JP2005109077A - Method of manufacturing solid electrolytic capacitor - Google Patents
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- JP2005109077A JP2005109077A JP2003339216A JP2003339216A JP2005109077A JP 2005109077 A JP2005109077 A JP 2005109077A JP 2003339216 A JP2003339216 A JP 2003339216A JP 2003339216 A JP2003339216 A JP 2003339216A JP 2005109077 A JP2005109077 A JP 2005109077A
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- electrolytic capacitor
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- 239000003990 capacitor Substances 0.000 title claims abstract description 71
- 239000007787 solid Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 229920001721 polyimide Polymers 0.000 claims abstract description 13
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000003577 thiophenes Chemical class 0.000 claims description 4
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 5
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 229920002978 Vinylon Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 acetonitrile Chemical compound 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 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
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 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 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、静電容量、ＥＳＲ特性及び耐電圧特性の向上を図った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 with improved electrostatic capacity, ESR characteristics, and withstand voltage characteristics.
タンタルあるいはアルミニウム等のような弁作用を有する金属を利用した電解コンデンサは、陽極側対向電極としての弁作用金属を焼結体あるいはエッチング箔等の形状にして誘電体を拡面化することにより、小型で大きな容量を得ることができることから、広く一般に用いられている。特に、電解質に固体電解質を用いた固体電解コンデンサは、小型、大容量、低等価直列抵抗であることに加えて、チップ化しやすく、表面実装に適している等の特質を備えていることから、電子機器の小型化、高機能化、低コスト化に欠かせないものとなっている。 An electrolytic capacitor using a metal having a valve action such as tantalum or aluminum is obtained by expanding the dielectric by making the valve action metal as the anode-side counter electrode into the shape of a sintered body or an etching foil. Since it is small and a large capacity can be obtained, it is widely used. In particular, a solid electrolytic capacitor using a solid electrolyte as an electrolyte has features such as small size, large capacity, low equivalent series resistance, easy to chip, and suitable for surface mounting. It is indispensable for miniaturization, high functionality and low cost of electronic equipment.
この種の固体電解コンデンサにおいて、小型、大容量用途としては、一般に、アルミニウム等の弁作用金属からなる陽極箔と陰極箔を、セパレータを介在させて巻回してコンデンサ素子を形成し、このコンデンサ素子に駆動用電解液を含浸し、アルミニウム等の金属製ケースや合成樹脂製のケースにコンデンサ素子を収納し、密閉した構造を有している。なお、陽極材料としては、アルミニウムを初めとしてタンタル、ニオブ、チタン等が使用され、陰極材料には、陽極材料と同種の金属が用いられる。 In this type of solid electrolytic capacitor, as a small-sized and large-capacity application, in general, an anode foil and a cathode foil made of valve metal such as aluminum are wound with a separator interposed therebetween to form a capacitor element. A capacitor element is housed in a case made of metal such as aluminum or a case made of synthetic resin and impregnated with a driving electrolyte solution. As the anode material, aluminum, tantalum, niobium, titanium and the like are used, and as the cathode material, the same kind of metal as the anode material is used.
また、固体電解コンデンサに用いられる固体電解質としては、二酸化マンガンや７、７、８、８−テトラシアノキノジメタン（ＴＣＮＱ）錯体が知られているが、近年、反応速度が緩やかで、かつ陽極電極の酸化皮膜層との密着性に優れたポリエチレンジオキシチオフェン（以下、ＰＥＤＴと記す）等の導電性ポリマーに着目した技術（特許文献１参照）が存在している。 As solid electrolytes used for solid electrolytic capacitors, manganese dioxide and 7,7,8,8-tetracyanoquinodimethane (TCNQ) complexes are known. There is a technique (see Patent Document 1) that focuses on a conductive polymer such as polyethylenedioxythiophene (hereinafter referred to as PEDT) having excellent adhesion to an oxide film layer of an electrode.
このような巻回型のコンデンサ素子にＰＥＤＴ等の導電性ポリマーからなる固体電解質層を形成するタイプの固体電解コンデンサは、以下のようにして作成される。まず、アルミニウム等の弁作用金属からなる陽極箔の表面を塩化物水溶液中での電気化学的なエッチング処理により粗面化して、多数のエッチングピットを形成した後、ホウ酸アンモニウム等の水溶液中で電圧を印加して誘電体となる酸化皮膜層を形成する（化成）。陽極箔と同様に、陰極箔もアルミニウム等の弁作用金属からなるが、その表面にはエッチング処理を施すのみである。 A solid electrolytic capacitor of a type in which a solid electrolyte layer made of a conductive polymer such as PEDT is formed on such a wound capacitor element is produced as follows. First, the surface of the anode foil made of valve action metal such as aluminum is roughened by electrochemical etching treatment in an aqueous chloride solution to form many etching pits, and then in an aqueous solution such as ammonium borate. A voltage is applied to form an oxide film layer serving as a dielectric (chemical conversion). Similar to the anode foil, the cathode foil is made of a valve metal such as aluminum, but the surface is only subjected to etching treatment.
このようにして表面に酸化皮膜層が形成された陽極箔とエッチングピットのみが形成された陰極箔とを、セパレータを介して巻回してコンデンサ素子を形成する。続いて、修復化成を施したコンデンサ素子に、３，４−エチレンジオキシチオフェン（以下、ＥＤＴと記す）等の重合性モノマーと酸化剤溶液をそれぞれ吐出し、あるいは両者の混合液に浸漬して、コンデンサ素子内で重合反応を促進し、ＰＥＤＴ等の導電性ポリマーからなる固体電解質層を生成する。その後、このコンデンサ素子を有底筒状の外装ケースに収納し、ケースの開口部を封ロゴムで封止して固体電解コンデンサを作成する。
ところで、近年、電子情報機器はデジタル化され、さらにこれらの電子情報機器の心臓部であるマイクロプロセッサ（ＭＰＵ）の駆動周波数の高速化が進んでいる。これに伴って、消費電力の増大化が進み、発熱による信頼性の問題が顕在化してきたため、その対策として駆動電圧の低減化が図られてきた。 By the way, in recent years, electronic information devices have been digitized, and the driving frequency of a microprocessor (MPU) which is the heart of these electronic information devices has been increased. Along with this, the power consumption has been increasing and the problem of reliability due to heat generation has become obvious. Therefore, the drive voltage has been reduced as a countermeasure.
上記駆動電圧の低減化を図るため、マイクロプロセッサに高精度な電力を供給する回路として電圧制御モジュールと呼ばれるＤＣ−ＤＣコンバーターが広く使用されており、その出力側コンデンサには、電圧降下を防ぐためＥＳＲの低いコンデンサが多数用いられている。このような低ＥＳＲ特性を有するコンデンサとして、上述したような固体電解コンデンサが実用化され、多用されている。 In order to reduce the drive voltage, a DC-DC converter called a voltage control module is widely used as a circuit for supplying highly accurate power to the microprocessor, and the output side capacitor is used to prevent a voltage drop. Many capacitors with low ESR are used. As the capacitor having such a low ESR characteristic, the solid electrolytic capacitor as described above has been put into practical use and widely used.
しかしながら、マイクロプロセッサの駆動周波数の高速化は著しく、それに伴って消費電力がさらに増大し、それに対応するために電圧降下を防ぐためのコンデンサからの供給電力のさらなる増大化が求められている。すなわち、大きな電力を短時間で供給することができなければならず、このために固体電解コンデンサには大容量化、小型化、低電圧化と共に、さらに優れたＥＳＲ特性が要求されている。 However, the increase in the driving frequency of the microprocessor is remarkable, and accordingly, the power consumption further increases, and in order to cope with this, further increase in the power supplied from the capacitor for preventing the voltage drop is required. That is, a large amount of power must be able to be supplied in a short time. For this reason, solid electrolytic capacitors are required to have higher ESR characteristics as well as larger capacity, smaller size, and lower voltage.
また、近年、上述したような固体電解コンデンサへの高電圧仕様の要求が高まっており、特に２０〜３０Ｖの高耐電圧が要求されている。しかしながら、このような高い定格電圧を有する固体電解コンデンサを得ようとすると、エージング工程においてショートの発生する割合が多く、歩留まりが低いという問題点があった。
なお、このような問題点は、重合性モノマーとしてＥＤＴを用いた場合に限らず、他のチオフェン誘導体、ピロール、アニリン等を用いた場合にも同様に生じていた。
In recent years, demands for high voltage specifications for the solid electrolytic capacitors as described above are increasing, and in particular, a high withstand voltage of 20 to 30 V is required. However, when trying to obtain a solid electrolytic capacitor having such a high rated voltage, there is a problem that the ratio of occurrence of a short circuit is high in the aging process and the yield is low.
Such a problem occurs not only when EDT is used as the polymerizable monomer but also when other thiophene derivatives, pyrrole, aniline, and the like are used.
本発明は、上述したような従来技術の問題点を解決するために提案されたものであり、その目的は、静電容量が高く、ＥＳＲ特性が良好で、耐電圧特性をさらに向上させて、エージング工程での歩留まりを高め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。 The present invention has been proposed in order to solve the above-described problems of the prior art, and its purpose is to have a high electrostatic capacity, good ESR characteristics, and further improve withstand voltage characteristics, An object of the present invention is to provide a method of manufacturing a solid electrolytic capacitor that can increase the yield in the aging process.
本発明者等は、上記課題を解決すべく鋭意検討を重ねた結果、本発明を完成するに至ったものである。すなわち、本出願人が別途特許出願している、リフロー後のＬＣの上昇を防止するのに顕著な効果が得られるポリイミドシリコーン処理を行うと共に、さらに耐電圧を向上させて、エージング工程での歩留まりを高めるべく、ビニル基を有する化合物を含有させたセパレータを用い、煮沸処理を行うことによりセパレータに含有されたビニル基を有する化合物の一部を除去した後、ポリイミドシリコーン皮膜を形成すると良好な結果が得られることを見出したものである。
なお、本明細書中における「ビニル基を有する化合物」とは、後述する例に示したようなビニル基を有する化合物の重合体をいうものとする。
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present applicant has applied for a patent separately, and performs a polyimide silicone treatment that is effective in preventing an increase in LC after reflow, and further improves the withstand voltage, yielding in the aging process When a separator containing a vinyl group-containing compound is used to increase the boiling point, a portion of the vinyl group-containing compound contained in the separator is removed by boiling, and then a polyimide silicone film is formed. Has been found to be obtained.
In the present specification, the “compound having a vinyl group” refers to a polymer of a compound having a vinyl group as shown in the examples described later.
（固体電解コンデンサの製造方法）
本発明に係る固体電解コンデンサの製造方法は以下の通りである。すなわち、表面に酸化皮膜層が形成された陽極箔と陰極箔を、ビニル基を有する化合物を含有するセパレータを介して巻回してコンデンサ素子を形成し、このコンデンサ素子を煮沸処理した後、修復化成を施す。その後、このコンデンサ素子をポリイミドシリコーンの０．０５〜２０ｗｔ％のケトン系溶液に浸漬し、引き上げた後、４０〜１００℃で溶媒を蒸発させ、その後、１５０〜２００℃で熱処理する。
続いて、このコンデンサ素子に重合性モノマーと酸化剤を含浸させて、コンデンサ素子内で導電性ポリマーの重合反応を発生させ、固体電解質層を形成する。そして、このコンデンサ素子を外装ケースに収納し、開口端部を封ロゴムで封止し、固体電解コンデンサを形成する。
(Method for manufacturing solid electrolytic capacitor)
The manufacturing method of the solid electrolytic capacitor according to the present invention is as follows. That is, an anode foil and a cathode foil having an oxide film layer formed on the surface thereof are wound through a separator containing a vinyl group-containing compound to form a capacitor element. After boiling the capacitor element, a restoration process is performed. Apply. Thereafter, the capacitor element is immersed in a 0.05-20 wt% ketone-based solution of polyimide silicone, pulled up, evaporated at 40-100 ° C., and then heat-treated at 150-200 ° C.
Subsequently, the capacitor element is impregnated with a polymerizable monomer and an oxidizing agent to cause a polymerization reaction of a conductive polymer in the capacitor element, thereby forming a solid electrolyte layer. And this capacitor | condenser element is accommodated in an exterior case, an opening edge part is sealed with sealing rubber | gum, and a solid electrolytic capacitor is formed.
（セパレータ）
通常、合成繊維を主体とする固体電解コンデンサ用セパレータは、合成繊維とこれらを接合するバインダーから構成されている。このバインダーとしては、合成樹脂そのものを用いたり、合成樹脂を繊維状にして、セパレータの作成工程で溶融させて主体繊維を接合させている。本発明においては、このようなセパレータの主体繊維又はバインダーにビニル基を有する化合物を含有させたセパレータを用いることにより、良好な結果が得られたものである。
(Separator)
Usually, a separator for a solid electrolytic capacitor mainly composed of synthetic fibers is composed of synthetic fibers and a binder for joining them. As this binder, synthetic resin itself is used, or synthetic resin is made into a fiber shape and melted in a separator manufacturing process to bond main fibers. In the present invention, good results were obtained by using a separator containing a compound having a vinyl group in the main fiber or binder of such a separator.
なお、セパレータの主体繊維又はバインダーに含有させるビニル基を有する化合物の量は、セパレータ重量の５〜４０ｗｔ％が好ましい。その理由は、この範囲とすることで、巻回工程に必要なセパレータの強度を得ることができるからである。さらに、煮沸処理でビニル基を有する化合物を溶出させてセパレータの密度を下げ、その後の素子内に形成される導電性ポリマーを増大させ、さらに、導電性の低いビニル基を有する化合物を除去して、ＥＳＲを下げることができるからである。 The amount of the compound having a vinyl group contained in the main fiber or binder of the separator is preferably 5 to 40 wt% of the separator weight. The reason is that the strength of the separator required for the winding process can be obtained by setting the amount within this range. Furthermore, the compound having a vinyl group is eluted by boiling treatment to lower the density of the separator, increase the conductive polymer formed in the subsequent device, and further remove the compound having a vinyl group with low conductivity. This is because the ESR can be lowered.
ここで、ビニル基を有する化合物としては、ポリビニルアルコール（以下、ＰＶＡと記す）、ポリ酢酸ビニル、ポリビニルピロリドン、ポリアクリルアミド等を用いることができるが、なかでもＰＶＡがより好ましい。具体的には、セパレータの主体繊維にＰＶＡ繊維（ビニロン）や未延伸のビニロンを用いても良いし、バインダーにＰＶＡポリマーや未延伸のビニロンを用いても良い。例えば、繊維径が３．０〜１２．０μｍのビニロン繊維を所定のカット長の短繊維とし、所定のバインダーを用いて、任意の手段により不織布としたものを用いることができる。 Here, as the compound having a vinyl group, polyvinyl alcohol (hereinafter referred to as PVA), polyvinyl acetate, polyvinyl pyrrolidone, polyacrylamide and the like can be used, and among them, PVA is more preferable. Specifically, PVA fiber (vinylon) or unstretched vinylon may be used as the main fiber of the separator, and PVA polymer or unstretched vinylon may be used as the binder. For example, it is possible to use a vinylon fiber having a fiber diameter of 3.0 to 12.0 μm as a short fiber having a predetermined cut length and a non-woven fabric by an arbitrary means using a predetermined binder.
なお、セパレータにビニル基を有する化合物を含有させる方法としては、上述したような主体繊維やバインダーを、ビニル基を有する化合物から構成する方法（言い換えれば、ビニル基を有する化合物をセパレータの構成成分として含有させる方法）の他に、セパレータをビニル基を有する化合物の溶液に浸漬する方法や、ビニル基を有する化合物を塗布する方法を用いることもできる。 In addition, as a method of including a compound having a vinyl group in the separator, a method in which the main fibers and the binder as described above are composed of a compound having a vinyl group (in other words, a compound having a vinyl group is used as a component of the separator). In addition to the method of inclusion, a method of immersing the separator in a solution of a compound having a vinyl group or a method of applying a compound having a vinyl group can also be used.
（ポリイミドシリコーン）
ポリイミドシリコーンを溶解する溶媒としては、ポリイミドシリコーンの溶解性の良好なケトン系溶媒が好ましく、シクロヘキサノン、アセトン、メチルエチルケトン等を用いることができる。
また、ポリイミドシリコーンの濃度は、０．０５〜２０ｗｔ％、好ましくは１．５〜９ｗｔ％、さらに好ましくは２〜６ｗｔ％である。濃度がこの範囲未満では耐圧が十分ではなく、この範囲を超えると静電容量が低下する。
(Polyimide silicone)
As a solvent for dissolving polyimide silicone, a ketone solvent having good solubility of polyimide silicone is preferable, and cyclohexanone, acetone, methyl ethyl ketone, and the like can be used.
Moreover, the density | concentration of a polyimide silicone is 0.05-20 wt%, Preferably it is 1.5-9 wt%, More preferably, it is 2-6 wt%. If the concentration is less than this range, the withstand voltage is not sufficient, and if it exceeds this range, the capacitance decreases.
（煮沸処理）
煮沸処理は、１００℃に加熱した水にコンデンサ素子を浸漬し、数分間加熱を続けることにより行う。そして、この煮沸処理により、セパレータに含まれるビニル基を有する化合物の残存量を５〜５０％とすることが好ましく、５〜２５％とすることがより好ましい。
なお、セパレータに含まれるビニル基を有する化合物の残存量の調整は、煮沸回数を変えることにより行うことが好ましい。煮沸処理時間を長くすると、水中のビニル基を有する化合物の濃度が上がって、溶出しにくくなるためである。
(Boiling treatment)
The boiling treatment is performed by immersing the capacitor element in water heated to 100 ° C. and continuing heating for several minutes. And by this boiling process, it is preferable to make the residual amount of the compound which has a vinyl group contained in a separator into 5 to 50%, and it is more preferable to set it as 5 to 25%.
The residual amount of the compound having a vinyl group contained in the separator is preferably adjusted by changing the number of boiling times. This is because if the boiling treatment time is lengthened, the concentration of the compound having a vinyl group in water increases and it becomes difficult to elute.
（ＥＤＴ及び酸化剤）
重合性モノマーとしてＥＤＴを用いた場合、コンデンサ素子に含浸するＥＤＴとしては、ＥＤＴモノマーを用いることができるが、ＥＤＴと揮発性溶媒とを１：０〜１：３の体積比で混合したモノマー溶液を用いることもできる。
前記揮発性溶媒としては、ペンタン等の炭化水素類、テトラヒドロフラン等のエーテル類、ギ酸エチル等のエステル類、アセトン等のケトン類、メタノール等のアルコール類、アセトニトリル等の窒素化合物等を用いることができるが、なかでも、メタノール、エタノール、アセトン等が好ましい。
(EDT and oxidizing agent)
When EDT is used as the polymerizable monomer, EDT monomer can be used as EDT impregnated in the capacitor element, but a monomer solution in which EDT and a volatile solvent are mixed at a volume ratio of 1: 0 to 1: 3. Can also be used.
Examples of the volatile solvent include hydrocarbons such as pentane, ethers such as tetrahydrofuran, esters such as ethyl formate, ketones such as acetone, alcohols such as methanol, nitrogen compounds such as acetonitrile, and the like. Of these, methanol, ethanol, acetone and the like are preferable.
また、酸化剤としては、エタノールに溶解したパラトルエンスルホン酸第二鉄、過ヨウ素酸もしくはヨウ素酸の水溶液を用いることができ、酸化剤の溶媒に対する濃度は４０〜６５ｗｔ％が好ましく、４５〜５７ｗｔ％がより好ましい。酸化剤の溶媒に対する濃度が高い程、ＥＳＲは低減する。なお、酸化剤の溶媒としては、上記モノマー溶液に用いた揮発性溶媒を用いることができ、なかでもエタノールが好適である。酸化剤の溶媒としてエタノールが好適であるのは、蒸気圧が低いため蒸発しやすく、残存する量が少ないためであると考えられる。 As the oxidizing agent, an aqueous solution of ferric paratoluenesulfonate, periodic acid or iodic acid dissolved in ethanol can be used, and the concentration of the oxidizing agent with respect to the solvent is preferably 40 to 65 wt%, and 45 to 57 wt%. % Is more preferable. The higher the oxidant concentration in the solvent, the lower the ESR. As the oxidant solvent, the volatile solvent used in the monomer solution can be used, and ethanol is particularly preferable. Ethanol is suitable as the oxidant solvent because it is easy to evaporate due to its low vapor pressure and the remaining amount is small.
（修復化成の化成液）
修復化成の化成液としては、リン酸二水素アンモニウム、リン酸水素二アンモニウム等のリン酸系の化成液、ホウ酸アンモニウム等のホウ酸系の化成液、アジピン酸アンモニウム等のアジピン酸系の化成液を用いることができるが、なかでも、リン酸二水素アンモニウムを用いることが望ましい。また、浸漬時間は、５〜１２０分が望ましい。
(Chemical solution for restoration conversion)
As the chemical solution for restoration chemical conversion, phosphoric acid type chemicals such as ammonium dihydrogen phosphate and diammonium hydrogen phosphate, boric acid type chemicals such as ammonium borate, and adipic acid type chemicals such as ammonium adipate, etc. Although a liquid can be used, it is preferable to use ammonium dihydrogen phosphate. The immersion time is preferably 5 to 120 minutes.
（他の重合性モノマー）
本発明に用いられる重合性モノマーとしては、上記ＥＤＴの他に、ＥＤＴ以外のチオフェン誘導体、アニリン、ピロール、フラン、アセチレンまたはそれらの誘導体であって、所定の酸化剤により酸化重合され、導電性ポリマーを形成するものであれば適用することができる。なお、チオフェン誘導体としては、下記の構造式のものを用いることができる。
As the polymerizable monomer used in the present invention, in addition to the above EDT, a thiophene derivative other than EDT, aniline, pyrrole, furan, acetylene or a derivative thereof, which is oxidatively polymerized with a predetermined oxidizing agent, is a conductive polymer. As long as it forms, it can be applied. As the thiophene derivative, one having the following structural formula can be used.
（作用・効果）
本発明の構成で、静電容量が高く、ＥＳＲ特性が良好で、耐電圧特性をさらに向上させることができる固体電解コンデンサを得ることができる理由は、以下の通りと考えられる。
すなわち、ビニル基を有する化合物を含有するセパレータを用いてコンデンサ素子を形成し、このコンデンサ素子を煮沸処理することにより、セパレータに含有されたビニル基を有する化合物が溶出し、溶出したビニル基を有する化合物とポリイミドシリコーンの層が形成され、その結果、酸化皮膜と導電性ポリマーとの密着性が向上し、さらに、この２層構造によって耐電圧が上昇するためであると考えられる。
(Action / Effect)
The reason why a solid electrolytic capacitor having a high electrostatic capacity, good ESR characteristics, and further improved withstand voltage characteristics can be obtained with the structure of the present invention is considered as follows.
That is, a capacitor element is formed using a separator containing a compound having a vinyl group, and the capacitor element is boiled to elute the compound having a vinyl group contained in the separator, thereby having the eluted vinyl group. A layer of the compound and the polyimide silicone is formed. As a result, the adhesion between the oxide film and the conductive polymer is improved, and the withstand voltage is increased by this two-layer structure.
本発明によれば、静電容量が高く、ＥＳＲ特性が良好で、耐電圧特性をさらに向上させて、エージング工程での歩留まりを高め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ができる。 According to the present invention, it is possible to provide a method for manufacturing a solid electrolytic capacitor that has a high capacitance, good ESR characteristics, can further improve the withstand voltage characteristics, and can increase the yield in the aging process.
続いて、以下のようにして製造した実施例及び比較例に基づいて本発明をさらに詳細に説明する。 Subsequently, the present invention will be described in more detail based on Examples and Comparative Examples manufactured as follows.
（実施例１）
主体繊維にＰＥＴ繊維を４９ｗｔ％含み、ＰＶＡポリマーをバインダーとして用いたセパレータを用い、以下のようにして固体電解コンデンサを作成した。表面に酸化皮膜層が形成された陽極箔と陰極箔に電極引き出し手段を接続し、両電極箔を上記のセパレータを介して巻回してコンデンサ素子を形成した。そして、このコンデンサ素子に煮沸処理を施し、乾燥した後、再度煮沸処理を行った。この煮沸処理〜乾燥処理を数回繰り返して、ＰＶＡの残存量を５０％とした後、リン酸二水素アンモニウム水溶液に４０分間浸漬して、修復化成を行った。その後、このコンデンサ素子をポリイミドシリコーンの２ｗｔ％シクロヘキサノン溶液に浸漬し、引き上げた後、１７０℃で１時間熱処理した。なお、ＰＶＡの残存量は、液体クロマトグラフィー定量分析によって求めた。
続いて、所定の容器に、ＥＤＴとｐ−トルエンスルホン酸第二鉄の４０ｗｔ％ブタノール溶液を、その重量比が１：３となるように注入して混合液を調製し、コンデンサ素子を上記混合液に１０秒間浸漬してコンデンサ素子にＥＤＴと酸化剤を含浸した。そして、このコンデンサ素子を１２０℃の恒温槽内に１時間放置して、コンデンサ素子内でＰＥＤＴの重合反応を発生させ、固体電解質層を形成した。その後、このコンデンサ素子を有底筒状のアルミニウムケースに収納し、封ロゴムで封止し、固体電解コンデンサを形成した。なお、この固体電解コンデンサの定格電圧は２５ＷＶ、定格容量は１０μＦである。
(Example 1)
A solid electrolytic capacitor was prepared as follows using a separator containing 49 wt% PET fiber as the main fiber and using a PVA polymer as a binder. An electrode lead means was connected to the anode foil and the cathode foil each having an oxide film layer formed on the surface, and both electrode foils were wound through the separator to form a capacitor element. The capacitor element was boiled, dried, and boiled again. This boiling treatment to drying treatment were repeated several times to make the remaining amount of PVA 50%, and then immersed in an aqueous solution of ammonium dihydrogen phosphate for 40 minutes to perform restoration conversion. Thereafter, this capacitor element was immersed in a 2 wt% cyclohexanone solution of polyimide silicone, pulled up, and then heat treated at 170 ° C. for 1 hour. The residual amount of PVA was determined by liquid chromatography quantitative analysis.
Subsequently, a 40 wt% butanol solution of EDT and ferric p-toluenesulfonate is poured into a predetermined container so that the weight ratio thereof is 1: 3 to prepare a mixed solution, and the capacitor element is mixed as described above. The capacitor element was impregnated with EDT and an oxidizing agent by dipping in the solution for 10 seconds. Then, this capacitor element was left in a constant temperature bath at 120 ° C. for 1 hour to cause a polymerization reaction of PEDT in the capacitor element, thereby forming a solid electrolyte layer. Then, this capacitor | condenser element was accommodated in the bottomed cylindrical aluminum case, and it sealed with sealing rubber | gum, and formed the solid electrolytic capacitor. This solid electrolytic capacitor has a rated voltage of 25 WV and a rated capacity of 10 μF.
（実施例２）
煮沸処理により、ＰＶＡの残存量を２５％とした。その他は、実施例１と同様の条件及び工程で固体電解コンデンサを作成した。
（実施例３）
煮沸処理により、ＰＶＡの残存量を１５％とした。その他は、実施例１と同様の条件及び工程で固体電解コンデンサを作成した。
（実施例４）
煮沸処理により、ＰＶＡの残存量を５％とした。その他は、実施例１と同様の条件及び工程で固体電解コンデンサを作成した。
(Example 2)
The residual amount of PVA was 25% by boiling treatment. Otherwise, a solid electrolytic capacitor was prepared under the same conditions and steps as in Example 1.
(Example 3)
The residual amount of PVA was set to 15% by boiling treatment. Otherwise, a solid electrolytic capacitor was prepared under the same conditions and steps as in Example 1.
Example 4
The residual amount of PVA was set to 5% by boiling treatment. Otherwise, a solid electrolytic capacitor was prepared under the same conditions and steps as in Example 1.
（比較例１）
煮沸処理を行わず、ＰＶＡの残存量を１００％とした。その他は、実施例１と同様の条件及び工程で固体電解コンデンサを作成した。
（比較例２）
煮沸処理を行わず、ＰＶＡの残存量を１００％とし、ポリイミドシリコーン溶液への浸漬も行わなかった。その他は、実施例１と同様の条件及び工程で固体電解コンデンサを作成した。
(Comparative Example 1)
No boiling treatment was performed, and the residual amount of PVA was 100%. Otherwise, a solid electrolytic capacitor was prepared under the same conditions and steps as in Example 1.
(Comparative Example 2)
The boiling treatment was not performed, the residual amount of PVA was 100%, and the immersion in the polyimide silicone solution was not performed. Otherwise, a solid electrolytic capacitor was prepared under the same conditions and steps as in Example 1.
［比較結果］
上記の方法により得られた実施例及び比較例について、初期特性を調べたところ、表１に示したような結果が得られた。
The initial characteristics of the examples and comparative examples obtained by the above methods were examined. The results shown in Table 1 were obtained.
表１から明らかなように、ＰＶＡの残存量が２５〜５％の実施例２〜４は、静電容量が９．５〜９．６μＦ、ＥＳＲは０．０３３〜０．０３４Ωと良好な結果が得られた。また、実施例２〜３は、ショート電圧が５０．６〜５１．７Ｖと高い値を示した。
また、このような初期のショート電圧の向上に伴って、定格電圧が２５ＷＶの固体電解コンデンサにおいて、エージング時の歩留まりが７０％から９５％へ大幅に改善された。
As is clear from Table 1, Examples 2 to 4 having a residual amount of PVA of 25 to 5% have a good capacitance of 9.5 to 9.6 μF and an ESR of 0.033 to 0.034Ω. was gotten. In Examples 2 to 3, the short voltage was as high as 50.6 to 51.7 V.
As the initial short-circuit voltage is improved, the yield during aging is greatly improved from 70% to 95% in the solid electrolytic capacitor having a rated voltage of 25 WV.
Claims (5)
前記セパレータにビニル基を有する化合物を含有させ、このセパレータを用いて巻回したコンデンサ素子を煮沸処理した後、修復化成を行い、その後にコンデンサ素子をポリイミドシリコーン溶液に浸漬し、そのコンデンサ素子に、前記重合性モノマーと酸化剤を含浸させ、前記導電性ポリマーからなる固体電解質層を形成することを特徴とする固体電解コンデンサの製造方法。 In a method for producing a solid electrolytic capacitor in which a capacitor element obtained by winding an anode foil and a cathode foil through a separator is impregnated with a polymerizable monomer and an oxidizing agent to form a solid electrolyte layer made of a conductive polymer,
The separator containing a compound having a vinyl group, the capacitor element wound using the separator is boiled, and then subjected to restoration conversion, and then the capacitor element is immersed in a polyimide silicone solution, A method for producing a solid electrolytic capacitor, comprising impregnating the polymerizable monomer and an oxidizing agent to form a solid electrolyte layer made of the conductive polymer.
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| JP2003339216A Expired - Fee Related JP4529403B2 (en) | 2003-09-30 | 2003-09-30 | Manufacturing method of solid electrolytic capacitor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007258422A (en) * | 2006-03-23 | 2007-10-04 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and its manufacturing method |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0135491B2 (en) * | 1982-03-18 | 1989-07-25 | Nippon Chemicon | |
| JPH0819380B2 (en) * | 1987-05-11 | 1996-02-28 | 住友化学工業株式会社 | Method for producing thick film insulator forming composition |
| JPH09293639A (en) * | 1996-04-26 | 1997-11-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and manufacture thereof |
| JP2003100565A (en) * | 2001-09-27 | 2003-04-04 | Nippon Chemicon Corp | Method of manufacturing solid electrolytic capacitor |
| JP2003109853A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacturing method |
| WO2003035739A1 (en) * | 2001-10-19 | 2003-05-01 | Hitachi Chemical Co., Ltd. | Electroconductive resin composition and electronic parts using the same |
| JP2003257795A (en) * | 2001-12-27 | 2003-09-12 | Nippon Chemicon Corp | Solid electrolytic capacitor |
| WO2004030004A1 (en) * | 2002-09-30 | 2004-04-08 | Nippon Chemi-Con Corporation | Solid electrolytic capacitor |
| JP2004335124A (en) * | 2003-04-30 | 2004-11-25 | Shin Etsu Chem Co Ltd | Impregnant for polyimide silicone electronic component |
-
2003
- 2003-09-30 JP JP2003339216A patent/JP4529403B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0135491B2 (en) * | 1982-03-18 | 1989-07-25 | Nippon Chemicon | |
| JPH0819380B2 (en) * | 1987-05-11 | 1996-02-28 | 住友化学工業株式会社 | Method for producing thick film insulator forming composition |
| JPH09293639A (en) * | 1996-04-26 | 1997-11-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and manufacture thereof |
| JP2003100565A (en) * | 2001-09-27 | 2003-04-04 | Nippon Chemicon Corp | Method of manufacturing solid electrolytic capacitor |
| JP2003109853A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacturing method |
| WO2003035739A1 (en) * | 2001-10-19 | 2003-05-01 | Hitachi Chemical Co., Ltd. | Electroconductive resin composition and electronic parts using the same |
| JP2003257795A (en) * | 2001-12-27 | 2003-09-12 | Nippon Chemicon Corp | Solid electrolytic capacitor |
| WO2004030004A1 (en) * | 2002-09-30 | 2004-04-08 | Nippon Chemi-Con Corporation | Solid electrolytic capacitor |
| JP2004335124A (en) * | 2003-04-30 | 2004-11-25 | Shin Etsu Chem Co Ltd | Impregnant for polyimide silicone electronic component |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007258422A (en) * | 2006-03-23 | 2007-10-04 | Sanyo Electric Co Ltd | Solid electrolytic capacitor and its manufacturing method |
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| JP4529403B2 (en) | 2010-08-25 |
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