JP2022143093A - Separator for solid electrolytic capacitor and solid electrolytic capacitor - Google Patents
Separator for solid electrolytic capacitor and solid electrolytic capacitor Download PDFInfo
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Abstract
Description
本発明は、固体電解コンデンサ用セパレータ及び固体電解コンデンサに関する。以下、「固体電解コンデンサ用セパレータ」を「セパレータ」と略記する場合がある。また、「固体電解コンデンサ」を「コンデンサ」と略記する場合がある。 The present invention relates to a solid electrolytic capacitor separator and a solid electrolytic capacitor. Hereinafter, "separator for solid electrolytic capacitor" may be abbreviated as "separator". Also, "solid electrolytic capacitor" may be abbreviated as "capacitor".
固体電解質として、ポリピロールやポリチオフェンなどの導電性高分子を用いる固体電解コンデンサ（固体電解キャパシタ）では、箔状の陽極電極及び陰極電極を、セパレータを介して巻き取り、巻回素子を形成し、この巻回素子中のセパレータに導電性高分子の重合液を含浸させて重合させたり、導電性高分子分散液を含浸させたりすることによって、セパレータを覆う導電性高分子膜が形成される。 In a solid electrolytic capacitor (solid electrolytic capacitor) using a conductive polymer such as polypyrrole or polythiophene as a solid electrolyte, a foil-shaped anode electrode and a cathode electrode are wound up with a separator interposed therebetween to form a wound element. A conductive polymer film covering the separators is formed by impregnating the separators in the wound element with a polymerized liquid of the conductive polymer for polymerization or by impregnating the separators with a conductive polymer dispersion.
従来、コンデンサのセパレータとしては、エスパルトや麻パルプなどの天然セルロース繊維、溶剤紡糸セルロース繊維、再生セルロース繊維等のセルロース繊維の叩解物を主体とする紙製セパレータが使用されている（特許文献１及び２）。これら紙セパレータ中のセルロース繊維は、導電性高分子を重合する際に用いる酸化剤と反応して導電性高分子の重合を阻害することから、重合を阻害しないように、予め炭化処理が施される。炭化処理によって紙製セパレータの強度は著しく低下するため、強度が低下した紙製セパレータに形成した導電性高分子膜は破れやすく、ショートや漏れ電流不良率が高くなる問題があった。近年、電子機器の高機能化、小型・軽量化による利用分野の拡大に伴い、コンデンサの使用環境、条件が厳しくなっており、コンデンサのリフロー耐熱性の要求温度も高くなってきている。 Conventionally, as separators for capacitors, paper separators mainly composed of beating of cellulose fibers such as natural cellulose fibers such as esparto and hemp pulp, solvent-spun cellulose fibers, and regenerated cellulose fibers have been used (Patent Document 1 and 2). The cellulose fibers in these paper separators react with the oxidizing agent used in polymerizing the conductive polymer and inhibit the polymerization of the conductive polymer. be. Since the strength of paper separators is significantly reduced by carbonization, the conductive polymer film formed on the paper separators with reduced strength is easily broken, resulting in problems such as short circuits and high leakage current defect rates. In recent years, with the expansion of fields of application due to the increasing sophistication and miniaturization and weight reduction of electronic devices, the environment and conditions in which capacitors are used have become more severe, and the required temperature for reflow heat resistance of capacitors has also increased.
そのため、リフロー耐熱性を有するセパレータとして、フィブリル化耐熱性繊維を含む不織布を用いたセパレータが検討されている（特許文献３～１３）。しかし、原料に用いるフィブリル化耐熱性繊維がセパレータの空隙を埋めることによって、導電性高分子の重合液又は導電性高分子分散液の含浸性が不均一となり、コンデンサのＥＳＲ（等価直列抵抗）が高くなる場合があった。また、リフロー処理後のＥＳＲが悪化する場合があった。 Therefore, as a separator having reflow heat resistance, a separator using a nonwoven fabric containing fibrillated heat-resistant fibers has been studied (Patent Documents 3 to 13). However, since fibrillated heat-resistant fibers used as a raw material fill the voids of the separator, the impregnation of the conductive polymer polymerization liquid or conductive polymer dispersion liquid becomes uneven, and the ESR (equivalent series resistance) of the capacitor decreases. It was sometimes higher. In addition, the ESR after reflow treatment may deteriorate.
本発明の課題は、耐熱性に優れた固体電解コンデンサ用セパレータと、ＥＳＲが低く、リフロー処理後もＥＳＲが変化し難い固体電解コンデンサを提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a separator for a solid electrolytic capacitor with excellent heat resistance, and a solid electrolytic capacitor with a low ESR that does not easily change even after reflow treatment.
上記課題は、下記手段によって解決された。 The above problems have been solved by the following means.
（１）湿式不織布からなる固体電解コンデンサ用セパレータにおいて、湿式不織布が、１０～３０質量％のフィブリル化耐熱性繊維、６０～８５質量％の非フィブリル化合成短繊維、１～１０質量％のフィブリル化天然セルロース繊維を含有し、かつ、平均孔径が２．８～１７．０μｍであり、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８０％以上であり、２０．０μｍ超の孔径頻度が２０％以下であることを特徴とする固体電解コンデンサ用セパレータ。
（２）上記（１）記載の固体電解コンデンサ用セパレータを含有する固体電解コンデンサ。
(1) A solid electrolytic capacitor separator made of a wet-laid nonwoven fabric, wherein the wet-laid nonwoven fabric contains 10 to 30% by mass of fibrillated heat-resistant fibers, 60 to 85% by mass of non-fibrillated synthetic short fibers, and 1 to 10% by mass of fibrils. It contains modified natural cellulose fibers, has an average pore size of 2.8 to 17.0 μm, has a pore size frequency in the range of 2.0 to 20.0 μm that is 80% or more of the total pore size, and has a pore size of more than 20.0 μm. A separator for a solid electrolytic capacitor, characterized by having a pore size frequency of 20% or less.
(2) A solid electrolytic capacitor containing the separator for a solid electrolytic capacitor according to (1) above.
本発明によれば、耐熱性に優れた固体電解コンデンサ用セパレータと、ＥＳＲが低く、リフロー処理後もＥＳＲが変化し難い固体電解コンデンサを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the separator for solid electrolytic capacitors excellent in heat resistance and the solid electrolytic capacitor whose ESR is low and ESR does not change easily even after reflow processing can be provided.
＜固体電解コンデンサ＞
本発明において、固体電解コンデンサは、電解質として、導電性を有する機能性高分子（導電性高分子）を用いる固体電解コンデンサを指す。導電性を有する機能性高分子としては、ポリピロール、ポリチオフェン、ポリアニリン、ポリアセチレン、ポリアセン、これらの誘導体などが挙げられる。本発明において、固体電解コンデンサは、これらの機能性高分子と電解液を併用した、ハイブリッド電解コンデンサであっても良い。電解液としては、イオン解離性の塩を溶解させた水溶液、イオン解離性の塩を溶解させた有機溶媒、イオン性液体（固体溶融塩）などが挙げられるが、これらに限定されるものではない。有機溶媒としては、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、アセトニトリル（ＡＮ）、γ－ブチロラクトン（ＢＬ）、ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフラン（ＴＨＦ）、ジメトキシエタン（ＤＭＥ）、ジメトキシメタン（ＤＭＭ）、スルホラン（ＳＬ）、ジメチルスルホキシド（ＤＭＳＯ）、エチレングリコール、プロピレングリコールなどが挙げられる。
<Solid electrolytic capacitor>
In the present invention, a solid electrolytic capacitor refers to a solid electrolytic capacitor using a conductive functional polymer (conductive polymer) as an electrolyte. Examples of conductive functional polymers include polypyrrole, polythiophene, polyaniline, polyacetylene, polyacene, and derivatives thereof. In the present invention, the solid electrolytic capacitor may be a hybrid electrolytic capacitor in which these functional polymers and an electrolytic solution are used together. Examples of the electrolytic solution include, but are not limited to, an aqueous solution in which an ionically dissociative salt is dissolved, an organic solvent in which an ionically dissociative salt is dissolved, an ionic liquid (solid molten salt), and the like. . Examples of organic solvents include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), acetonitrile (AN), γ-butyrolactone (BL), dimethylformamide (DMF), tetrahydrofuran (THF). ), dimethoxyethane (DME), dimethoxymethane (DMM), sulfolane (SL), dimethylsulfoxide (DMSO), ethylene glycol, propylene glycol and the like.
＜フィブリル化耐熱性繊維＞
本発明において、フィブリル化耐熱性繊維とは、融点又は熱分解温度が２５０℃以上であり、高圧ホモジナイザー、リファイナー、ビーター、ミル、摩砕装置などを用いて微細化処理され、フィルム状でなく、主に繊維軸と平行な方向に非常に細かく分割された部分を有する繊維状で、少なくとも一部の繊維径が１μｍ以下になっている繊維である。
<Fibrillated heat-resistant fiber>
In the present invention, fibrillated heat-resistant fibers have a melting point or thermal decomposition temperature of 250° C. or higher, are finely processed using a high-pressure homogenizer, refiner, beater, mill, grinding device, etc., are not film-like, It is a fibrous fiber having very finely divided portions mainly in the direction parallel to the fiber axis, and at least a portion of which has a fiber diameter of 1 μm or less.
融点又は熱分解温度が２５０℃以上の耐熱性繊維としては、例えば、全芳香族ポリアミド、全芳香族ポリエステル、ポリフェニレンスルフィド、ポリ－ｐ－フェニレンベンゾビスチアゾール、ポリ－ｐ－フェニレンベンゾビスオキサゾール、ポリベンゾイミダゾール、ポリエーテルエーテルケトン、ポリアミドイミド、ポリイミド、ポリテトラフルオロエチレン、アクリル類からなる単繊維又は複合繊維が挙げられる。これらの中でも全芳香族ポリアミドが電解液との親和性に優れるため好ましい。 Heat-resistant fibers having a melting point or thermal decomposition temperature of 250° C. or higher include, for example, wholly aromatic polyamide, wholly aromatic polyester, polyphenylene sulfide, poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole, poly Benzimidazole, polyetheretherketone, polyamide-imide, polyimide, polytetrafluoroethylene, and acrylics may be used as single or composite fibers. Among these, the wholly aromatic polyamide is preferable because of its excellent affinity with the electrolytic solution.
フィブリル化耐熱性繊維の変法濾水度は０～７００ｍｌであることが好ましく、より好ましくは３０～６００ｍｌであり、さらに好ましくは１００～５００ｍｌであり、特に好ましくは２００～４５０ｍｌである。フィブリル化耐熱性繊維の変法濾水度が７００ｍｌ超である場合、フィブリル化があまり進んでいないため、太い幹繊維が多く存在して、繊維径分布が広くなり、地合斑や厚み斑が生じる場合がある。また、フィブリル化耐熱性繊維の変法濾水度が０ｍｌ未満である場合、ＥＳＲが高くなる場合がある。フィブリル化耐熱性繊維のフィブリル化が進むと、変法濾水度は下がり続ける。そして、変法濾水度が０ｍｌに達した後も、さらにフィブリル化すると、繊維がメッシュを通りすぎるようになり、変法濾水度が逆に上昇し始める。本発明では、このように、変法濾水度が逆上昇し始めた状態を「変法濾水度が０ｍｌ未満」と称している。 The modified freeness of the fibrillated heat-resistant fiber is preferably 0-700 ml, more preferably 30-600 ml, still more preferably 100-500 ml, and particularly preferably 200-450 ml. When the modified freeness of the fibrillated heat-resistant fiber is more than 700 ml, the fibrillation is not so advanced, so many thick trunk fibers are present, the fiber diameter distribution is widened, and texture unevenness and thickness unevenness occur. may occur. Moreover, when the modified freeness of the fibrillated heat-resistant fiber is less than 0 ml, the ESR may become high. As the fibrillation of the fibrillated heat-resistant fiber progresses, the modified freeness continues to decrease. Even after the modified freeness reaches 0 ml, if the fibers are further fibrillated, the fibers will pass through the mesh, and the modified freeness will start to rise. In the present invention, the state in which the modified freeness starts to reversely rise is called "the modified freeness is less than 0 ml".
なお、「変法濾水度」とは、「ふるい板として線径０．１４ｍｍ、目開き０．１８ｍｍの８０メッシュ金網を用い、試料濃度を０．１質量％にした以外はＪＩＳ Ｐ８１２１－２：２０１２に準拠して測定した値」である。 In addition, "modified freeness" refers to "using an 80-mesh wire mesh with a wire diameter of 0.14 mm and an opening of 0.18 mm as a sieve plate, and a sample concentration of 0.1% by mass, except that JIS P8121-2 : 2012".
フィブリル化耐熱性繊維において、質量加重平均繊維長は、０．１０ｍｍ以上２．００ｍｍ以下であることが好ましく、０．２０ｍｍ以上１．５０ｍｍ以下であることがより好ましい。また、長さ加重平均繊維長は、０．１０ｍｍ以上２．００ｍｍ以下であることが好ましく、０．３０～１．００ｍｍであることがより好ましく、０．４０～０．７５ｍｍであることがさらに好ましく、０．５０～０．７０ｍｍであることが特に好ましい。平均繊維長が好ましい範囲よりも短い場合、セパレータから脱落する場合やセパレータが毛羽立つ場合があり、平均繊維長が好ましい範囲よりも長い場合、ダマになる場合がある。 The fibrillated heat-resistant fiber preferably has a mass-weighted average fiber length of 0.10 mm or more and 2.00 mm or less, more preferably 0.20 mm or more and 1.50 mm or less. In addition, the length-weighted average fiber length is preferably 0.10 mm or more and 2.00 mm or less, more preferably 0.30 to 1.00 mm, and further preferably 0.40 to 0.75 mm. Preferably, it is particularly preferably between 0.50 and 0.70 mm. If the average fiber length is shorter than the preferred range, the separator may fall off or become fuzzy, and if the average fiber length is longer than the preferred range, lumps may occur.
本発明において、質量加重平均繊維長と長さ加重平均繊維長は、ＫａｊａａｎｉＦｉｂｅｒＬａｂＶ３．５（Ｍｅｔｓｏ Ａｕｔｏｍａｔｉｏｎ社製）を使用して、投影繊維長（Ｐｒｏｊ）モードにおいて測定した質量加重平均繊維長（Ｌ（ｗ））と長さ加重平均繊維長（Ｌ（ｌ））である。 In the present invention, the mass-weighted average fiber length and the length-weighted average fiber length are the mass-weighted average fiber length (L ( w)) and the length-weighted average fiber length (L(l)).
フィブリル化耐熱性繊維の平均繊維幅は、０．５μｍ以上４０．０μｍ以下が好ましく、３．０μｍ以上３５．０μｍ以下がより好ましく、５．０μｍ以上３０．０μｍ以下がさらに好ましい。平均繊維幅が４０．０μｍを超えた場合、セパレータの厚みを薄くし難くなる場合があり、平均繊維幅が０．５μｍ未満の場合、地合斑や厚み斑が生じる場合がある。 The average fiber width of the fibrillated heat-resistant fibers is preferably 0.5 μm or more and 40.0 μm or less, more preferably 3.0 μm or more and 35.0 μm or less, and even more preferably 5.0 μm or more and 30.0 μm or less. If the average fiber width exceeds 40.0 μm, it may be difficult to reduce the thickness of the separator, and if the average fiber width is less than 0.5 μm, uneven texture and uneven thickness may occur.
本発明において、フィブリル化耐熱性繊維の平均繊維幅は、ＫａｊａａｎｉＦｉｂｅｒＬａｂＶ３．５（Ｍｅｔｓｏ Ａｕｔｏｍａｔｉｏｎ社製）を使用して測定した繊維幅（Ｆｉｂｅｒ Ｗｉｄｔｈ）である。 In the present invention, the average fiber width of fibrillated heat-resistant fibers is the fiber width measured using Kajaani FiberLab V3.5 (manufactured by Metso Automation).
フィブリル化耐熱性繊維の含有率は、セパレータに含まれる繊維全体に対して、１０～３０質量％であり、１２～２８質量％がより好ましく、１５～２５質量％がさらに好ましい。該含有率が１０質量％未満である場合、耐熱性が低くなる。該含有率が３０質量％を超えると、セパレータが緻密になり過ぎ、ＥＳＲが高くなる。 The content of fibrillated heat-resistant fibers is 10 to 30% by mass, more preferably 12 to 28% by mass, even more preferably 15 to 25% by mass, based on the total fibers contained in the separator. If the content is less than 10% by mass, the heat resistance will be low. If the content exceeds 30% by mass, the separator becomes too dense and the ESR increases.
＜非フィブリル化合成短繊維＞
非フィブリル化合成短繊維は、ポリオレフィン、ポリエステル、ポリ酢酸ビニル、エチレン－酢酸ビニル共重合体、ポリアミド、アクリル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルエーテル、ポリビニルケトン、ポリエーテル、ポリビニルアルコール、ジエン、ポリウレタン、フェノール、メラミン、フラン、尿素、アニリン、不飽和ポリエステル、フッ素、シリコーン、これらの誘導体などの樹脂からなる短繊維、上記した耐熱性繊維が挙げられる。非フィブリル化合成短繊維は、セパレータの引張強度や突刺強度を強くする。
<Non-fibrillated synthetic short fibers>
Non-fibrillated synthetic staple fibers include polyolefins, polyesters, polyvinyl acetates, ethylene-vinyl acetate copolymers, polyamides, acrylics, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl ethers, polyvinyl ketones, polyethers, polyvinyl alcohols, dienes, Short fibers made of resins such as polyurethane, phenol, melamine, furan, urea, aniline, unsaturated polyester, fluorine, silicone, and derivatives thereof, and the heat-resistant fibers described above can be used. The non-fibrillated synthetic short fibers increase the tensile strength and puncture strength of the separator.
非フィブリル化合成短繊維は、単一の樹脂からなる繊維（単繊維）であっても良いし、２種以上の樹脂からなる複合繊維であっても良い。また、本発明のセパレータに含まれる非フィブリル化合成短繊維は、１種でも良いし、２種類以上を組み合わせて使用しても良い。複合繊維は、芯鞘型、偏芯型、サイドバイサイド型、海島型、オレンジ型、多重バイメタル型が挙げられる。 The non-fibrillated synthetic short fibers may be fibers (single fibers) made of a single resin, or composite fibers made of two or more resins. In addition, the non-fibrillated synthetic short fibers contained in the separator of the present invention may be of one kind, or two or more kinds thereof may be used in combination. Composite fibers include core-sheath type, eccentric type, side-by-side type, sea-island type, orange type, and multi-bimetal type.
非フィブリル化合成短繊維の繊度は、０．００７～２．５ｄｔｅｘが好ましく、０．０２～２．０ｄｔｅｘがより好ましく、０．１～１．１ｄｔｅｘがさらに好ましく、０．１～０．６ｄｔｅｘが特に好ましい。繊度が２．５ｄｔｅｘを超えた場合、厚さ方向における繊維本数が少なくなるため、厚みを薄くしにくくなる。繊度が０．００７ｄｔｅｘ未満の場合、繊維の安定製造が困難になる。 The fineness of the non-fibrillated synthetic staple fibers is preferably 0.007 to 2.5 dtex, more preferably 0.02 to 2.0 dtex, still more preferably 0.1 to 1.1 dtex, and 0.1 to 0.6 dtex. Especially preferred. If the fineness exceeds 2.5 dtex, the number of fibers in the thickness direction decreases, making it difficult to reduce the thickness. If the fineness is less than 0.007 dtex, stable production of fibers becomes difficult.
非フィブリル化合成短繊維の繊維長としては、１ｍｍ以上１０ｍｍ以下が好ましく、１ｍｍ以上６ｍｍ以下がより好ましい。繊維長が１０ｍｍを超えた場合、地合不良となることがある。一方、繊維長が１ｍｍ未満の場合には、セパレータの機械的強度が弱くなる場合がある。 The fiber length of the non-fibrillated synthetic short fibers is preferably 1 mm or more and 10 mm or less, more preferably 1 mm or more and 6 mm or less. If the fiber length exceeds 10 mm, poor formation may occur. On the other hand, if the fiber length is less than 1 mm, the mechanical strength of the separator may become weak.
非フィブリル化合成短繊維の含有率は、セパレータに含まれる繊維全体に対して、６０～８５質量％であり、６２～８０質量％がより好ましく、６５～７５質量％がさらに好ましい。該含有率が６０質量％未満である場合、セパレータの機械的強度が弱くなる。該含有率が８５質量％を超えた場合、耐熱性が低くなる。 The content of non-fibrillated synthetic short fibers is 60 to 85% by mass, more preferably 62 to 80% by mass, and even more preferably 65 to 75% by mass, based on the total fibers contained in the separator. If the content is less than 60% by mass, the mechanical strength of the separator will be weak. If the content exceeds 85% by mass, the heat resistance becomes low.
＜フィブリル化天然セルロース繊維＞
フィブリル化天然セルロース繊維は、溶剤紡糸セルロース繊維等のフィブリル化再生セルロース繊維に比べ、繊維１本の太さの均一性が劣る傾向にあるが、繊維間の物理的な絡みと水素結合力が強いという特徴を有する。フィブリル化天然セルロース繊維の変法濾水度は０～４００ｍｌであることが好ましく、５０～３５０ｍｌがより好ましく、７０～３００ｍｌがさらに好ましく、９０～２５０ｍｌが特に好ましい。該変法濾水度が４００ｍｌを超えると、繊維径分布が広くなり、地合斑や厚み斑になる場合がある。フィブリル化天然セルロース繊維のフィブリル化が進むと、変法濾水度は下がり続ける。そして、変法濾水度が０ｍｌに達した後もフィブリル化した状態を「変法濾水度が０ｍｌ未満」と称している。該変法濾水度が０ｍｌ未満の場合、セパレータから脱落する場合やセパレータが毛羽立つ場合がある。
<Fibrillated natural cellulose fiber>
Compared to fibrillated regenerated cellulose fibers such as solvent-spun cellulose fibers, fibrillated natural cellulose fibers tend to be inferior in uniformity in the thickness of each fiber, but have strong physical entanglement and hydrogen bonding between fibers. It has the characteristics of The modified freeness of fibrillated natural cellulose fibers is preferably 0 to 400 ml, more preferably 50 to 350 ml, still more preferably 70 to 300 ml, and particularly preferably 90 to 250 ml. When the modified freeness exceeds 400 ml, the fiber diameter distribution becomes wide, and uneven texture and uneven thickness may occur. As fibrillated natural cellulose fibers become more fibrillated, the modified freeness continues to decrease. The state of fibrillation even after the modified freeness reaches 0 ml is called "modified freeness less than 0 ml". If the modified freeness is less than 0 ml, the liquid may drop from the separator or the separator may become fuzzy.
フィブリル化天然セルロース繊維の長さ加重平均繊維長は、０．１０～２．００ｍｍであることが好ましく、０．１０～１．００ｍｍであることがより好ましく、０．１０～０．５０ｍｍであることがさらに好ましく、０．１０～０．４０ｍｍであることが特に好ましい。該長さ加重平均繊維長が０．１０ｍｍ未満である場合、セパレータから脱落する場合やセパレータが毛羽立つ場合があり、２．００ｍｍより長い場合、ダマになる場合がある。 The length-weighted average fiber length of fibrillated natural cellulose fibers is preferably 0.10 to 2.00 mm, more preferably 0.10 to 1.00 mm, and 0.10 to 0.50 mm. is more preferable, and 0.10 to 0.40 mm is particularly preferable. When the length-weighted average fiber length is less than 0.10 mm, the fibers may fall off from the separator or the separator may become fuzzy.
フィブリル化天然セルロース繊維の原料としては、針葉樹パルプや広葉樹パルプ等の木材パルプ；コットンリンターパルプ、コットンパルプ、麻、バガス、ケナフ、竹、藁等を由来とする非木材パルプ；等を使用することができる。中でも、フィブリル化後の繊維強度や品質の安定性やセルロース純度の観点から、コットン由来の原料が好ましい。 As raw materials for fibrillated natural cellulose fibers, wood pulp such as softwood pulp and hardwood pulp; non-wood pulp derived from cotton linter pulp, cotton pulp, hemp, bagasse, kenaf, bamboo, straw, etc.; can be done. Among them, raw materials derived from cotton are preferable from the viewpoint of fiber strength after fibrillation, quality stability, and cellulose purity.
フィブリル化天然セルロース繊維は、リファイナー、ビーター、ミル、摩砕装置、高速の回転刃により剪断力を与える回転刃式ホモジナイザー、高速で回転する円筒形の内刃と固定された外刃との間で剪断力を生じる二重円筒式の高速ホモジナイザー、超音波による衝撃で微細化する超音波破砕器、繊維懸濁液に少なくとも２０ＭＰａの圧力差を与えて小径のオリフィスを通過させて高速度とし、これを衝突させて急減速することにより繊維に剪断力、切断力を加える高圧ホモジナイザー等で処理されたもので、この中でも、特に高圧ホモジナイザーで処理されたものが好ましい。 Fibrillated natural cellulose fibers are processed by refiners, beaters, mills, grinders, rotary blade homogenizers that apply shear force with high-speed rotating blades, and between cylindrical inner blades rotating at high speed and fixed outer blades. A double-cylinder high-speed homogenizer that produces a shearing force, an ultrasonic crusher that micronizes by ultrasonic impact, and a pressure difference of at least 20 MPa to the fiber suspension to pass through a small diameter orifice to a high speed, which are treated with a high-pressure homogenizer or the like that applies a shearing force and a cutting force to the fibers by colliding the fibers and rapidly decelerating them.
フィブリル化天然セルロース繊維の含有率は、セパレータに含まれる繊維全体に対して、１～１０質量％であり、１～９質量％がより好ましく、１～８質量％がさらに好ましい。該含有率が１質量％未満である場合、セパレータの機械的強度が弱くなり、また、コンデンサのショート不良が起きやすくなる。該含有率が１０質量％を超えると、セパレータが緻密になり過ぎ、ＥＳＲが高くなる。 The content of fibrillated natural cellulose fibers is 1 to 10% by mass, more preferably 1 to 9% by mass, even more preferably 1 to 8% by mass, based on the total fibers contained in the separator. If the content is less than 1% by mass, the mechanical strength of the separator is weakened, and short-circuit failure of the capacitor is likely to occur. If the content exceeds 10% by mass, the separator becomes too dense and the ESR increases.
＜固体電解コンデンサ用セパレータ＞
本発明のセパレータは、湿式不織布からなるセパレータであり、湿式不織布が、１０～３０質量％のフィブリル化耐熱性繊維、６０～８５質量％の非フィブリル化合成短繊維、１～１０質量％のフィブリル化天然セルロース繊維を含有し、かつ、平均孔径が２．８～１７．０μｍであり、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８０％以上であり、２０．０μｍ超の孔径頻度が２０％以下であることを特徴とする。本発明によれば、セパレータの空隙を過度に塞ぐことなく、均一な細孔分布とすることができることから、導電性高分子の重合液の含浸性が均一となり、コンデンサのＥＳＲを低くすることができる。また、リフロー処理後もＥＳＲが変化し難いという効果を達成できる。さらに、セパレータが微細で耐熱性の高いフィブリル化耐熱性繊維を含むことにより、セパレータの熱寸法安定性が向上し、耐熱性に優れたセパレータを得ることができる。
<Separator for Solid Electrolytic Capacitor>
The separator of the present invention is a separator made of a wet-laid nonwoven fabric, and the wet-laid nonwoven fabric contains 10 to 30% by mass of fibrillated heat-resistant fibers, 60 to 85% by mass of nonfibrillated synthetic short fibers, and 1 to 10% by mass of fibrils. It contains modified natural cellulose fibers, has an average pore size of 2.8 to 17.0 μm, has a pore size frequency in the range of 2.0 to 20.0 μm that is 80% or more of the total pore size, and has a pore size of more than 20.0 μm. It is characterized by having a pore diameter frequency of 20% or less. According to the present invention, since a uniform pore distribution can be obtained without excessively clogging the voids of the separator, the impregnation of the conductive polymer with the polymerization liquid becomes uniform, and the ESR of the capacitor can be lowered. can. In addition, it is possible to achieve the effect that the ESR is difficult to change even after the reflow treatment. Furthermore, since the separator contains fine fibrillated heat-resistant fibers with high heat resistance, the thermal dimensional stability of the separator is improved, and a separator excellent in heat resistance can be obtained.
セパレータの平均孔径は、２．８～１７．０μｍであり、３．０～１５．０μｍがより好ましく、３．２～１３．０μｍがさらに好ましい。平均孔径が２．８μｍ未満である場合、セパレータが緻密になり過ぎ、ＥＳＲが高くなる。平均孔径が１７．０μｍを超える場合、セパレータの緻密性が不足し、コンデンサのショート不良が起きやすくなる。 The separator has an average pore size of 2.8 to 17.0 μm, more preferably 3.0 to 15.0 μm, even more preferably 3.2 to 13.0 μm. If the average pore size is less than 2.8 μm, the separator will be too dense and the ESR will be high. If the average pore size exceeds 17.0 μm, the denseness of the separator is insufficient, and short circuits tend to occur in the capacitor.
本発明のセパレータは、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８０％以上であり、２０．０μｍ超の孔径頻度が２０％以下である。セパレータの孔径頻度がこの範囲であることによって、孔の分布がなだらかに広く分布することがないため、セパレータの均一性が高くなり、導電性高分子の重合液の含浸性が均一となり、ＥＳＲを低くすることができる。セパレータの孔径頻度がこの範囲を外れると、セパレータの均一性が下がり、ＥＳＲが高くなり、また、リフロー処理後にＥＳＲが変化する。 In the separator of the present invention, the frequency of pore diameters in the range of 2.0 to 20.0 μm is 80% or more of the total pore diameter, and the frequency of pore diameters exceeding 20.0 μm is 20% or less. When the pore diameter frequency of the separator is within this range, the pore distribution is not smooth and wide, so that the uniformity of the separator becomes high, the impregnation of the conductive polymer with the polymerization liquid becomes uniform, and the ESR is reduced. can be lowered. If the pore size frequency of the separator is out of this range, the uniformity of the separator decreases, the ESR increases, and the ESR changes after the reflow treatment.
セパレータの孔径頻度は、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８５％以上であり、２０．０μｍ超の孔径頻度が１５％以下であることがより好ましく、２．０～２０．０μｍの範囲の孔径頻度が全孔径の９０％以上であり、２０．０μｍ超の孔径頻度が１０％以下であることがさらに好ましい。 Regarding the pore size frequency of the separator, the pore size frequency in the range of 2.0 to 20.0 μm is 85% or more of the total pore size, and the pore size frequency of more than 20.0 μm is more preferably 15% or less. More preferably, the frequency of pore diameters in the range of 20.0 μm is 90% or more of the total pore diameter, and the frequency of pore diameters greater than 20.0 μm is 10% or less.
本発明において、平均孔径が２．８～１７．０μｍであり、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８０％以上であり、２０．０μｍ超の孔径頻度が２０％以下であるセパレータとする方法としては、繊維の繊維径、繊維の含有率、セパレータの坪量、セパレータの厚み等の調整、湿式抄紙法における抄紙網の選定、抄紙スラリー濃度、抄紙スラリーの温度の調整、抄紙スラリーへの増粘剤添加量、分散剤添加量の調整、脱水強度の調整などが挙げられる。抄紙スラリーの分散が均一となり、セパレータの細孔分布を均一とすることができることから、抄紙スラリーへ増粘剤や分散剤を添加することが好ましい。 In the present invention, the average pore diameter is 2.8 to 17.0 μm, the frequency of pore diameters in the range of 2.0 to 20.0 μm is 80% or more of the total pore diameter, and the frequency of pore diameters exceeding 20.0 μm is 20% or less. As a method for making a separator, the fiber diameter of the fiber, the content of the fiber, the basis weight of the separator, the thickness of the separator, etc. are adjusted, the selection of the papermaking net in the wet papermaking method, the papermaking slurry concentration, and the temperature of the papermaking slurry are adjusted. , adjustment of the amount of thickener added to the papermaking slurry, adjustment of the amount of dispersant added, adjustment of dewatering strength, and the like. It is preferable to add a thickener or a dispersant to the papermaking slurry because the dispersion of the papermaking slurry becomes uniform and the pore distribution of the separator can be made uniform.
増粘剤としては、カルボキシメチルセルロース、デンプン、ポリ酢酸ビニル、ポリ乳酸、ポリグリコール酸、ポリアクリルアミド、ポリエチレンオキシド等が挙げられる。これらの中でもポリアクリルアミド、ポリエチレンオキシドが好ましい。 Examples of thickening agents include carboxymethylcellulose, starch, polyvinyl acetate, polylactic acid, polyglycolic acid, polyacrylamide, polyethylene oxide and the like. Among these, polyacrylamide and polyethylene oxide are preferred.
本発明において、平均孔径・孔径頻度は、ＰＭＩ社製、商品名：パームポロメーターＣＦＰ－１５００Ａを用いて、ハーフドライ試験法（ＡＳＴＭ Ｅ１２９４－８９）に準じて測定した孔径分布から求めた、セパレータの平均孔径、孔径頻度である。区間幅０．１μｍとした孔径分布から全区間のうち、区間２．０～２０．０μｍの比率（％）及び２０．０μｍ超の比率（％）を求め、孔径頻度とした。 In the present invention, the average pore size and pore size frequency are obtained from the pore size distribution measured according to the half-dry test method (ASTM E1294-89) using PMI Co., Ltd., trade name: Perm Porometer CFP-1500A. is the average pore size and pore size frequency. From the pore size distribution with a section width of 0.1 μm, the ratio (%) of the section of 2.0 to 20.0 μm and the ratio (%) of the section exceeding 20.0 μm were obtained and used as the pore size frequency.
本発明において、セパレータの坪量は、８～２２ｇ／ｍ２が好ましく、９～２０ｇ／ｍ２がより好ましく、１０～１８ｇ／ｍ２がさらに好ましい。坪量が２２ｇ／ｍ２を超える場合、ＥＳＲが高くなり過ぎる場合がある。坪量が８ｇ／ｍ２未満である場合、十分な強度を得ることが難しい場合や耐熱性が劣る場合がある。なお、坪量は、ＪＩＳ Ｐ８１２４：２０１１（紙及び板紙－坪量測定法）に規定された方法に基づき測定される。 In the present invention, the basis weight of the separator is preferably 8-22 g/m 2 , more preferably 9-20 g/m 2 , and even more preferably 10-18 g/m 2 . If the basis weight exceeds 22 g/m 2 , the ESR may become too high. If the basis weight is less than 8 g/m 2 , it may be difficult to obtain sufficient strength or the heat resistance may be poor. The basis weight is measured according to the method specified in JIS P8124:2011 (Paper and paperboard—Method for measuring basis weight).
本発明において、セパレータの厚みは、１５～７０μｍが好ましく、２０～６７μｍがより好ましく、２５～６５μｍがさらに好ましい。厚みが７０μｍを超える場合、ＥＳＲが高くなり過ぎる場合がある。厚みが１５μｍ未満である場合、十分な強度を得ることが難しい場合や耐熱性が劣る場合がある。なお、厚みは、ＪＩＳ Ｃ２３００－２：２０１０に規定された方法に基づき、５Ｎ荷重時の外側マイクロメーターにより測定されたセパレータ１枚の値である。 In the present invention, the thickness of the separator is preferably 15 to 70 μm, more preferably 20 to 67 μm, even more preferably 25 to 65 μm. If the thickness exceeds 70 μm, the ESR may become too high. If the thickness is less than 15 μm, it may be difficult to obtain sufficient strength or the heat resistance may be poor. The thickness is the value of one sheet of separator measured with an outer micrometer under a load of 5N based on the method specified in JIS C2300-2:2010.
本発明において、セパレータは、湿式抄紙法で製造された湿式不織布である。湿式抄紙法は、繊維を水に分散して均一な抄紙スラリーとし、この抄紙スラリーを抄紙機で漉きあげて湿潤ウェブを得、湿潤ウェブを乾燥させて湿式不織布を作製する。抄紙機としては、円網、長網、傾斜型、傾斜短網等の抄紙網を単独で使用する抄紙機や、これらの抄紙網を複数組み合わせた複合抄紙機が挙げられる。湿式不織布を製造する工程においては、必要に応じて、水流交絡処理を施しても良い。抄紙スラリーには、繊維原料の他に、必要に応じて、分散剤、増粘剤、消泡剤などを適宜添加することができる。湿式不織布に対して、熱処理、カレンダー処理、熱カレンダー処理などの加工処理を施しても良い。 In the present invention, the separator is a wet-laid nonwoven fabric produced by a wet-laid papermaking method. In the wet papermaking method, fibers are dispersed in water to form a uniform papermaking slurry, the papermaking slurry is drawn up by a paper machine to obtain a wet web, and the wet web is dried to produce a wet nonwoven fabric. Examples of the paper machine include a paper machine that uses a paper machine such as a cylinder machine, a fourdrinier, an inclined type, or an inclined short machine, and a composite paper machine that combines a plurality of these paper machines. In the process of producing the wet-laid nonwoven fabric, a hydroentangling treatment may be applied, if necessary. To the papermaking slurry, a dispersant, a thickener, an antifoaming agent, and the like can be appropriately added in addition to the fiber raw material, if necessary. The wet-laid nonwoven fabric may be subjected to processing such as heat treatment, calendering, and heat calendering.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は本実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Ａ１：変法濾水度２５０ｍｌのフィブリル化全芳香族ポリアミド
Ａ２：変法濾水度３５０ｍｌのフィブリル化ポリイミド
Ｂ１：繊度０．１ｄｔｅｘ、繊維長３ｍｍのポリエステル短繊維
Ｂ２：繊度０．３ｄｔｅｘ、繊維長３ｍｍのポリエステル短繊維
Ｂ３：繊度１．１ｄｔｅｘ、繊維長５ｍｍの熱融着性芯鞘ポリエステル短繊維
Ｂ４：繊度０．１ｄｔｅｘ、繊維長３ｍｍのアクリル短繊維
Ｃ１：変法濾水度２７０ｍｌ、長さ加重平均繊維長０．２２ｍｍのフィブリル化天然セルロース繊維
Ｃ２：変法濾水度５００ｍｌの麻パルプ
A1: Fibrillated wholly aromatic polyamide with a modified freeness of 250 ml A2: Fibrillated polyimide with a modified freeness of 350 ml B1: Polyester short fibers with a fineness of 0.1 dtex and a fiber length of 3 mm B2: A fineness of 0.3 dtex and a fiber length 3 mm polyester staple fiber B3: Heat-fusible core-sheath polyester staple fiber with a fineness of 1.1 dtex and a fiber length of 5 mm B4: Acrylic staple fiber with a fineness of 0.1 dtex and a fiber length of 3 mm C1: Modified freeness of 270 ml, length Fibrillated natural cellulose fiber C2 with a weighted average fiber length of 0.22 mm: hemp pulp with a modified freeness of 500 ml
＜セパレータ＞
（実施例１）
表１に示した原料と配合量に従って調成した抄紙用スラリーに、分子量１４００万のアニオン性ポリアクリルアミド系増粘剤を全繊維に対して０．６質量％になるように添加し、５分間均一になるまで撹拌した後、円網・円網コンビネーション抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す実施例１のセパレータを作製した。
<Separator>
(Example 1)
An anionic polyacrylamide thickener having a molecular weight of 14,000,000 was added to the papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 so as to be 0.6% by mass based on the total fibers, and the mixture was allowed to stand for 5 minutes. After stirring until uniform, a wet web was obtained using a cylinder/cylinder combination paper machine and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet-laid nonwoven fabric. Thereafter, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering to prepare the separator of Example 1 shown in Table 2.
（実施例２、３）
表１に示した原料と配合量に従って調成した抄紙用スラリーに、分子量１４００万のアニオン性ポリアクリルアミド系増粘剤を全繊維に対して０．６質量％になるように添加し、５分間均一になるまで撹拌した後、円網・傾斜コンビネーション抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す実施例２、３のセパレータを作製した。
(Examples 2 and 3)
An anionic polyacrylamide thickener having a molecular weight of 14,000,000 was added to the papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 so as to be 0.6% by mass based on the total fibers, and the mixture was allowed to stand for 5 minutes. After stirring until uniform, a wet web was obtained using a cylinder/inclined combination paper machine and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet-laid nonwoven fabric. After that, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering.
（実施例４）
表１に示した原料と配合量に従って調成した抄紙用スラリーに、分子量１４００万のアニオン性ポリアクリルアミド系増粘剤を全繊維に対して０．６質量％になるように添加し、５分間均一になるまで撹拌した後、円網・円網コンビネーション抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す実施例４のセパレータを作製した。
(Example 4)
An anionic polyacrylamide thickener having a molecular weight of 14,000,000 was added to the papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 so as to be 0.6% by mass based on the total fibers, and the mixture was allowed to stand for 5 minutes. After stirring until uniform, a wet web was obtained using a cylinder/cylinder combination paper machine and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet-laid nonwoven fabric. After that, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering.
（実施例５）
表１に示した原料と配合量に従って調成した抄紙用スラリーに、分子量１４００万のアニオン性ポリアクリルアミド系増粘剤を全繊維に対して０．６質量％になるように添加し、５分間均一になるまで撹拌した後、円網抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す実施例５のセパレータを作製した。
(Example 5)
An anionic polyacrylamide thickener having a molecular weight of 14,000,000 was added to the papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 so as to be 0.6% by mass based on the total fibers, and the mixture was allowed to stand for 5 minutes. After stirring until uniform, a wet web was obtained using a cylinder paper machine and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet-laid nonwoven fabric. After that, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering.
（実施例６）
表１に示した原料と配合量に従って調成した抄紙用スラリーに、分子量１４００万のアニオン性ポリアクリルアミド系増粘剤を全繊維に対して０．６質量％になるように添加し、５分間均一になるまで撹拌した後、傾斜抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す実施例６のセパレータを作製した。
(Example 6)
An anionic polyacrylamide thickener having a molecular weight of 14,000,000 was added to the papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 so as to be 0.6% by mass based on the total fibers, and the mixture was allowed to stand for 5 minutes. After stirring until uniform, a wet web was obtained using an inclined paper machine and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet-laid nonwoven fabric. Thereafter, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering to prepare the separator of Example 6 shown in Table 2.
（比較例１）
表１に示した原料と配合量に従って調成した抄紙用スラリーから、円網・円網コンビネーション抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す比較例１のセパレータを作製した。
(Comparative example 1)
A wet web is obtained from the slurry for papermaking prepared according to the raw materials and blending amounts shown in Table 1 using a cylinder/cylinder combination paper machine, and dried with a cylinder dryer at a surface temperature of 140°C to form a wet nonwoven fabric. Obtained. Thereafter, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering to prepare a separator of Comparative Example 1 shown in Table 2.
（比較例２）
表１に示した原料と配合量に従って調成した抄紙用スラリーから、円網・傾斜コンビネーション抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す比較例２のセパレータを作製した。
(Comparative example 2)
A wet web is obtained from a papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 using a combination cylinder/inclined paper machine, and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet nonwoven fabric. rice field. Thereafter, both surfaces of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering to prepare a separator of Comparative Example 2 shown in Table 2.
（比較例３～６）
表１に示した原料と配合量に従って調成した抄紙用スラリーから、円網抄紙機を用いて湿潤ウェブを得て、表面温度１４０℃のシリンダードライヤーによって乾燥して、湿式不織布を得た。その後、２００℃に加熱した金属ロールに、湿式不織布の両面を接触させて熱処理し、さらにカレンダー処理して厚み調整し、表２に示す比較例３～６のセパレータを作製した。
(Comparative Examples 3-6)
A wet web was obtained from a papermaking slurry prepared according to the raw materials and blending amounts shown in Table 1 using a cylinder paper machine, and dried with a cylinder dryer at a surface temperature of 140°C to obtain a wet nonwoven fabric. Thereafter, both sides of the wet nonwoven fabric were brought into contact with metal rolls heated to 200° C. for heat treatment, and the thickness was adjusted by calendering to prepare separators of Comparative Examples 3 to 6 shown in Table 2.
＜実施例１～６及び比較例１～５の評価用固体電解コンデンサの作製＞
厚み５０μｍ、エッチング孔１～５μｍのアルミニウム箔の表面を酸化処理して、酸化アルミニウム誘電体を形成させ、これを陽極として用いた。酸化処理する前のアルミニウム箔を陰極として用いた。実施例１～６及び比較例１～５の固体電解コンデンサ用セパレータを陽極の誘電体上に配置し、陰極と合わせて巻き取り、固体電解コンデンサ素子を作製した。この素子を３，４－エチレンジオキシチオフェン：ｐ－トルエンスルホン酸第二鉄の５０質量％ブタノール溶液を質量比で１：２０になるように混合した溶液（導電性高分子モノマー液）に浸漬し、引き上げて２００℃で３０分加熱してポリエチレンジオキシチオフェンを重合した。この素子をメタノールで洗浄してセパレータに残留している未反応の３，４－エチレンジオキシチオフェンとｐ－トルエンスルホン酸第二鉄を除去した後、１２０℃で乾燥させた。同様に、ポリエチレンジオキシチオフェンの重合作業をもう１回繰り返した後、素子をアルミニウム製外装缶に収納して封口し、定格電圧２５Ｖ、定格静電容量３３μＦの固体電解コンデンサを作製した。
<Production of solid electrolytic capacitors for evaluation of Examples 1 to 6 and Comparative Examples 1 to 5>
An aluminum foil having a thickness of 50 μm and an etching hole of 1 to 5 μm was oxidized on its surface to form an aluminum oxide dielectric, which was used as an anode. An aluminum foil before oxidation treatment was used as a cathode. The separators for solid electrolytic capacitors of Examples 1 to 6 and Comparative Examples 1 to 5 were arranged on the dielectric of the anode, combined with the cathode, and rolled up to produce a solid electrolytic capacitor element. This element was immersed in a solution (conductive polymer monomer solution) in which 3,4-ethylenedioxythiophene:ferric p-toluenesulfonate in 50 mass% butanol solution was mixed in a mass ratio of 1:20. Then, it was pulled up and heated at 200° C. for 30 minutes to polymerize polyethylenedioxythiophene. This element was washed with methanol to remove unreacted 3,4-ethylenedioxythiophene and ferric p-toluenesulfonate remaining on the separator, and then dried at 120.degree. Similarly, after repeating the polymerization of polyethylenedioxythiophene one more time, the element was housed in an aluminum outer can and sealed to produce a solid electrolytic capacitor with a rated voltage of 25 V and a rated capacitance of 33 μF.
＜比較例６の評価用固体電解コンデンサの作製＞
厚み５０μｍ、エッチング孔１～５μｍのアルミニウム箔の表面を酸化処理して、酸化アルミニウム誘電体を形成させ、これを陽極として用いた。酸化処理する前のアルミニウム箔を陰極として用いた。比較例６の固体電解コンデンサ用セパレータを陽極の誘電体上に配置し、陰極と合わせて巻き取り、固体電解コンデンサ素子を作製した。この素子を２３０℃で２時間加熱してセパレータを炭化処理した後、３，４－エチレンジオキシチオフェン：ｐ－トルエンスルホン酸第二鉄の５０質量％ブタノール溶液を質量比で１：２０になるように混合した溶液（導電性高分子モノマー液）に浸漬し、引き上げて２００℃で３０分加熱してポリエチレンジオキシチオフェンを重合した。この素子をメタノールで洗浄してセパレータに残留している未反応の３，４－エチレンジオキシチオフェンとｐ－トルエンスルホン酸第二鉄を除去した後、１２０℃で乾燥させた。同様に、ポリエチレンジオキシチオフェンの重合作業をもう１回繰り返した後、素子をアルミニウム製外装缶に収納して封口し、定格電圧２５Ｖ、定格静電容量３３μＦの固体電解コンデンサを作製した。
<Preparation of Solid Electrolytic Capacitor for Evaluation of Comparative Example 6>
An aluminum foil having a thickness of 50 μm and an etching hole of 1 to 5 μm was oxidized on its surface to form an aluminum oxide dielectric, which was used as an anode. An aluminum foil before oxidation treatment was used as a cathode. The separator for a solid electrolytic capacitor of Comparative Example 6 was arranged on the dielectric of the anode, combined with the cathode, and wound up to produce a solid electrolytic capacitor element. After heating this device at 230° C. for 2 hours to carbonize the separator, a 50% by mass butanol solution of 3,4-ethylenedioxythiophene:ferric p-toluenesulfonate was added at a mass ratio of 1:20. It was immersed in the solution (conducting polymer monomer solution) mixed in the manner described above, pulled out, and heated at 200° C. for 30 minutes to polymerize polyethylenedioxythiophene. This element was washed with methanol to remove unreacted 3,4-ethylenedioxythiophene and ferric p-toluenesulfonate remaining on the separator, and then dried at 120.degree. Similarly, after repeating the polymerization of polyethylenedioxythiophene once more, the device was housed in an aluminum outer can and sealed to produce a solid electrolytic capacitor with a rated voltage of 25 V and a rated capacitance of 33 μF.
［耐熱性］
セパレータを１００ｍｍ巾×１００ｍｍ長さに切り、耐熱ガラス板に挟んで、１８０℃の恒温乾燥機に１時間静置し、長さ方向及び巾方向の収縮率を算出した。長さ方向及び巾方向の収縮率の平均値が２．７％未満であれば「○」、２．７％以上３．０％未満であれば「△」、３．０％以上であれば「×」で表し、表３に示した。
[Heat-resistant]
The separator was cut into 100 mm wide×100 mm long pieces, sandwiched between heat-resistant glass plates, left to stand in a constant temperature dryer at 180° C. for 1 hour, and the shrinkage ratios in the length direction and width direction were calculated. If the average value of the shrinkage rate in the length direction and the width direction is less than 2.7%, it is "○". If it is 2.7% or more and less than 3.0%, it is "△". It is represented by “x” and shown in Table 3.
［ＥＳＲ］
実施例及び比較例の固体電解コンデンサのＥＳＲを、２０℃、１００ｋＨｚの条件で測定し、２０個の平均値が３０ｍΩ未満であれば「○」、３０ｍΩ以上３５ｍΩ未満であれば「△」、３５ｍΩ以上であれば「×」で表し、表３に示した。
[ESR]
The ESR of the solid electrolytic capacitors of Examples and Comparative Examples was measured under conditions of 20°C and 100 kHz. If the average value of 20 capacitors was less than 30 mΩ, the result was "○". If it is more than that, it is indicated by "x" and shown in Table 3.
［リフロー後ＥＳＲ変化］
実施例及び比較例の固体電解コンデンサを２６０℃の半田浴に１０秒間浸漬して取り出し、２０℃まで冷却する。これを１サイクルとして、２サイクル繰り返した後の固体電解コンデンサのＥＳＲを、２０℃、１００ｋＨｚの条件で測定し、２０個の平均値をリフロー後ＥＳＲとした。リフロー後ＥＳＲがリフロー前ＥＳＲに比べ、１．０５倍未満であれば「○」、１．０５倍以上１．１０倍未満であれば「△」、１．１０倍以上であれば「×」で表し、表３に示した。
[Change in ESR after reflow]
The solid electrolytic capacitors of Examples and Comparative Examples are immersed in a solder bath at 260°C for 10 seconds, taken out, and cooled to 20°C. This was regarded as one cycle, and the ESR of the solid electrolytic capacitor after repeating two cycles was measured under conditions of 20° C. and 100 kHz, and the average value of 20 samples was taken as the post-reflow ESR. If the ESR after reflow is less than 1.05 times the ESR before reflow, it is marked "○"; and shown in Table 3.
実施例１～６の固体電解コンデンサ用セパレータは、１０～３０質量％のフィブリル化耐熱性繊維、６０～８５質量％の非フィブリル化合成短繊維、１～１０質量％のフィブリル化天然セルロース繊維を含有し、かつ、平均孔径が２．８～１７．０μｍであり、２．０～２０．０μｍの範囲の孔径頻度が全孔径の８０％以上であり、２０．０μｍ超の孔径頻度が２０％以下である湿式不織布であるため、セパレータの耐熱性、コンデンサのＥＳＲに優れていた。また、リフロー後ＥＳＲ変化の悪化も少なかった。 The solid electrolytic capacitor separators of Examples 1 to 6 contain 10 to 30% by mass of fibrillated heat-resistant fibers, 60 to 85% by mass of non-fibrillated synthetic short fibers, and 1 to 10% by mass of fibrillated natural cellulose fibers. and the average pore size is 2.8 to 17.0 μm, the frequency of pore sizes in the range of 2.0 to 20.0 μm is 80% or more of the total pore size, and the frequency of pore sizes exceeding 20.0 μm is 20% Since the wet-laid nonwoven fabric has the following properties, the heat resistance of the separator and the ESR of the capacitor were excellent. In addition, deterioration in ESR change after reflow was small.
一方、比較例１の固体電解コンデンサ用セパレータは、フィブリル化耐熱性繊維の含有量が少ないため、耐熱性が劣っていた。また、平均孔径が大きく、２．０～２０．０μｍの範囲の孔径頻度が低く、２０．０μｍ超の孔径頻度が高いことから、リフロー後ＥＳＲ変化が大きかった。 On the other hand, the solid electrolytic capacitor separator of Comparative Example 1 was inferior in heat resistance because the content of fibrillated heat-resistant fibers was small. In addition, the average pore size was large, the frequency of pore diameters in the range of 2.0 to 20.0 μm was low, and the frequency of pore diameters exceeding 20.0 μm was high, resulting in a large change in ESR after reflow.
比較例２の固体電解コンデンサ用セパレータは、フィブリル化耐熱性繊維の含有量が多く、平均孔径が小さいため、コンデンサのＥＳＲが劣っていた。 The solid electrolytic capacitor separator of Comparative Example 2 contained a large amount of fibrillated heat-resistant fibers and had a small average pore size, so the ESR of the capacitor was inferior.
比較例３の固体電解コンデンサ用セパレータは、フィブリル化天然セルロース繊維の含有量が多いため、コンデンサのＥＳＲが劣っていた。 The solid electrolytic capacitor separator of Comparative Example 3 had a large content of fibrillated natural cellulose fibers, so the ESR of the capacitor was inferior.
比較例４の固体電解コンデンサ用セパレータは、フィブリル化天然セルロース繊維を含有量が少なく、２．０～２０．０μｍの範囲の孔径頻度が低く、２０．０μｍ超の孔径頻度が高いことから、リフロー後ＥＳＲ変化が大きかった。 The solid electrolytic capacitor separator of Comparative Example 4 has a low content of fibrillated natural cellulose fibers, a low frequency of pore diameters in the range of 2.0 to 20.0 μm, and a high frequency of pore diameters exceeding 20.0 μm. The post-ESR change was large.
比較例５の固体電解コンデンサ用セパレータは、２．０～２０．０μｍの範囲の孔径頻度が低く、２０．０μｍ超の孔径頻度が高いことから、リフロー後ＥＳＲ変化が大きかった。 The separator for a solid electrolytic capacitor of Comparative Example 5 had a low frequency of pore diameters in the range of 2.0 to 20.0 μm and a high frequency of pore diameters exceeding 20.0 μm, resulting in a large change in ESR after reflow.
比較例６の固体電解コンデンサ用セパレータは、フィブリル化耐熱性繊維を含有しないため、耐熱性が劣っていた。また、２．０～２０．０μｍの範囲の孔径頻度が低く、２０．０μｍ超の孔径頻度が高いことから、リフロー後ＥＳＲ変化が大きかった。 The solid electrolytic capacitor separator of Comparative Example 6 did not contain fibrillated heat-resistant fibers, and thus was inferior in heat resistance. In addition, since the frequency of pore diameters in the range of 2.0 to 20.0 μm was low and the frequency of pore diameters exceeding 20.0 μm was high, the ESR change after reflow was large.
実施例１～５の比較から、実施例１の固体電解コンデンサ用セパレータと比較して、フィブリル化耐熱性繊維の含有量が多いことから、実施例２～５の固体電解コンデンサ用セパレータの耐熱性は優れていた。また、実施例１～６の比較から、実施例１の固体電解コンデンサ用セパレータと比較して、平均孔径が小さく、２．０～２０．０μｍの範囲の孔径頻度が高く、２０．０μｍ超の孔径頻度が低いことから、実施例２～６の固体電解コンデンサ用セパレータでは、リフロー後ＥＳＲ変化が小さく、優れていた。 From the comparison of Examples 1 to 5, the content of fibrillated heat-resistant fibers is higher than that of the solid electrolytic capacitor separator of Example 1, so the heat resistance of the solid electrolytic capacitor separators of Examples 2 to 5 is high. was excellent. Further, from a comparison of Examples 1 to 6, compared to the solid electrolytic capacitor separator of Example 1, the average pore size is smaller, the pore size frequency in the range of 2.0 to 20.0 μm is higher, and the pore size of more than 20.0 μm is high. Since the frequency of pore diameters is low, the separators for solid electrolytic capacitors of Examples 2 to 6 were excellent with small changes in ESR after reflow.
実施例１～４及び６の比較から、実施例２の固体電解コンデンサ用セパレータと比較して、坪量が小さく、厚みが薄く、平均孔径が大きいことから、実施例１、３、４及び６の固体電解コンデンサ用セパレータでは、コンデンサのＥＳＲが優れていた。 From the comparison of Examples 1 to 4 and 6, compared with the solid electrolytic capacitor separator of Example 2, the basis weight is smaller, the thickness is smaller, and the average pore size is larger. The ESR of the capacitor was excellent in the separator for the solid electrolytic capacitor of No.
実施例１、３～６の比較から、実施例５の固体電解コンデンサ用セパレータと比較して、フィブリル化耐熱性繊維の含有量が少ないことから、実施例１、３、４及び６の固体電解コンデンサ用セパレータでは、コンデンサのＥＳＲが優れていた。 From the comparison of Examples 1, 3 to 6, compared to the solid electrolytic capacitor separator of Example 5, the content of the fibrillated heat-resistant fiber is small, so the solid electrolytes of Examples 1, 3, 4 and 6 The capacitor ESR was excellent for the capacitor separator.
実施例２～６の比較から、実施例６の固体電解コンデンサ用セパレータと比較して、坪量が大きく、厚いことから、実施例２～５の固体電解コンデンサ用セパレータでは、コンデンサの耐熱性が優れていた。 From the comparison of Examples 2 to 6, the solid electrolytic capacitor separator of Example 6 has a larger basis weight and is thicker than the solid electrolytic capacitor separator of Example 6. Therefore, the solid electrolytic capacitor separator of Examples 2 to 5 has a heat resistance of the capacitor. was excellent.
本発明は、固体電解コンデンサ用セパレータ又はハイブリッド電解コンデンサ用セパレータとして好適に利用できる。 INDUSTRIAL APPLICABILITY The present invention can be suitably used as a separator for solid electrolytic capacitors or a separator for hybrid electrolytic capacitors.
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