JP4750498B2 - Manufacturing method of solid electrolytic capacitor - Google Patents
Manufacturing method of solid electrolytic capacitor Download PDFInfo
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- JP4750498B2 JP4750498B2 JP2005220313A JP2005220313A JP4750498B2 JP 4750498 B2 JP4750498 B2 JP 4750498B2 JP 2005220313 A JP2005220313 A JP 2005220313A JP 2005220313 A JP2005220313 A JP 2005220313A JP 4750498 B2 JP4750498 B2 JP 4750498B2
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- 239000003990 capacitor Substances 0.000 title claims description 108
- 239000007787 solid Substances 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 239000004065 semiconductor Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 59
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 31
- 239000004020 conductor Substances 0.000 claims description 27
- 229920001940 conductive polymer Polymers 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 19
- -1 alkali metal salts Chemical class 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
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- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
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- 239000000463 material Substances 0.000 claims description 3
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
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- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
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- 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 claims 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 claims description 2
- 239000010410 layer Substances 0.000 description 89
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- 239000007864 aqueous solution Substances 0.000 description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 5
- 229940090948 ammonium benzoate Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- ROSDCCJGGBNDNL-UHFFFAOYSA-N [Ta].[Pb] Chemical compound [Ta].[Pb] ROSDCCJGGBNDNL-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004301 calcium benzoate Substances 0.000 description 2
- 235000010237 calcium benzoate Nutrition 0.000 description 2
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WDFRPGSFUWIUDH-UHFFFAOYSA-N ethanol naphthalene-1-carboxylic acid Chemical compound C(C)O.C1(=CC=CC2=CC=CC=C12)C(=O)O WDFRPGSFUWIUDH-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000004300 potassium benzoate Substances 0.000 description 2
- 235000010235 potassium benzoate Nutrition 0.000 description 2
- 229940103091 potassium benzoate Drugs 0.000 description 2
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- AJFGAOLLUBJXNE-UHFFFAOYSA-N iron;naphthalene-1-sulfonic acid Chemical compound [Fe].C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 AJFGAOLLUBJXNE-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
本発明は、固体電解コンデンサの製造方法に関する。さらに詳しく言えば、導電体粉末の焼結体を、電解質として芳香族カルボン酸またはその塩類を使用した溶液中で化成して誘電体酸化皮膜層を形成した後、半導体層及び電極層を順次積層し、外装樹脂で封口する固体電解コンデンサの製造方法に関する。 The present invention relates to a method for manufacturing a solid electrolytic capacitor. More specifically, a sintered body of conductor powder is formed in a solution using an aromatic carboxylic acid or a salt thereof as an electrolyte to form a dielectric oxide film layer, and then a semiconductor layer and an electrode layer are sequentially stacked. The present invention also relates to a method for manufacturing a solid electrolytic capacitor that is sealed with an exterior resin.
各種電子機器に使用される高容量なコンデンサの一つとして導電体に、誘電体酸化皮膜、半導体層及び電極層を順次積層した固体電解コンデンサ素子を外装樹脂で封口した固体電解コンデンサがある。 As one of high-capacity capacitors used in various electronic devices, there is a solid electrolytic capacitor in which a solid electrolytic capacitor element in which a dielectric oxide film, a semiconductor layer and an electrode layer are sequentially laminated on a conductor is sealed with an exterior resin.
固体電解コンデンサは、表面層に微細な細孔を有するアルミニウム箔や、内部に微小な細孔を有するタンタル粉の焼結体を一方の電極（導電体）として、その電極の表層に形成した誘電体層とその誘電体層上に設けられた他方の電極（通常は、半導体層）及び他方の電極上に積層された電極層とから構成されたコンデンサ素子を樹脂で封口して作製されている。同一体積の導電体では、細孔が小さく細孔量が多いほど導電体内部の表面積が大きくなるために、その導電体から作製したコンデンサの容量は大きなものとなる。 Solid electrolytic capacitors consist of an aluminum foil with fine pores in the surface layer and a sintered body of tantalum powder with fine pores inside as one electrode (conductor) formed on the surface of the electrode. It is made by sealing a capacitor element composed of a body layer and the other electrode (usually a semiconductor layer) provided on the dielectric layer and an electrode layer laminated on the other electrode with a resin. . In a conductor having the same volume, the surface area inside the conductor increases as the pores are smaller and the amount of pores is larger, so that the capacity of a capacitor made from the conductor increases.
昨今の固体電解コンデンサは、低ＥＳＲ（等価直列抵抗）であることが要求されるために、内部の半導体層としてもっぱら導電性高分子が使用される。
導電性高分子を半導体層とする固体電解コンデンサでは、導電体を電解質溶液で化成処理して表面に誘電体層を形成し、その上に導電性高分子からなる半導体層を形成する。
Since recent solid electrolytic capacitors are required to have low ESR (equivalent series resistance), a conductive polymer is exclusively used as an internal semiconductor layer.
In a solid electrolytic capacitor using a conductive polymer as a semiconductor layer, a conductor is subjected to chemical conversion treatment with an electrolyte solution to form a dielectric layer on the surface, and a semiconductor layer made of the conductive polymer is formed thereon.
化成処理用の電解質としては、一般に、鉱酸、有機酸及びこれらの塩類が用いられる。例えば、特開平０３−２８５３２１号公報（特許文献１）には硫酸化成が記載され、特開２００４−１６５３４０号公報（特許文献２）には脂肪族カルボン酸またはその塩による化成が開示され、特開２００４−４０１３４号公報（特許文献３）には中性塩と燐酸の連続化成が記載されている。しかしながら、これらの電解質で化成処理して誘電体層を形成したコンデンサでは、実装時の熱衝撃（リフロー時の加熱）によってＥＳＲが上昇するという問題があった。このようなＥＳＲの上昇は誘電体酸化皮膜層と半導体層の熱膨張係数の違いによる実装時の熱衝撃（リフロー時の加熱）での両層の剥がれよるものと考えられる。 As the electrolyte for chemical conversion treatment, mineral acids, organic acids and salts thereof are generally used. For example, Japanese Patent Application Laid-Open No. 03-285321 (Patent Document 1) describes sulfate conversion, and Japanese Patent Application Laid-Open No. 2004-165340 (Patent Document 2) discloses conversion with an aliphatic carboxylic acid or a salt thereof. Kai 2004-40134 (Patent Document 3) describes continuous formation of a neutral salt and phosphoric acid. However, capacitors having a dielectric layer formed by chemical conversion treatment with these electrolytes have a problem that ESR increases due to thermal shock during mounting (heating during reflow). Such an increase in ESR is considered to be due to peeling of both layers due to thermal shock (heating during reflow) during mounting due to the difference in thermal expansion coefficient between the dielectric oxide film layer and the semiconductor layer.
本発明の課題は、誘電体酸化皮膜層と半導体層の熱膨張係数の違いによる実装時の熱衝撃（リフロー時の加熱）での両層の剥がれを緩和、すなわちＥＳＲ上昇を緩和することができる固体電解コンデンサの製造方法を提供することにある。 An object of the present invention is to reduce peeling of both layers due to a thermal shock (heating during reflow) during mounting due to a difference in thermal expansion coefficient between a dielectric oxide film layer and a semiconductor layer, that is, to reduce an ESR rise. It is providing the manufacturing method of a solid electrolytic capacitor.
本発明者らは、前記課題に鑑み鋭意検討した結果、特にＣＶ値の大きな導電体（焼結体）を用いたとき、電解質として少なくとも１種の芳香族カルボン酸を用いて化成処理を行うとＥＳＲの熱変化が低減され、実装時の熱衝撃（リフロー時の加熱）によるＥＳＲ上昇を緩和することができ、半田処理したときにＥＳＲの大きなものが出現することがないこと、特にコンデンサの導電体（焼結体）のＣＶ値がタンタルでは１０万μＦ・Ｖ／ｇ以上、ニオブでは１５万μＦ・Ｖ／ｇ以上のもの、あるいは体積が４ｍｍ3以上の焼結体の場合に効果的であることを見出し、本発明を完成した。 As a result of intensive studies in view of the above problems, the present inventors have conducted chemical conversion treatment using at least one aromatic carboxylic acid as an electrolyte, particularly when a conductor (sintered body) having a large CV value is used. ESR thermal change is reduced, ESR rise due to thermal shock during mounting (heating during reflow) can be mitigated, and no large ESR appears when soldering, especially in capacitor Effective when the sintered body has a CV value of 100,000 μF · V / g or more for tantalum, 150,000 μF · V / g or more for niobium, or a volume of 4 mm 3 or more. As a result, the present invention was completed.
なお、従来技術として有機酸あるいはその塩を用いた化成処理が知られ、有機酸の例として芳香族カルボン酸も挙げられているが、実施例レベルで芳香族カルボン酸を開示した先行技術はなく、また芳香族カルボン酸またはその塩を用いたときにＥＳＲの熱変化が低減されることを記載あるいは示唆した先行技術もない。 In addition, chemical conversion treatment using an organic acid or a salt thereof is known as a conventional technique, and an aromatic carboxylic acid is also cited as an example of an organic acid, but there is no prior art that disclosed an aromatic carboxylic acid at an example level There is also no prior art that describes or suggests that the thermal change of ESR is reduced when an aromatic carboxylic acid or a salt thereof is used.
本発明において、化成処理に芳香族カルボン酸またはその塩を用いたときＥＳＲの熱変化が低減される理由の詳細は必ずしも明らかではないが、以下のように考えられる。すなわち、電解質のアニオンは形成された誘電体層に取り込まれるが、誘電体層表層のアニオンの芳香族環は、半導体層の導電性高分子の二重結合部分とπ電子相互作用を起こし電荷移動錯体を形成する。芳香族環にＯＣＯ-基が付いていると芳香族環のπ電子は広がり、電荷移動錯体の強度が増す。この電荷移動錯体が生じることによって、誘電体層と半導体層の熱膨張係数の違いによる実装時の熱衝撃での両層の剥がれを緩和すると考えられる。ＣＶ値が大きく体積が大きな焼結体は、焼結体細孔内部まで半導体層充填が困難なために、誘電体層と半導体層との接触量（いわゆる被覆率）が比較的に小さいので、この場合に特にＥＳＲ劣化を緩和する効果がある。 In the present invention, details of the reason why the thermal change of ESR is reduced when an aromatic carboxylic acid or a salt thereof is used for the chemical conversion treatment are not necessarily clear, but are considered as follows. In other words, the anion of the electrolyte is taken into the formed dielectric layer, but the aromatic ring of the anion on the surface of the dielectric layer causes a π-electron interaction with the double bond portion of the conductive polymer of the semiconductor layer, resulting in charge transfer. Form a complex. If the OCO 2 - group is attached to the aromatic ring, the π electrons of the aromatic ring will spread and the strength of the charge transfer complex will increase. The generation of this charge transfer complex is considered to reduce peeling of both layers due to a thermal shock during mounting due to a difference in thermal expansion coefficient between the dielectric layer and the semiconductor layer. Since the sintered body having a large CV value and a large volume is difficult to fill the semiconductor layer into the pores of the sintered body, the contact amount (so-called coverage) between the dielectric layer and the semiconductor layer is relatively small. In this case, there is an effect of particularly mitigating ESR degradation.
すなわち、本発明は、以下の固体電解コンデンサの製造方法、その製造方法により作製した固体電解コンデンサ及びその用途に関する。 That is, this invention relates to the manufacturing method of the following solid electrolytic capacitors, the solid electrolytic capacitor produced by the manufacturing method, and its use.
１．導電体粉末の焼結体に陽極リードを接続し、電解質を含む化成溶液中で化成して焼結体に誘電体酸化皮膜を形成した後、半導体層及び電極層を順次積層した固体電解コンデンサ素子を外装樹脂で封口する固体電解コンデンサの製造方法において、化成溶液として芳香族カルボン酸またはその塩類を含む溶液を使用することを特徴とする固体電解コンデンサの製造方法。
２．陽極リードが、線、箔または板状である前記１に記載の固体電解コンデンサの製造方法。
３．陽極リードの材質が、タンタル、アルミニウム、ニオブ、チタン、またはこれら弁作用金属を主成分とする合金である前記１または２に記載の固体電解コンデンサの製造方法。
４．導電体が、タンタル、ニオブ、チタン及びアルミニウムから選ばれる少なくとも１種を主成分とする金属あるいは合金、酸化ニオブ、またはこれら金属、合金及び酸化ニオブから選ばれる少なくとも２種以上の混合物である前記１記載の固体電解コンデンサの製造方法。
５．導電体粉末の焼結体が、ＣＶ値１０万μＦ・Ｖ／ｇ以上のタンタルを主成分とする金属の焼結体である前記１に記載の固体電解コンデンサの製造方法。
６．導電体粉末の焼結体が、ＣＶ値１５万μＦ・Ｖ／ｇ以上のニオブを主成分とする金属の焼結体である前記１に記載の固体電解コンデンサの製造方法。
７．導電体粉末の焼結体が、４ｍｍ3以上の体積を有する焼結体である前記１乃至６のいずれか１項に記載の固体電解コンデンサの製造方法。
８．芳香族カルボン酸が安息香酸、サリチル酸、ナフタレンカルボン酸、ナフタレンジカルボン酸、無水安息香酸、アニス酸、これらのアンモニウム塩、アルカリ金属塩、アルカリ土類金属塩、マンガン塩及びニッケル塩から選択される前記１記載の固体電解コンデンサの製造方法。
９．半導体層が、有機半導体層及び無機半導体層から選ばれる少なくとも１種である前記１に記載の固体電解コンデンサの製造方法。
１０．有機半導体が、ベンゾピロリン４量体とクロラニルからなる有機半導体、テトラチオテトラセンを主成分とする有機半導体、テトラシアノキノジメタンを主成分とする有機半導体、下記一般式（１）または（２）
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である前記９に記載の固体電解コンデンサの製造方法。
１１．一般式（１）で示される繰り返し単位を含む導電性高分子が、下記一般式（３）
で示される構造単位を繰り返し単位として含む導電性高分子である前記１０に記載の固体電解コンデンサの製造方法。
１２．導電性高分子が、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、及びこれらの置換誘導体及び共重合体から選択される前記１０に記載の固体電解コンデンサの製造方法。
１３．導電性高分子が、ポリ（３，４−エチレンジオキシチオフェン）である前記１１または１２に記載の固体電解コンデンサの製造方法。
１４．無機半導体が、二酸化モリブデン、二酸化タングステン、二酸化鉛、及び二酸化マンガンから選ばれる少なくとも１種の化合物である前記９に記載の固体電解コンデンサの製造方法。
１５．半導体の電導度が１０-2〜１０3Ｓ／ｃｍの範囲である前記９に記載の固体電解コンデンサの製造方法。
１６．前記１乃至１５のいずれかに１項に記載の製造方法により得られる固体電解コンデンサ。
１７．前記１６に記載の固体電解コンデンサを使用した電子回路。
１８．前記１６に記載の固体電解コンデンサを使用した電子機器。
1. A solid electrolytic capacitor element in which an anode lead is connected to a sintered body of conductive powder, formed in a chemical solution containing an electrolyte to form a dielectric oxide film on the sintered body, and then a semiconductor layer and an electrode layer are sequentially stacked. In the manufacturing method of the solid electrolytic capacitor which seals by exterior resin, the solution containing aromatic carboxylic acid or its salt is used as a chemical conversion solution.
2. 2. The method for producing a solid electrolytic capacitor as described in 1 above, wherein the anode lead is wire, foil or plate.
3. 3. The method for producing a solid electrolytic capacitor as described in 1 or 2 above, wherein the material of the anode lead is tantalum, aluminum, niobium, titanium, or an alloy containing these valve metals as a main component.
4). The above-mentioned 1 wherein the conductor is a metal or alloy containing at least one selected from tantalum, niobium, titanium and aluminum, niobium oxide, or a mixture of at least two selected from these metals, alloys and niobium oxide. The manufacturing method of the solid electrolytic capacitor of description.
5. 2. The method for producing a solid electrolytic capacitor as described in 1 above, wherein the sintered body of the conductor powder is a sintered body of a metal mainly composed of tantalum having a CV value of 100,000 μF · V / g or more.
6). 2. The method for producing a solid electrolytic capacitor as described in 1 above, wherein the sintered body of the conductor powder is a sintered body of metal mainly composed of niobium having a CV value of 150,000 μF · V / g or more.
7). 7. The method for producing a solid electrolytic capacitor according to any one of 1 to 6, wherein the sintered body of the conductor powder is a sintered body having a volume of 4 mm 3 or more.
8). The aromatic carboxylic acid is selected from benzoic acid, salicylic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, benzoic anhydride, anisic acid, ammonium salts thereof, alkali metal salts, alkaline earth metal salts, manganese salts and nickel salts A method for producing a solid electrolytic capacitor according to 1.
9. 2. The method for producing a solid electrolytic capacitor as described in 1 above, wherein the semiconductor layer is at least one selected from an organic semiconductor layer and an inorganic semiconductor layer.
10. An organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
10. The method for producing a solid electrolytic capacitor as described in 9 above, which is at least one selected from organic semiconductors whose main component is a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula (1) with a dopant.
11. The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
11. The method for producing a solid electrolytic capacitor as described in 10 above, wherein the polymer is a conductive polymer containing a structural unit represented by
12 11. The method for producing a solid electrolytic capacitor as described in 10 above, wherein the conductive polymer is selected from polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof.
13. 13. The method for producing a solid electrolytic capacitor as described in 11 or 12 above, wherein the conductive polymer is poly (3,4-ethylenedioxythiophene).
14 10. The method for producing a solid electrolytic capacitor as described in 9 above, wherein the inorganic semiconductor is at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, and manganese dioxide.
15. 10. The method for producing a solid electrolytic capacitor as described in 9 above, wherein the electrical conductivity of the semiconductor is in the range of 10 −2 to 10 3 S / cm.
16. 16. A solid electrolytic capacitor obtained by the manufacturing method according to any one of 1 to 15.
17. 17. An electronic circuit using the solid electrolytic capacitor as described in 16 above.
18. 17. An electronic device using the solid electrolytic capacitor as described in 16 above.
本発明は、誘電体酸化皮膜を形成する際に用いる化成用溶液として、芳香族カルボン酸またはその塩を含む溶液を使用することを特徴とする固体電解コンデンサの製造方法を提供したものであり、本発明によれば、実装時の熱衝撃（リフロー時の加熱）によるＥＳＲ上昇を緩和できる固体電解コンデンサを製造することができる。 The present invention provides a method for producing a solid electrolytic capacitor characterized by using a solution containing an aromatic carboxylic acid or a salt thereof as a chemical conversion solution used when forming a dielectric oxide film, ADVANTAGE OF THE INVENTION According to this invention, the solid electrolytic capacitor which can relieve the ESR raise by the thermal shock at the time of mounting (heating at the time of reflow) can be manufactured.
本発明の固体電解コンデンサの製造方法及び固体電解コンデンサの一形態を説明する。本発明の固体電解コンデンサは、例えば弁作用金属からなる導電体粉末の焼結体に、誘電体酸化皮膜、半導体層及び電極層を順次積層して作製される。 An embodiment of a method for producing a solid electrolytic capacitor and a solid electrolytic capacitor of the present invention will be described. The solid electrolytic capacitor of the present invention is produced, for example, by sequentially laminating a dielectric oxide film, a semiconductor layer, and an electrode layer on a sintered body of a conductor powder made of a valve metal.
本発明の導電体の好ましい例として、タンタル、ニオブ、これらの金属を主成分とする合金粉、または一酸化ニオブ等の粉を成形し焼結した内部に微細な空孔が多数存在する焼結体、及び表面がエッチング処理されたアルミニウム箔を挙げることができる。なお、主成分とは５０質量％以上の成分である。 As a preferred example of the conductor of the present invention, tantalum, niobium, alloy powders mainly composed of these metals, or powders such as niobium monoxide are formed and sintered. The body and the aluminum foil whose surface was etched can be mentioned. The main component is a component of 50% by mass or more.
粒径が細かい粉を使用して焼結体を作製すると、質量あたりの比表面積が大きな焼結体が作製できる。本発明の方法は、導電体としてこのような焼結体を用いたコンデンサで効果的である。例えば、ＣＶ値（電解液で測定したときの容量と化成電圧の積）がタンタルを主成分とする金属粉では１０万μＦ・Ｖ／ｇ以上、ニオブを主成分とする金属粉または一酸化ニオブ粉では１５万μＦ・Ｖ／ｇ以上となる高ＣＶ値（高比表面積）を有するもの、あるいは大きさが４ｍｍ3以上の焼結体に利用すると、本発明の方法は特に効果的である。 When a sintered body is produced using powder having a small particle size, a sintered body having a large specific surface area per mass can be produced. The method of the present invention is effective for a capacitor using such a sintered body as a conductor. For example, in the case of a metal powder whose main component is tantalum, the CV value (product of capacity and conversion voltage when measured with an electrolyte) is 100,000 μF · V / g or more, and the metal powder or niobium monoxide that has niobium as the main component. The method of the present invention is particularly effective when used for a powder having a high CV value (high specific surface area) of 150,000 μF · V / g or more, or a sintered body having a size of 4 mm 3 or more.
導電体には引き出しリードを直接接続することが可能であるが、粉状の導電体を成形または成形後焼結した形状とする場合は、成形時に別途用意した引き出しリードの一部を導電体と共に成形し、引き出しリードの成形外部の箇所を、コンデンサの一方の電極の引き出しリードとすることもできる。 The lead can be directly connected to the conductor. However, if the powdered conductor is molded or formed into a sintered shape after molding, a part of the lead that was prepared separately at the time of molding together with the conductor It is also possible to form the lead lead of the one electrode of the capacitor at a location outside the lead lead.
陽極リードは、線状でも、箔状でも板状でもよい。また陽極リードを成形体に植設せずに、焼結体を作製した後に接続してもよい。陽極リードの材質としては、タンタル、アルミニウム、ニオブ、チタン、これら弁作用金属を主成分とする合金が使用される。また、陽極リードの一部を、炭化、燐化、ホウ化、窒化、硫化、酸化から選ばれた少なくとも１種の処理を行ってから使用してもよい。 The anode lead may be linear, foil, or plate. Further, the anode lead may be connected after the sintered body is produced without being implanted in the molded body. As the material of the anode lead, tantalum, aluminum, niobium, titanium, or an alloy mainly composed of these valve metals is used. Further, a part of the anode lead may be used after being subjected to at least one treatment selected from carbonization, phosphide, boride, nitridation, sulfidation, and oxidation.
陽極リードを成形体に植設する場合、陽極リードの焼結体内の深さは、好ましくは焼結体の１／３以上、より好ましくは２／３以上とすると焼結体の強度が維持できて後述するコンデンサ素子の外装封口時の熱的、物理的な封止応力に対する耐性が向上するために好ましい。 When the anode lead is implanted in the molded body, the strength of the sintered body can be maintained if the depth of the anode lead in the sintered body is preferably 1/3 or more, more preferably 2/3 or more of the sintered body. This is preferable because resistance to thermal and physical sealing stress at the time of external sealing of the capacitor element described later is improved.
後記する半導体層が、陽極リードを有する導電体の場合は陽極リードの上部にまで、導電体の一部を陽極部とした場合は陽極部にまで付着してコンデンサがショートすることを防ぐために、焼結体と陽極リードまたは陽極部の境界部（陽極リードまたは陽極部側）に絶縁性樹脂を鉢巻状に付着させて絶縁を図ってもよい。 In order to prevent a capacitor from being short-circuited by a semiconductor layer, which will be described later, attached to the upper part of the anode lead in the case of a conductor having an anode lead, and to the anode part if a part of the conductor is an anode part, Insulation may be achieved by attaching an insulating resin in a headband shape to the boundary between the sintered body and the anode lead or the anode part (anode lead or anode part side).
本発明においては、焼結体及び陽極リードの一部の表面に誘電体酸化皮膜層を形成させる。誘電体酸化皮膜層としては、Ｔａ2Ｏ5、Ａｌ2Ｏ3、ＴｉＯ2、Ｎｂ2Ｏ5等の金属酸化物から選ばれる少なくとも１つを主成分とする誘電体層が挙げられる。誘電体層は、前記陽極基体を電解液中で化成することによって得ることができる。 In the present invention, a dielectric oxide film layer is formed on part of the surfaces of the sintered body and the anode lead. Examples of the dielectric oxide film layer include a dielectric layer mainly composed of at least one selected from metal oxides such as Ta 2 O 5 , Al 2 O 3 , TiO 2 , and Nb 2 O 5 . The dielectric layer can be obtained by forming the anode substrate in an electrolytic solution.
本発明では半導体層に導電体高分子を用いるため、誘電体皮膜酸化層形成時の化成には電解質溶液を使用する。
本発明では電解質溶液として、芳香族カルボン酸またはその塩の溶液を使用することが必須である。芳香族カルボン酸及びその塩類との具体例としては、安息香酸、サリチル酸、ナフタレンカルボン酸、ナフタレンジカルボン酸、無水安息香酸、アニス酸、これらのアンモニウム塩、アルカリ金属塩、アルカリ土類金属塩、マンガン塩、ニッケル塩が挙げられる。
In the present invention, since a conductive polymer is used for the semiconductor layer, an electrolyte solution is used for the formation when the dielectric film oxide layer is formed.
In the present invention, it is essential to use a solution of an aromatic carboxylic acid or a salt thereof as the electrolyte solution. Specific examples of aromatic carboxylic acids and salts thereof include benzoic acid, salicylic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, benzoic anhydride, anisic acid, ammonium salts thereof, alkali metal salts, alkaline earth metal salts, manganese Salt and nickel salt.
本発明においては、上記電解質が溶解または一部溶解した水、アルコール（エタノール等）の少なくとも１種を溶媒とした電解液を用いる。溶媒としては水が好ましいが、水に対する溶解度が低い化合物及び塩類の場合には水とアルコールの混合溶媒あるいはアルコールを使用する。化成液濃度は、一般に0.05〜３０質量％、好ましくは0.1〜１５質量％である。濃度が低すぎると化成に時間がかかり、濃度が高すぎても性能は向上しない。化成時間としては、数分〜数日間であり、数時間〜２０時間が好ましい。 In the present invention, an electrolytic solution using at least one of water and alcohol (ethanol or the like) in which the electrolyte is dissolved or partially dissolved as a solvent is used. As the solvent, water is preferable, but in the case of compounds and salts having low solubility in water, a mixed solvent of water and alcohol or alcohol is used. The chemical conversion liquid concentration is generally 0.05 to 30% by mass, preferably 0.1 to 15% by mass. If the concentration is too low, chemical conversion takes time, and if the concentration is too high, the performance is not improved. The chemical formation time is from several minutes to several days, preferably from several hours to 20 hours.
本発明の誘電体層上に形成される半導体層の代表例として、有機半導体及び無機半導体から選ばれる少なくとも１種の化合物が挙げられる。 A typical example of the semiconductor layer formed on the dielectric layer of the present invention is at least one compound selected from an organic semiconductor and an inorganic semiconductor.
有機半導体の具体例としては、下記一般式（１）または（２）で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体が挙げられる。 Specific examples of the organic semiconductor include an organic semiconductor mainly composed of a conductive polymer obtained by doping a polymer including a repeating unit represented by the following general formula (1) or (2) with a dopant.
式（１）及び（２）において、Ｒ1〜Ｒ4は各々独立して、水素原子、炭素数１〜６のアルキル基または炭素数１〜６のアルコキシ基を表し、Ｘは酸素、イオウまたは窒素原子を表し、Ｒ5はＸが窒素原子のときのみ存在して水素原子または炭素数１〜６のアルキル基を表し、Ｒ1とＲ2及びＲ3とＲ4は、互いに結合して環状になっていてもよい。 In the formulas (1) and (2), R 1 to R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and X represents oxygen, sulfur or Represents a nitrogen atom, R 5 is present only when X is a nitrogen atom and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 and R 3 and R 4 are bonded to each other to form a ring It may be.
さらに、本発明においては、前記一般式（１）で示される繰り返し単位を含む導電性高分子は、好ましくは下記一般式（３）で示される構造単位を繰り返し単位として含む導電性高分子が挙げられる。 Furthermore, in the present invention, the conductive polymer containing a repeating unit represented by the general formula (1) is preferably a conductive polymer containing a structural unit represented by the following general formula (3) as a repeating unit. It is done.
式中、Ｒ6及びＲ7は各々独立して、水素原子、炭素数１〜６の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、または該アルキル基が互いに任意の位置で結合して、２つの酸素原子を含む少なくとも１つ以上の５〜７員環の飽和炭化水素の環状構造を形成する置換基を表す。また、前記環状構造には置換されていてもよいビニレン結合を有するもの、置換されていてもよいフェニレン構造のものも含まれる。 In the formula, R 6 and R 7 are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl group is bonded to each other at an arbitrary position. And a substituent that forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen atoms. The cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted.
このような化学構造を含む導電性高分子は、荷電されており、ドーパントがドープされる。ドーパントは特に限定されず公知のドーパントが使用できる。 A conductive polymer containing such a chemical structure is charged and doped with a dopant. A dopant is not specifically limited, A well-known dopant can be used.
式（１）〜（３）で示される繰り返し単位を含む高分子としては、例えば、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、及びこれらの置換誘導体や共重合体などが挙げられる。中でもポリピロール、ポリチオフェン及びこれらの置換誘導体（例えば、ポリ（３，４−エチレンジオキシチオフェン）等）が好ましい。 Examples of the polymer containing the repeating unit represented by the formulas (1) to (3) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof. Etc. Of these, polypyrrole, polythiophene, and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene)) are preferable.
無機半導体の具体例としては、二酸化モリブデン、二酸化タングステン、二酸化鉛、二酸化マンガン等から選ばれる少なくとも１種の化合物が挙げられる。 Specific examples of the inorganic semiconductor include at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, manganese dioxide and the like.
上記有機半導体及び無機半導体として、電導度１０-2〜１０3Ｓ／ｃｍの範囲のものを使用すると、作製したコンデンサのＥＳＲ値がより小さくなり好ましい。 When the organic semiconductor and the inorganic semiconductor have a conductivity in the range of 10 −2 to 10 3 S / cm, it is preferable because the ESR value of the manufactured capacitor becomes smaller.
本発明において半導体層の導電性高分子は、電解重合法、化学重合法、気相重合法及びこれらを組み合わせた方法で作製できるが、コンデンサ製造初期のＥＳＲが良好な電解重合法が好ましい。 In the present invention, the conductive polymer of the semiconductor layer can be produced by an electrolytic polymerization method, a chemical polymerization method, a gas phase polymerization method, or a combination of these methods.
本発明においては、半導体層を形成する際に生じる誘電体層の微小な欠陥を修復するために、再化成を行ってもよい。また、半導体層形成と再化成を複数回繰り返してもよいし、繰り返し時の半導体層形成条件と再化成条件を変更してもよい。通常、半導体層形成を止める場合、半導体層形成溶液から導電体を引き上げて洗浄・乾燥を行うが、半導体層形成・半導体層形成停止・洗浄・乾燥工程の繰り返しを複数回行ってから再化成工程に入れてもよい。理由は定かでないが、連続して半導体層を形成するよりも半導体層形成時間を同じにして半導体層形成・半導体層形成停止・洗浄・乾燥を行うことを繰り返すほうが、半導体層質量が上昇する場合がある。 In the present invention, re-formation may be performed in order to repair minute defects in the dielectric layer generated when the semiconductor layer is formed. Moreover, the semiconductor layer formation and re-formation may be repeated a plurality of times, or the semiconductor layer formation conditions and the re-formation conditions at the time of repetition may be changed. Normally, when stopping the semiconductor layer formation, the conductor is pulled up from the semiconductor layer formation solution and washed and dried. However, the semiconductor layer formation / semiconductor layer formation stop / cleaning / drying process is repeated several times before the re-forming process You may put in. The reason is not clear, but the semiconductor layer mass rises by repeating the semiconductor layer formation, semiconductor layer formation stop, washing, and drying with the same semiconductor layer formation time rather than continuously forming the semiconductor layer There is.
再化成は、前述した化成による誘電体層の形成方法と同様にして行うことも、従来の電解液中で行うことも可能であるが、本発明の誘電体層形成方法と同様の電解液中で行う方が作製した固体電解コンデンサのＥＳＲ値が低いために好ましい。また、ドーパントを電解質とした化成液でもよい。通常、再化成電圧は、化成電圧以下で行われる。 The re-chemical conversion can be performed in the same manner as the dielectric layer forming method by chemical conversion described above or in a conventional electrolytic solution, but in the electrolytic solution similar to the dielectric layer forming method of the present invention. Is preferable because the ESR value of the produced solid electrolytic capacitor is low. Moreover, the chemical conversion liquid which used the dopant as electrolyte may be sufficient. Usually, the re-forming voltage is performed below the forming voltage.
本発明では、前述した方法等で形成された半導体層の上に電極層を設けらる。電極層は、例えば、導電ペーストの固化、メッキ、金属蒸着、耐熱性の導電樹脂フィルムの付着等により形成することができる。導電ペーストとしては、銀ペースト、銅ペースト、アルミニウムペースト、カーボンペースト、ニッケルペースト等が好ましい。これらは１種を用いても２種以上を用いてもよい。２種以上を用いる場合は混合してもよく、または別々の層として重ねてもよい。導電ペーストを適用した後、空気中に放置するか、または加熱して固化させる。固化後の導電ペースト層の厚さは、一層あたり通常約0.1〜約２００μｍである。 In the present invention, an electrode layer is provided on the semiconductor layer formed by the above-described method or the like. The electrode layer can be formed, for example, by solidification of a conductive paste, plating, metal deposition, adhesion of a heat-resistant conductive resin film, or the like. As the conductive paste, silver paste, copper paste, aluminum paste, carbon paste, nickel paste and the like are preferable. These may be used alone or in combination of two or more. When using 2 or more types, they may be mixed or may be stacked as separate layers. After applying the conductive paste, it is left in the air or heated to solidify. The thickness of the conductive paste layer after solidification is usually about 0.1 to about 200 μm per layer.
導電性ペーストは、通常導電粉を４０〜９７質量％含む。４０質量％未満であると作製した導電ペーストの導電性が小さく、９７質量％を超えると、導電ペーストの接着性が小さくなる。導電ペーストに前述した半導体層を形成する導電性高分子や金属酸化物の粉を混合して使用してもよい。 The conductive paste usually contains 40 to 97% by mass of conductive powder. When the content is less than 40% by mass, the conductivity of the produced conductive paste is small, and when it exceeds 97% by mass, the adhesion of the conductive paste is reduced. You may mix and use the conductive polymer and metal oxide powder which form the semiconductor layer mentioned above in the electrically conductive paste.
メッキとしては、ニッケルメッキ、銅メッキ、銀メッキ、金メッキ、アルミニウムメッキ等が挙げられる。また蒸着金属としては、アルミニウム、ニッケル、銅、銀、金等が挙げられる。 Examples of the plating include nickel plating, copper plating, silver plating, gold plating, and aluminum plating. Examples of the deposited metal include aluminum, nickel, copper, silver, and gold.
具体的には、例えば半導体層が形成された導電体の上にカーボンペースト、銀ペーストを順次積層し電極層が形成される。 Specifically, for example, an electrode layer is formed by sequentially laminating a carbon paste and a silver paste on a conductor on which a semiconductor layer is formed.
このようにして電極層まで積層して陰極部を形成したコンデンサ素子が作製される。
以上のような構成の本発明のコンデンサ素子は、例えば、樹脂モールド、樹脂ケース、金属性の外装ケース、樹脂のディッピング、ラミネートフイルムによる外装などの外装により各種用途のコンデンサ製品とすることができる。これらの中でも、樹脂モールド外装を行ったチップ状コンデンサが、小型化と低コスト化が簡単に行えるので好ましい。
In this way, a capacitor element in which the cathode layer is formed by stacking up to the electrode layer is manufactured.
The capacitor element of the present invention having the above-described configuration can be made into a capacitor product for various uses by, for example, an exterior such as a resin mold, a resin case, a metallic exterior case, a resin dipping, or an exterior with a laminate film. Among these, a chip-shaped capacitor with a resin mold is preferable because it can be easily reduced in size and cost.
樹脂モールド外装に使用される樹脂の種類としては、エポキシ樹脂、フェノール樹脂、アルキッド樹脂等固体電解コンデンサの封止に使用される公知の樹脂が採用できるが、各樹脂とも一般に市販されている低応力樹脂を使用すると、封止時に起きるコンデンサ素子への封止応力の発生を緩和することができるために好ましい。また、樹脂封口するための製造機としてトランスファーマシンが好んで使用される。 As the type of resin used for the resin mold exterior, known resins used for sealing solid electrolytic capacitors such as epoxy resin, phenol resin, alkyd resin, etc. can be adopted, but each resin is generally commercially available with low stress. Use of a resin is preferable because generation of sealing stress to the capacitor element that occurs during sealing can be reduced. A transfer machine is preferably used as a manufacturing machine for sealing the resin.
このように作製されたコンデンサは、電極層形成時や外装時の熱的及び／または物理的な誘電体層の劣化を修復するために、エージング処理を行ってもよい。エージング方法は、コンデンサに所定の電圧（通常、定格電圧の２倍以内）を印加することによって行われる。エージング時間や温度は、コンデンサの種類、容量、定格電圧によって最適値が変化するので予め実験によって決定されるが、通常、時間は、数分から数日、温度は電圧印加冶具の熱劣化を考慮して３００℃以下で行われる。エージングの雰囲気は、空気中でもよいし、アルゴン、窒素、ヘリウム等のガス中でもよい。また、減圧、常圧、加圧下のいずれの条件で行ってもよいが、水蒸気を供給しながら、または水蒸気を供給した後に前記エージングを行うと誘電体層の安定化が進む場合がある。水蒸気の供給方法の１例として、エージングの炉中に置いた水溜めから熱により水蒸気を供給する方法が挙げられる。 The capacitor thus fabricated may be subjected to an aging treatment in order to repair the deterioration of the thermal and / or physical dielectric layer at the time of electrode layer formation or exterior. The aging method is performed by applying a predetermined voltage (usually within twice the rated voltage) to the capacitor. Aging time and temperature are determined in advance by experiment because optimum values vary depending on the type, capacity, and rated voltage of the capacitor.Normally, the time is several minutes to several days, and the temperature takes into account the thermal deterioration of the voltage application jig. At 300 ° C. or lower. The aging atmosphere may be air or a gas such as argon, nitrogen, or helium. Moreover, although it may be performed under any conditions of reduced pressure, normal pressure, and increased pressure, stabilization of the dielectric layer may progress if the aging is performed while supplying water vapor or after supplying water vapor. One example of a method for supplying water vapor is a method for supplying water vapor by heat from a water reservoir placed in an aging furnace.
電圧印加方法は、直流、任意の波形を有する交流、直流に重畳した交流やパルス電流等の任意の電流を流すように設計することができる。エージングの途中に一旦電圧印加を止め、再度電圧印加を行うことも可能である。 The voltage application method can be designed to flow an arbitrary current such as a direct current, an alternating current having an arbitrary waveform, an alternating current superimposed on the direct current, or a pulse current. It is also possible to stop the voltage application once during the aging and apply the voltage again.
本発明で製造されたコンデンサは、例えば、中央演算回路や電源回路等の高容量で低ＥＳＲのコンデンサを必要とする回路に好ましく用いることができる。これらの回路は、パソコン、サーバー、カメラ、ゲーム機、ＤＶＤ、ＡＶ機器、携帯電話等の各種デジタル機器や、各種電源等の電子機器に利用可能である。本発明で製造されたコンデンサは、高容量でＥＳＲ性能がよいことから、これを用いることにより性能が良好な電子回路及び電子機器を得ることができる。 The capacitor manufactured by the present invention can be preferably used for a circuit that requires a high capacity and low ESR capacitor, such as a central processing circuit and a power supply circuit. These circuits can be used in various digital devices such as personal computers, servers, cameras, game machines, DVDs, AV devices, and mobile phones, and electronic devices such as various power supplies. Since the capacitor manufactured according to the present invention has a high capacity and good ESR performance, it is possible to obtain an electronic circuit and an electronic device with good performance by using the capacitor.
以下、本発明の具体例についてさらに詳細に説明するが、以下の例により本発明は限定されるものではない。なお、特に記載がない限り下記例中の％は、質量％を表す。 Hereinafter, specific examples of the present invention will be described in more detail, but the present invention is not limited to the following examples. Unless otherwise specified,% in the following examples represents mass%.
実施例１：
ＣＶ（容量と化成電圧の積）１５万μＦ・Ｖ／ｇのタンタル粉を使用し、大きさ1.0×1.3×3.3ｍｍの焼結体を作製した（焼結温度1310℃、焼結時間２０分、質量29.0ｍｇ、焼結体密度5.9ｇ／ｃｍ3、タンタルリード線0.40ｍｍφ、焼結体の4.5ｍｍ寸法の長手方向と平行にタンタルリード線の一部3.0ｍｍが埋設されていて焼結体から突き出たリード線１０ｍｍ部が陽極部となる。）。陽極となる焼結体を１％安息香酸水溶液にリード線の一部を除いて浸漬し、陰極のタンタル板電極との間に９Ｖを印加し、６５℃で４００分化成してＴａ2Ｏ5からなる誘電体酸化皮膜層を形成した。この焼結体のリード線を除いて、２０質量％トルエンスルホン酸鉄水溶液に浸漬し引き上げ１０５℃で１５分乾燥することを５回繰り返した。
Example 1:
CV (product of capacity and conversion voltage) 150,000 μF · V / g tantalum powder was used to produce a sintered body with a size of 1.0 × 1.3 × 3.3 mm (sintering temperature 1310 ° C., sintering time 20 minutes) , Mass 29.0 mg, sintered body density 5.9 g / cm 3 , tantalum lead wire 0.40 mmφ, part of tantalum lead wire 3.0 mm embedded in the longitudinal direction of 4.5 mm dimension of sintered body, sintered body The 10 mm portion of the lead wire protruding from the anode becomes the anode portion). The sintered body to be the anode is dipped in a 1% benzoic acid aqueous solution except for a part of the lead wire, 9V is applied between the cathode and the tantalum plate electrode, and the Ta 2 O 5 is differentiated to 400 at 65 ° C. A dielectric oxide film layer comprising: Except for the lead wire of this sintered body, immersion in a 20% by mass aqueous solution of toluenesulfonic acid iron and pulling up and drying at 105 ° C. for 15 minutes was repeated 5 times.
引き続き焼結体を２質量％ナフタレンスルホン酸とピロールモノマーが不溶な部分も存在するほど充分投入されている２０質量％エチレングリコールと水の混合溶液が入った槽（槽自身にタンタル箔が貼られていて外部電極になる）に浸漬し、焼結体のリード線を陽極に、外部電極を陰極にして８０μＡ、３℃で１時間通電し、誘電体層上に半導体層を形成した。焼結体を引き上げ水洗・アルコール洗浄・乾燥し、さらに１％安息香酸中で６５℃、７Ｖで１５分再化成を行った。引き上げ水洗・アルコール洗浄１５分・乾燥した。このような半導体層形成と再化成の工程を６回行ってナフタレンスルホン酸イオンを主ドーパントとするポリピロールからなる半導体層を形成した。続いて半導体層上にカーボンペーストを付着させ乾燥し、さらに銀ペースト層を積層した後乾燥して電極層を形成しコンデンサ素子を７６個作製した。別途用意した外部電極であるリードフレームの一対の両先端に、焼結体側のリード線と電極層の銀ペースト側（1.3×3.3ｍｍ側）が載るように焼結体２個を方向を揃えて隙間無く置き、前者はスポット溶接で、後者は銀ペーストで電気的・機械的に接続した。その後、リードフレームの一部を除いてエポキシ樹脂でトランスファーモールドし、モールド外のリードフレームの所定部を切断後外装に沿って折り曲げ加工して外部端子とした大きさ6.0×3.2×1.8ｍｍのチップ状コンデンサ素子を作製した。その後、１３５℃で４時間、３Ｖでエージングし、さらに１５０℃で１２時間放置して最終的な固体電解コンデンサを３８個作製した。 Subsequently, the sintered body was filled with a 20 wt% ethylene glycol and water mixed solution in which the 2 wt% naphthalene sulfonic acid and the pyrrole monomer were insoluble enough (a tantalum foil was applied to the tank itself). Then, the semiconductor lead was formed on the dielectric layer by applying current at 80 μA and 3 ° C. for 1 hour with the lead wire of the sintered body as the anode and the external electrode as the cathode. The sintered body was pulled up, washed with water, washed with alcohol and dried, and further re-formed in 1% benzoic acid at 65 ° C. and 7 V for 15 minutes. Pulled up, washed with water, washed with alcohol for 15 minutes and dried. The semiconductor layer formation and re-chemical conversion steps were performed 6 times to form a semiconductor layer made of polypyrrole having naphthalene sulfonate ions as the main dopant. Subsequently, a carbon paste was deposited on the semiconductor layer and dried, and further a silver paste layer was laminated and then dried to form an electrode layer, thereby producing 76 capacitor elements. The two sintered bodies are aligned so that the lead wire on the sintered body side and the silver paste side (1.3 x 3.3 mm side) of the electrode layer are placed on both ends of a pair of lead frames, which are external electrodes prepared separately. Placed without gaps, the former was spot welded and the latter was electrically and mechanically connected with silver paste. After that, a part of the lead frame is removed and transfer molded with epoxy resin, and a predetermined size of the lead frame outside the mold is cut and then bent along the exterior to make an external terminal 6.0 × 3.2 × 1.8mm chip A capacitor element was produced. Thereafter, it was aged at 3 ° C. for 4 hours at 135 ° C., and further allowed to stand at 150 ° C. for 12 hours to produce 38 final solid electrolytic capacitors.
実施例２：
実施例１において、再化成液を１％アントラキノンスルホン酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Example 2:
A solid electrolytic capacitor was produced in the same manner as in Example 1, except that the re-chemical conversion solution was changed to 1% anthraquinonesulfonic acid aqueous solution.
実施例３：
実施例１において、再化成液を１０％安息香酸アンモニウム水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Example 3:
A solid electrolytic capacitor was produced in the same manner as in Example 1 except that the re-chemical conversion solution was changed to a 10% aqueous ammonium benzoate solution in Example 1.
実施例４：
実施例１において、化成液を１０％安息香酸アンモニウム水溶液、再化成液を１０％安息香酸アンモニウム水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Example 4:
A solid electrolytic capacitor was produced in exactly the same manner as in Example 1 except that the chemical conversion solution was changed to a 10% ammonium benzoate aqueous solution and the re-chemical conversion solution was changed to a 10% ammonium benzoate aqueous solution.
実施例５：
実施例１において、化成液を１０％安息香酸アンモニウム水溶液、再化成液を１％安息香酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Example 5:
A solid electrolytic capacitor was produced in the same manner as in Example 1 except that the chemical conversion solution was changed to 10% ammonium benzoate aqueous solution and the re-chemical conversion solution was changed to 1% benzoic acid aqueous solution.
実施例６：
実施例１において、化成液を１０％安息香酸アンモニウム水溶液、再化成液を２％ナフタレンスルホン酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Example 6:
A solid electrolytic capacitor was produced in exactly the same manner as in Example 1 except that the chemical conversion solution was a 10% ammonium benzoate aqueous solution and the re-chemical conversion solution was a 2% naphthalenesulfonic acid aqueous solution.
比較例１：
実施例１において、化成液を１％燐酸水溶液、再化成液を１％燐酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Comparative Example 1:
A solid electrolytic capacitor was produced in the same manner as in Example 1, except that the chemical conversion solution was changed to 1% phosphoric acid aqueous solution and the re-chemical conversion solution was changed to 1% phosphoric acid aqueous solution.
比較例２：
実施例１において、化成液を１％硫酸水溶液、再化成液を１％硫酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Comparative Example 2:
A solid electrolytic capacitor was fabricated in exactly the same manner as in Example 1, except that the chemical conversion solution was 1% sulfuric acid aqueous solution and the re-chemical conversion solution was 1% sulfuric acid aqueous solution.
比較例３：
実施例１において、化成液を0.1％酢酸水溶液、再化成液を0.1％酢酸水溶液とした以外は実施例１と全く同様にして固体電解コンデンサを作製した。
Comparative Example 3:
A solid electrolytic capacitor was fabricated in exactly the same manner as in Example 1, except that the chemical conversion solution was 0.1% acetic acid aqueous solution and the re-chemical conversion solution was 0.1% acetic acid aqueous solution.
実施例７：
ニオブインゴットの水素脆性を利用して粉砕したニオブ一次粉（平均粒径0.33μｍ）を造粒し平均粒径１４０μｍのニオブ粉（微粉であるために表面が自然酸化されていて全体として酸素9600ｐｐｍ存在する）を得た。次に４５０℃の窒素雰囲気中に放置しさらに７００℃のアルゴン中に放置することにより、窒化量9500ｐｐｍの一部窒化したニオブ粉（ＣＶ285000μＦ・Ｖ／ｇ）とした。このニオブ粉を0.38ｍｍφのニオブ線と共に成形した後1260℃で焼結することにより、大きさ1.0×1.3×3.3ｍｍ（質量15.6ｍｇ、ニオブ線がリード線となり焼結体内部に3.0ｍｍ、外部に１０ｍｍ存在する。）の焼結体（導電体）を以下の７６個となるように複数個作製した。
Example 7:
Niobium primary powder (average particle size 0.33μm) pulverized using hydrogen embrittlement of niobium ingot is granulated and niobium powder with an average particle size of 140μm (the surface is naturally oxidized because it is a fine powder, and there is 9600ppm oxygen as a whole. Obtained). Next, it was left in a nitrogen atmosphere at 450 ° C. and then in argon at 700 ° C. to obtain a partially nitrided niobium powder (CV285000 μF · V / g) having a nitriding amount of 9500 ppm. After forming this niobium powder with niobium wire of 0.38mmφ and sintering at 1260 ° C, size 1.0 × 1.3 × 3.3mm (mass 15.6mg, niobium wire becomes lead wire, 3.0mm inside the sintered body, external A plurality of sintered bodies (conductors) having a thickness of 10 mm were prepared so as to have the following 76 pieces.
続いて、５％安息香酸カリウム水溶液で８０℃、２０Ｖ、７時間化成することにより、焼結体表面とリード線の一部に五酸化二ニオブを主成分とする誘電体層を形成した。引き続き、該焼結体を２０質量％ナフタレンスルホン酸鉄アルコール溶液に浸漬した後乾燥し、さらに１０質量％トルエンスルホン酸水溶液中８０℃、１５Ｖ、１５分再化成することを交互に５回繰り返した。さらに、１質量％アントラキノンスルホン酸と、３，４−エチレンジオキシチオフェンが不溶な部分も存在するほど充分投入されている水と３０質量％エチレングリコール混合溶液中に焼結体部分を浸漬し、リード線を陽極に溶液中に配置されたステンレス板を陰極にして室温で７０μＡの定電流（電解効果トランジスターと抵抗で電流値を決定した）を流して電解重合を５０分行い、水溶液から引き上げ水洗浄・アルコール洗浄・乾燥を行った後、５％安息香酸カリウム水溶液中で８０℃、１４Ｖ、１５分間再化成を行った。この電解重合と再化成を８回繰り返して誘電体層上にアントラキノンスルホン酸イオンを主ドーパントとするポリチオフェン誘導体からなる半導体層を形成した。 Subsequently, a dielectric layer mainly composed of niobium pentoxide was formed on the surface of the sintered body and a part of the lead wire by chemical conversion with a 5% aqueous potassium benzoate solution at 80 ° C., 20 V for 7 hours. Subsequently, the sintered body was dipped in a 20% by mass naphthalenesulfonic acid iron alcohol solution, dried, and further re-formed in a 10% by mass toluenesulfonic acid aqueous solution at 80 ° C., 15 V for 15 minutes alternately 5 times. . Furthermore, 1% by mass anthraquinone sulfonic acid, 3,4-ethylenedioxythiophene is immersed in water and 30% by mass ethylene glycol mixed solution sufficiently charged so that there is also an insoluble part, With a stainless steel plate placed in the solution with the lead wire as the anode and a cathode as a cathode, a constant current of 70 μA (current value was determined by the field effect transistor and resistance) was passed at room temperature to conduct electropolymerization for 50 minutes. After washing, alcohol washing, and drying, re-chemical conversion was performed in a 5% aqueous potassium benzoate solution at 80 ° C., 14 V, for 15 minutes. This electrolytic polymerization and re-chemical conversion were repeated 8 times to form a semiconductor layer made of a polythiophene derivative containing anthraquinone sulfonate ion as a main dopant on the dielectric layer.
続いて半導体層上にカーボンペーストを積層して乾燥し、さらに銀ペーストを積層した後乾燥して電極層を形成し固体電解コンデンサ素子を６０個作製した。別途用意した外部電極であるリードフレームの一対の両先端に、焼結体側のリード線と電極層側の銀ペースト側（1.3×3.3ｍｍ側）が載るように焼結体２個を方向を揃えて隙間無く置き、前者はスポット溶接で、後者は銀ペーストで電気的・機械的に接続した。その後、リードフレームの一部を除いてエポキシ樹脂でトランスファーモールドし、モールド外のリードフレームの所定部を切断後外装に沿って折り曲げ加工して外部端子とした大きさ6.0×3.2×1.8ｍｍのチップ状コンデンサを作製した。続いて、１２５℃で７Ｖ、３時間エージングした後１５０℃で６時間放置した。さらにピ−ク温度２６０℃で２３０℃の領域が３５秒のトンネル炉を２回通過させて最終的なチップ状固体電解コンデンサを３８個得た。 Subsequently, a carbon paste was laminated on the semiconductor layer and dried, and further a silver paste was laminated and then dried to form an electrode layer, thereby producing 60 solid electrolytic capacitor elements. The two sintered bodies are aligned so that the lead wire on the sintered body side and the silver paste side (1.3 x 3.3 mm side) on the electrode layer side are placed on both ends of a pair of lead frames, which are external electrodes prepared separately. The former was spot welded and the latter was electrically and mechanically connected with silver paste. After that, a part of the lead frame is removed and transfer molded with epoxy resin, and a predetermined size of the lead frame outside the mold is cut and then bent along the exterior to make an external terminal 6.0 × 3.2 × 1.8mm chip A capacitor was produced. Subsequently, after aging at 125 ° C. for 7 V for 3 hours, it was left at 150 ° C. for 6 hours. Further, 38 final chip-shaped solid electrolytic capacitors were obtained by passing twice through a tunnel furnace having a peak temperature of 260 ° C. and a region of 230 ° C. for 35 seconds.
実施例８：
実施例７において、化成液を８％安息香酸カルシウム水溶液、再化成液を８％安息香酸カルシウム水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 8:
A solid electrolytic capacitor was produced in exactly the same manner as in Example 7, except that the chemical conversion solution was an 8% calcium benzoate aqueous solution and the re-chemical conversion solution was an 8% calcium benzoate aqueous solution.
実施例９：
実施例７において、化成液を１０％安息香酸マンガン水溶液、再化成液を１０％安息香酸マンガン水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 9:
A solid electrolytic capacitor was fabricated in exactly the same manner as in Example 7, except that the chemical conversion solution was changed to a 10% manganese benzoate aqueous solution and the re-chemical conversion solution was changed to a 10% manganese benzoate aqueous solution.
実施例１０：
実施例７において、化成液を0.5％ナフタレンカルボン酸エタノール５０％水溶液、再化成液を0.5％ナフタレンカルボン酸エタノール５０％水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 10:
A solid electrolytic capacitor was produced in the same manner as in Example 7, except that the chemical conversion liquid was changed to 0.5% naphthalenecarboxylic acid ethanol 50% aqueous solution and the rechemical conversion liquid was changed to 0.5% naphthalenecarboxylic acid ethanol 50% aqueous solution.
実施例１１：
実施例７において、化成液を0.1％ナフタレンジカルボン酸エタノール７０％水溶液、再化成液を0.1％ナフタレンジカルボン酸エタノール７０％水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 11:
A solid electrolytic capacitor was produced in exactly the same manner as in Example 7, except that the chemical conversion solution was a 0.1% naphthalenedicarboxylic acid ethanol 70% aqueous solution and the re-chemical conversion solution was a 0.1% naphthalenedicarboxylic acid ethanol 70% aqueous solution.
実施例１２：
実施例７において、化成液を0.1％安息香酸無水物エタノール８０％水溶液、再化成液を0.1％安息香酸無水物エタノール８０％水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 12:
A solid electrolytic capacitor was produced in the same manner as in Example 7 except that the chemical conversion solution was changed to 0.1% benzoic anhydride ethanol 80% aqueous solution and the re-chemical conversion solution was changed to 0.1% benzoic anhydride ethanol 80% aqueous solution. did.
実施例１３：
実施例７において、化成液を１％安息香酸水溶液、再化成液を１％安息香酸水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Example 13:
A solid electrolytic capacitor was produced in the same manner as in Example 7 except that the chemical conversion solution was changed to 1% benzoic acid aqueous solution and the re-chemical conversion solution was changed to 1% benzoic acid aqueous solution.
比較例４：
実施例７において、化成液を0.1％燐酸水溶液、再化成液を0.1％燐酸水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Comparative Example 4:
A solid electrolytic capacitor was produced in the same manner as in Example 7, except that the chemical conversion solution was changed to 0.1% phosphoric acid aqueous solution and the re-chemical conversion solution was changed to 0.1% phosphoric acid aqueous solution.
比較例５：
実施例７において、化成液を２％プロピオン酸水溶液、再化成液を２％プロピオン酸水溶液とした以外は実施例７と全く同様にして固体電解コンデンサを作製した。
Comparative Example 5:
A solid electrolytic capacitor was fabricated in exactly the same manner as in Example 7, except that the chemical conversion solution was changed to a 2% aqueous propionic acid solution and the re-chemical conversion solution was changed to a 2% aqueous propionic acid solution.
実施例１４：
実施例１において、ＣＶ値を１０万μＦ・Ｖ／ｇの焼結体を使用した以外は実施例１と同様にして固体電解コンデンサを作製した。
Example 14:
A solid electrolytic capacitor was produced in the same manner as in Example 1, except that a sintered body having a CV value of 100,000 μF · V / g was used.
実施例１５：
実施例７において、ＣＶ値を1５万μＦ・Ｖ／ｇのニオブ粉（表面酸素量8200ｐｐｍ、平均粒径0.54μｍ）を使用した以外は実施例７と同様にして固体電解コンデンサを作製した。
Example 15:
A solid electrolytic capacitor was produced in the same manner as in Example 7 except that niobium powder having a CV value of 150,000 μF · V / g (surface oxygen content 8200 ppm, average particle size 0.54 μm) was used.
比較例６：
実施例１４において、化成液を１％燐酸水溶液、再化成液を１％燐酸水溶液とした以外は実施例１４と同様にして固体電解コンデンサを作製した。
Comparative Example 6:
A solid electrolytic capacitor was produced in the same manner as in Example 14 except that the chemical conversion solution was changed to 1% phosphoric acid aqueous solution and the re-chemical conversion solution was changed to 1% phosphoric acid aqueous solution.
比較例７：
実施例１５において、化成液を0.1％燐酸水溶液、再化成液を0.1％燐酸水溶液とした以外は実施例１５と同様にして固体電解コンデンサを作製した。
Comparative Example 7:
A solid electrolytic capacitor was produced in the same manner as in Example 15 except that the chemical conversion solution was changed to 0.1% phosphoric acid aqueous solution and the re-chemical conversion solution was changed to 0.1% phosphoric acid aqueous solution.
試験例：固体電解コンデンサの容量及びＥＳＲの測定
以上の実施例１〜１５、比較例１〜７で作製した各コンデンサについて容量及び実装試験前後のＥＳＲを以下の方法により測定した。
実装試験：
ピーク温度が２６０℃、２３０℃が３０秒のリフロー炉を３回通過させた。
コンデンサの容量：
ヒューレットパッカード社製ＬＣＲ測定器を用い、室温１２０Ｈｚで測定した。
ＥＳＲ値：
コンデンサの等価直列抵抗を１００ｋＨｚで測定した。
測定結果（３８個の平均値）を表１に示す。
Test Example: Measurement of Capacity and ESR of Solid Electrolytic Capacitor The capacity and ESR before and after the mounting test were measured for each of the capacitors prepared in Examples 1 to 15 and Comparative Examples 1 to 7 by the following method.
Mounting test:
A reflow furnace having a peak temperature of 260 ° C. and 230 ° C. of 30 seconds was passed three times.
Capacitor capacity:
Measurement was performed at room temperature of 120 Hz using an LCR measuring instrument manufactured by Hewlett-Packard Company.
ESR value:
The equivalent series resistance of the capacitor was measured at 100 kHz.
The measurement results (average value of 38 pieces) are shown in Table 1.
実施例１〜６及び実施例７〜８、比較例１〜５より、化成液及び再化成液に芳香族カルボン酸またはその塩を用いると、実装試験後のＥＳＲの上昇が抑制されることがわかる。
また化成液と再化成液が異なる場合でも、いずれも芳香族カルボン酸またはその塩であれば、同様の効果が得られることがわかる。
さらに、実施例１４〜１５、比較例６〜７より、使用する焼結体がタンタルの場合ＣＶ値が１０万μＦ・Ｖ／ｇ以上、ニオブの場合ＣＶ値が１５万μＦ・Ｖ／ｇ以上であると、化成液及び再化成液に芳香族カルボン酸またはその塩を用いると、実装試験後のＥＳＲの上昇が抑制されることがわかる。
From Examples 1-6, Examples 7-8, and Comparative Examples 1-5, when aromatic carboxylic acid or its salt is used for a chemical conversion liquid and a rechemical conversion liquid, the raise of ESR after a mounting test is suppressed. Recognize.
Moreover, even if a chemical conversion liquid and a rechemical conversion liquid differ, if both are aromatic carboxylic acid or its salt, it turns out that the same effect is acquired.
Furthermore, from Examples 14 to 15 and Comparative Examples 6 to 7, when the sintered body to be used is tantalum, the CV value is 100,000 μF · V / g or more, and in the case of niobium, the CV value is 150,000 μF · V / g or more. When the aromatic carboxylic acid or the salt thereof is used for the chemical conversion liquid and the rechemical conversion liquid, it is understood that the increase in ESR after the mounting test is suppressed.
Claims (18)
A solid electrolytic capacitor element in which an anode lead is connected to a sintered body of conductive powder, formed in a chemical solution containing an electrolyte to form a dielectric oxide film on the sintered body, and then a semiconductor layer and an electrode layer are sequentially stacked. In a method for producing a solid electrolytic capacitor in which an outer resin is sealed , a solution containing an aromatic carboxylic acid or a salt thereof at a concentration of 0.05 to 30% by mass is used as a chemical conversion solution. Method.
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である請求項９に記載の固体電解コンデンサの製造方法。 An organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
The method for producing a solid electrolytic capacitor according to claim 9, which is at least one selected from organic semiconductors mainly composed of a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula (1) with a dopant.
で示される構造単位を繰り返し単位として含む導電性高分子である請求項１０に記載の固体電解コンデンサの製造方法。 The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
The method for producing a solid electrolytic capacitor according to claim 10, wherein the polymer is a conductive polymer including a structural unit represented by
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