
【式】）、４，4′−ビス（４−ジ
メチルアミノアニリノ）ジフエニルアミン（一般
式(1)においてｎは２、R1、R2はCH3、R3はＨ、
R4は[Formula]), 4,4'-bis(4-dimethylaminoanilino)diphenylamine (in general formula (1), n is 2, R 1 and R 2 are CH 3 , R 3 is H,
R 4 is
【式】）、４，4′−ビス
（４−ジメチルアミノ−Ｎ−メチルアニリノ）−Ｎ
−メチルジフエニルアミン（一般式(1)においてｎ
は２、R1、R2、R3はCH3、R4は
[Formula]), 4,4'-bis(4-dimethylamino-N-methylanilino)-N
-methyldiphenylamine (n in general formula (1))
is 2, R 1 , R 2 , R 3 is CH 3 , R 4 is
【式】）等があげられる。これ
らの化合物の製造方法は、特に制限されるもので
はなく、従来公知の方法を用いることができる。
例えば、Ｎ，N′−ビス（４−ジメチルアミノフ
エニル）−ｐ−フエニレンの場合には、ｐ−フエ
ニレンジアミンとＮ，Ｎ−ジメチルアニリンを適
当な酸化剤（例えば塩化亜鉛）の存在下で縮合さ
せる方法によつて製造することができる。
上記のアニリン系化合物は、その製造方法がド
ーパントになりうる化合物を使用して製造し、そ
の生成物の電気伝導度が10-2〜103S・cm-1の範囲
内にある場合を除き、ドーパントをドーピングし
てその電気伝導度を10-2〜103S・cm-1の範囲にし
ておくことが必要である。本発明においては、ア
ニリン系化合物の製造時にドーパントとなりうる
化合物を使用して製造したアニリン系化合物を含
めて電導性アニリン系化合物と称する。なお、製
造方法がドーパントになりうる化合物を使用して
化合物を製造した場合、このドーパントを適当な
方法で除いてから、新たにドーパントをドープし
てもよい。
ドーピングは化学的ドーピング、電気化学的ド
ーピングのいずれの方法を採用してもよい。
化学的にドーピングするドーパントとしては、
従来知られている種々の電子受容性化合物および
電子供与性化合物、即ち、（）ヨウ素、臭素お
よびヨウ化臭素の如きハロゲン、（）五フツ化
ヒ素、五フツ化アンチモン、四フツ化ケイ素、五
塩化リン、五フツ化リン、塩化アルミニウム、臭
化アルミニウムおよびフツ化アルミニウムの如き
金属ハロゲン化物、（）硫酸、硝酸フルオロ硫
酸、トリフルオロメタン硫酸およびクロロ硫酸の
如きプロトン酸、（）三酸化イオウ、二酸化窒
素、ジフルオロスルホニルパーオキシドの如き酸
化剤、（）AgClO4、（）テトラシアノエチレ
ン、テトラシアノキノジメタン、クロラニール、
２，３−ジクロル−５，６−ジシアノパラベンゾ
キノン、２，３−ジブロム−５，６−ジシアノパ
ラベンゾキノン、（）Li、Na、Ｋの如きアルカ
リ金属等をあげることができる。
一方、電気化学的にドーピングするドーパント
としては、(i)PF6 -、SbF6 -、AsF6 -、SbCl6 -の如
きVa族の元素のハロゲン化物アニオン、BF4 -の
如きａ族の元素のハロゲン化物アニオン、I-
（I3 -）、Br-、Cl-の如きハロゲンアニオン、
ClO4 -の如き過塩素酸アニオンなどの陰イオン・
ドーパントおよび(ii)Li+、Na+、K+の如きアルカ
リ金属イオン、R4N+（Ｒ：炭素数１〜20の炭化
水素基）の如き４級アンモニウムイオンなどの陽
イオン・ドーパント等をあげることができるが、
必ずしもこれ等に限定されるものではない。
上述の陰イオン・ドーパントおよび陽イオン・
ドーパントを与える化合物の具体例としては
LiPF6、LiSbF6、LiAsF6、LiClO4、NaI、
NaPF6、NaSbF6、NaAsF6、NaClO4、KI、
KPF6、KSbF6、KAsF6、KClO4、〔（ｎ−
Bu）4N〕+・（AsF6）-、〔（ｎ−Bu）4N〕+・（PF6）-
、
〔（ｎ−Bu）4N〕+・ClO4 -、LiAlCl4、LiBF4、
NO・AsF6、NO2・AsF6、NO・BF4、NO2・
BF4、NO・PF6をあげることができるが必ずし
もこれ等に限定されるものではない。これらのド
ーパントは一種類、または二種類以上を混合して
使用してもよい。
前記以外の陰イオン・ドーパントとしてはHF2
アニオンであり、また、前記以外の陽イオン・ド
ーパントとしては次式（）で表わされるピリリ
ウムまたはピリジウム・カチオン：
（式中、Ｘは酸素原子または窒素原子、R′は水
素原子または炭素数が１〜15のアルキル基、炭素
数６〜15のアリール（aryl）基、R″はハロゲン
原子または炭素数が１〜10のアルキル基、炭素数
が６〜15のアリール（aryl）基、ｍはＸが酸素原
子のとき０であり、Ｘが窒素原子のとき１であ
る。ｎは０または１〜５である。）
または次式（）もしくは（）で表わされる
カルボニウム・カチオン：
および
〔上式中、R1、R2、R3は水素原子（R1、R2、R3
は同時に水素原子であることはない）、炭素数１
〜15のアルキル基、アリル（allyl）基、炭素数
６〜15のアリール（allyl）基または−OR5基、但
しR5は炭素数が１〜10のアルキル基または炭素
数６〜15のアリール（aryl）基を示し、R4は水
素原素、炭素数が１〜15のアルキル基、炭素数６
〜15のアリール基である。〕
である。
用いられるHF2アニオンは通常、下記の一般式
（）、（）または（）：
R4′N・HF2 （）
Ｍ・HF2 （）
〔但し、上式中R′、R″は水素原子または炭素数
が１〜15のアルキル基、炭素数６〜15のアリール
（aryl）基、Ｒは炭素数が１〜10のアルキル基、
炭素数６〜15のアリール（aryl）基、Ｘは酸素原
子または窒素原子、ｎは０または５以下の正の整
数である。Ｍはアルカリ金属である〕
で表わされる化合物（フツ化水素塩）を適当な有
機溶媒に溶解することによつて得られる。上式
（）、（）および（）で表わされる化合物の
具体例としてはH4N・HF2、ｎ−Bu4N・HF2、
Na・HF2、Ｋ・HF2、Li・HF2および[Formula]) etc. The method for producing these compounds is not particularly limited, and conventionally known methods can be used.
For example, in the case of N,N'-bis(4-dimethylaminophenyl)-p-phenylene, p-phenylenediamine and N,N-dimethylaniline are combined in the presence of a suitable oxidizing agent (e.g. zinc chloride). It can be produced by a method of condensation. The above aniline compounds are manufactured using a compound that can be used as a dopant, and the electrical conductivity of the product is within the range of 10 -2 to 10 3 S cm -1 . , it is necessary to dope the material with a dopant so that its electrical conductivity is in the range of 10 −2 to 10 3 S·cm −1 . In the present invention, aniline compounds manufactured using a compound that can serve as a dopant during the production of aniline compounds are also referred to as conductive aniline compounds. In addition, when a compound is manufactured using a compound that can be a dopant, the dopant may be removed by an appropriate method and then a new dopant may be doped. For doping, either chemical doping or electrochemical doping may be used. As dopants for chemical doping,
Various electron-accepting and electron-donating compounds known in the art include () halogens such as iodine, bromine and bromine iodide, () arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, Metal halides such as phosphorus chloride, phosphorus pentafluoride, aluminum chloride, aluminum bromide and aluminum fluoride, () protic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid, () sulfur trioxide, dioxide Nitrogen, oxidizing agents such as difluorosulfonyl peroxide, ()AgClO 4 , ()tetracyanoethylene, tetracyanoquinodimethane, chloranil,
Examples include 2,3-dichloro-5,6-dicyanoparabenzoquinone, 2,3-dibromo-5,6-dicyanoparabenzoquinone, and alkali metals such as ()Li, Na, and K. On the other hand, dopants for electrochemical doping include (i) halide anions of Va group elements such as PF 6 - , SbF 6 - , AsF 6 - , and SbCl 6 - , and A group elements such as BF 4 - ; halide anion, I -
Halogen anions such as (I 3 - ), Br - , Cl - ,
Anions such as perchlorate anions such as ClO 4 -
Dopants and (ii) cations/dopants such as alkali metal ions such as Li + , Na + , K + and quaternary ammonium ions such as R 4 N + (R: hydrocarbon group having 1 to 20 carbon atoms). I can give you, but
It is not necessarily limited to these. The above-mentioned anion/dopant and cation/dopant
Specific examples of compounds that provide dopants include
LiPF 6 , LiSbF 6 , LiAsF 6 , LiClO 4 , NaI,
NaPF6 , NaSbF6 , NaAsF6 , NaClO4 , KI,
KPF 6 , KSbF 6 , KAsF 6 , KClO 4 , [(n-
Bu) 4 N] +・(AsF 6 ) - , [(n-Bu) 4 N] +・(PF 6 ) -
,
[(n-Bu) 4 N] +・ClO 4 - , LiAlCl 4 , LiBF 4 ,
NO・AsF 6 , NO 2・AsF 6 , NO・BF 4 , NO 2・
Examples include BF 4 and NO/PF 6 , but are not necessarily limited to these. These dopants may be used alone or in combination of two or more. Anion dopants other than those mentioned above include HF 2
It is an anion, and as a cation dopant other than the above, pyrylium or pyridium cation represented by the following formula (): (In the formula, ~10 alkyl group, aryl group having 6 to 15 carbon atoms, m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom. n is 0 or 1 to 5. ) or a carbonium cation represented by the following formula () or (): and [In the above formula, R 1 , R 2 , R 3 are hydrogen atoms (R 1 , R 2 , R 3
is not a hydrogen atom at the same time), carbon number is 1
-15 alkyl group, allyl group, aryl group having 6 to 15 carbon atoms or -OR 5 group, provided that R 5 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms (aryl) group, R 4 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and 6 carbon atoms.
~15 aryl groups. ] It is. The HF 2 anion used typically has the following general formula (), () or (): R 4 'N·HF 2 () M·HF 2 () [However, in the above formula, R', R'' is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, R is an alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 15 carbon atoms, X is an oxygen atom or a nitrogen atom, and n is 0 or a positive integer of 5 or less. M is an alkali metal] It can be obtained by dissolving a compound represented by (hydrogen fluoride salt) in a suitable organic solvent. Specific examples of compounds represented by the above formulas (), () and () include H 4 N.HF 2 , n-Bu 4 N.HF 2 ,
Na・HF 2 , K・HF 2 , Li・HF 2 and
【式】
をあげることができる。
上記式（）で表わされるピリリウムもしくは
ピリジニウムカチオンは、式（）で表わされる
カチオンとClO4 -、BF2 -、AlCl4 -、FeCl4 -、
SnCl5 -、PF6 -、PCl6 -、SbF6 -、AsF6 -、
CF3SO3 -、HF2 -等のアニオンとの塩を適当な有
機溶媒に溶解することによつて得られる。そのよ
うな塩の具体例としては[Formula] can be given. The pyrylium or pyridinium cation represented by the above formula () is a cation represented by the formula () and ClO 4 - , BF 2 - , AlCl 4 - , FeCl 4 - ,
SnCl 5 - , PF 6 - , PCl 6 - , SbF 6 - , AsF 6 - ,
It can be obtained by dissolving a salt with an anion such as CF 3 SO 3 - or HF 2 - in an appropriate organic solvent. Examples of such salts include
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
等をあげることができる。
上記式（）または（）で表わされるカルボ
ニウム・カチオンの具体例としては（C6H5）3C+、
（CH3）3C+、[Formula] etc. can be given. Specific examples of carbonium cations represented by the above formula () or () are (C 6 H 5 ) 3 C + ,
( CH3 ) 3C + ,
【式】をあげるこ
とができる。
これらのカルボニウムカチオンは、それらと陰
イオンの塩（カルボニウム塩）を適当な有機溶媒
に溶解することによつて得られる。ここで用いら
れる陰イオンの代表例としては、BF4 -、AlCl4 -、
AlBr3Cl-、FeCl4 -、SnCl3 -、PF6 -、PCl6 -、
SbCl6 -、SbF6 -、ClO4 -、CF3SO3 -等をあげるこ
とができ、また、カルボニウム塩の具体例として
は、例えば（C6H5）3C・BF4、（CH3）3C・BF4、
HCO・AlCl4、HCO・BF4、C6H5CO・SnCl5等
をあげることができる。
本発明における固体コンデンサの陽極には、ア
ルミニウム、タンタル、ニオブ等の金属箔、また
はそれらの金属粉の焼結体が用いられる。金属箔
の場合には、表面をエツチングして細孔をもたせ
る。金属箔または焼結体は、例えばホウ酸アンモ
ニウムの液中で電極酸化され、金属箔または焼結
体の上に誘電体の薄層が形成される。
本発明における電導性アニリン系化合物は、こ
の誘電体の薄層と接触し、一部が細孔の中まで進
入する。図に本発明の一具体例である固体電解コ
ンデンサで金属薄を使用した場合の概略を示し
た。
以下に実施例および比較例をあげて、本発明を
さらに詳細に説明する。
なお、実施例および比較例において作成された
各固体電解コンデンサの特性値を一括して表に示
した。
実施例 １
厚さ100μｍのアルミニウム箔（純度99.99％）
を陽極とし、直流、交流を交互使用して、箔の表
面を電気化学的にエツチングして平均細孔径が
2μｍで、比表面積が12m2／ｇの多孔質アルミニ
ウム箔とした。次いで、このエツチング処理した
アルミニウム箔をホウ酸アンモニウムの液中に浸
漬し、液中で電気化学的にアルミニウム箔の上に
誘電体の箔層を形成した。
一方、ｐ−フエニレンジアミン0.046モルとＮ，
Ｎ−ジメチルアニリン0.092モルを12％塩酸220ml
に溶解させた。これに０℃でクロム酸ナトリウム
0.044モルを水40mlに溶かした溶液を加え、引き
続いて塩化亜鉛15ｇを水50mlに溶かした溶液を加
えた。生成した沈澱物を50℃の水に溶かし、20ｇ
のチオ硫酸ナトリウムをアンモニア水200mlに溶
かした溶液を用いて再結晶させた。この結晶を減
圧下に乾燥させ、Ｎ，N′−ビス（４−ジメチル
アミノフエニル）−ｐ−フエニレンジアミンを得
た。この化合物を175℃で融解させ、前記した誘
電体層に塗布した。減圧脱気と塗布を繰り返し、
充分細孔まで化合物を満たした。次いで、化合物
層にヨウ素蒸気を10時間あてて化合物にヨウ素を
ドープし、ヨウ素をドープした化合を電導性化合
物とする固体電解質層を形成した。陰極にアルミ
ニウム箔を使用し、樹脂封口して固体電解コンデ
ンサを作成した。このときの電導性化合物の電導
度は0.8S・cm-1であつた。
実施例 ２
実施例１と同様な方法で得たＮ，N′−ビス
（４−ジメチルアミノフエニル）−ｐ−フエニレン
ジアミン0.0073モルを70mlのテトラヒドロフラン
に溶かし、フエニルリチウム0.017モルと１時間
反応させた。これに、テトラヒドロフラン15mlに
溶かしたヨウ化メチル0.017モルを加え、１時間
放置した。これにさらに少量のチオ硫酸ナトリウ
ムを加えた後、水で洗い、有機層を硫酸マグネシ
ウムで乾燥した。有機層を分離し、液をドライア
ツプした。残渣をエタノールから再結晶し、Ｎ，
N′−ビス（４−ジメチルアミノフエニル）−Ｎ，
N′−ジメチル−ｐ−フエニレンジアミンを得た。
一方、実施例１と同様な方法で得た誘電体の薄
層に、前記化合物を160℃で融解して塗布した。
減圧脱気と塗布を繰り返して充分細孔まで化合物
を満たした。次いで、化合物層にヨウ素蒸気を10
時間あてて化合物にヨウ素をドープし、ヨウ素を
ドープした化合物を電導性化合物とする固体電解
質層を形成した。陰極にアルミニウム箔を使用
し、樹脂封口して固体電解コンデンサを作成し
た。このときの電導性化合物の電導度は0.4S・cm
-1であつた。
比較例 １
実施例１と同じ誘電体層をもつたアルミニウム
箔を使用し、従来の二酸化マンガンを固体電解質
とし、陰極をアルミニウム箔として固体電解コン
デンサを作成した。
実施例 ３
タンタル粉末の焼結体をリン酸水溶液中で陽極
酸化して、誘電体皮膜を形成させた後、タンタル
素子を実施例１と同じ方法で得たＮ，N′−ビス
（４−ジメチルアミノフエニル）−ｐ−フエニレン
ジアミンのエタノール溶液に浸漬し、乾燥した。
この浸漬、乾燥の操作を繰り返した。次いで、こ
の素子をNO+・BF4 -のニトロメタン溶液に浸し
て、BF4 -をドープし電導性化合物からなる固体
電解質層を形成した。次に、銀ケースで囲つて陰
極とし、陽極とのつなぎ部を樹脂封口し、固体電
解コンデンサを作成した。このときの電導性化合
物の電導度は、3S・cm-1であつた。
比較例 ２
従来の二酸化マンガン固体電解質からなるタン
タル粉末焼結体を使つた固体電解コンデンサを作
成した。[Formula] can be given. These carbonium cations can be obtained by dissolving salts of them and anions (carbonium salts) in a suitable organic solvent. Representative examples of anions used here include BF 4 - , AlCl 4 - ,
AlBr 3 Cl - , FeCl 4 - , SnCl 3 - , PF 6 - , PCl 6 - ,
Specific examples of carbonium salts include (C 6 H 5 ) 3 C ・ BF 4 , ( CH 3 ) 3 C・BF 4 ,
Examples include HCO・AlCl 4 , HCO・BF 4 , C 6 H 5 CO・SnCl 5 and the like. For the anode of the solid capacitor in the present invention, a metal foil of aluminum, tantalum, niobium, or the like, or a sintered body of metal powder thereof is used. In the case of metal foil, the surface is etched to create pores. The metal foil or sintered body is electrolytically oxidized, for example in a solution of ammonium borate, to form a thin layer of dielectric material on the metal foil or sintered body. The electrically conductive aniline compound in the present invention comes into contact with this dielectric thin layer, and a portion of it enters into the pores. The figure schematically shows a case where a thin metal is used in a solid electrolytic capacitor which is a specific example of the present invention. EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples below. Note that the characteristic values of each solid electrolytic capacitor produced in Examples and Comparative Examples are collectively shown in the table. Example 1 100 μm thick aluminum foil (99.99% purity)
is used as an anode, and the surface of the foil is electrochemically etched using alternating direct current and alternating current to reduce the average pore diameter.
A porous aluminum foil with a diameter of 2 μm and a specific surface area of 12 m 2 /g was used. Next, this etched aluminum foil was immersed in an ammonium borate solution, and a dielectric foil layer was electrochemically formed on the aluminum foil in the solution. On the other hand, 0.046 mol of p-phenylenediamine and N,
0.092 mol of N-dimethylaniline in 220 ml of 12% hydrochloric acid
It was dissolved in Add sodium chromate to this at 0°C.
A solution of 0.044 mol in 40 ml of water was added, followed by a solution of 15 g of zinc chloride in 50 ml of water. Dissolve the generated precipitate in 50℃ water and add 20g
It was recrystallized using a solution of sodium thiosulfate dissolved in 200 ml of aqueous ammonia. The crystals were dried under reduced pressure to obtain N,N'-bis(4-dimethylaminophenyl)-p-phenylenediamine. This compound was melted at 175°C and applied to the dielectric layer described above. Repeat vacuum degassing and application.
The pores were sufficiently filled with the compound. Next, iodine vapor was applied to the compound layer for 10 hours to dope the compound with iodine, thereby forming a solid electrolyte layer in which the iodine-doped compound was used as a conductive compound. A solid electrolytic capacitor was created by using aluminum foil for the cathode and sealing it with resin. The conductivity of the conductive compound at this time was 0.8S·cm -1 . Example 2 0.0073 mol of N,N'-bis(4-dimethylaminophenyl)-p-phenylenediamine obtained in the same manner as in Example 1 was dissolved in 70 ml of tetrahydrofuran and mixed with 0.017 mol of phenyllithium for 1 hour. Made it react. To this was added 0.017 mol of methyl iodide dissolved in 15 ml of tetrahydrofuran, and the mixture was allowed to stand for 1 hour. After adding a small amount of sodium thiosulfate to this, the mixture was washed with water and the organic layer was dried over magnesium sulfate. The organic layer was separated and the liquid was dried up. The residue was recrystallized from ethanol, N,
N'-bis(4-dimethylaminophenyl)-N,
N'-dimethyl-p-phenylenediamine was obtained. On the other hand, the above compound was melted at 160° C. and applied to a dielectric thin layer obtained in the same manner as in Example 1.
Vacuum degassing and coating were repeated to sufficiently fill the pores with the compound. Then add iodine vapor to the compound layer for 10
The compound was doped with iodine over time to form a solid electrolyte layer using the iodine-doped compound as a conductive compound. A solid electrolytic capacitor was created by using aluminum foil for the cathode and sealing it with resin. The conductivity of the conductive compound at this time is 0.4S・cm
It was -1 . Comparative Example 1 A solid electrolytic capacitor was produced using an aluminum foil having the same dielectric layer as in Example 1, using conventional manganese dioxide as a solid electrolyte, and using aluminum foil as a cathode. Example 3 A tantalum powder sintered body was anodized in an aqueous phosphoric acid solution to form a dielectric film, and then a tantalum element was prepared using N,N′-bis(4- It was immersed in an ethanol solution of p-phenylenediamine (dimethylaminophenyl) and dried.
This dipping and drying operation was repeated. Next, this element was immersed in a nitromethane solution of NO + BF 4 - and doped with BF 4 - to form a solid electrolyte layer made of a conductive compound. Next, the cathode was surrounded by a silver case, and the joint with the anode was sealed with resin to create a solid electrolytic capacitor. The conductivity of the conductive compound at this time was 3S·cm -1 . Comparative Example 2 A solid electrolytic capacitor was produced using a tantalum powder sintered body made of a conventional manganese dioxide solid electrolyte.
【表】【table】
【表】
表から明らかなように、本発明によるドーパン
トをドープした電導性アニリン系化合物を電解質
とする固体電解コンデンサは、従来の二酸化マン
ガンを電解質とする固体電解コンデンサに比して
誘電損失漏れ電流が小さく、定格電圧が高く、高
耐電圧の固体電解コンデンサを作成することがで
きる。また、本発明による固体電解コンデンサの
定量×定格電圧の値は、二酸化マンガンを用いた
固体電解コンデンサに比して大きく、同じ形状な
らば大容量を得ることができる。[Table] As is clear from the table, the solid electrolytic capacitor using a conductive aniline compound doped with a dopant according to the present invention as an electrolyte has a higher dielectric loss leakage current than the conventional solid electrolytic capacitor using manganese dioxide as an electrolyte. It is possible to create a solid electrolytic capacitor with a small capacity, high rated voltage, and high withstand voltage. In addition, the value of fixed quantity x rated voltage of the solid electrolytic capacitor according to the present invention is larger than that of a solid electrolytic capacitor using manganese dioxide, and a large capacity can be obtained with the same shape.
図は、本発明による固体電解コンデンサの一具
体例を示す断面図である。
１……陽極リード線、２……陽極、３……酸化
被膜、４……陰極、５……陰極リード線、６……
電導性アニリン系化合物、７……樹脂。
The figure is a sectional view showing a specific example of a solid electrolytic capacitor according to the present invention. 1... Anode lead wire, 2... Anode, 3... Oxide film, 4... Cathode, 5... Cathode lead wire, 6...
Conductive aniline compound, 7...Resin.
Claims (1)
素数が６以下の飽和炭化水素基であり、ｎは２〜
６の整数である。） で表わされるアニリン系化合物にドーパントをド
ープして得られる電導性アニリン系化合物を固体
電解質とすることを特徴とする固体電解コンデン
サ。[Claims] 1. General formula (In the formula, R 1 , R 2 , R 3 and R 4 are hydrogen or a saturated hydrocarbon group having 6 or less carbon atoms, and n is 2 to
It is an integer of 6. ) A solid electrolytic capacitor characterized in that a conductive aniline compound obtained by doping an aniline compound represented by the following formula with a dopant is used as a solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21244284A JPS6191914A (en) | 1984-10-12 | 1984-10-12 | Solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21244284A JPS6191914A (en) | 1984-10-12 | 1984-10-12 | Solid electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6191914A JPS6191914A (en) | 1986-05-10 |
| JPH0552658B2 true JPH0552658B2 (en) | 1993-08-06 |
Family
ID=16622676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21244284A Granted JPS6191914A (en) | 1984-10-12 | 1984-10-12 | Solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6191914A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2631896B2 (en) * | 1989-06-30 | 1997-07-16 | 日東電工株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
| WO2019146506A1 (en) * | 2018-01-25 | 2019-08-01 | キヤノン株式会社 | Compound, liquid composition, thermal transfer recording sheet, toner, resist composition for color filter, and color filter |
-
1984
- 1984-10-12 JP JP21244284A patent/JPS6191914A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6191914A (en) | 1986-05-10 |
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| EXPY | Cancellation because of completion of term |