JPH03127813A - Manufacture of solid electrolytic capacitor - Google Patents
Manufacture of solid electrolytic capacitorInfo
- Publication number
- JPH03127813A JPH03127813A JP1267682A JP26768289A JPH03127813A JP H03127813 A JPH03127813 A JP H03127813A JP 1267682 A JP1267682 A JP 1267682A JP 26768289 A JP26768289 A JP 26768289A JP H03127813 A JPH03127813 A JP H03127813A
- Authority
- JP
- Japan
- Prior art keywords
- capacitor
- capacitor element
- manufacturing
- solid electrolytic
- esr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 title claims abstract description 16
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000011800 void material Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 2
- 239000002052 molecular layer Substances 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 abstract description 9
- 239000010406 cathode material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance 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
- 229930192474 thiophene Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GPHFILLEJDZWIK-UHFFFAOYSA-K 2-dodecylbenzenesulfonate;iron(3+) Chemical compound [Fe+3].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O GPHFILLEJDZWIK-UHFFFAOYSA-K 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、陰極としてピロール、チオフェンおよびフラ
ン等の複素環式化合物の酸化重合体よりなる導電性高分
子を用いる固体電解コンデンサの製造方法に利用され、
特に、耐熱性および耐候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。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a solid electrolytic capacitor using a conductive polymer made of an oxidized polymer of a heterocyclic compound such as pyrrole, thiophene, and furan as a cathode. used,
In particular, the present invention relates to a method of manufacturing a solid electrolytic capacitor with improved heat resistance and weather resistance.
本発明は、皮膜形成金属表面に形成された酸化皮膜層を
誘電体層とし、この誘電体層上に形成された複素環式化
合物の酸化重合体よりなる導電性高分子層を陰極とし、
さらにこの導電性高分子層上に導電体層を積層したコン
デンサ素子を、外装封止してコンデンサを製造する固体
電解コンデンサの製造方法において、
前記コンデンサ素子の作製時およびまたは作製後外装封
止前に、そのコンデンサ素子内の空隙中に酸素の濃度が
１容量％以下である不活性ガスを導入する工程を設ける
ことにより、
耐熱性および耐候性に優れた固体電解コンデンサを製造
できるようにしたものである。The present invention provides an oxide film layer formed on the surface of a film-forming metal as a dielectric layer, a conductive polymer layer formed on the dielectric layer made of an oxidized polymer of a heterocyclic compound as a cathode,
Furthermore, in a method for manufacturing a solid electrolytic capacitor, in which a capacitor is manufactured by externally sealing a capacitor element in which a conductive layer is laminated on the conductive polymer layer, the capacitor element is manufactured and/or after manufacturing and before the external sealing. A solid electrolytic capacitor with excellent heat resistance and weather resistance can be manufactured by incorporating a process of introducing an inert gas with an oxygen concentration of 1% by volume or less into the void inside the capacitor element. It is.
従来、固体電解コンデンサには二酸化マンガンやＴＣＮ
Ｑ錯塩が陰極物質として用いられている。Conventionally, solid electrolytic capacitors use manganese dioxide or TCN.
A Q complex salt is used as the cathode material.
しかし、前者ではその抵抗値が大きい、製造工程が煩雑
であるという欠点があり、後者においては耐熱性が悪い
という欠点がある。そこで複素環式化合物重合体よりな
る導電性高分子を陰極とする固体電解コンデンサが提案
されている（特開昭６０３７１１４号公報など）。However, the former has the drawbacks of high resistance and a complicated manufacturing process, while the latter has the drawback of poor heat resistance. Therefore, a solid electrolytic capacitor using a conductive polymer made of a heterocyclic compound polymer as a cathode has been proposed (Japanese Patent Laid-Open Publication No. 6037114, etc.).
複素環式化合物よりなる導電性高分子を陰極物質とする
固体電解コンデンサの外装には、通常エポキシ樹脂およ
びシリコン樹脂等を用いた樹脂ケース中へ封止する方法
が用いられている。エポキシ樹脂あるいはその他の樹脂
でも、その硬化に際しては６０〜２００℃で１〜１０時
間の加熱を要するのがほとんどであり、この加熱硬化の
過程でコンデンサ素子のＥＳＲ（等価直列抵抗）が増大
する問題がある。また、素子からの陰極リードの取出し
を行う際にも、同様に、ＥＳＲが増大するという問題が
ある。さらには、外装を終了したコンデンサについても
同様に、高温耐熱試験を行うとＥＳＲが増大していくと
いう問題がある。For the exterior of a solid electrolytic capacitor whose cathode material is a conductive polymer made of a heterocyclic compound, a method of sealing the capacitor in a resin case using epoxy resin, silicone resin, etc. is usually used. Most epoxy resins and other resins require heating at 60 to 200°C for 1 to 10 hours to cure, and the problem is that the ESR (equivalent series resistance) of the capacitor element increases during this heating and curing process. There is. Furthermore, when taking out the cathode lead from the element, there is a similar problem of increased ESR. Furthermore, there is a similar problem in that the ESR increases when a high temperature heat resistance test is performed on a capacitor that has been packaged.
これらの現象はポリピロール等の導電性高分子が酸素お
よび熱により劣化してしまうことによると言われており
、酸素原子を含まないかあるいは活性酸素を発生しない
樹脂等でバリア層を設ける方法（特開平１−１３７６１
９号公報）、外装工程に至る熱処理を不活性ガス中で行
う方法（特開昭６３１８１３０９号公報）等が提案され
ている。しかし、本発明者らが検討したところ、これら
の方法を講じても特性の低下は完全には防ぎきれず、−
層の耐熱性および耐候性の向上が求められていた。These phenomena are said to be caused by the deterioration of conductive polymers such as polypyrrole due to oxygen and heat. Kaihei 1-13761
9), a method in which the heat treatment leading to the packaging step is carried out in an inert gas (Japanese Patent Application Laid-Open No. 63181309), etc. have been proposed. However, the present inventors have investigated that even if these methods are used, the deterioration of characteristics cannot be completely prevented, and -
There was a need to improve the heat resistance and weather resistance of the layer.
本発明の目的は、前記の課題を解決することにより、外
装封止さらには耐熱性試験を行っても静電容量の低下が
極めて小さく、かつＥＳＲの増大の小さい固体電解コン
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 provide a method for manufacturing a solid electrolytic capacitor that exhibits a very small decrease in capacitance and a small increase in ESR even after being packaged and subjected to a heat resistance test, by solving the above-mentioned problems. It's about doing.
本発明者らは、種々検討の結果、熱処理工程を行う前に
コンデンサ素子内部の微細孔中に不活性ガスを導入する
ことにより前記課題を解決できることを見出し本発明に
至った。すなわち、本発明は、皮膜形成金属表面に酸化
皮膜からなる誘電体層を形成する工程、この誘電体層上
に陰極として複素環式化合物の酸化重合体よりなる導電
性高分子層を積層する工程、およびこの導電性高分子層
上に導電体層を積層する工程を含みコンデンサ素子を作
製する工程と、このコンデンサ素子を外装封止してコン
デンサを作製する工程とを備えた固体電解コンデンサの
製造方法において、前記コンデンサ素子の作製時および
または作製後外装封止前に、そのコンデンサ素子内の空
隙中に酸素の濃度がｌ容量％以下である不活性ガスを導
入する工程を備えたことを特徴とする。As a result of various studies, the present inventors have found that the above problem can be solved by introducing an inert gas into the micropores inside the capacitor element before performing the heat treatment process, leading to the present invention. That is, the present invention comprises a step of forming a dielectric layer made of an oxide film on the surface of a film-forming metal, and a step of laminating a conductive polymer layer made of an oxidized polymer of a heterocyclic compound as a cathode on the dielectric layer. , manufacturing a solid electrolytic capacitor comprising: a step of manufacturing a capacitor element including a step of laminating a conductor layer on the conductive polymer layer; and a step of manufacturing a capacitor by externally sealing the capacitor element. The method is characterized by comprising the step of introducing an inert gas having an oxygen concentration of 1% by volume or less into the void inside the capacitor element during the production of the capacitor element and/or after the production and before the exterior sealing. shall be.
本発明が適用可能な複素環式化合物重合体よりなる導電
性高分子としては、ピロール、チオフェン、フラン、お
よびこれらの誘導体の重合物が挙げられるが、これらの
うちでもポリピロールが好ましい。Examples of the conductive polymer made of a heterocyclic compound polymer to which the present invention can be applied include polymers of pyrrole, thiophene, furan, and derivatives thereof, and among these, polypyrrole is preferred.
また、不活性ガスとは、ポリピロールに対して酸化およ
び脱ドープ等の影響をおよぼさない気体のことで、具体
的には、Ｈｅ、Ｎｅ、Ａｒ５ＫｒおよびＸｅ等の希ガス
類や、ＣＯ２およびＮ２ガスが挙げられる。これらの不
活性ガスは単独ではもちろんのこと、数種の混合気体で
も使用可能である。また、酸素の含有量は厳密に０であ
る必要はなく、本発明者らの検討の結果、酸素含有量が
１容量％以下であれば、所期の効果が得られることが明
らかになった。In addition, inert gas is a gas that does not affect polypyrrole by oxidizing or dedoping, and specifically includes rare gases such as He, Ne, Ar5Kr and Xe, CO2 and N2 gas. can be mentioned. These inert gases can be used alone or in a mixture of several types. Furthermore, the oxygen content does not have to be strictly zero, and as a result of the inventors' studies, it has become clear that the desired effect can be obtained as long as the oxygen content is 1% by volume or less. .
また、コンデンサ素子内の空隙中に前記不活性ガスを充
填する方法としては、コンデンサ素子作製の各工程（導
電性高分子の充填、洗浄、乾燥さらには陰極リードの引
出し等）を不活性ガス雰囲気下で行うのが好ましいが、
装置上あるいは工程上の問題により困難な場合には、例
えば、大気中で導電性高分子を充填した皮膜形成金属多
孔体、あるいは、それに導電性塗料を大気中で塗布・含
浸させて組上げたコンデンサ素子を減圧下に置き、コン
デンサ素子内の空隙中に残存する空気（酸素）等を除去
した後に不活性ガスを常圧あるいは高圧で導入すること
によっても本発明の目的は充分に達成できる。従って、
本発明は、コンデンサ素子を構成する皮膜形成金属の多
孔体中に導電性高分子を充填するいずれの方法（電解酸
化重合法、化学酸化重合法および導電性高分子の溶融物
、あるいは溶液を含浸させる方法、またはこれらを併用
する方法等）にも適用可能である。In addition, as a method of filling the void inside the capacitor element with the inert gas, each step of capacitor element manufacturing (filling of conductive polymer, cleaning, drying, drawing out the cathode lead, etc.) is carried out in an inert gas atmosphere. It is preferable to do it below,
If this is difficult due to equipment or process problems, for example, a capacitor assembled by forming a film-forming metal porous body filled with a conductive polymer in the atmosphere, or by coating and impregnating it with a conductive paint in the atmosphere. The object of the present invention can also be fully achieved by placing the element under reduced pressure and removing air (oxygen) remaining in the void inside the capacitor element and then introducing an inert gas at normal pressure or high pressure. Therefore,
The present invention is applicable to any method of filling a conductive polymer into a porous body of film-forming metal constituting a capacitor element (electrolytic oxidation polymerization method, chemical oxidation polymerization method, and impregnation with a melt or solution of a conductive polymer). It is also applicable to a method in which the
本発明は、複素環式化合物よりなる導電性高分子を陰極
材料とする固体電解コンデンサの製造において、外装封
止等熱処理工程の前に、コンデンサ素子内部の空隙中に
、酸素濃度ｌ容量％以下の不活性ガスを導入し、高温状
態下における酸素とポリピロール等の導電性高分子との
反応を未然に防止する。これにより、外装樹脂を硬化す
るための加熱や、さらに、その後の耐熱試験を大気中で
行っても、複素環式化合物よりなる導電性高分子の導電
率の低下が小さく、したがってＥＲ３，ｔａｎδおよび
静電容量等コンデンサ特性の熱劣化の度合いが小さなコ
ンデンサが得られる。In the production of solid electrolytic capacitors using a conductive polymer made of a heterocyclic compound as a cathode material, the present invention provides an oxygen concentration of 1% by volume or less in a void inside a capacitor element before a heat treatment process such as exterior sealing. An inert gas is introduced to prevent the reaction between oxygen and conductive polymers such as polypyrrole under high temperature conditions. As a result, even when heating is performed to cure the exterior resin and a subsequent heat resistance test is performed in the air, the conductivity of the conductive polymer made of a heterocyclic compound is small, and therefore ER3, tan δ and A capacitor with a small degree of thermal deterioration of capacitor characteristics such as capacitance can be obtained.
以下、実施例を上げて本発明を具体的に説明するが、本
発明はこれら実施例にのみ限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.
実施例■
ｌＸ１ｃｍ２角のエツチングアルミ箔に高純度アルミ製
の陽極リードをスポット溶接した後、ホウ酸アンモニウ
ム水溶液中、６０Ｖで化成処理を行い酸化皮膜を形成さ
せ、水洗、乾燥させた。Example 2 A high-purity aluminum anode lead was spot-welded to a 1×1 cm square etched aluminum foil, and then subjected to chemical conversion treatment at 60 V in an aqueous ammonium borate solution to form an oxide film, washed with water, and dried.
このリード付アルミ化成箔をドデシルベンゼンスルホン
酸−鉄（ＩＩＩ）塩の２５容量％−メタノール溶液に浸
漬した後、デシケーク中で１５分間減圧乾燥を行った。This chemically formed aluminum foil with leads was immersed in a 25% by volume methanol solution of dodecylbenzenesulfonic acid-iron(III) salt, and then dried under reduced pressure in a desicake for 15 minutes.
さらにデシケータ内部に酸素濃度が１容量％以下である
Ｎ２ガスを導入し常圧に戻した。この後、常温、常圧下
でピロールモノマー蒸気と３０分間接触させ、このアル
ミ箔上でピロールを重合させた。これをメタノールで洗
浄し、デシケーク中で１５分間減圧乾燥を行った後、先
と同様にデシケータ内部に酸素濃度が１容量％以下であ
るＮ２ガスを導入し常圧に戻した。以上の一連の操作を
６回繰返すことにより、このアルミ箔の表面は濃黒縁色
のポリピロールで被覆された。反応前後の重量変化から
求めたアルミ箔微細孔へのポリピロールの充填率は９０
％であった。Furthermore, N2 gas having an oxygen concentration of 1% by volume or less was introduced into the desiccator to return the pressure to normal pressure. Thereafter, the aluminum foil was brought into contact with pyrrole monomer vapor for 30 minutes at room temperature and pressure to polymerize pyrrole on the aluminum foil. After washing this with methanol and drying under reduced pressure in a desiccator for 15 minutes, N2 gas having an oxygen concentration of 1% by volume or less was introduced into the desiccator as before to return it to normal pressure. By repeating the above series of operations six times, the surface of this aluminum foil was coated with polypyrrole with a deep black edge color. The filling rate of polypyrrole into the micropores of aluminum foil, determined from the weight change before and after the reaction, was 90.
%Met.
以下の工程は大気中で連続的に行った。まず銀ペースト
を用いて陰極リードの引出しを行い、コンデンサ素子を
組み上げた。得られたコンデンサ素子は、１２０Ｈｚに
おいて７．５６μＦの静電容量を有し、ｔａｎδは０．
０１以下であった。静電容量の変化率は２５０ｋＨｚま
でｌ０％以下、またｔａｎδも１５０ｋＨｚまで０．１
以下であった。共振点（５４０ｋＨｚ）におけるＥＳＲ
は３２ｍΩであった。The following steps were performed continuously in the atmosphere. First, the cathode lead was drawn out using silver paste, and the capacitor element was assembled. The obtained capacitor element has a capacitance of 7.56 μF at 120 Hz and a tan δ of 0.
It was 01 or less. The rate of change in capacitance is less than 10% up to 250kHz, and tan δ is 0.1 up to 150kHz.
It was below. ESR at resonance point (540kHz)
was 32 mΩ.
次に、このコンデンサ素子をエポキシ樹脂中に浸漬し、
１５０℃、３０分間の加熱硬化をおこなって外装を施し
てコンデンサを完成させた。完成したコンデンササンプ
ルにつき、コンデンサ素子と同様に容量、ｔａｎδおよ
びＥＳＲの測定を行った。Next, this capacitor element is immersed in epoxy resin,
The capacitor was completed by heating and curing at 150° C. for 30 minutes and applying an exterior cover. The capacitance, tan δ, and ESR of the completed capacitor sample were measured in the same manner as the capacitor element.
１２０Ｈｚにおける容量およびｔａｎδは外装前とほぼ
同じで、それぞれ７．５４μＦおよび０．０１以下であ
り、また、共振点におけるＥＳＲは３４ｍΩであった。The capacitance and tan δ at 120 Hz were almost the same as before packaging, being 7.54 μF and 0.01 or less, respectively, and the ESR at the resonance point was 34 mΩ.
緒特性の周波数依存性についても樹脂外装の前後におい
て変化は無かった。There was also no change in the frequency dependence of the mechanical properties before and after the resin coating.
さらに、このコンデンササンプルについて１５０℃での
加熱を行い、そのＥＳＲの変化を測定した。Further, this capacitor sample was heated at 150° C., and the change in ESR was measured.
５００時間経過した後の共振点におけるＥＳＲは３８ｍ
Ωであった。ESR at resonance point after 500 hours is 38m
It was Ω.
比較例１
デシケータ内でサンプルを減圧乾燥した後、常圧に戻す
際に空気を導入した以外は実施例１と同様にしてコンデ
ンササンプルを作製した。樹脂モールド前のコンデンサ
素子は、１２０１１ｚにおいて７，４５μＦの静電容量
を有し、ｔａｎδは０，０１以下であった。静電容量の
変化率は３００ｋｔｌｚまで１０％以下であり、共振点
（５６０ｋＨｚ）におけるＥＳＲは３５ｍΩであった。Comparative Example 1 A capacitor sample was produced in the same manner as in Example 1, except that after drying the sample under reduced pressure in a desiccator, air was introduced when returning to normal pressure. The capacitor element before resin molding had a capacitance of 7.45 μF at 12011z, and tan δ was 0.01 or less. The rate of change in capacitance was 10% or less up to 300 ktlz, and the ESR at the resonance point (560 kHz) was 35 mΩ.
このコンデンサ素子をエポキシ樹脂で外装すると、１２
０１（ｚにおける容量およびｔａｎδの値は樹脂０
モールド前と同じであったものの、静電容量の変化率は
３０ｋＨｚより上の周波数領域で１０％以上の減少を示
し、共振点（５６０ｋＨｚ）におけるＥＳＲも７６ｍΩ
と増大した。When this capacitor element is covered with epoxy resin, 12
Although the capacitance and tan δ values at 01 (z were the same as before resin 0 molding, the rate of change in capacitance decreased by more than 10% in the frequency range above 30 kHz, and the ESR at the resonance point (560 kHz) decreased. Also 76mΩ
and increased.
このコンデンササンプルを１５０℃で加熱すると、加熱
開始から２００時間経過した時点で、共振点におけるＥ
ＳＲが２．８Ωと、コンデンサ素子のときの８０倍にま
で増大した。また、これに伴い、周波数特性も劣化して
おり、その静電容量は１０ｋＨｚにおいて、１２０）ｉ
ｚでの値の８０％にまで減少した。When this capacitor sample is heated at 150°C, the E at the resonance point is
The SR was 2.8Ω, which was 80 times higher than when using a capacitor element. Additionally, along with this, the frequency characteristics have also deteriorated, and the capacitance is 120)i at 10kHz.
It decreased to 80% of the value at z.
比較例２
比較例１と同様の方法によりコンデンササンプルを作製
した。樹脂モールド前のコンデンサ素子は、１２０Ｈｚ
において７．５２μＦの静電容量を有し、ｔａｎδは０
．０１以下であった。静電容量の変化率は３００ｋＨｚ
まで１０％以下であり、共振点（５６０ｋＨｚ）におけ
るＥＳＲは４３ｍΩであった。Comparative Example 2 A capacitor sample was produced in the same manner as Comparative Example 1. The capacitor element before resin molding is 120Hz
has a capacitance of 7.52 μF and tan δ is 0
．． It was 01 or less. The rate of change of capacitance is 300kHz
The ESR at the resonance point (560 kHz) was 43 mΩ.
このコンデンサ素子を、エポキシ樹脂中に浸漬し、Ｎ２
雰囲気下１５０℃、３０分間加熱硬化を行い外装すると
、１２０Ｈｚにおける静電容量およびｊａｎδ■
の値は樹脂モールド前と同じであったものの、静電容量
の変化率は２５ｋＨｚ以上の周波数領域で１０％以上の
減少を示し、共振点（５６０ｋＨｚ）におけるＥＳＲは
９３ｍΩと増大した。This capacitor element is immersed in epoxy resin and N2
When the capacitance was heat-cured for 30 minutes at 150℃ in an atmosphere and packaged, the capacitance at 120Hz and the value of janδ■ were the same as before resin molding, but the rate of change in capacitance was 10% in the frequency range of 25kHz or higher. The ESR at the resonance point (560 kHz) increased to 93 mΩ.
さらに、これをＮ２雰囲気下、１５０℃で加熱すると、
加熱開始から２００時間経過した時点で、共振点におけ
るＥＳＲが１，２Ωと、コンデンサ素子のときの３０倍
にまで増大した。また、これに伴い、周波数特性も劣化
しており、その静電容量は１０ｋＨｚにおいて、１２０
Ｈｚでの値の８０％にまで減少した。Furthermore, when this is heated at 150°C under N2 atmosphere,
After 200 hours had passed from the start of heating, the ESR at the resonance point had increased to 1.2Ω, which was 30 times that of the capacitor element. Along with this, the frequency characteristics have also deteriorated, and the capacitance is 120 at 10kHz.
It decreased to 80% of the value in Hz.
実施例２
直径２ｍｍ、高さ２ｍｍの円柱状のタンタル微粉焼結体
ペレット（空隙率５０％〉を、硝酸水溶液中、１００Ｖ
で陽極酸化し、表面に酸化皮膜を形成させた。このペレ
ットを用いて、実施例１と同様の操作を行いタンタル固
体電解コンデンサを完成させた。Example 2 A cylindrical tantalum fine powder sintered body pellet (porosity 50%) with a diameter of 2 mm and a height of 2 mm was heated at 100 V in an aqueous nitric acid solution.
was anodized to form an oxide film on the surface. Using this pellet, the same operation as in Example 1 was carried out to complete a tantalum solid electrolytic capacitor.
樹脂モールド前のコンデンサ素子は、１２０Ｈｚにおい
て、静電容量４．８６μＦおよびｔａｎδは０．０１以
下であった。このコンデンサ素子の静電容量の変化率は
３００ｋＨｚまで１０％以下、またｔａｎδも２００ｋ
Ｈｚまで０，１以下であった。また、共振点（７６０ｋ
）ｌｚ）におけるＥＳＲは６８ｍΩであった。The capacitor element before resin molding had a capacitance of 4.86 μF and a tan δ of 0.01 or less at 120 Hz. The rate of change in capacitance of this capacitor element is less than 10% up to 300kHz, and the tan δ is also 200k.
It was below 0.1 Hz. Also, the resonance point (760k
) lz) was 68 mΩ.
これをエポキシ樹脂により外装したコンデンササンプル
につき、静電容量、ｔａｎδおよびＥＳＲを測定した。Capacitance, tan δ and ESR were measured for the capacitor sample which was packaged with epoxy resin.
１２（ＩＩ（ｚにおける容量およびｔａ’ｎδはそれぞ
れ４．８５μＦおよび０．０１以下であり、また、共振
点（７６０ｋｔｌｚ）におけるＥＳＲは６３ｍΩであっ
た。The capacitance at 12(II(z) and ta'nδ were 4.85 μF and 0.01 or less, respectively, and the ESR at the resonance point (760 ktlz) was 63 mΩ.
これらの緒特性の周波数依存性についても樹脂外装の前
後での変化は無かった。There was no change in the frequency dependence of these characteristics before and after the resin coating.
さらに、これを１５０℃で加熱を行い、そのＥＳＲの経
時変化を測定したが、加熱開始から５００時間後のＥＳ
Ｒは７１ｍΩと小さいものであった。Furthermore, this was heated at 150°C and the change in ESR over time was measured.
R was as small as 71 mΩ.
実施例３
実施例１で用いたのと同じリード付アルミ化戊箔上でポ
リピロールの電解酸化重合を行い、アルミ箔の微細孔内
をポリピロールで充填した。これを、メタノールで洗浄
し、デシケータ中で減圧乾燥を行った後、デシケータ内
に酸素の濃度が１容量％以下であるＡｒガスを導入して
常圧に戻した。Example 3 Polypyrrole was electrolytically oxidized and polymerized on the same leaded aluminized foil used in Example 1, and the micropores of the aluminum foil were filled with polypyrrole. After washing this with methanol and drying under reduced pressure in a desiccator, Ar gas having an oxygen concentration of 1% by volume or less was introduced into the desiccator to return to normal pressure.
３
次いで、実施例１と同様に銀ペーストを用いて陰極リー
ドを取付け、コンデンサ素子を組み上げた。3 Next, as in Example 1, a cathode lead was attached using silver paste, and a capacitor element was assembled.
得られたコンデンサ素子は、１２０Ｈｚにおいて７．４
５μＦの静電容量を有し、ｔａｎδは０．０１以下であ
った。静電容量の変化率は２７０ｋＨｚまで１０％以下
、またｔａｎδも１７０ｋｔｌｚまで０．１以下であっ
た。このコンデンサ素子の共振点（５４０ｋｔｌｚ）に
おけるＥＳＲは２９ｍΩであった。The resulting capacitor element has a frequency of 7.4 at 120Hz.
It had a capacitance of 5 μF, and tan δ was 0.01 or less. The rate of change in capacitance was 10% or less up to 270 kHz, and tan δ was also 0.1 or less up to 170 ktlz. The ESR at the resonance point (540 ktlz) of this capacitor element was 29 mΩ.
次に、このコンデンサ素子を実施例１と同様に大気中で
外装を施してコンデンサを完成させた。Next, this capacitor element was packaged in the atmosphere in the same manner as in Example 1 to complete a capacitor.
完成したコンデンササンプルにつき、コンデンサ素子と
同様に、容量ｔａｎδおよびＥＳＲの測定を行った。１
２０Ｈｚにおける容量およびｔａｎδはそれぞれ７．４
５μＦおよび０．０１以下であり、また、共振点におけ
るＥＳＲは３１ｍΩであり、これらの緒特性の周波数依
存性についても樹脂外装の前後において特性に変化が無
かった。The capacitance tan δ and ESR of the completed capacitor sample were measured in the same manner as for the capacitor element. 1
Capacity and tanδ at 20Hz are each 7.4
The ESR at the resonance point was 5 μF and 0.01 or less, and the ESR at the resonance point was 31 mΩ, and there was no change in the frequency dependence of these characteristics before and after the resin coating.
さらにこのコンデンササンプルについて１５０℃での加
熱を行い、そのＥＳＲの経時変化を測定した。加熱開始
５００時間後における共振点における４
ＥＳＲは３６ｍΩで、加熱によるＥＳＲの増加が極めて
小さかった。Further, this capacitor sample was heated at 150° C., and the change in ESR over time was measured. 4 ESR at the resonance point 500 hours after the start of heating was 36 mΩ, and the increase in ESR due to heating was extremely small.
以上説明したように、本発明によれば、耐熱性および耐
候性に優れた固体電解コンデンサを製造することができ
、その効果は大である。As explained above, according to the present invention, a solid electrolytic capacitor with excellent heat resistance and weather resistance can be manufactured, and the effects thereof are significant.
５5
Claims (1)
成する工程、この誘電体層上に陰極として複素環式化合
物の酸化重合体よりなる導電性高分子層を積層する工程
、およびこの導電性高分子層上に導電体層を積層する工
程を含みコンデンサ素子を作製する工程と、このコンデ
ンサ素子を外装封止してコンデンサを作製する工程とを
備えた固体電解コンデンサの製造方法において、 前記コンデンサ素子の作製時およびまたは作製後外装封
止前に、そのコンデンサ素子内の空隙中に酸素の濃度が
１容量％以下である不活性ガスを導入する工程を備えた ことを特徴とする固体電解コンデンサの製造方法。1. A step of forming a dielectric layer made of an oxide film on the surface of the film-forming metal, a step of laminating a conductive polymer layer made of an oxidized polymer of a heterocyclic compound as a cathode on the dielectric layer, and a step of laminating the conductive polymer layer made of an oxidized polymer of a heterocyclic compound on the dielectric layer. A method for manufacturing a solid electrolytic capacitor, comprising a step of manufacturing a capacitor element including a step of laminating a conductor layer on a molecular layer, and a step of manufacturing a capacitor by externally sealing the capacitor element, the capacitor element A solid electrolytic capacitor comprising a step of introducing an inert gas having an oxygen concentration of 1% by volume or less into the void in the capacitor element during the production and/or after the production and before the exterior sealing. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1267682A JPH03127813A (en) | 1989-10-13 | 1989-10-13 | Manufacture of solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1267682A JPH03127813A (en) | 1989-10-13 | 1989-10-13 | Manufacture of solid electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03127813A true JPH03127813A (en) | 1991-05-30 |
Family
ID=17448067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1267682A Pending JPH03127813A (en) | 1989-10-13 | 1989-10-13 | Manufacture of solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03127813A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0720188A2 (en) * | 1994-12-28 | 1996-07-03 | Nec Corporation | Heat resistant conducting polymer, solid electrolytic capacitor using the same and method for fabricating such capacitor |
| US5586000A (en) * | 1993-12-28 | 1996-12-17 | Nec Corporation | Solid electrolytic capacitor and process for production thereof |
| US6506007B1 (en) | 1997-12-17 | 2003-01-14 | Kawasaki Jukogyo Kabushiki Kaisha | Fastening bolt |
| JP2007281268A (en) * | 2006-04-10 | 2007-10-25 | Nichicon Corp | Solid electrolytic capacitor and its manufacturing method |
| GB2461765A (en) * | 2008-04-01 | 2010-01-20 | Avx Corp | Hermetically sealed ceramic housing for an electrolytic capacitor |
| WO2010070878A1 (en) * | 2008-12-15 | 2010-06-24 | 昭和電工株式会社 | Solid electrolytic capacitor and method for manufacturing same |
| JP2012099812A (en) * | 2010-11-01 | 2012-05-24 | Avx Corp | Solid electrolytic capacitor for high voltage and high temperature application |
| US8194395B2 (en) | 2009-10-08 | 2012-06-05 | Avx Corporation | Hermetically sealed capacitor assembly |
| US8279584B2 (en) | 2010-08-12 | 2012-10-02 | Avx Corporation | Solid electrolytic capacitor assembly |
| US8300387B1 (en) | 2011-04-07 | 2012-10-30 | Avx Corporation | Hermetically sealed electrolytic capacitor with enhanced mechanical stability |
| US8379372B2 (en) | 2011-04-07 | 2013-02-19 | Avx Corporation | Housing configuration for a solid electrolytic capacitor |
| US9508492B2 (en) | 2011-04-07 | 2016-11-29 | Avx Corporation | Manganese oxide capacitor for use in extreme environments |
| US9754730B2 (en) | 2015-03-13 | 2017-09-05 | Avx Corporation | Low profile multi-anode assembly in cylindrical housing |
| US9767964B2 (en) | 2011-04-07 | 2017-09-19 | Avx Corporation | Multi-anode solid electrolytic capacitor assembly |
| US9824826B2 (en) | 2013-05-13 | 2017-11-21 | Avx Corporation | Solid electrolytic capacitor containing conductive polymer particles |
| US9865401B2 (en) | 2012-08-30 | 2018-01-09 | Avx Corporation | Method for manufacturing solid electrolytic capacitor, and solid electrolytic capacitor |
| US9892862B2 (en) | 2013-05-13 | 2018-02-13 | Avx Corporation | Solid electrolytic capacitor containing a pre-coat layer |
| US9928963B2 (en) | 2015-03-13 | 2018-03-27 | Avx Corporation | Thermally conductive encapsulant material for a capacitor assembly |
| US10297393B2 (en) | 2015-03-13 | 2019-05-21 | Avx Corporation | Ultrahigh voltage capacitor assembly |
| US11081288B1 (en) | 2018-08-10 | 2021-08-03 | Avx Corporation | Solid electrolytic capacitor having a reduced anomalous charging characteristic |
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| US11756742B1 (en) | 2019-12-10 | 2023-09-12 | KYOCERA AVX Components Corporation | Tantalum capacitor with improved leakage current stability at high temperatures |
| US11763998B1 (en) | 2020-06-03 | 2023-09-19 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor |
-
1989
- 1989-10-13 JP JP1267682A patent/JPH03127813A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5586000A (en) * | 1993-12-28 | 1996-12-17 | Nec Corporation | Solid electrolytic capacitor and process for production thereof |
| US5951840A (en) * | 1994-12-28 | 1999-09-14 | Nec Corporation | Heat resistant conducting polymer, solid electrolytic capacitor using the same and method for fabricating such capacitor |
| EP0720188A3 (en) * | 1994-12-28 | 2001-04-04 | Nec Corporation | Heat resistant conducting polymer, solid electrolytic capacitor using the same and method for fabricating such capacitor |
| EP0720188A2 (en) * | 1994-12-28 | 1996-07-03 | Nec Corporation | Heat resistant conducting polymer, solid electrolytic capacitor using the same and method for fabricating such capacitor |
| US6506007B1 (en) | 1997-12-17 | 2003-01-14 | Kawasaki Jukogyo Kabushiki Kaisha | Fastening bolt |
| JP2007281268A (en) * | 2006-04-10 | 2007-10-25 | Nichicon Corp | Solid electrolytic capacitor and its manufacturing method |
| GB2461765B (en) * | 2008-04-01 | 2012-06-20 | Avx Corp | Hermetically sealed capacitor assembly |
| GB2461765A (en) * | 2008-04-01 | 2010-01-20 | Avx Corp | Hermetically sealed ceramic housing for an electrolytic capacitor |
| US8576544B2 (en) | 2008-04-01 | 2013-11-05 | Avx Corporation | Hermetically sealed capacitor assembly |
| US8094434B2 (en) | 2008-04-01 | 2012-01-10 | Avx Corporation | Hermetically sealed capacitor assembly |
| JP4547466B2 (en) * | 2008-12-15 | 2010-09-22 | 昭和電工株式会社 | Solid electrolytic capacitor and manufacturing method thereof |
| JPWO2010070878A1 (en) * | 2008-12-15 | 2012-05-24 | 昭和電工株式会社 | Solid electrolytic capacitor and manufacturing method thereof |
| US8529642B2 (en) | 2008-12-15 | 2013-09-10 | Showa Denko K.K. | Solid electrolytic capacitor and method for producing the same |
| WO2010070878A1 (en) * | 2008-12-15 | 2010-06-24 | 昭和電工株式会社 | Solid electrolytic capacitor and method for manufacturing same |
| US8194395B2 (en) | 2009-10-08 | 2012-06-05 | Avx Corporation | Hermetically sealed capacitor assembly |
| US8279584B2 (en) | 2010-08-12 | 2012-10-02 | Avx Corporation | Solid electrolytic capacitor assembly |
| JP2012099812A (en) * | 2010-11-01 | 2012-05-24 | Avx Corp | Solid electrolytic capacitor for high voltage and high temperature application |
| US9224541B2 (en) | 2010-11-01 | 2015-12-29 | Avx Corporation | Solid electrolytic capacitor for use in high voltage and high temperature applications |
| US8824122B2 (en) | 2010-11-01 | 2014-09-02 | Avx Corporation | Solid electrolytic capacitor for use in high voltage and high temperature applications |
| US8379372B2 (en) | 2011-04-07 | 2013-02-19 | Avx Corporation | Housing configuration for a solid electrolytic capacitor |
| US9508492B2 (en) | 2011-04-07 | 2016-11-29 | Avx Corporation | Manganese oxide capacitor for use in extreme environments |
| US8300387B1 (en) | 2011-04-07 | 2012-10-30 | Avx Corporation | Hermetically sealed electrolytic capacitor with enhanced mechanical stability |
| US9767964B2 (en) | 2011-04-07 | 2017-09-19 | Avx Corporation | Multi-anode solid electrolytic capacitor assembly |
| US9865401B2 (en) | 2012-08-30 | 2018-01-09 | Avx Corporation | Method for manufacturing solid electrolytic capacitor, and solid electrolytic capacitor |
| US9892862B2 (en) | 2013-05-13 | 2018-02-13 | Avx Corporation | Solid electrolytic capacitor containing a pre-coat layer |
| US9824826B2 (en) | 2013-05-13 | 2017-11-21 | Avx Corporation | Solid electrolytic capacitor containing conductive polymer particles |
| US9754730B2 (en) | 2015-03-13 | 2017-09-05 | Avx Corporation | Low profile multi-anode assembly in cylindrical housing |
| US9928963B2 (en) | 2015-03-13 | 2018-03-27 | Avx Corporation | Thermally conductive encapsulant material for a capacitor assembly |
| US10297393B2 (en) | 2015-03-13 | 2019-05-21 | Avx Corporation | Ultrahigh voltage capacitor assembly |
| US11081288B1 (en) | 2018-08-10 | 2021-08-03 | Avx Corporation | Solid electrolytic capacitor having a reduced anomalous charging characteristic |
| US11380492B1 (en) | 2018-12-11 | 2022-07-05 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor |
| US11756742B1 (en) | 2019-12-10 | 2023-09-12 | KYOCERA AVX Components Corporation | Tantalum capacitor with improved leakage current stability at high temperatures |
| US11763998B1 (en) | 2020-06-03 | 2023-09-19 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor |
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