JPH05121273A - Manufacture of solid electrolyte capacitor - Google Patents
Manufacture of solid electrolyte capacitorInfo
- Publication number
- JPH05121273A JPH05121273A JP30849591A JP30849591A JPH05121273A JP H05121273 A JPH05121273 A JP H05121273A JP 30849591 A JP30849591 A JP 30849591A JP 30849591 A JP30849591 A JP 30849591A JP H05121273 A JPH05121273 A JP H05121273A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic polymerization
- polymerization
- electrolytic
- monomer
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003990 capacitor Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000007784 solid electrolyte Substances 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 92
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 238000010979 pH adjustment Methods 0.000 abstract 4
- 230000003252 repetitive effect Effects 0.000 abstract 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 24
- 239000003115 supporting electrolyte Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 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 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は固体電解コンデンサの製
造方法に関し、さらに詳しく言えば、導電性高分子物質
からなる固体電解質を備えた固体電解コンデンサの製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a solid electrolytic capacitor, and more particularly to a method for manufacturing a solid electrolytic capacitor provided with a solid electrolyte made of a conductive polymer material.
【０００２】[0002]
【従来の技術】アルミニウムの陽極箔に導電性高分子物
質（ポリピロールやポリチォフェンなどの複素環式化合
物）からなる固体電解質を形成するには、化学酸化重合
と電解重合の２段階の工程を行なうようにしている。2. Description of the Related Art In order to form a solid electrolyte made of a conductive polymer substance (heterocyclic compound such as polypyrrole or polythiophene) on an aluminum anode foil, a two-step process of chemical oxidative polymerization and electrolytic polymerization is performed. I have to.
【０００３】ポリピロールを例にとって説明すると、ま
ず、アルミニウムからなる陽極箔に陽極端子としてのタ
ブ端子を溶接もしくはかしめにより取り付け、ピロール
モノマー溶液中に浸漬する。次に、酸化剤を含む溶液中
に浸漬し、陽極箔の表面（誘電体酸化被膜）に化学酸化
重合膜を形成する。Taking polypyrrole as an example, first, a tab terminal as an anode terminal is attached to an anode foil made of aluminum by welding or caulking, and immersed in a pyrrole monomer solution. Next, it is dipped in a solution containing an oxidizing agent to form a chemically oxidized polymerized film on the surface (dielectric oxide film) of the anode foil.
【０００４】しかる後、ピロールを主剤とする電解重合
液中に浸漬し、給電端子を例えば陽極端子に接触させて
箔表面に給電する。この場合、給電端子がプラス、電解
重合液の容器側がマイナスとされる。所定時間の通電に
より、化学酸化重合膜上に電解重合膜が形成される。After that, it is immersed in an electrolytic polymerization solution containing pyrrole as a main component, and a power supply terminal is brought into contact with, for example, an anode terminal to supply power to the foil surface. In this case, the power supply terminal is positive and the electrolytic polymerization solution container side is negative. An electrolytic polymerized film is formed on the chemically oxidized polymerized film by applying electricity for a predetermined time.
【０００５】[0005]
【発明が解決しようとする課題】ところで、電解重合液
には水の溶媒中にピロールを例えば０．２ｍｏｌ／ｌ
（リットル）、支持電解質としてのアルキルナフタレン
スルホン酸ナトリウムを０．２ｍｏｌ／ｌ程度混合した
ものが用いられるが、数ロット連続して用いると、その
組成が変化し、通常では５〜６ロット目で電解重合膜の
生成が不均一となり、特性不良が多発していた。By the way, in the electrolytic polymerization solution, pyrrole is used in a solvent of water, for example, 0.2 mol / l.
(Liter), a mixture of sodium alkylnaphthalene sulfonate as a supporting electrolyte in a proportion of about 0.2 mol / l is used, but when several lots are continuously used, the composition is changed, and usually 5 to 6 lots are used. The generation of the electrolytically polymerized film became non-uniform, and the characteristic defects frequently occurred.
【０００６】そのため、従来では電解重合液の使用回数
に限度を定め、その入れ替えを行なって製品特性の安定
化を図っているが、電解重合液は高価であるため、コス
ト的に好ましくない。また、その都度作業の中断を余儀
なくされるため、生産性の面でも問題とされていた。Therefore, in the past, the number of times the electrolytic polymerization liquid was used was limited and replaced to stabilize the product characteristics. However, the electrolytic polymerization liquid is expensive, which is not preferable in terms of cost. Further, the work is forced to be interrupted each time, which is also a problem in terms of productivity.
【０００７】[0007]
【課題を解決するための手段】本発明は、電解重合液の
組成変化をｐＨおよび重合電圧により知ることができる
ことに着目してなされたもので、その構成上の特徴は、
アルミニウムの陽極箔に導電性高分子物質からなる固体
電解質を形成するにあたって、化学酸化重合法により化
学酸化重合膜を形成し、次に電解重合液中に浸漬し電解
重合法により同化学酸化重合膜上に電解重合膜を形成す
るようにした固体電解コンデンサの製造方法において、
上記電解重合液のｐＨを測定するｐＨ測定手段と、電解
重合時に上記陽極箔に対して印加される重合電圧を測定
する重合電圧測定手段と、上記電解重合液にそのモノマ
ーを補給するモノマー補給手段と、同電解重合液に酸ま
たはアルカリのｐＨ調整液を供給するｐＨ調整液供給手
段と、中央処理制御手段（ＣＰＵ）とを備え、上記ｐＨ
測定手段および上記重合電圧測定手段からの検出信号に
基づいて同ＣＰＵにより上記モノマー補給手段と上記ｐ
Ｈ調整液供給手段を制御して、上記電解重合液のｐＨと
モノマー濃度を制御しながら電解重合膜を形成するよう
にしたことにある。The present invention has been made paying attention to the fact that the compositional change of an electrolytic polymerization solution can be known from pH and polymerization voltage.
When forming a solid electrolyte made of a conductive polymer substance on an aluminum anode foil, a chemical oxidation polymerization film is formed by a chemical oxidation polymerization method, and then it is immersed in an electrolytic polymerization solution and the chemical oxidation polymerization film is formed by the electrolytic polymerization method. In the method for producing a solid electrolytic capacitor, which is formed by forming an electrolytic polymer film on the
PH measuring means for measuring the pH of the electrolytic polymerization solution, polymerization voltage measuring means for measuring the polymerization voltage applied to the anode foil during electrolytic polymerization, and monomer replenishing means for replenishing the electrolytic polymerization solution with the monomer. And a pH adjusting liquid supply means for supplying an acid or alkali pH adjusting liquid to the electrolytic polymerization solution, and a central processing control means (CPU).
Based on the detection signals from the measuring means and the polymerization voltage measuring means, the CPU supplies the monomer replenishing means and the p
It is to control the H adjusting liquid supply means to form the electrolytic polymerization film while controlling the pH and the monomer concentration of the electrolytic polymerization liquid.
【０００８】本発明において、電解重合液はモノマーと
支持電解質と溶媒からなる。モノマーには、ピロール、
チオフェン、フランなどの複素環式化合物が用いられ
る。その濃度は、０．０１〜５．０ｍｏｌ／ｌ好ましく
は０．０５〜３．０ｍｏｌ／ｌが良い。In the present invention, the electrolytic polymerization liquid comprises a monomer, a supporting electrolyte and a solvent. The monomers include pyrrole,
Heterocyclic compounds such as thiophene and furan are used. The concentration is 0.01 to 5.0 mol / l, preferably 0.05 to 3.0 mol / l.
【０００９】支持電解質には、Ｐ−トルエンスルホン
酸、ナフタレンスルホン酸、ベンゼンスルホン酸などの
スルホン酸、安息香酸、アジピン酸、シュウ酸、フタル
酸などのカルボン酸、フェニルリン酸、ナフチルリン酸
などのリン酸、フェニルホウ酸などのホウ酸が単独であ
るいは混合して用いられるが、その濃度は０．０１〜
５．０ｍｏｌ／ｌ好ましくは０．０５〜３．０ｍｏｌ／
ｌが良い。Examples of the supporting electrolyte include sulfonic acids such as P-toluenesulfonic acid, naphthalenesulfonic acid and benzenesulfonic acid, carboxylic acids such as benzoic acid, adipic acid, oxalic acid and phthalic acid, phenylphosphoric acid and naphthylphosphoric acid. Boric acid such as phosphoric acid and phenylboric acid may be used alone or as a mixture, and the concentration thereof is 0.01-
5.0 mol / l Preferably 0.05-3.0 mol /
l is good.
【００１０】溶媒には、水、エタノール、プロパノール
などのプロトン性溶媒とアセトニトリル、プロピレンカ
ーボネイト、Ｎ，Ｎ−ジメチルホルムアミドなどの非プ
ロトン性溶媒が単独であるいは混合して用いられる。溶
媒の種類は支持電解質により適宜選択される。As the solvent, a protic solvent such as water, ethanol or propanol and an aprotic solvent such as acetonitrile, propylene carbonate or N, N-dimethylformamide may be used alone or in combination. The type of solvent is appropriately selected depending on the supporting electrolyte.
【００１１】[0011]
【作用】電解重合に際して、支持電解質として用いられ
る、例えばアルキルナフタレンスルホン酸ナトリウムの
内のアルキルナフタレンスルホン酸は電解重合膜の生成
に取り込まれるため、ナトリウムのみが電解重合液中に
残される。したがって、例えば新液のｐＨが７であった
としても、電解重合による使用を重ねるごとにそのｐＨ
は９．５，１０．３，１０．８と上昇する。In the electrolytic polymerization, for example, alkylnaphthalenesulfonic acid in sodium alkylnaphthalenesulfonate used as a supporting electrolyte is incorporated in the formation of the electropolymerized film, so that only sodium is left in the electrolytic polymerization solution. Therefore, for example, even if the pH of the new liquid is 7, the pH of the new liquid will be changed each time it is used by electrolytic polymerization.
Rises to 9.5, 10.3, 10.8.
【００１２】また、重合電圧については、図２のピロー
ル濃度と重合電圧の関連グラフに示されているように、
ピロール濃度の低下に伴って、重合電圧が高くなる傾向
を示す。Regarding the polymerization voltage, as shown in the relation graph of the pyrrole concentration and the polymerization voltage in FIG.
The polymerization voltage tends to increase as the pyrrole concentration decreases.
【００１３】本発明においては、これらの知見に基づ
き、ｐＨ測定手段にて電解重合液のｐＨを監視し、ま
た、重合電圧測定手段にて陽極箔に印加される重合電圧
を測定し、それらの値に基づいて適宜電解重合液にその
モノマーを補給するとともに、ｐＨ調整液を供給して、
同電解重合液の組成を常に所定の範囲に保持するように
している。In the present invention, on the basis of these findings, the pH of the electrolytic polymerization solution is monitored by the pH measuring means, and the polymerization voltage applied to the anode foil is measured by the polymerization voltage measuring means. Based on the value, while appropriately replenishing the monomer to the electrolytic polymerization liquid, and supplying the pH adjusting liquid,
The composition of the electrolytic polymerization solution is always kept within a predetermined range.
【００１４】本発明においては、上記電解重合液のｐＨ
を７．０〜１１．０の範囲に、より好ましくは７．０〜
８．５の範囲に保ち、また、モノマー濃度を０．０１〜
５．０ｍｏｌ／ｌに保ちながら、電解重合膜を形成す
る。In the present invention, the pH of the electrolytic polymerization solution is
To 7.0 to 11.0, more preferably 7.0 to
Keep in the range of 8.5 and keep the monomer concentration from 0.01 to
An electrolytic polymerized film is formed while maintaining it at 5.0 mol / l.
【００１５】[0015]
【実施例】図１には本発明を実施する上で用いられる装
置の一例が示されている。これによると、同装置は所定
容積の電解重合槽１を備えている。この実施例では、同
電解重合槽１内には、水を溶媒として、その中にピロー
ルを０．２ｍｏｌ／ｌと、支持電解質としてのアルキル
ナフタレンスルホン酸ナトリウムを０．２ｍｏｌ／ｌと
を混合した電解重合液Ｌが入れられている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 shows an example of an apparatus used for carrying out the present invention. According to this, the apparatus is equipped with the electrolytic polymerization tank 1 having a predetermined volume. In this example, in the electrolytic polymerization tank 1, water was used as a solvent, and pyrrole was mixed therein with 0.2 mol / l and sodium alkylnaphthalenesulfonate as a supporting electrolyte was mixed with 0.2 mol / l. The electrolytic polymerization liquid L is contained.
【００１６】この装置は、電解重合槽１内において陽極
箔２に対して重合電圧を印加するための定電流の重合用
電源３のほかに、その印加電圧を測定する電圧計４を有
している。また、電解重合槽１内にピロールを補給する
ための補給槽５を備えている。This apparatus has a constant-current polymerization power source 3 for applying a polymerization voltage to the anode foil 2 in the electrolytic polymerization tank 1, and a voltmeter 4 for measuring the applied voltage. There is. A replenishment tank 5 for replenishing pyrrole is provided in the electrolytic polymerization tank 1.
【００１７】この場合、電圧計４にて測定された電圧信
号は第１の中央演算処理手段（ＣＰＵ）６に与えられ、
同ＣＰＵ６はその電圧信号に基づいて補給槽５の制御弁
５ａを開閉する。In this case, the voltage signal measured by the voltmeter 4 is given to the first central processing unit (CPU) 6,
The CPU 6 opens and closes the control valve 5a of the replenishment tank 5 based on the voltage signal.
【００１８】また、この電解重合槽１にはｐＨ測定槽
７、酸（例えば、アルキルナフタレンスルホン酸）が貯
蔵される酸槽８およびアルカリ液（例えば、アンモニ
ア）が貯蔵される塩基槽９が付設されている。The electrolytic polymerization tank 1 is additionally provided with a pH measuring tank 7, an acid tank 8 for storing an acid (for example, alkylnaphthalenesulfonic acid), and a base tank 9 for storing an alkaline liquid (for example, ammonia). Has been done.
【００１９】ｐＨ測定槽７には制御弁７ａを介して電解
重合槽１内の電解重合液Ｌが供給され、その電解重合液
ＬのｐＨがｐＨ電極１０によって検出される。なお、こ
の実施例とは異なり、ｐＨ測定槽７を省略してｐＨ電極
１０を直接電解重合槽１内に設けても良い。The electrolytic polymerization solution L in the electrolytic polymerization tank 1 is supplied to the pH measuring tank 7 through the control valve 7a, and the pH of the electrolytic polymerization solution L is detected by the pH electrode 10. Unlike this example, the pH measuring tank 7 may be omitted and the pH electrode 10 may be directly provided in the electrolytic polymerization tank 1.
【００２０】ｐＨ電極１０にて検出されたｐＨ検出信号
は、第２の中央演算処理手段（ＣＰＵ）１１に入力さ
れ、同ＣＰＵ１１はそのｐＨ検出信号に基づいて酸槽８
および塩基槽９の制御弁８ａ，９ａを開閉する。また、
この第２のＣＰＵ１１は、上記制御弁７ａおよびｐＨ測
定槽７の排出弁７ｂの開閉をも制御する。The pH detection signal detected by the pH electrode 10 is input to the second central processing unit (CPU) 11, and the CPU 11 outputs the acid bath 8 based on the pH detection signal.
Also, the control valves 8a and 9a of the base tank 9 are opened and closed. Also,
The second CPU 11 also controls the opening / closing of the control valve 7a and the discharge valve 7b of the pH measuring tank 7.
【００２１】なお、電解重合槽１とｐＨ測定槽７内に
は、その槽内の電解重合液を撹拌して均一化する撹拌翼
１２ａ，１２ｂがそれぞれ設けられている。The electrolytic polymerization tank 1 and the pH measuring tank 7 are provided with agitating blades 12a, 12b for agitating and homogenizing the electrolytic polymerization solution in the tank.
【００２２】電解重合膜を形成するには、前工程におい
て化学酸化重合法により化学酸化重合膜が形成された陽
極箔２を電解重合液Ｌ内に浸漬する。図１では１枚の箔
しか示されていないが、実際には数１０枚の箔がそれに
取付けられている陽極端子２ａを介して図示しないフー
プ材に吊下げられた状態で、１ロットとして処理され
る。To form the electrolytically polymerized film, the anode foil 2 on which the chemically oxidized polymerized film is formed by the chemical oxidative polymerization method in the previous step is immersed in the electrolytically polymerized liquid L. Although only one foil is shown in FIG. 1, several tens of foils are actually processed as one lot in a state of being suspended from a hoop material (not shown) via the anode terminal 2a attached thereto. To be done.
【００２３】陽極箔２に対して重合用電源３のプラス側
給電端子３ａを接触させる。なお、同重合用電源３のマ
イナス側給電端子３ｂは電解重合液Ｌ内に浸漬されてい
る。The positive side power supply terminal 3a of the polymerization power source 3 is brought into contact with the anode foil 2. The negative side power supply terminal 3b of the same power source 3 for polymerization is immersed in the electrolytic polymerization liquid L.
【００２４】この給電端子３ａ，３ｂを介して所定時間
通電することにより、陽極箔２の化学酸化重合膜上に電
解重合膜が形成されるのであるが、その重合電圧が電圧
計４によって読み取られ、その電圧検出信号が第１のＣ
ＰＵ６に入力される。An electric polymerization film is formed on the chemically oxidized polymerization film of the anode foil 2 by energizing for a predetermined time through the power supply terminals 3a and 3b. The polymerization voltage is read by the voltmeter 4. , The voltage detection signal is the first C
Input to PU6.
【００２５】第１のＣＰＵ６は同電圧検出信号の変化に
より、ピロールの減少度合いを感知し、予め定められて
いる基準値以下になった時点で制御弁５ａを開き、補給
槽５から適量（例えば、０．０３ｍｏｌ／ｌ程度）のピ
ロールを電解重合液Ｌに供給する。The first CPU 6 senses the degree of decrease of pyrrole by the change of the same voltage detection signal, opens the control valve 5a when it falls below a predetermined reference value, and opens an appropriate amount from the replenishment tank 5 (for example, , About 0.03 mol / l) to the electrolytic polymerization liquid L.
【００２６】これと並行して、第２のＣＰＵ１１により
制御弁７ａが一定時間ごとに開かれ、ｐＨ測定槽７に電
解重合液Ｌのサンプルが取り込まれる。ｐＨ電極１０に
より、同サンプルのｐＨ値が測定され、そのｐＨ測定信
号が第２のＣＰＵ１１に与えられる。なおｐＨ測定後、
同サンプルは排出弁７ｂを介して廃棄される。In parallel with this, the control valve 7a is opened by the second CPU 11 at regular intervals, and a sample of the electrolytic polymerization solution L is taken into the pH measuring tank 7. The pH value of the sample is measured by the pH electrode 10, and the pH measurement signal is given to the second CPU 11. After pH measurement,
The sample is discarded via the discharge valve 7b.
【００２７】第２のＣＰＵ１１はそのｐＨ測定信号によ
り、電解重合液Ｌが酸性となっている場合には、制御弁
９ａを開いて塩基槽９より適量のアルカリ液を電解重合
槽１に供給する。他方、電解重合液Ｌが塩基性となって
いる場合には、制御弁８ａを開いて酸槽８より適量の酸
を電解重合槽１に供給する。When the electrolytic polymerization liquid L is acidic, the second CPU 11 opens the control valve 9a and supplies an appropriate amount of alkaline liquid from the base tank 9 to the electrolytic polymerization tank 1 when the electrolytic polymerization liquid L is acidic. .. On the other hand, when the electrolytic polymerization liquid L is basic, the control valve 8a is opened to supply an appropriate amount of acid from the acid tank 8 to the electrolytic polymerization tank 1.
【００２８】このようにして、電解重合液Ｌのピロール
濃度とｐＨ値がほぼ一定に保たれ、製品の特性不良率が
大幅に改善される。また、高価な電解重合液Ｌを殆ど廃
棄することなく、その有効活用が図れる。In this way, the pyrrole concentration and pH value of the electropolymerization liquid L are kept substantially constant, and the characteristic defect rate of the product is greatly improved. Further, the expensive electrolytic polymerization liquid L can be effectively used without being discarded.
【００２９】上記実施例では第１のＣＰＵ６でピロール
の補給管理を行ない、第２のＣＰＵ１１でｐＨ管理を行
なうようにしているが、これは一例であって、その双方
の管理を同一のＣＰＵによって行なわせることも可能で
ある。In the above embodiment, the first CPU 6 manages the supply of pyrrole and the second CPU 11 manages the pH, but this is an example, and both managements are performed by the same CPU. It is also possible to have it performed.
【００３０】表１に、液管理を行なわない場合の従来例
と、本発明にしたがって液管理を行なった実施例につい
て、１ロットを５０個（陽極箔５０枚）として、その重
合電圧の変化状態、漏れ電流の平均値（μＡ）、等価直
列抵抗の平均値（ＥＳＲ；Ω）および不良率を比較対照
して示す。なお、この比較に用いられた製品は従来例、
実施例ともに定格１０Ｖ４．７μＦのアルミニウム固体
電解コンデンサであった。Table 1 shows the change state of the polymerization voltage for a conventional example in which the liquid is not controlled and an example in which the liquid is controlled according to the present invention, where one lot is 50 pieces (50 pieces of anode foil). The average value of leakage current (μA), the average value of equivalent series resistance (ESR; Ω), and the defective rate are shown for comparison. The products used for this comparison are conventional examples,
Both of the examples were aluminum solid electrolytic capacitors having a rating of 10V and 4.7 μF.
【００３１】[0031]
【表１】 [Table 1]
【００３２】なお、この表１において、重合電圧は初回
ロットにのみその印加電圧を記入し、それ以降のロット
については、同印加電圧を基準としてその増減分の電圧
値を記入している。また、不良率については、分母が１
ロットの製品数で、分子が不良品数を示している。In Table 1, the applied voltage is entered only for the first lot, and for the subsequent lots, the voltage values for the increment and decrement are entered based on the applied voltage. The denominator is 1 for the defect rate.
The numerator shows the number of defective products in the number of products in a lot.
【００３３】[0033]
【発明の効果】以上説明したように、本発明によれば、
ｐＨ測定手段と重合電圧測定手段を用いて、電解重合液
のｐＨ値とそのモノマー濃度をほぼ一定に管理するよう
にしたことにより、その電解重合液の繰り返し使用が可
能になるとともに、製品の不良率も改善される、などの
効果が奏される。As described above, according to the present invention,
By using the pH measuring means and the polymerization voltage measuring means to control the pH value of the electrolytic polymerization solution and the monomer concentration thereof to be substantially constant, the electrolytic polymerization solution can be repeatedly used and the product is defective. The rate is also improved.
【図１】本発明を実施する上で用いられる装置の一例を
示した模式図。FIG. 1 is a schematic diagram showing an example of an apparatus used for carrying out the present invention.
【図２】ピロール濃度と重合電圧の関連を示したグラ
フ。FIG. 2 is a graph showing the relationship between pyrrole concentration and polymerization voltage.
【符号の説明】 １ 電解重合槽 ２ 陽極箔 ３ 重合用電源 ４ 電圧計 ５ 補給槽 ６，１１ ＣＰＵ ７ ｐＨ測定槽 ８ 酸槽 ９ 塩基槽 １０ ｐＨ電極[Explanation of symbols] 1 electrolytic polymerization tank 2 anode foil 3 power supply for polymerization 4 voltmeter 5 replenishment tank 6, 11 CPU 7 pH measuring tank 8 acid tank 9 base tank 10 pH electrode
フロントページの続き (72)発明者 大久保 哲 神奈川県藤沢市辻堂新町２丁目２番１号 エルナ−株式会社内 (72)発明者 数原 学 神奈川県藤沢市辻堂新町２丁目２番１号 エルナ−株式会社内Front page continued (72) Inventor Satoshi Okubo 2-2-1 Tsujido Shinmachi, Fujisawa City, Kanagawa Elna Co., Ltd. Within the corporation
Claims (1)
からなる固体電解質を形成するにあたって、化学酸化重
合法により化学酸化重合膜を形成し、次に電解重合液中
に浸漬し電解重合法により同化学酸化重合膜上に電解重
合膜を形成するようにした固体電解コンデンサの製造方
法において、上記電解重合液のｐＨを測定するｐＨ測定
手段と、電解重合時に上記陽極箔に対して印加される重
合電圧を測定する重合電圧測定手段と、上記電解重合液
にそのモノマーを補給するモノマー補給手段と、同電解
重合液に酸またはアルカリのｐＨ調整液を供給するｐＨ
調整液供給手段と、中央演算処理手段（ＣＰＵ）とを備
え、上記ｐＨ測定手段および上記重合電圧測定手段から
の検出信号に基づいて同ＣＰＵにより上記モノマー補給
手段と上記ｐＨ調整液供給手段を制御して、上記電解重
合液のｐＨとモノマー濃度を制御しながら電解重合膜を
形成するようにしたことを特徴とする固体電解コンデン
サの製造方法。1. When forming a solid electrolyte made of a conductive polymer substance on an aluminum anode foil, a chemically oxidative polymerization film is formed by a chemical oxidative polymerization method and then immersed in an electrolytic polymerization solution and then electrolytically polymerized. In the method for producing a solid electrolytic capacitor in which an electrolytically polymerized film is formed on the same chemically oxidized polymerized film, a pH measuring means for measuring the pH of the electrolytically polymerized liquid and a voltage applied to the anode foil during electrolytic polymerization Polymerization voltage measuring means for measuring the polymerization voltage, monomer replenishing means for replenishing the above-mentioned electrolytic polymerization liquid with the monomer, and pH for supplying an acid or alkali pH adjusting liquid to the same electrolytic polymerization liquid
An adjusting liquid supply unit and a central processing unit (CPU) are provided, and the monomer replenishing unit and the pH adjusting liquid supply unit are controlled by the CPU based on detection signals from the pH measuring unit and the polymerization voltage measuring unit. Then, the method for producing a solid electrolytic capacitor is characterized in that the electrolytic polymerization film is formed while controlling the pH and the monomer concentration of the electrolytic polymerization solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30849591A JPH05121273A (en) | 1991-10-28 | 1991-10-28 | Manufacture of solid electrolyte capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30849591A JPH05121273A (en) | 1991-10-28 | 1991-10-28 | Manufacture of solid electrolyte capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05121273A true JPH05121273A (en) | 1993-05-18 |
Family
ID=17981703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30849591A Withdrawn JPH05121273A (en) | 1991-10-28 | 1991-10-28 | Manufacture of solid electrolyte capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05121273A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005038834A1 (en) * | 2003-10-20 | 2005-04-28 | Showa Denko K.K. | Production method of a capacitor |
| JP2008098401A (en) * | 2006-10-12 | 2008-04-24 | Sanyo Electric Co Ltd | Method for manufacturing solid-state electrolytic capacitor |
| JP2009164367A (en) * | 2008-01-08 | 2009-07-23 | Japan Carlit Co Ltd:The | Electrolytic solution for electrolytic polymerization and its use |
| EP2224796A1 (en) * | 2009-02-26 | 2010-09-01 | ZYRUS Beteiligungsgesellschaft mbH & Co. Patente I KG | Method for producing a metal structure on a substrate |
-
1991
- 1991-10-28 JP JP30849591A patent/JPH05121273A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005038834A1 (en) * | 2003-10-20 | 2005-04-28 | Showa Denko K.K. | Production method of a capacitor |
| US8026137B2 (en) | 2003-10-20 | 2011-09-27 | Showa Denko K.K. | Production method of a capacitor |
| JP2008098401A (en) * | 2006-10-12 | 2008-04-24 | Sanyo Electric Co Ltd | Method for manufacturing solid-state electrolytic capacitor |
| JP4762105B2 (en) * | 2006-10-12 | 2011-08-31 | 三洋電機株式会社 | Manufacturing method of solid electrolytic capacitor |
| JP2009164367A (en) * | 2008-01-08 | 2009-07-23 | Japan Carlit Co Ltd:The | Electrolytic solution for electrolytic polymerization and its use |
| EP2224796A1 (en) * | 2009-02-26 | 2010-09-01 | ZYRUS Beteiligungsgesellschaft mbH & Co. Patente I KG | Method for producing a metal structure on a substrate |
| WO2010097231A1 (en) * | 2009-02-26 | 2010-09-02 | Zyrus Beteiligungsgesellschaft Mbh & Co. Patente I Kg | Apparatus and method for producing a conductive structured polymer film |
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