JP3693299B2 - Electrolytic capacitor - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は陽極箔と陰極箔との間に、長網抄紙機にて紙層形成された高密度層と円網抄紙機にて紙層形成された低密度層とを抄紙機上で重ねて抄き合わせた電解紙を介在させて構成した電解コンデンサにかかり、特には中高圧用の電解コンデンサにおいて、耐電圧（絶縁破壊電圧）及びショート不良率を維持向上させるとともに電解液の含浸性及びインピーダンス特性をも同時に向上させるものである。
【０００２】
【従来の技術】
一般に電解コンデンサ、特にアルミ電解コンデンサは、陽極アルミ箔と陰極アルミ箔との間にセパレータとして電解紙を介在させて巻付け形成してコンデンサ素子を作成し、このコンデンサ素子を液状の電解液中に浸漬して電解質を含浸させ、封口して製作している。電解液としては通常エチレングリコール（ＥＧ），ジメチルホルムアミド（ＤＭＦ）又はγ−ブチロラクトン（ＧＢＬ）等を溶媒とし、これらの溶媒に硼酸やアジピン酸，アゼライン酸又はこれらのアンモニウム塩を溶解したものを用いてコンデンサ素子の両端から浸透させて製作している。
【０００３】
これら従来のアルミ電解コンデンサは電解紙中に電解液を含浸させているため、コンデンサとしてのインピーダンス特性、特に等価直列抵抗（以下ＥＳＲと略する）が高くなり易く、又使用中にも経時劣化するおそれがある。そのためインピーダンス特性を良くするために電解液の抵抗を下げたり、電解紙を薄くするか密度を低くすることが考えられる。しかしながら、電解液の抵抗値を下げると、アルミ箔に対して腐蝕性を与える原因となり、一方、電解紙を薄くしたり密度を低くすると、コンデンサ素子に巻き取る際にショート不良率が増大し、仮にショートしなかった場合でも製品化されて市場に出された後のショート不良率が高くなる難点がある。
【０００４】
そこで、インピーダンス特性を良くするために電解紙については構成する繊維の形状や配向性が検討され、電解紙の原料を通常の木材クラフトパルプからマニラ麻パルプ、エスパルトパルプに変更する手段が用いられている。そして、かかる原料によれば低密度紙を簡単に抄紙することができるため、インピーダンス特性が良く、しかも低密度紙であっても十分な引張強度を有しており、広く使用されて、相応の効果を挙げている。
【０００５】
しかし、これらはいずれも低密度紙であり、中高圧用の電解コンデンサのインピーダンス特性を向上するには不向きであった。従来、中高圧用の電解コンデンサにおいては耐電圧を確保するために充分な高い密度と厚さを有する電解紙が電気特性を犠牲にしても使用されているのである。
【０００６】
即ち、中高圧用の電解コンデンサに使用する電解紙は、使用電圧が高くなるほど陽極箔同士の接触による短絡事故、箔バリや端子取付部でのショートの危険性が増大するため、高叩解原料により長網抄紙機で抄紙されたピンホールの存在しない密度０．７０〜０．８８ｇ／ｃｍ3の高密度の電解紙（以下長網一重紙と略する）や長網一重紙の２枚使用のものが使用されている。特に近年、中高圧用の電解コンデンサの高信頼性化に伴い耐電圧の高い電解紙の要望が顕著となっている。
【０００７】
【発明が解決しようとする課題】
ここで、耐電圧と電解液の含浸性について述べれば次の通りである。先ず、耐電圧を向上させるためには電解紙の厚さを厚くするか、叩解度を進めた原料で密度を高くするのが通例である。電解紙の厚さを厚くすると電解液の保液性やショート不良の危険性を防止する上では有効であるが、ＥＳＲの悪化を招き、更にコンデンサ素子の大径化により小型化に対して不都合となる。一方、叩解の程度を示すＪＩＳ Ｐ ８１２１によるＣＳＦ（Ｃａｎａｄｉａｎ ＳｔａｎｄａｒｄＦｒｅｅｎｅｓｓ）の数値を小さくした原料で高密度に抄紙した電解紙は、耐電圧の向上に対しては有効であるが、繊維間の接触点が増加して繊維間空隙が減少することによりＥＳＲの悪化や電解液の含浸性を悪化させる結果となる。即ち、耐電圧を確保するために、電解紙の厚さを厚くし密度を高めると、一方においてＥＳＲの悪化と共に電解液の含浸性をも悪化させるという相反する結果となるのである。
【０００８】
よって、従来、中高圧用の電解コンデンサとして一般的に使用されている前記した０．７０〜０．８８ｇ／ｃｍ3の高密度の長網一重紙や長網一重紙の２枚使用の電解紙はＥＳＲの悪化と共に電解液の含浸性が極めて悪く、電解コンデンサ製作での生産性向上の阻害要因にもなっている。
【０００９】
そこで、出願人は先に電解紙にエンボス加工により凹状溝を幅方向に形成し含浸性を向上させた電解紙（特公昭６２−６２４５１）や、高叩解原料で抄紙した電解紙に抄紙後の二次加工によるエンボス加工により凹凸パターンを施して厚さを実質的に厚くすると共に密度を下げて、ＥＳＲと含浸性の双方を向上させた電解紙（特公平２−５２８４７）を提供し、相応の効果を発揮して好評を得ている。特に大型サイズや高信頼性の電解コンデンサへ採用されるに致っている。
【００１０】
しかしながら、これらは抄紙後の二次加工を必要とするため、種々の問題点が判明してきた。即ち、エンボスロールの加圧により強制的に紙面に凹凸を施すため、繊維劣化を免れず紙力強度が低下する。特に原紙厚さが薄く強度の弱い電解紙の場合は、エンボス加工により更に強度低下を招くため、比較的紙幅の狭いコンデンサにおいては、コンデンサ素子の巻取工程中に紙切れが発生する場合があり、返って生産性を低下させる等の問題が発生している。そのため、二次加工前の原紙の厚さが２５μｍ以下の電解紙の場合は実質上量産できていないのが現状である。更に、二次加工を必要とするため、製造工程が複雑化し、製造コストが高くなり電解紙自体が高価格となる。
【００１１】
そこで、本発明は上記事情に鑑みて、中高圧用の電解コンデンサにおいて、二次加工を施すことなく抄紙のみにて、耐電圧を維持向上させるとともに含浸性及びＥＳＲを同時に向上させて電気特性と共に生産性の高い電解コンデンサを提供することを目的とする。
【００１２】
【課題を解決するための手段】
本発明は上記目的を達成するために、陽極箔と陰極箔との間に長網抄紙機にて紙層形成された高密度層と円網抄紙機にて紙層形成された低密度層とを抄紙機上で重ねて抄き合わせた電解紙を介在してなる電解コンデンサにおいて、低密度層は、厚さが１０〜６０μｍ，密度が０．２０〜０．４０ｇ／ｃｍ ３ であるとともに原料として断面円形で硬質のコットンリンターパルプが４０％以上配合されており、高密度層は、厚さが１０〜５０μｍ，密度が０．８８〜１．００ｇ／ｃｍ ３ である構成を提供する。また、前記電解紙は全体厚さ２０〜１１０μｍ，全体密度０．５０〜０．８０ｇ／ｃｍ３である構成を提供する。
【００１３】
【作用】
上記構成の本発明によれば、高密度層と低密度層の二層構造とした電解紙を使用した電解コンデンサは高密度層の存在により電解紙全体として耐電圧を高く維持することができると共に、低密度層の存在により電解紙全体としてインピーダンス特性を向上させることができ、更に素子巻取工程を簡素化することができる。特に低密度層の原料として抄紙時の圧力によって変形し難く断面が円形状であるコットンリンターパルプを原料として使用したため、繊維が層状に積層され密度が高くなる原料との混合であっても、硬質な繊維が不均一に積層され、繊維間隙が生じて低密度抄紙が可能となる。特に高密度層を厚さ１０〜５０μｍ，密度０．８８〜１．００ｇ／ｃｍ３とし、低密度層を厚さ１０〜６０μｍ，密度０．２０〜０．４０ｇ／ｃｍ３の範囲とすることにより、電解液を含浸して繊維が膨潤しても液浸透に必要な繊維間隙を充分に保持することができて含浸性、保液性が向上されＥＳＲも良好となる。よって、これらの電解紙を使用して製作した中高圧用の電解コンデンサは、電解紙の含浸性、保液性が良好であるためエージングの際、酸化皮膜の欠陥部修復が円滑に行われ、ＥＳＲの低減化によりコンデンサの発熱が抑制されて、ガス発生を減少させることができると共に、電解紙自体が充分な耐電圧を保有しているため、エージングショート不良を格段に減少させることができる。従って従来困難とされてきた中高圧用の電解コンデンサのＥＳＲとエージングショート不良率の双方を同時に向上できると共に、コンデンサ製作の生産性をも向上させることができる。
【００１４】
【実施例】
以下に本発明の構成を各種実施例とともに説明する。本発明にかかる電解コンデンサは、長網抄紙機にて紙層形成された高密度層と、円網抄紙機にて紙層形成された低密度層とを抄紙機上で重ねて抄き合わせた電解紙（以下長網円網二重紙と略する）を介在してなる電解コンデンサにかかるものである。
【００１５】
高密度層と低密度層の二層構造からなる長網円網二重紙は、高叩解された原料で可能な限りの高密度層を形成させるか、従来と同密度域であれば厚さの厚い高密度層を形成することにより充分な耐電圧を保持することができる。同時に低密度層を逆に可能なかぎり密度を下げて十分な繊維間隙を保有した紙層として形成することにより電解液の保液性や含浸速度を向上させることができるのである。
【００１６】
長網円網二重紙の高密度層に使用する原料は特に限定はなく、高叩解が可能で高密度の紙層形成が可能な原料であれば何れであっても良く、適宜の天然繊維パルプを選択するのが適当であり、針葉樹クラフトパルプ、マニラ麻パルプ等が通常使用される。一方、低密度層に使用する原料としては、紙層形成の際の抄紙機上の圧力にて変形せず断面が円形状であって高密度化傾向のない硬質な天然繊維パルプ又は再生セルロース繊維を単独若しくはこれらの混合原料更に通常のクラフトパルプを混合したものを使用する。なお、硬質な繊維は少なくとも４０％以上配合されていることが好ましい。硬質な天然繊維としてはマニラ麻パルプ，サイザル麻パルプ，エスパルトパルプ，竹パルプ，コットンリンターパルプや、パルプ製造上公知で高αセルロースパルプを得る目的で施される冷アルカリ処理（以下マーセル化と略す）した針葉樹クラフトパルプ，広葉樹クラフトパルプ等を使用し、再生セルロース繊維としてはポリノジックレーヨン，有機溶剤紡糸レーヨン等を使用する。
【００１７】
そして、低密度層の厚みに応じて、薄く抄紙する場合には硬質で繊維径の細く、断面形状が真円のエスパルトパルプや広葉樹パルプ及びマーセル化広葉樹パルプの配合を多くし、厚く抄紙する場合には硬質で保液性が良く断面形状が円状で繊維径が比較的大きいサイザル麻パルプ，コットンリンターパルプ，マーセル化針葉樹パルプを多く配合した原料とする。
【００１８】
抄紙に際しては高密度層を長網抄紙機にて、低密度層を円網抄紙機にて抄紙するものであり、前記した原料を適度なＣＳＦの数値に叩解し、所定の厚さの低密度層を円網抄紙機にて抄紙し、長網側から抄き出される高密度層と貼り合わせ長網円網二重紙の電解紙とする。なお、電解コンデンサの電気的特性，ショート不良等に悪影響を及ぼさないように、塵やごみ、鉄微粒子が除去されていることが必要であり、原料の精選とともに除塵機により処理を施しておく必要がある。このようにして得られた電解紙を陽極アルミ箔と陰極アルミ箔との間に介在させて巻きつけ形成した後、液状の電解液を含浸させ、封口して電解コンデンサを製作する。
【００１９】
本発明は電解紙として高密度層と低密度層の二層構造を有する長網円網二重紙を使用しており、高密度層の密度が０．８８ｇ／ｃｍ３未満の場合には、高密度層の密度が耐電圧の向上のためには不足するため、長網円網二重紙全体としての耐電圧を向上させるために、低密度層に針葉樹クラフトパルプの如く断面が扁平状で抄紙した場合に繊維が積層され高密度化傾向となる原料の使用や、マニラ麻パルプ等のように比較的硬質で円形状の繊維であっても過度に叩解した原料を使用して低密度層自体の密度を高め、全体密度を高めて抄紙することが必要である。ところが、電解液の含浸工程においては、電解液はコンデンサ素子の両端からのみ浸透するので、低密度層の密度を高くすればするほど、電解液含浸による繊維の膨潤によって、繊維間隙が益々減少し、コンデンサ素子の両端部分で膨潤繊維によるパッキング作用が生じ、素子中央部まで含浸するのに非常に時間がかかると共に、電気特性が悪化する。そこで、本発明の好ましい実施例としては高密度層の密度を０．８８ｇ／ｃｍ３以上に高めることが適当である。一方含浸性の向上及びＥＳＲの向上のためには低密度層の密度が０．４０ｇ／ｃｍ３以上ではその効果が少ないため大幅に低密度とすることが適当であり、具体的には高密度層の密度が０．８８〜１．００ｇ／ｃｍ３、低密度層の密度が０．２０〜０．４０ｇ／ｃｍ３の範囲が効果が大きい。また、高密度層の厚さが１０μｍより薄くなると紙層形成は可能ではあっても、長網上での吸引脱水によるピンホールの存在しない良好な紙質を得るためには、生産性を度外視した抄紙速度の低下等、抄紙上の問題点が多くなる。逆に５０μｍよりも厚くなれば脱水困難や坪量増による繊維分散不良により地合不均一等の問題が発生してくる。そこで、高密度層の厚さが１０〜５０μｍ，低密度層の厚さが１０〜６０μｍの範囲が適当である。そして、長網円網二重紙全体として厚さ２０〜１１０μｍ，全体密度０．５０〜０．８０ｇ／ｃｍ３の範囲が適当である。現在の抄紙技術ではかかる密度０．８８ｇ／ｃｍ３以上や従来密度域でも厚さの厚い高密度層の紙層形成が可能であり、大幅に密度を低めた低密度層との抄き合わせ長網円網二重紙の製造が可能である。
【００２０】
以下に本発明にかかる電解コンデンサを得るための各種実施例及び使用した電解紙の評価結果と得られた電解コンデンサのＥＳＲ，エージングショート不良率等を測定した結果を各種比較例と対比して示す。なお各試料の各測定値は次ぎの測定方法によって行なった。
【００２１】
電解紙の評価方法
▲１▼厚さ，密度，引張強度
電解紙の厚さ，密度，引張強度はＪＩＳ Ｃ ２３０１（電解コンデンサ紙）に規定された方法で測定した。
【００２２】
▲２▼電解紙の電解液含浸後の耐電圧
５０×５０ｃｍの電解紙を所定の電解液にて１５ｍｍＨｇにて２時間真空含浸させ、更に８５℃で２時間熱処理をして測定用試料とする。次いで９９．９９％のアルミ箔をプレス成型し２０ｍｍφのアルミキャップを製作し、上部のアルミキャップ上に１００ｇの分銅をのせ、下部のアルミ平版の間に上記電解紙試料を介在させて、３０ｍＡの定電流により化成しショート発生電圧を測定した。
【００２３】
▲３▼電解紙のＥＳＲ
電解紙を３８ｍｍφに採取し、所定の電解液を１５ｍｍＨｇにて２時間真空含浸させ、更に８５℃で２時間熱処理をした後、３８ｍｍφの電極間に挟み２０℃，１０００ＨＺの周波数でＬＣＲメータによって測定した。
【００２４】
中高圧用の電解コンデンサの製作方法
陽極箔と陰極箔の間に両極が接触しないように電解紙を介在させ、アルミ箔端子を取付ながら巻取りして電解コンデンサ素子を作成した後、所定の電解液を含浸させてケースに封入し、エージングを行い、電解紙厚さ４０μｍ，５０μｍ紙は２００ＷＶ，１０００μＦの電解コンデンサを，電解紙厚さ９０μｍは４００ＷＶ，６８０μＦの電解コンデンサを製作した。
【００２５】
電解コンデンサの測定方法
▲１▼電解コンデンサ素子の含浸時間
２００ＷＶ，４００ＷＶの箔を使用して、コンデンサ素子巻を製作し、８５℃で４時間乾燥後、デシケータ内で室温まで冷却する。次いで他のデシケータ内のビーカーに入れ１５ｍｍＨｇまで減圧した後、負圧により所定の電解液をビーカー内に吸引し、ＬＣＲメーターで静電容量を測定して、箔から計算した理論容量の９８％以上になった時間を含浸時間とした。
【００２６】
▲２▼エージング中の不良率
各コンデンサ試料１００個について、定格電圧の約１１０％まで徐々に昇圧していき、エージングを行なう。この時のエージングショート，防爆弁の作動は無論、液漏れ，封口部の膨れ等の外観異常を含めたコンデンサの個数を１００個で除してショート不良率とした。
【００２７】
▲３▼ＥＳＲ（等価直列抵抗）
電解コンデンサのＥＳＲは２０℃，１０００ＨＺの周波数でＬＣＲメータによって測定した。
【００２８】
▲４▼静電容量
電解コンデンサの静電容量は温度２０℃，１２０ＨＺの周波数でＬＣＲメータで測定した。
【００２９】
▲５▼もれ電流
電解コンデンサのもれ電流はコンデンサの定格直流電圧を負荷して、５分後電流値を測定した。
【００３０】
実施例１
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ１８．３μｍ，密度０．９０５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、エスパルトパルプ６０％とマーセル化広葉樹クラフトパルプ４０％の混合原料をＣＳＦ７００ｍｌに叩解し、円網部分で厚さ１７．２μｍ，密度０．３７２ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ３５．５μｍ，全体密度０．６４７ｇ／ｃｍ3の長網円網二重紙を製作した。
【００３１】
実施例２
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２５．０μｍ，密度０．９７５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、エスパルトパルプ４０％とマーセル化広葉樹クラフトパルプ６０％の混合原料をＣＳＦ６８０ｍｌに叩解し、円網部分で厚さ１５．２μｍ，密度０．３６７ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ４０．２μｍ，全体密度０．７４５ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格２００ＷＶ，容量１０００μＦのアルミ電解コンデンサを製作した。
【００３２】
実施例３
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２５．１μｍ，密度０．９５５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、コットンリンターパルプ５０％と針葉樹クラフトパルプ５０％の混合原料をＣＳＦ７００ｍｌに叩解し、円網部分で厚さ２５．０μｍ，密度０．３２２ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ５０．１μｍ，全体密度０．６３９ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格２００ＷＶ，容量１０００μＦのアルミ電解コンデンサを製作した。
【００３３】
実施例４
マニラ麻パルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２９．５μｍ，密度０．８９５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、コットンリンターパルプ７０％と有機溶剤紡糸レーヨン３０％の混合原料をＣＳＦ７２０ｍｌに叩解し、円網部分で厚さ３０．５μｍ，密度０．２３８ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ６０．０μｍ，全体密度０．５６１ｇ／ｃｍ3の長網円網二重紙を製作した。
【００３４】
実施例５
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ３９．９μｍ，密度０．８８３ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、コットンリンターパルプ７０％とマーセル化針葉樹クラフトパルプ３０％の混合原料をＣＳＦ７００ｍｌに叩解し、円網部分で厚さ５０．２μｍ，密度０．３３７ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ９０．１μｍ，全体密度０．５７９ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格４００ＷＶ，容量６８０μＦのアルミ電解コンデンサを製作した。
【００３５】
比較例１
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．１μｍ，密度０．７４５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ３５０ｍｌに叩解した原料で厚さ１４．８μｍ，密度０．５２４ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ３４．９μｍ，全体密度０．６５１ｇ／ｃｍ3の長網円網二重紙を製作した。これは実施例１に対応させた電解紙である。
【００３６】
比較例２
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．１μｍ，密度０．８４１ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ２５０ｍｌに叩解した原料で厚さ１０．１μｍ，密度０．６２５ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ３０．２μｍ，全体密度０．７６８ｇ／ｃｍ3の長網円網二重紙を製作した後、エンボス加工にて厚さ３５．５μｍ，密度０．６５４ｇ／ｃｍ3のエンボス加工紙を製作した。これは実施例１に対応したエンボス加工の電解紙である。
【００３７】
比較例３
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．１μｍ，密度０．８６１ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ３００ｍｌに叩解した原料で厚さ２０．０μｍ，密度０．６４５ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ４０．１μｍ，全体密度０．７５３ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格２００ＷＶ，１０００μＦのアルミ電解コンデンサを製作した。これは実施例２に対応した電解紙及び電解コンデンサである。
【００３８】
比較例４
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２１．２μｍ，密度０．７７２ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ５００ｍｌに叩解した原料で厚さ２９．６μｍ，密度０．５２８ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ５０．８μｍ，全体密度０．６３０ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格２００ＷＶ，１０００μＦのアルミ電解コンデンサを製作した。これは実施例３に対応した電解紙及び電解コンデンサである。
【００３９】
比較例５
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．１μｍ，密度０．８６４ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ３００ｍｌに叩解した原料で厚さ２０．５μｍ，密度０．６５８ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ４０．６μｍ，全体密度０．７６０ｇ／ｃｍ3の長網円網二重紙を製作した後、エンボス加工にて厚さ４９．４μｍ，密度０．６２５ｇ／ｃｍ3のエンボス加工紙を製作した。ついで、この二重紙を電解紙として定格２００ＷＶ，１０００μＦのアルミ電解コンデンサを製作した。これは実施例３に対応した電解紙及び電解コンデンサである。
【００４０】
比較例６
マニラ麻パルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．２μｍ，密度０．７４５ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、マニラ麻パルプを叩解機でＣＳＦ５５０ｍｌに叩解し、円網部分で厚さ４０．０μｍ，密度０．４６５ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ６０．２μｍ，全体密度０．５５９ｇ／ｃｍ3の長網円網二重紙を製作した。これは実施例４に対応した電解紙である。
【００４１】
比較例７
針葉樹クラフトパルプを叩解機でＣＳＦ５ｍｌ以下まで叩解したものを長網の抄紙原料とし、厚さ２０．４μｍ，密度０．７６７ｇ／ｃｍ3の高密度紙を長網部分で抄紙しつつ、円網部分では針葉樹クラフトパルプをＣＳＦ６００ｍｌに叩解した原料で厚さ７０．１μｍ，密度０．５２８ｇ／ｃｍ3の紙を抄紙して抄き合せ、全体厚さ９０．５μｍ，全体密度０．５８２ｇ／ｃｍ3の長網円網二重紙を製作した。ついで、この二重紙を電解紙として定格４００ＷＶ，容量６８０μＦのアルミ電解コンデンサを製作した。これは実施例５に対応した電解紙及び電解コンデンサである。
【００４２】
以上のようにして得た実施例１〜５の電解紙の評価結果を表１に、比較例１〜７の電解紙の評価結果を表２に示す。また実施例２，３，５と比較例３，４，５，７に係わる電解コンデンサの含浸速度，エージング時のショート不良率，容量，漏れ電流，ＥＳＲの測定結果を表３に示す。
【００４３】
【表１】
【表２】
【表３】
表１，表２，表３の結果に示した通り、高密度層と硬質繊維を使用した低密度層の二層構造とした長網円網二重紙からなる電解紙を使用したことにより、耐電圧，ＥＳＲ，電解液含浸速度，エージング時のショート不良率共に優れた特性を有しており、しかも紙として充分な引張強度をも有している。特に表１の実施例１は密度を高密度層で０．８８ｇ／ｃｍ３以上のより高密度に、低密度層で０．４０ｇ／ｃｍ３以下のより低密度とした好ましい数値範囲内としたものであり、具体的には厚さ１８．３μｍ，密度０．９０５ｇ／ｃｍ３の高密度層と、硬質で繊維径の細いエスパルトパルプとマーセル化広葉樹クラフトパルプを混合し、厚さ１７．２μｍ，密度０．３７２ｇ／ｃｍ３の低密度層を抄き合せた長網円網二重紙であり、密度を高密度層で０．８８ｇ／ｃｍ３以下の０．７４５ｇ／ｃｍ３とし、低密度層で０．４０ｇ／ｃｍ３以上の０．５２４ｇ／ｃｍ３とした比較例１よりも引張強度は同等ではあるものの、耐電圧及びＥＳＲにおいて改善の効果が大きい。また、比較例２は抄紙後のエンボス加工により、実施例１と略同一の全体厚さ、密度としたものであるが、抄紙のみにより製作した実施例１の方が引張強度，ＥＳＲ共に格段に改善されている。
【００４７】
同様に実施例２は高密度側を厚さ２５．０μｍ，密度０．９７５ｇ／ｃｍ3とし、低密度側を厚さ１５．２μｍ，密度０．３６７ｇ／ｃｍ3としたものであるが、全体厚さ，密度を略同一とした比較例３に比してよりＥＳＲの改善効果が大きく、コンデンサ素子の電解液含浸速度も約１／３に短縮されている。
【００４８】
実施例３は厚さ２５．１μｍ，密度０．９５５ｇ／ｃｍ3の高密度層と硬質，高吸液性で比較的繊維径の大きいコットンリンターパルプと通常の針葉樹クラフトパルプを混合して低密度層を抄紙し抄き合せたものであり、略同一全体厚さ，密度の比較例４及び比較例５のエンボス加工紙に比してより引張強度，耐電圧，ＥＳＲ共に改善され、エージングショート不良率は０％となっている。また、含浸速度は比較例４に比較して１／２以下となり、含浸速度改善目的に製作している比較例５のエンボス加工紙とほぼ同等まで改善されている。
【００４９】
実施例４は高密度側を厚さ２９．５μｍ，密度０．８９５ｇ／ｃｍ3とし、低密度側はコットンリンターパルプと有機溶剤紡糸レーヨンを混合して、厚さ３０．５μｍ，密度０．２３８ｇ／ｃｍ3の超低密度紙を抄き合せ全体厚さ６０．０μｍ，密度０．５６１ｇ／ｃｍ3としたものである。比較例６は高密度層，低密度層共にマニラ麻パルプを使用した長網円網二重紙であるが、実施例４の方が耐電圧、ＥＳＲ共により大幅に改善されている。
【００５０】
さらに実施例５は高密度側を厚さ３９．９μｍ，密度０．８８３ｇ／ｃｍ3で高密度層を形成し、低密度側はコットンリンターパルプとマーセル化針葉樹クラフトパルプを混合して抄紙し高密度層と抄き合せ、全体厚さ９０．１μｍ，密度０．５７９ｇ／ｃｍ3として、比較例７と略同一厚さ，密度としたものであるが、耐電圧，ＥＳＲ共の改善のみならず、電解液の含浸速度は１／２に，エージングショート不良率は３％から０％により改善されている。
【００５１】
【発明の効果】
以上詳細に説明した本発明によれば、高密度層と低密度層の二層構造とした電解紙を使用したため、高密度層の存在により電解紙全体として耐電圧を高く維持することができると共に、低密度層の存在により電解紙全体としてインピーダンス特性を向上させることができ、更に素子巻取工程を簡素化することができる。特に低密度層の原料として抄紙時の圧力によって変形し難く断面が円形状であるコットンリンターパルプを原料として使用したことにより、繊維が層状に積層され密度が高くなる原料との混合であっても、硬質な繊維が不均一に積層され、繊維間隙が生じて低密度抄紙が可能となる。特に高密度層を厚さ１０〜５０μｍ，密度０．８８〜１．００ｇ／ｃｍ３とし、低密度層を厚さ１０〜６０μｍ，密度０．２０〜０．４０ｇ／ｃｍ３の範囲とすることにより、電解液を含浸して繊維が膨潤しても液浸透に必要な繊維間隙を充分に保持することができて含浸性、保液性が向上されＥＳＲも良好となる。よって、これらの電解紙を使用して製作した中高圧用の電解コンデンサは、電解紙の含浸性、保液性が良好であるためエージングの際、酸化皮膜の欠陥部修復が円滑に行われ、ＥＳＲの低減化によりコンデンサの発熱が抑制されて、ガス発生を現象させることができると共に、電解紙自体が充分な耐電圧を保有しているため、エージングショート不良を格段に減少させることができる。従って従来困難とされてきた中高圧用の電解コンデンサのＥＳＲとエージングショート不良率の双方を同時に向上できると共に、コンデンサ製作の生産性をも向上させることができる。[0001]
[Industrial application fields]
The present invention is provided between an anode foil and a cathode foil., A high-density layer formed with a paper web machine and a low-density layer formed with a circular paper machine were layered together on a paper machine.It is applied to the electrolytic capacitor constructed by interposing electrolytic paper, especially in the medium and high voltage electrolytic capacitor, maintaining and improving the withstand voltage (dielectric breakdown voltage) and short-circuit defect rate, and simultaneously impregnating electrolyte and impedance characteristics It is to improve.
[0002]
[Prior art]
In general, electrolytic capacitors, particularly aluminum electrolytic capacitors, are formed by winding electrolytic paper as a separator between an anode aluminum foil and a cathode aluminum foil to form a capacitor element, and this capacitor element is placed in a liquid electrolyte. It is manufactured by dipping and impregnating with electrolyte and sealing. As an electrolytic solution, ethylene glycol (EG), dimethylformamide (DMF), γ-butyrolactone (GBL) or the like is generally used as a solvent, and boric acid, adipic acid, azelaic acid or an ammonium salt thereof is dissolved in these solvents. It is manufactured by infiltrating from both ends of the capacitor element.
[0003]
Since these conventional aluminum electrolytic capacitors are impregnated with electrolytic solution in electrolytic paper, impedance characteristics as a capacitor, in particular, equivalent series resistance (hereinafter abbreviated as ESR) are likely to be high, and also deteriorate over time during use. There is a fear. Therefore, in order to improve the impedance characteristics, it is conceivable to reduce the resistance of the electrolytic solution, or to make the electrolytic paper thinner or lower in density. However, lowering the resistance value of the electrolytic solution causes corrosiveness to the aluminum foil. On the other hand, if the electrolytic paper is made thinner or the density is lowered, the short-circuit defect rate increases when winding the capacitor element, Even if there is no short circuit, there is a problem that the short circuit defect rate after being commercialized and put on the market becomes high.
[0004]
Therefore, in order to improve the impedance characteristics, the shape and orientation of the constituent fibers of the electrolytic paper are studied, and means for changing the raw material of the electrolytic paper from normal wood kraft pulp to Manila hemp pulp and esparto pulp are used. Yes. According to such a raw material, low-density paper can be easily made, so that impedance characteristics are good, and even low-density paper has sufficient tensile strength and is widely used. Has an effect.
[0005]
However, these are all low-density papers and are not suitable for improving the impedance characteristics of medium- and high-voltage electrolytic capacitors. Conventionally, in medium- and high-voltage electrolytic capacitors, electrolytic paper having a sufficiently high density and thickness to ensure a withstand voltage is used even at the expense of electrical characteristics.
[0006]
In other words, the electrolytic paper used for medium- and high-voltage electrolytic capacitors increases the risk of short-circuit accidents due to contact between anode foils, foil burrs, and short-circuits at terminal mounting points as the operating voltage increases. Density of 0.70 to 0.88 g / cm without pinholes made by a long paper machineThreeHigh-density electrolytic paper (hereinafter abbreviated as long net single paper) and two long net single paper are used. In particular, in recent years, the demand for electrolytic paper having a high withstand voltage has become remarkable with the increase in the reliability of electrolytic capacitors for medium and high voltages.
[0007]
[Problems to be solved by the invention]
Here, the withstand voltage and the impregnation property of the electrolytic solution are described as follows. First, in order to improve the withstand voltage, it is usual to increase the thickness of the electrolytic paper or increase the density with a raw material with advanced beating degree. Increasing the thickness of the electrolytic paper is effective in preventing electrolyte retention and risk of short-circuit failure, but it causes ESR deterioration and further increases the size of the capacitor element, which is inconvenient for downsizing. It becomes. On the other hand, an electrolytic paper made with high density with a raw material with a small CSF (Canadian Standard Freeness) value according to JIS P 8121 indicating the degree of beating is effective for improving the withstand voltage, but the contact point between fibers. As a result of the increase in the inter-fiber voids, the ESR deteriorates and the electrolyte impregnation property deteriorates. That is, when the thickness of the electrolytic paper is increased and the density is increased in order to ensure the withstand voltage, there is a conflicting result that, on the one hand, the ESR is deteriorated and the electrolyte impregnation is also deteriorated.
[0008]
Therefore, the above-described 0.70 to 0.88 g / cm, which is generally used as an electrolytic capacitor for medium and high pressures.ThreeElectrolytic paper using two sheets of high-density single-sheet long paper and single-sheet long-sheet paper has a very poor electrolyte impregnation property along with the deterioration of ESR, which has been an obstacle to productivity improvement in the production of electrolytic capacitors. .
[0009]
Therefore, the applicant first formed electrolytic grooves (Japanese Examined Patent Publication 62-62451) in which concave grooves were formed in the width direction by embossing on electrolytic paper to improve impregnation, and electrolytic paper made with high beating material after paper making. An electrolytic paper (Japanese Patent Publication No. 2-52847) is provided which has an uneven pattern formed by embossing by secondary processing to substantially increase the thickness and reduce the density, thereby improving both ESR and impregnation. Has gained popularity with its effects. In particular, it is suitable for large size and high reliability electrolytic capacitors.
[0010]
However, since these require secondary processing after papermaking, various problems have been found. That is, since the paper surface is forcibly made uneven by pressurizing the embossing roll, fiber strength is unavoidable and the paper strength is reduced. In particular, in the case of electrolytic paper with a thin base paper thickness and weak strength, the strength is further reduced by embossing, so in a capacitor with a relatively narrow paper width, a piece of paper may occur during the winding process of the capacitor element. There are problems, such as a decrease in productivity. For this reason, in the case of the electrolytic paper having a thickness of 25 μm or less before the secondary processing, the present situation is that the mass production is not practically possible. Further, since secondary processing is required, the manufacturing process is complicated, the manufacturing cost is increased, and the electrolytic paper itself is expensive.
[0011]
Therefore, in view of the above circumstances, the present invention, in an electrolytic capacitor for medium and high voltage, maintains and improves the withstand voltage and improves the impregnation and ESR at the same time with only the papermaking without performing secondary processing, together with the electrical characteristics. An object is to provide a highly productive electrolytic capacitor.
[0012]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a high-density layer in which a paper layer is formed between a positive foil and a negative foil by a long paper machine, and a low-density layer in which a paper layer is formed by a circular paper machine. In the electrolytic capacitor that interposes the electrolyzed paper that is made by layering on the paper machine,The low density layer has a thickness of 10 to 60 μm and a density of 0.20 to 0.40 g / cm. 3 As well as40% or more of hard cotton linter pulp with a circular cross section is blended as a raw materialThe high-density layer has a thickness of 10 to 50 μm and a density of 0.88 to 1.00 g / cm. 3 InProvide a configuration.Also,The electrolytic paper has an overall thickness of 20 to 110 μm and an overall density of 0.50 to 0.80 g / cm.3Provide a configuration that is
[0013]
[Action]
According to the present invention configured as described above, the electrolytic capacitor using the electrolytic paper having a two-layer structure of the high density layer and the low density layer can maintain a high withstand voltage as the entire electrolytic paper due to the presence of the high density layer. Impedance characteristics of the entire electrolytic paper can be improved due to the presence of the low-density layer, and the element winding process can be simplified.Butit can. In particular, as a raw material for the low density layer, it is difficult to be deformed by the pressure during papermaking, and the cross section is circularRucoTon Linter PalTheSince it is used as a raw material, even if it is mixed with a raw material in which the fibers are laminated in layers and the density is increased, hard fibers are laminated non-uniformly, resulting in fiber gaps and low density papermaking. In particular, the high-density layer has a thickness of 10 to 50 μm and a density of 0.88 to 1.00 g / cm.3And a low density layer having a thickness of 10 to 60 μm and a density of 0.20 to 0.40 g / cm3By setting the amount within the above range, even when the fibers are impregnated and the fibers swell, the fiber gaps necessary for liquid permeation can be sufficiently maintained, the impregnation property and the liquid retention property are improved, and the ESR is also improved. Therefore, the electrolytic capacitors for medium and high pressure produced using these electrolytic papers have good impregnation properties and liquid retention properties of the electrolytic paper, so that during the aging, defective portions of the oxide film are smoothly repaired, By reducing the ESR, heat generation of the capacitor can be suppressed and gas generation can be reduced. In addition, since the electrolytic paper itself has a sufficient withstand voltage, aging short-circuit defects can be significantly reduced. Accordingly, it is possible to simultaneously improve both the ESR and the aging short-circuit defect rate of the medium- and high-voltage electrolytic capacitors, which have been considered difficult, and to improve the productivity of capacitor production.
[0014]
【Example】
The configuration of the present invention will be described below together with various examples. According to the present inventionElectrolytic capacitors areA high-density layer with a paper layer formed by a long paper machine and a low-density layer with a paper layer formed by a circular paper machine are overlapped on the paper machine.Electrolytic paper(Hereafter, abbreviated as long web double paper)It is applied to the electrolytic capacitor formed by interposing.
[0015]
A long-mesh round double-layered paper consisting of a two-layer structure consisting of a high-density layer and a low-density layer can be formed as much as possible with a high-beaten raw material, or the thickness can be as long as the same density range as before. By forming a thick high-density layer, a sufficient withstand voltage can be maintained. At the same time, by reducing the density as much as possible and forming the paper layer as a paper layer having a sufficient fiber gap, it is possible to improve the electrolyte retention and impregnation rate.
[0016]
The raw material used for the high-density layer of the long-mesh round net double paper is not particularly limited, and any raw material can be used as long as it is capable of forming a high-density paper layer that can be beaten at high density. It is appropriate to select pulp, and softwood kraft pulp, Manila hemp pulp and the like are usually used. On the other hand, the raw material used for the low density layer is a hard natural fiber pulp or regenerated cellulose fiber that is not deformed by the pressure on the paper machine at the time of paper layer formation and has a circular cross section and does not tend to increase in density. Or a mixture of these raw materials and ordinary kraft pulp. In addition, it is preferable that hard fiber is blended at least 40% or more. Hard natural fibers include manila hemp pulp, sisal hemp pulp, esparto pulp, bamboo pulp, cotton linter pulp, and cold alkali treatment (hereinafter abbreviated as mercerization) applied for the purpose of obtaining high alpha cellulose pulp. ) Softwood kraft pulp, hardwood kraft pulp, etc. are used, and polynosic rayon, organic solvent spinning rayon, etc. are used as regenerated cellulose fibers.
[0017]
And according to the thickness of the low-density layer, when making paper thinly, increase the blend of hard and thin fiber diameter, round shape cross section of esparto pulp, hardwood pulp and mercerized hardwood pulp, and make paper thickly In some cases, it is a raw material containing a large amount of sisal hemp pulp, cotton linter pulp, and mercerized softwood pulp that is hard, has good liquid retention, has a circular cross-sectional shape, and a relatively large fiber diameter.
[0018]
When making paper, the high density layer is made with a long paper machine, and the low density layer is made with a circular paper machine. The above raw materials are beaten to an appropriate CSF value, and a low density with a predetermined thickness is obtained. The layers are made with a circular paper machine, and a high-density layer drawn from the long mesh side is bonded to an electroplated paper with a long mesh double-bonded paper. In addition, it is necessary to remove dust, dust, and iron fine particles so as not to adversely affect the electrical characteristics and short-circuit defects of the electrolytic capacitor. There is. The electrolytic paper thus obtained is wound between an anode aluminum foil and a cathode aluminum foil, and then impregnated with a liquid electrolytic solution and sealed to produce an electrolytic capacitor.
[0019]
The present invention uses a long net double paper having a two-layer structure of a high density layer and a low density layer as electrolytic paper.HaveThe density of the high-density layer is 0.88 g / cm3In the case where the density is less than that, the density of the high-density layer is insufficient for improving the withstand voltage. In the case of paper making with a flat cross section like this, the use of raw materials that tend to be dense due to the lamination of fibers, or the use of raw materials that are excessively beaten even with relatively hard and circular fibers such as Manila hemp pulp Therefore, it is necessary to increase the density of the low-density layer itself and increase the overall density to make paper. However, in the electrolytic solution impregnation step, the electrolytic solution penetrates only from both ends of the capacitor element. Therefore, the higher the density of the low density layer, the more the fiber gap is reduced due to the swelling of the fiber by the electrolytic solution impregnation. The packing action by the swollen fibers occurs at both ends of the capacitor element, and it takes a very long time to impregnate up to the center of the element, and the electrical characteristics deteriorate. Therefore, as a preferred embodiment of the present invention, the density of the high density layer is 0.88 g / cm.3It is appropriate to increase it above. On the other hand, in order to improve impregnation and ESR, the density of the low density layer is 0.40 g / cm.3Since the effect is small in the above, it is appropriate to make the density significantly low. Specifically, the density of the high-density layer is 0.88 to 1.00 g / cm.3The density of the low density layer is 0.20 to 0.40 g / cm.3The range is very effective. In addition, although the paper layer can be formed when the thickness of the high-density layer is less than 10 μm, in order to obtain good paper quality without pinholes due to suction dewatering on a long net, productivity was ignored. There are many problems on paper making, such as a decrease in paper making speed. On the other hand, if it becomes thicker than 50 μm, problems such as uneven formation occur due to difficulty in dehydration and poor fiber dispersion due to increased basis weight. Therefore, it is appropriate that the high density layer has a thickness of 10 to 50 μm and the low density layer has a thickness of 10 to 60 μm. And, as a whole of the long-mesh circular double paper, the thickness is 20 to 110 μm, and the overall density is 0.50 to 0.80 g / cm.3The range of is appropriate. With the current papermaking technology, this density is 0.88 g / cm.3As described above, it is possible to form a thick high-density paper layer even in the conventional density region, and it is possible to manufacture a long-mesh double-sheet double paper by combining with a low-density layer having a significantly reduced density.
[0020]
The various examples for obtaining the electrolytic capacitor according to the present invention and the evaluation results of the electrolytic paper used and the results of measuring the ESR, the aging short defect rate, etc. of the obtained electrolytic capacitor are shown in comparison with various comparative examples. . In addition, each measured value of each sample was performed by the following measuring method.
[0021]
Electrolytic paper evaluation method
(1) Thickness, density, tensile strength
The thickness, density, and tensile strength of the electrolytic paper were measured by the methods specified in JIS C 2301 (electrolytic capacitor paper).
[0022]
(2) Withstand voltage after electrolytic paper impregnation with electrolytic paper
A 50 × 50 cm electrolytic paper is vacuum impregnated with a predetermined electrolytic solution at 15 mmHg for 2 hours, and further heat-treated at 85 ° C. for 2 hours to obtain a measurement sample. Next, a 99.99% aluminum foil was press-molded to produce a 20 mmφ aluminum cap, a 100 g weight was placed on the upper aluminum cap, and the electrolytic paper sample was interposed between the lower aluminum lithographic plates, and a current of 30 mA was obtained. A short-circuit occurrence voltage was measured by formation with a constant current.
[0023]
(3) Electrolytic paper ESR
Take the electrolytic paper to 38mmφ, vacuum impregnate the prescribed electrolyte solution at 15mmHg for 2 hours, heat-treat at 85 ° C for 2 hours, then sandwich between 38mmφ electrodes and measure with LCR meter at 20 ° C and 1000HZ frequency did.
[0024]
Manufacturing method of medium and high voltage electrolytic capacitors
An electrolytic paper is interposed between the anode foil and the cathode foil so that both electrodes do not contact each other, and an electrolytic capacitor element is created by winding while attaching an aluminum foil terminal, and then impregnated with a predetermined electrolyte and sealed in a case. Aging was performed, and electrolytic capacitors having a thickness of 40 μm and 50 μm were manufactured as electrolytic capacitors of 200 WV and 1000 μF, and an electrolytic capacitor having a thickness of 90 μm as 400 WV and 680 μF.
[0025]
Electrolytic capacitor measurement method
(1) Impregnation time of electrolytic capacitor element
Capacitor element windings are manufactured using 200 WV and 400 WV foils, dried at 85 ° C. for 4 hours, and then cooled to room temperature in a desiccator. Next, after putting in a beaker in another desiccator and reducing the pressure to 15 mmHg, a predetermined electrolytic solution is sucked into the beaker by negative pressure, and the electrostatic capacity is measured with an LCR meter. More than 98% of the theoretical capacity calculated from the foil The time at which this was reached was taken as the impregnation time.
[0026]
(2) Defect rate during aging
About 100 capacitor samples, the pressure is gradually increased to about 110% of the rated voltage, and aging is performed. The operation of the aging short and explosion-proof valve at this time is, of course, the number of capacitors including the appearance abnormality such as liquid leakage and the swelling of the sealing part is divided by 100 to obtain the short-circuit defect rate.
[0027]
(3) ESR (Equivalent Series Resistance)
The ESR of the electrolytic capacitor was measured with an LCR meter at 20 ° C. and a frequency of 1000 HZ.
[0028]
(4) Capacitance
The capacitance of the electrolytic capacitor was measured with an LCR meter at a temperature of 20 ° C. and a frequency of 120 HZ.
[0029]
(5) Leakage current
For the leakage current of the electrolytic capacitor, the rated DC voltage of the capacitor was loaded, and the current value was measured after 5 minutes.
[0030]
Example 1
Conifer kraft pulp beaten to a CSF of 5ml or less with a beating machine is used as a papermaking material for a long net, thickness 18.3μm, density 0.905g / cmThreeWhile making a paper of a high-density paper with a long mesh portion, a mixed raw material of 60% esparto pulp and 40% mercerized hardwood kraft pulp was beaten into 700 ml of CSF, and the circular mesh portion had a thickness of 17.2 μm and a density of 0.372 g / cmThreePaper and paper together, the overall thickness is 35.5μm, the overall density is 0.647g / cmThreeMade a long web of double mesh paper.
[0031]
Example 2
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long net, thickness 25.0 μm, density 0.975 g / cmThreeWhile making a high density paper with a long mesh part, beat mixed raw material of 40% esparto pulp and 60% mercerized hardwood kraft pulp into 680 ml of CSF, and the thickness of the circular mesh part is 15.2 μm and the density is 0.367 g / cmThreePaper and paper together, the total thickness is 40.2μm, the overall density is 0.745g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 200 WV and a capacity of 1000 μF was manufactured using this double paper as electrolytic paper.
[0032]
Example 3
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beating machine is used as a papermaking raw material for a long net, thickness 25.1 μm, density 0.955 g / cmThreeWhile making high-density paper with a long mesh part, a mixed raw material of 50% cotton linter pulp and 50% softwood kraft pulp was beaten into 700 ml of CSF, and the thickness of the circular mesh part was 25.0 μm and the density was 0.322 g / cm.ThreePaper and paper together, the overall thickness is 50.1μm, the overall density is 0.639g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 200 WV and a capacity of 1000 μF was manufactured using this double paper as electrolytic paper.
[0033]
Example 4
Manila hemp pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long net, thickness 29.5 μm, density 0.895 g / cmThreeWhile making a paper of high density paper with a long mesh part, a mixed raw material of 70% cotton linter pulp and 30% organic solvent spinning rayon was beaten into 720 ml of CSF, and the thickness of the circular mesh part was 30.5 μm and the density was 0.238 g / cmThreePaper and paper together, total thickness 60.0μm, total density 0.561g / cmThreeMade a long web of double mesh paper.
[0034]
Example 5
Conifer kraft pulp beaten to a CSF of 5 ml or less with a beating machine is used as a papermaking material for a long net, thickness 39.9 μm, density 0.883 g / cmThreeWhile making a paper of high density paper with a long mesh portion, a mixed raw material of 70% cotton linter pulp and 30% mercerized softwood kraft pulp was beaten into 700 ml of CSF, and the thickness of the circular mesh portion was 50.2 μm and the density was 0.337 g / cmThreePaper and paper together, the overall thickness is 90.1μm, the overall density is 0.579g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 400 WV and a capacity of 680 μF was manufactured using this double paper as electrolytic paper.
[0035]
Comparative Example 1
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beating machine is used as a papermaking raw material for a long net, thickness 20.1 μm, density 0.745 g / cmThreeWhile making high-density paper with a long mesh portion, the circular mesh portion is made of a raw material obtained by beating softwood kraft pulp into 350 ml of CSF, and has a thickness of 14.8 μm and a density of 0.524 g / cm.ThreePaper and paper together, the total thickness 34.9μm, the overall density 0.651g / cmThreeMade a long web of double mesh paper. This is an electrolytic paper corresponding to Example 1.
[0036]
Comparative Example 2
Coniferous kraft pulp beaten to a CSF of 5ml or less with a beater is used as a papermaking raw material for a long net, thickness 20.1μm, density 0.841g / cmThreeWhile making a high-density paper with a long mesh portion, the circular mesh portion is made of a raw material obtained by beating softwood kraft pulp into 250 ml of CSF and having a thickness of 10.1 μm and a density of 0.625 g / cm.ThreePaper and paper together, the overall thickness is 30.2μm, the overall density is 0.768g / cmThreeAfter producing a long-mesh round double paper, the thickness was 35.5 μm and the density was 0.654 g / cm by embossing.ThreeOf embossed paper. This is an embossed electrolytic paper corresponding to Example 1.
[0037]
Comparative Example 3
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long net, thickness 20.1 μm, density 0.861 g / cmThreeWhile making high-density paper with a long mesh portion, the circular mesh portion is made of a raw material obtained by beating softwood kraft pulp into 300 ml of CSF, and has a thickness of 20.0 μm and a density of 0.645 g / cm.ThreePaper and paper together, the total thickness is 40.1μm, the overall density is 0.753g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 200 WV and 1000 μF was manufactured using this double paper as electrolytic paper. This is an electrolytic paper and an electrolytic capacitor corresponding to Example 2.
[0038]
Comparative Example 4
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long net, thickness 21.2 μm, density 0.772 g / cmThreeWhile making high-density paper with a long mesh portion, the circular mesh portion is made of a raw material obtained by beating softwood kraft pulp into CSF 500 ml, thickness 29.6 μm, density 0.528 g / cmThreePaper and paper together, total thickness 50.8μm, total density 0.630g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 200 WV and 1000 μF was manufactured using this double paper as electrolytic paper. This is an electrolytic paper and an electrolytic capacitor corresponding to Example 3.
[0039]
Comparative Example 5
Coniferous kraft pulp beaten to a CSF of 5ml or less with a beater is used as a papermaking raw material for a long net, thickness 20.1μm, density 0.864g / cmThreeWhile making high-density paper with a long mesh portion, the circular mesh portion is made of a raw material obtained by beating coniferous kraft pulp into 300 ml of CSF and has a thickness of 20.5 μm and a density of 0.658 g / cm.ThreePaper and paper together, the overall thickness is 40.6μm, the overall density is 0.760g / cmThreeAfter manufacturing a long-mesh circular double paper, the thickness was 49.4 μm and the density was 0.625 g / cm by embossing.ThreeOf embossed paper. Next, an aluminum electrolytic capacitor having a rating of 200 WV and 1000 μF was manufactured using this double paper as electrolytic paper. This is an electrolytic paper and an electrolytic capacitor corresponding to Example 3.
[0040]
Comparative Example 6
Manila hemp pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long net, thickness 20.2 μm, density 0.745 g / cmThreeWhile making high-density paper with a long mesh part, Manila hemp pulp was beaten to 550 ml of CSF with a beater, and the thickness of the circular mesh part was 40.0 μm and the density was 0.465 g / cm.ThreePaper and paper together, the overall thickness is 60.2μm, the overall density is 0.559g / cmThreeMade a long web of double mesh paper. This is an electrolytic paper corresponding to Example 4.
[0041]
Comparative Example 7
Coniferous kraft pulp beaten to a CSF of 5 ml or less with a beater is used as a papermaking raw material for a long web, thickness 20.4 μm, density 0.767 g / cmThreeWhile making a high-density paper with a long mesh part, the circular mesh part is made of a raw material obtained by beating softwood kraft pulp into 600 ml of CSF, and has a thickness of 70.1 μm and a density of 0.528 g / cm.ThreePaper and paper together, total thickness 90.5μm, total density 0.582g / cmThreeMade a long web of double mesh paper. Next, an aluminum electrolytic capacitor having a rating of 400 WV and a capacity of 680 μF was manufactured using this double paper as electrolytic paper. This is an electrolytic paper and an electrolytic capacitor corresponding to Example 5.
[0042]
The evaluation results of the electrolytic papers of Examples 1 to 5 obtained as described above are shown in Table 1, and the evaluation results of the electrolytic papers of Comparative Examples 1 to 7 are shown in Table 2. Table 3 shows the measurement results of the electrolytic capacitor impregnation rate, the short-circuit failure rate during aging, the capacity, the leakage current, and the ESR according to Examples 2, 3, and 5 and Comparative Examples 3, 4, 5, and 7.
[0043]
[Table 1]
[Table 2]
[Table 3]
As shown in the results of Table 1, Table 2, and Table 3, electrolytic paper made of a long-mesh circular double paper having a two-layer structure of a high-density layer and a low-density layer using hard fibers was used.ByIn addition, it has excellent characteristics such as withstand voltage, ESR, electrolyte impregnation rate, and short-circuit defect rate during aging, and also has sufficient tensile strength as paper. In particular, in Example 1 of Table 1, the density is 0.88 g / cm in the high density layer.30.40 g / cm for the higher density and lower density layer3The lower density is within the preferable numerical range described below. Specifically, the thickness is 18.3 μm and the density is 0.905 g / cm.3A high-density layer, hard and thin esparto pulp and mercerized hardwood kraft pulp are mixed, thickness 17.2 μm, density 0.372 g / cm3A long-mesh round double-layered paper made by combining low-density layers with a density of 0.88 g / cm for the high-density layer.30.745g / cm below3And 0.40 g / cm for the low density layer30.524g / cm above3Although the tensile strength is equal to that of Comparative Example 1 described above, the effect of improving the withstand voltage and ESR is large. In Comparative Example 2, the overall thickness and density were substantially the same as in Example 1 by embossing after paper making, but Example 1 produced only by paper making has much higher tensile strength and ESR. It has been improved.
[0047]
Similarly, in Example 2, the high density side has a thickness of 25.0 μm and a density of 0.975 g / cm.ThreeThe low density side is 15.2 μm thick and the density is 0.367 g / cm.ThreeHowever, the effect of improving ESR is greater than that of Comparative Example 3 in which the overall thickness and density are substantially the same, and the electrolytic solution impregnation rate of the capacitor element is shortened to about 1/3.
[0048]
Example 3 has a thickness of 25.1 μm and a density of 0.955 g / cm.ThreeA high density layer and a hard, highly liquid absorbent cotton linter pulp with a relatively large fiber diameter and ordinary softwood kraft pulp are mixed together to produce a low density layer, which are combined, and have approximately the same overall thickness. Compared with the embossed paper of density comparative example 4 and comparative example 5, the tensile strength, withstand voltage and ESR are improved, and the aging short-circuit defect rate is 0%. Further, the impregnation speed is ½ or less compared with Comparative Example 4, which is improved to almost the same as the embossed paper of Comparative Example 5 manufactured for the purpose of improving the impregnation speed.
[0049]
In Example 4, the high density side has a thickness of 29.5 μm and a density of 0.895 g / cm.ThreeOn the low density side, cotton linter pulp and organic solvent spinning rayon are mixed to obtain a thickness of 30.5 μm and a density of 0.238 g / cm.ThreeMade of ultra-low density paper, total thickness 60.0μm, density 0.561g / cmThreeIt is what. Comparative Example 6 is a long-mesh circular double paper using Manila hemp pulp for both the high-density layer and the low-density layer, but Example 4 is greatly improved by both withstand voltage and ESR.
[0050]
Further, in Example 5, the high density side has a thickness of 39.9 μm and a density of 0.883 g / cm.ThreeA high density layer is formed on the low density side, and the paper is made by mixing cotton linter pulp and mercerized softwood kraft pulp, and combined with the high density layer, the total thickness is 90.1 μm, the density is 0.579 g / cmThreeAs in Comparative Example 7, the thickness and density were almost the same, but not only the improvement in the withstand voltage and ESR, but also the electrolyte impregnation rate was reduced to 1/2, and the aging short-circuit defect rate was from 3% to 0. %.
[0051]
【The invention's effect】
According to the present invention described in detail above, since the electrolytic paper having a two-layer structure of the high-density layer and the low-density layer is used, the withstand voltage can be maintained high as the entire electrolytic paper due to the presence of the high-density layer. The presence of the low-density layer can improve the impedance characteristics of the entire electrolytic paper, and can further simplify the element winding process. In particular, as a raw material for the low density layer, it is difficult to be deformed by the pressure during papermaking, and the cross section is circularRucoTon Linter PalTheBy using it as a raw material, even when mixing with a raw material in which fibers are laminated in layers and the density is increased, hard fibers are laminated non-uniformly, resulting in fiber gaps and low density papermaking. In particular, the high-density layer has a thickness of 10 to 50 μm and a density of 0.88 to 1.00 g / cm.3And a low density layer having a thickness of 10 to 60 μm and a density of 0.20 to 0.40 g / cm3By setting the amount within the above range, even when the fibers are impregnated and the fibers swell, the fiber gaps necessary for liquid permeation can be sufficiently maintained, the impregnation property and the liquid retention property are improved, and the ESR is also improved. Therefore, the electrolytic capacitors for medium and high pressure produced using these electrolytic papers have good impregnation properties and liquid retention properties of the electrolytic paper, so that during the aging, defective portions of the oxide film are smoothly repaired, By reducing the ESR, heat generation of the capacitor can be suppressed and gas generation can be caused, and since the electrolytic paper itself has a sufficient withstand voltage, aging short-circuit defects can be significantly reduced. Accordingly, it is possible to simultaneously improve both the ESR and the aging short-circuit defect rate of the medium- and high-voltage electrolytic capacitors, which have been considered difficult, and to improve the productivity of capacitor production.
Claims (2)
低密度層は、厚さが１０〜６０μｍ，密度が０．２０〜０．４０ｇ／ｃｍ ３ であるとともに原料として断面円形で硬質のコットンリンターパルプが４０％以上配合されており、高密度層は、厚さが１０〜５０μｍ，密度が０．８８〜１．００ｇ／ｃｍ ３ であることを特徴とする電解コンデンサ。Between the anode foil and the cathode foil, a high-density layer formed with a paper web machine and a low-density layer formed with a circular paper machine are overlapped on the paper machine and laminated together. In electrolytic capacitors that are made by interposing electrolytic paper,
The low-density layer has a thickness of 10 to 60 [mu] m, density has been formulated hard cotton linter pulp 40% or more circular cross section as a starting material with a 0.20~0.40g / cm 3, high density layer electrolytic capacitor thickness of 10 to 50 [mu] m, density, wherein 0.88~1.00g / cm 3 der Rukoto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34151892A JP3693299B2 (en) | 1992-11-27 | 1992-11-27 | Electrolytic capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34151892A JP3693299B2 (en) | 1992-11-27 | 1992-11-27 | Electrolytic capacitor |
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| Publication Number | Publication Date |
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| JPH06168848A JPH06168848A (en) | 1994-06-14 |
| JP3693299B2 true JP3693299B2 (en) | 2005-09-07 |
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| JP34151892A Expired - Lifetime JP3693299B2 (en) | 1992-11-27 | 1992-11-27 | Electrolytic capacitor |
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