JP6339869B2 - Capacitor separator - Google Patents
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- JP6339869B2 JP6339869B2 JP2014121124A JP2014121124A JP6339869B2 JP 6339869 B2 JP6339869 B2 JP 6339869B2 JP 2014121124 A JP2014121124 A JP 2014121124A JP 2014121124 A JP2014121124 A JP 2014121124A JP 6339869 B2 JP6339869 B2 JP 6339869B2
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- 239000003990 capacitor Substances 0.000 title claims description 110
- 239000000835 fiber Substances 0.000 claims description 156
- 229920003043 Cellulose fiber Polymers 0.000 claims description 72
- 229920002678 cellulose Polymers 0.000 claims description 28
- 239000001913 cellulose Substances 0.000 claims description 28
- 229920002994 synthetic fiber Polymers 0.000 claims description 19
- 239000012209 synthetic fiber Substances 0.000 claims description 19
- 238000010009 beating Methods 0.000 claims description 7
- 230000000052 comparative effect Effects 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 206010061592 cardiac fibrillation Diseases 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000002600 fibrillogenic effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 208000033978 Device electrical impedance issue Diseases 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
本発明は、キャパシタ用セパレータ(以下、「セパレータ」と略記する場合がある)に関する。 The present invention relates to a capacitor separator (hereinafter sometimes abbreviated as “separator”).
近年、大容量キャパシタの開発が主流になっており、そのためには、キャパシタの内部抵抗を更に低くすることが課題である。キャパシタの内部抵抗を低くするには、電極材、集電体や電解液などの改良も必要であるが、キャパシタ用セパレータに負うところも大きいため、内部抵抗を低減しうるセパレータが要望されている。 In recent years, development of large-capacity capacitors has become mainstream, and for that purpose, it is a problem to further reduce the internal resistance of the capacitors. In order to reduce the internal resistance of the capacitor, it is necessary to improve the electrode material, the current collector, and the electrolytic solution. However, since there is a large burden on the capacitor separator, a separator that can reduce the internal resistance is desired. .
従来、セパレータとしては、叩解可能な溶剤紡糸セルロース繊維の叩解原料を主体とする紙製セパレータが提案されている(例えば、特許文献1参照)。 Conventionally, as a separator, a paper separator mainly composed of a beating raw material of solvent-spun cellulose fibers that can be beaten has been proposed (see, for example, Patent Document 1).
しかしながら、この紙製セパレータは20.0μm未満の厚みにした場合、内部抵抗が高くなることがあり、機械強度も極端に弱くなるため、セパレータを低厚みにできない問題があった。また、特許文献1では、溶剤紡糸セルロース繊維のフィブリル化状態が濾水度で把握されている。濾水度でフィブリル化状態を管理し、溶剤紡糸セルロースの配合量を増やした場合、セパレータを10.0μm未満の低厚みに調整しにくい問題があった。 However, when the thickness of the paper separator is less than 20.0 μm, the internal resistance may be increased and the mechanical strength may be extremely reduced, so that there is a problem that the thickness of the separator cannot be reduced. Moreover, in patent document 1, the fibrillation state of solvent-spun cellulose fiber is grasped | ascertained by the freeness. When the fibrillation state was controlled by the freeness and the amount of solvent-spun cellulose was increased, there was a problem that it was difficult to adjust the separator to a low thickness of less than 10.0 μm.
本発明の課題は、上記実情を鑑みたものであって、低厚みで機械強度が強いキャパシタ用セパレータを提供することにある。また、内部抵抗及び内部短絡不良率が低く、漏れ電流も小さいキャパシタを得ることが可能なキャパシタ用セパレータを提供することにある。 An object of the present invention is to provide a capacitor separator having a low thickness and a high mechanical strength in view of the above circumstances. Another object of the present invention is to provide a capacitor separator capable of obtaining a capacitor having a low internal resistance and internal short-circuit failure rate and a small leakage current.
上記課題を解決するために鋭意研究した結果、
(1)フィブリル化した溶剤紡糸セルロース繊維と合成繊維とフィブリル化天然セルロースからなるキャパシタ用セパレータにおいて、幹部分の最大繊維径が8.0μm未満になるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を50質量%以上含有することを特徴とするキャパシタ用セパレータ、
(2)坪量が5.0〜8.0g/m2である(1)に記載のキャパシタ用セパレータ、
(3)厚さが7.0〜10.0μmである(1)又は(2)に記載のキャパシタ用セパレータ、
(4)引張強度が250N/m以上である(1)〜(3)のいずれかに記載のキャパシタ用セパレータ、
を見出した。
As a result of earnest research to solve the above problems,
(1) A fibrillated solvent-spun cellulose that has been beaten until the maximum fiber diameter of the trunk portion is less than 8.0 μm in a capacitor separator made of fibrillated solvent-spun cellulose fiber, synthetic fiber, and fibrillated natural cellulose. Capacitor separator comprising 50% by mass or more of fibers,
(2) The capacitor separator according to (1), wherein the basis weight is 5.0 to 8.0 g / m 2 .
(3) The capacitor separator according to (1) or (2), wherein the thickness is 7.0 to 10.0 μm,
(4) The capacitor separator according to any one of (1) to (3), wherein the tensile strength is 250 N / m or more,
I found.
本発明のキャパシタ用セパレータは、フィブリル化した溶剤紡糸セルロース繊維の幹部分の最大繊維径が9.0μm未満になるまで叩解を進めたものを50質量%以上含有する。従来、キャパシタ用セパレータの分野において、フィブリル化した溶剤紡糸セルロース繊維のフィブリル化状態は、濾水度、繊維長、繊維長分布等の物性で規定されていた。本発明における検討の結果、これらの物性によって、フィブリル化の状態を管理していても、低厚みで機械強度が強いセパレータが得られない場合があることがわかった。本発明では、幹部分の最大繊維径を9.0μm未満になるまで叩解が進められたフィブリル化した溶剤紡糸セルロース繊維を用いることで、該溶剤紡糸セルロース繊維の配合量を50質量%以上に増やしても、セパレータの厚さを9.0μm未満に調整できるようになる。また、該溶剤紡糸セルロース繊維と合成繊維が絡み合い、低坪量・低厚みでありながら、引張強度等の機械強度を高めることができる。その結果、セパレータとしてのハンドリング性や内部短絡不良抑制効果を飛躍的に向上させることができる。さらに、キャパシタ用セパレータをより緻密で薄くすることができるため、キャパシタの内部抵抗を低く抑えることができ、キャパシタの漏れ電流を小さくすることができるキャパシタ用セパレータを得ることができる。 The capacitor separator of the present invention contains 50% by mass or more of those that have been beaten until the maximum fiber diameter of the trunk portion of the fibrillated solvent-spun cellulose fiber is less than 9.0 μm. Conventionally, in the field of capacitor separators, the fibrillated state of fibrillated solvent-spun cellulose fibers has been defined by physical properties such as freeness, fiber length, and fiber length distribution. As a result of studies in the present invention, it has been found that, depending on these physical properties, a separator having a low thickness and a high mechanical strength may not be obtained even if the state of fibrillation is controlled. In the present invention, the blended amount of the solvent-spun cellulose fiber is increased to 50% by mass or more by using the fibrillated solvent-spun cellulose fiber that has been beaten until the maximum fiber diameter of the trunk portion is less than 9.0 μm. However, the thickness of the separator can be adjusted to less than 9.0 μm. Further, the solvent-spun cellulose fiber and the synthetic fiber are entangled, and the mechanical strength such as tensile strength can be increased while having a low basis weight and a low thickness. As a result, the handling property as a separator and the effect of suppressing internal short circuit failure can be dramatically improved. Furthermore, since the capacitor separator can be made denser and thinner, the capacitor internal resistance can be kept low, and a capacitor separator that can reduce the leakage current of the capacitor can be obtained.
以下、本発明のキャパシタ用セパレータについて詳細に説明する。 Hereinafter, the capacitor separator of the present invention will be described in detail.
本発明におけるキャパシタとは、対向する2つの電極間に誘電体又は電気二重層を挟んだ形で構成されてなる蓄電機能を有するものである。誘電体を用いるものとしては、アルミ電解コンデンサやタンタル電解コンデンサが挙げられ、電気二重層を用いるものとしては、電気二重層キャパシタが挙げられる。電気二重層キャパシタの電極としては、一対の分極性電極、一方が分極性電極でもう片面が非分極性電極の組み合わせのいずれでも良い。キャパシタの電解液は、水溶液系、有機電解液系のいずれでも良い。 The capacitor in the present invention has a power storage function configured by sandwiching a dielectric or electric double layer between two opposing electrodes. Examples of using a dielectric include an aluminum electrolytic capacitor and a tantalum electrolytic capacitor, and examples of using an electric double layer include an electric double layer capacitor. The electrode of the electric double layer capacitor may be a pair of polarizable electrodes, one of which is a polarizable electrode and the other of which is a nonpolarizable electrode. The electrolytic solution for the capacitor may be either an aqueous solution type or an organic electrolyte type.
本発明における溶剤紡糸セルロース繊維とは、従来のビスコースレーヨンや銅アンモニアレーヨンのように、セルロースを一旦セルロース誘導体に化学的に変換させたのち再度セルロースに戻す、いわゆる再生セルロース繊維と異なり、セルロースを化学的に変化させることなく、アミンオキサイドに溶解させた紡糸原液を水中に乾湿式紡糸してセルロースを析出させた繊維を指す。 The solvent-spun cellulose fiber in the present invention is different from the so-called regenerated cellulose fiber in which cellulose is once chemically converted into a cellulose derivative and then returned to cellulose like conventional viscose rayon or copper ammonia rayon. This refers to a fiber in which cellulose is precipitated by dry and wet spinning of a spinning stock solution dissolved in amine oxide in water without being chemically changed.
溶剤紡糸セルロース繊維は、繊維長軸方向に分子が高度に配列しているため、湿潤状態で摩擦等の機械的な力が加えられると、繊維の表面から徐々にフィブリル化が進み、細くて長い微細繊維が、幹から枝分かれしたように生成する。フィブリル化とは、フィルム状ではなく、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、少なくとも一部が繊維径1μm以下になっている繊維を指す。本発明では、溶剤紡糸セルロース繊維の幹部分の最大繊維径が9.0μm未満になるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を用いることが好ましい。溶剤紡糸セルロース繊維の幹部分の最大繊維径は、8.0μm未満がより好ましく、7.0μm未満が更に好ましい。幹部分の最大繊維径が9.0μm以上の場合、フィブリル化した溶剤紡糸セルロース繊維の配合量を50質量%以上とした場合では、坪量を低減調整しても、又は、カレンダー処理や熱カレンダー処理の線圧を最大限調整しても、セパレータの厚みを9.0μm未満にすることが困難となる。一方、幹部分の最大繊維径が2.0μm未満の場合、繊維長が短くなりやすく、繊維同士の絡みが低下するため、セパレータの機械強度が低下する場合があるので、幹部分の最大繊維径は2.0μm以上であることが好ましい。本発明において、最大繊維径は、セパレータ断面の走査型電子顕微鏡観察により、セパレータを形成するフィブリル化した溶剤紡糸セルロース繊維の幹部分の一番長い直径の繊維径を計測し、無作為に選んだ100本の繊維における平均値である。 Solvent-spun cellulose fibers have a high degree of molecular alignment in the longitudinal direction of the fiber. When mechanical force such as friction is applied in a wet state, fibrillation gradually proceeds from the fiber surface, making it thin and long. Fine fibers are generated as if branched from the trunk. Fibrilization refers to a fiber that is not film-like but has a portion that is divided into a very fine portion mainly in a direction parallel to the fiber axis, and at least a portion of which has a fiber diameter of 1 μm or less. In the present invention, it is preferable to use a fibrillated solvent-spun cellulose fiber that has been beaten until the maximum fiber diameter of the trunk portion of the solvent-spun cellulose fiber is less than 9.0 μm. The maximum fiber diameter of the trunk portion of the solvent-spun cellulose fiber is more preferably less than 8.0 μm, and still more preferably less than 7.0 μm. When the maximum fiber diameter of the trunk portion is 9.0 μm or more, when the blended amount of the fibrillated solvent-spun cellulose fibers is 50% by mass or more, even if the basis weight is reduced, calendering or thermal calendar Even if the linear pressure of the treatment is adjusted to the maximum, it becomes difficult to make the thickness of the separator less than 9.0 μm. On the other hand, if the maximum fiber diameter of the trunk portion is less than 2.0 μm, the fiber length tends to be short and the entanglement between the fibers decreases, so the mechanical strength of the separator may decrease, so the maximum fiber diameter of the trunk portion Is preferably 2.0 μm or more. In the present invention, the maximum fiber diameter was randomly selected by measuring the fiber diameter of the longest diameter of the trunk portion of the fibrillated solvent-spun cellulose fiber forming the separator by scanning electron microscope observation of the separator cross section. Average value for 100 fibers.
フィブリル化した溶剤紡糸セルロース繊維を作製する方法としては、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が挙げられる。この中でも特にリファイナーが好ましい。 A fibrillated solvent-spun cellulose fiber is prepared by a refiner, a beater, a mill, an attritor, a rotary blade homogenizer that applies shear force with a high-speed rotary blade, and a cylindrical inner blade that rotates at high speed. Double-cylindrical high-speed homogenizer that generates shearing force between the outer blades, ultrasonic crusher that is refined by impact by ultrasonic waves, and passes through a small-diameter orifice by applying a pressure difference of at least 20 MPa to the fiber suspension. And a high-pressure homogenizer that applies a shearing force and a cutting force to the fiber by causing a high speed and colliding with this to rapidly decelerate. Of these, refiners are particularly preferred.
溶剤紡糸セルロース繊維のフィブリル化前の繊度(繊維径)は、1.4dtex(約11.0μm)以下が好ましく、1.25dtex(約9.5μm)以下がより好ましい。1.4dtexを超えた繊維、例えば、1.7dtex(約11.5μm)の繊維を叩解した場合、フィブリル化して枝分かれした繊維径が1.0μm以下の繊維と、叩解処理の過程で、大幹成分から割繊して分かれた中幹成分である繊維径が2.0〜4.0μmの繊維の他に、幹部分の最大繊維径が9.0μm超えの繊維(例えば、最大繊維径が9.5μmの繊維)が残ってしまい、フィブリル化した溶剤紡糸セルロース繊維の配合量を増やした場合、セパレータの厚さを9.0μm以下に潰すことが難しくなる。一方、例えば、1.25dtexの繊維を叩解した場合、フィブリル化して枝分かれした繊維径が1.0μm以下の繊維と、叩解処理の過程で、大幹成分から割繊して分かれた中幹成分の繊維径が1.0〜3.0μmの繊維が得られ、最大でも8.0μm未満にまで幹部分の最大繊維径を細くすることが可能である。そのため、配合量を増やした場合でも、セパレータの厚さを8.0μm以下にまで潰すことが可能である。 The fineness (fiber diameter) of the solvent-spun cellulose fiber before fibrillation is preferably 1.4 dtex (about 11.0 μm) or less, more preferably 1.25 dtex (about 9.5 μm) or less. When fibers exceeding 1.4 dtex, for example, 1.7 dtex (about 11.5 μm) fibers are beaten, fibers having a fiber diameter of 1.0 μm or less that are fibrillated and branched, In addition to fibers having a fiber diameter of 2.0 to 4.0 μm, which is a medium trunk component divided by splitting from the components, fibers having a maximum fiber diameter of more than 9.0 μm in the trunk portion (for example, a maximum fiber diameter of 9 .5 μm fiber) remains, and when the blended amount of the fibrillated solvent-spun cellulose fiber is increased, it becomes difficult to crush the thickness of the separator to 9.0 μm or less. On the other hand, for example, when a 1.25 dtex fiber is beaten, a fibrillated and branched fiber having a fiber diameter of 1.0 μm or less and a middle trunk component separated by splitting from a major trunk component in the process of beating A fiber having a fiber diameter of 1.0 to 3.0 μm is obtained, and the maximum fiber diameter of the trunk portion can be reduced to a maximum of less than 8.0 μm. Therefore, even when the blending amount is increased, the thickness of the separator can be crushed to 8.0 μm or less.
フィブリル化した溶剤紡糸セルロース繊維の長さ加重平均繊維長は、JAPAN TAPPI 紙パルプ試験方法No.52「紙及びパルプの繊維長 試験方法(光学的自動計測法)」に準じて、繊維長測定装置(例えば、Fiber Lab、Metso Automation K.K製)で測定することができる。フィブリル化した溶剤紡糸セルロース繊維の長さ加重平均繊維長は、0.2〜3.0mmが好ましく、0.5〜2.0mmがより好ましく、0.7〜1.1mmが更に好ましい。繊維長が0.2mmより短いと、セパレータから脱落する場合やセパレータの機械強度が低下する場合があり、3.0mmより長いと、繊維のフィブリル化が不十分となり、内部短絡不良率が高くなる場合や繊維がもつれてダマになることがあり、厚みむらが生じる場合がある。 The length-weighted average fiber length of the fibrillated solvent-spun cellulose fiber is determined by the JAPAN TAPPI paper pulp test method no. In accordance with 52 “Fiber length test method of paper and pulp (automatic optical measurement method)”, it can be measured with a fiber length measuring device (for example, manufactured by Fiber Lab, Metso Automation KK). The length-weighted average fiber length of the fibrillated solvent-spun cellulose fiber is preferably 0.2 to 3.0 mm, more preferably 0.5 to 2.0 mm, and still more preferably 0.7 to 1.1 mm. When the fiber length is shorter than 0.2 mm, the separator may fall off or the mechanical strength of the separator may be lowered. When the fiber length is longer than 3.0 mm, the fiber becomes insufficiently fibrillated and the internal short circuit defect rate increases. In some cases, the fibers may become tangled and become lumpy, resulting in uneven thickness.
本発明のキャパシタ用セパレータは、幹部分の最大繊維径が9.0μm未満になるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を50質量%以上含有する。フィブリル化した溶剤紡糸セルロース繊維の含有量は、50〜90質量%がより好ましく、60〜80質量%が更に好ましい。フィブリル化した溶剤紡糸セルロース繊維の含有率が50質量%未満の場合、低坪量とした時に、電解液の保液性が不十分で、キャパシタの内部抵抗が高くなる。また、セパレータの緻密性が不十分で、キャパシタの内部短絡不良率や漏れ電流が高くなる。フィブリル化した溶剤紡糸セルロース繊維の含有率が90質量%を超える場合、合成繊維の含有量が減少するため、セパレータの機械強度が低下する場合がある。また、カレンダー処理や熱カレンダー処理による厚さ調整において、フィブリル化した溶剤紡糸セルロースが空隙を埋めてしまい、保液性が低下して、キャパシタの内部抵抗が高くなる場合がある。 The capacitor separator of the present invention contains 50% by mass or more of fibrillated solvent-spun cellulose fibers that have been beaten until the maximum fiber diameter of the trunk portion is less than 9.0 μm. The content of the fibrillated solvent-spun cellulose fiber is more preferably 50 to 90% by mass, and still more preferably 60 to 80% by mass. When the content of the fibrillated solvent-spun cellulose fiber is less than 50% by mass, when the basis weight is low, the liquid retentivity of the electrolytic solution is insufficient and the internal resistance of the capacitor is increased. Further, the density of the separator is insufficient, and the internal short circuit defect rate and the leakage current of the capacitor are increased. When the content rate of the fibrillated solvent-spun cellulose fiber exceeds 90% by mass, the content of the synthetic fiber decreases, so that the mechanical strength of the separator may decrease. In addition, in the thickness adjustment by the calendar process or the heat calendar process, the fibrillated solvent-spun cellulose may fill the gap, resulting in a decrease in liquid retention and an increase in the internal resistance of the capacitor.
本発明のキャパシタ用セパレータに使用される合成繊維としては、ポリエステル、アクリル、ポリオレフィン、全芳香族ポリエステル、全芳香族ポリエステルアミド、ポリアミド、半芳香族ポリアミド、全芳香族ポリアミド、全芳香族ポリエーテル、全芳香族ポリカーボネート、ポリイミド、ポリアミドイミド(PAI)、ポリエーテルエーテルケトン(PEEK)、ポリフェニレンスルフィド(PPS)、ポリ−p−フェニレンベンゾビスオキサゾール(PBO)、ポリベンゾイミダゾール(PBI)、ポリテトラフルオロエチレン(PTFE)、エチレン−ビニルアルコール共重合体などの樹脂からなる単繊維や複合繊維を挙げることができる。これらの合成繊維は、単独で使用しても良いし、2種類以上の組み合わせで使用しても良い。また、各種の分割型複合繊維を分割させたものを使用しても良い。この中でも、ポリエステル、アクリル、ポリオレフィン、全芳香族ポリエステル、全芳香族ポリエステルアミド、ポリアミド、半芳香族ポリアミド、全芳香族ポリアミドが好ましく、ポリエステル、アクリル、ポリオレフィンが更に好ましい。ポリエステル、アクリル、ポリオレフィンを使用すると、他の合成繊維よりも各繊維とフィブリル化した溶剤紡糸セルロース繊維とが均一に絡み合ってネットワーク構造を形成しやすいため、表面の平滑性がより高く、緻密性や機械強度に優れたキャパシタ用セパレータを得ることができる。 Synthetic fibers used in the capacitor separator of the present invention include polyester, acrylic, polyolefin, wholly aromatic polyester, wholly aromatic polyester amide, polyamide, semi-aromatic polyamide, wholly aromatic polyamide, wholly aromatic polyether, Totally aromatic polycarbonate, polyimide, polyamideimide (PAI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), poly-p-phenylenebenzobisoxazole (PBO), polybenzimidazole (PBI), polytetrafluoroethylene Examples thereof include single fibers and composite fibers made of a resin such as (PTFE) and ethylene-vinyl alcohol copolymer. These synthetic fibers may be used alone or in combination of two or more. Moreover, you may use what divided | segmented various split type composite fibers. Among these, polyester, acrylic, polyolefin, wholly aromatic polyester, wholly aromatic polyester amide, polyamide, semi-aromatic polyamide, and wholly aromatic polyamide are preferable, and polyester, acrylic, and polyolefin are more preferable. When polyester, acrylic, and polyolefin are used, each fiber and fibrillated solvent-spun cellulose fibers are more easily entangled with each other than other synthetic fibers to easily form a network structure. A capacitor separator having excellent mechanical strength can be obtained.
合成繊維の平均繊維径は0.1〜3.5μmが好ましく、0.1〜2.5μmがより好ましく、0.1〜1.5μmが更に好ましい。平均繊維径が0.1μm未満では、繊維が細すぎて、セパレータから脱落する場合があり、平均繊維径が3.5μmより太いと、セパレータの厚みを薄くすることが困難になる場合や緻密性が不十分となり、繊維本数が減るため、セパレータの機械強度が低下する場合がある。また、セパレータの厚さを薄くすると、最大細孔径が拡大し、キャパシタの内部短絡不良率が高くなる。本発明において、平均繊維径は、セパレータ断面の走査型電子顕微鏡観察により、セパレータを形成する繊維の面積を計測し、真円に換算した繊維径を計測し、無作為に選んだ100本の繊維における平均値である。 The average fiber diameter of the synthetic fiber is preferably 0.1 to 3.5 μm, more preferably 0.1 to 2.5 μm, and still more preferably 0.1 to 1.5 μm. If the average fiber diameter is less than 0.1 μm, the fibers may be too thin and fall off from the separator. If the average fiber diameter is greater than 3.5 μm, it may be difficult to reduce the thickness of the separator or the denseness. Becomes insufficient, and the number of fibers decreases, which may reduce the mechanical strength of the separator. Moreover, if the thickness of the separator is reduced, the maximum pore diameter is increased, and the internal short circuit defect rate of the capacitor is increased. In the present invention, the average fiber diameter is determined by measuring the area of the fiber forming the separator by observing the cross section of the separator with a scanning electron microscope, measuring the fiber diameter converted into a perfect circle, and randomly selecting 100 fibers. Is an average value.
合成繊維の繊維長は0.1〜10mmが好ましく、0.5〜5mmがより好ましく、1〜3mmが更に好ましい。繊維長が0.1mmより短いと、セパレータから脱落することがあり、10mmより長いと、繊維がもつれてダマになることがあり、厚みむらが生じる場合がある。 The fiber length of the synthetic fiber is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and still more preferably 1 to 3 mm. If the fiber length is shorter than 0.1 mm, it may fall off from the separator, and if it is longer than 10 mm, the fiber may become entangled and become lumpy, resulting in uneven thickness.
本発明のキャパシタ用セパレータは、合成繊維を5〜40質量%含有することが好ましい。構成繊維の含有量は10〜30質量%がより好ましく、15〜25質量%が更に好ましい。合成繊維の含有量が5質量%未満の場合、セパレータの機械強度が弱くなり、また、低厚さとした際、抵抗を示すインピーダンスの上昇が大きくなる。合成繊維の含有率が40質量%を超えた場合、低坪量とした場合、電解液の保液性が不十分で、キャパシタの内部抵抗が高くなることや、セパレータの緻密性が不十分で、キャパシタの内部短絡不良率や漏れ電流のバラツキが高くなることがある。 The capacitor separator of the present invention preferably contains 5 to 40% by mass of synthetic fiber. The content of the constituent fibers is more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass. When the content of the synthetic fiber is less than 5% by mass, the mechanical strength of the separator becomes weak, and when the thickness is reduced, the increase in impedance indicating resistance increases. If the synthetic fiber content exceeds 40% by mass, and the basis weight is low, the electrolyte retainability is insufficient, the internal resistance of the capacitor is high, and the separator is insufficiently dense. In some cases, the internal short-circuit defect rate of the capacitor and the variation in leakage current may increase.
本発明のキャパシタ用セパレータは、フィブリル化天然セルロースを含有している。その含有量は10質量%以下が好ましく、7質量%以下がより好ましく、5質量%以下が更に好ましい。溶剤紡糸セルロース繊維は、微細化処理によって繊維の長軸に平行に細かく分割されやすく、分割後の繊維1本1本における繊維径の均一性が高いため、平均繊維長が短くなるほど、繊維同士が絡みにくくなり、天然セルロース繊維よりも繊維ネットワークを形成しにくいと考えられる。これに対し、天然セルロース繊維は、微細化の程度が進むほど、繊維の幹から細かいフィブリルが多数裂けた状態になるため、繊維径の均一性は溶剤紡糸セルロース繊維よりも劣る傾向にある。しかし、フィブリルを介して繊維同士が物理的に絡みやすく、水素結合力も高いために、繊維ネットワークを形成しやすいという特徴を有する。フィブリル化天然セルロースの含有率が10質量%を超えると、セパレータ表面にフィルムを形成し、イオン伝導性が阻害されることで、キャパシタの内部抵抗が高くなることや、放電特性が低くなることがある。フィブリル化天然セルロースの含有量が2質量%未満の場合には、繊維ネットワークが減少するため、セパレータの機械強度が低下することや、キャパシタの内部短絡不良率や漏れ電流が悪化することがある。 The capacitor separator of the present invention contains fibrillated natural cellulose. The content is preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less. The solvent-spun cellulose fiber is easily divided finely in parallel with the long axis of the fiber by the refining treatment, and the uniformity of the fiber diameter in each fiber after division is high. It is thought that it becomes difficult to form a fiber network rather than a natural cellulose fiber. On the other hand, as the degree of refinement of natural cellulose fibers increases, a number of fine fibrils are torn from the fiber trunk, so the uniformity of fiber diameter tends to be inferior to that of solvent-spun cellulose fibers. However, the fibers are easily entangled with each other through the fibrils, and the hydrogen bonding force is high, so that the fiber network is easily formed. When the content of fibrillated natural cellulose exceeds 10% by mass, a film is formed on the separator surface, and the ionic conductivity is hindered, thereby increasing the internal resistance of the capacitor and decreasing the discharge characteristics. is there. When the content of the fibrillated natural cellulose is less than 2% by mass, the fiber network is decreased, so that the mechanical strength of the separator may be decreased, and the internal short circuit defect rate and the leakage current of the capacitor may be deteriorated.
本発明のキャパシタ用セパレータに使用されるフィブリル化天然セルロースは、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。 The fibrillated natural cellulose used in the capacitor separator of the present invention includes a refiner, a beater, a mill, an attritor, a rotary blade homogenizer that applies shearing force by a high-speed rotary blade, a cylindrical inner blade that rotates at high speed, Double-cylindrical high-speed homogenizer that generates a shearing force with a fixed outer blade, ultrasonic crusher that is refined by impact by ultrasonic waves, and a small-diameter orifice by applying a pressure difference of at least 20 MPa to the fiber suspension Is treated with a high-pressure homogenizer that applies shearing force or cutting force to the fiber by causing the fiber to pass through and high speed, and then rapidly decelerating. Among these, those treated with a high-pressure homogenizer are particularly preferable. .
本発明のキャパシタ用セパレータは、円網、長網、短網、傾斜型短網等の抄紙方式の中から1種の抄紙方式を有する抄紙機、同種又は異種の2種以上の抄紙方式を組み合わせてなるコンビネーション抄紙機などを用いて抄紙する方法によって製造することができる。原料スラリーには、繊維原料の他に、必要に応じて、分散剤、増粘剤、無機填料、有機填料、消泡剤などを適宜添加することができ、5〜0.001質量%程度の固形分濃度に原料スラリーを調製する。この原料スラリーをさらに所定濃度に希釈して抄紙し、乾燥する。抄紙して得られたキャパシタ用セパレータは、必要に応じて、カレンダー処理、熱カレンダー処理、熱処理などが施される。 The capacitor separator of the present invention is a combination of a paper machine having one type of paper making method among two types of paper making methods such as a circular net, a long net, a short net, and an inclined short net, and a combination of two or more types of paper making methods of the same type or different types. It can manufacture by the method of paper-making using the combination paper machine etc. which become. In addition to the fiber raw material, a dispersant, a thickener, an inorganic filler, an organic filler, an antifoaming agent, and the like can be appropriately added to the raw material slurry, if necessary, and about 5 to 0.001% by mass. Prepare raw slurry to solid content concentration. The raw slurry is further diluted to a predetermined concentration to make a paper, and then dried. The capacitor separator obtained by papermaking is subjected to calendering, thermal calendering, heat treatment, etc., as necessary.
キャパシタ用セパレータの坪量は、5.0〜15.0g/m2が好ましく、5.0〜10.0g/m2がより好ましく、5.0〜8.0g/m2が更に好ましい。5.0g/m2未満では、十分な機械強度が得られない場合があり、正極と負極との間の絶縁性が不十分で、キャパシタの内部短絡不良率や漏れ電流が悪化する場合がある。15.0g/m2を超えると、キャパシタの内部抵抗が高くなる場合や、放電特性が低くなる場合がある。本発明のセパレータの坪量は、JIS P8124に準拠して測定した値である。本発明では、幹部分の最大繊維径を9.0μm未満になるまで叩解が進められたフィブリル化した溶剤紡糸セルロース繊維を用いることで、該溶剤紡糸セルロース繊維の配合量を50質量%以上に増やしても、セパレータの厚さを9.0μm未満に調整できるようになる。また、該溶剤紡糸セルロース繊維と合成繊維が絡み合い、低坪量・低厚みでありながら、引張強度等の機械強度を高めることができる。その結果、セパレータとしてのハンドリング性や内部短絡不良抑制効果を飛躍的に向上させることができる。さらに、キャパシタ用セパレータをより緻密で薄くすることができるため、キャパシタの内部抵抗を低く抑えることができ、放電特性や漏れ電流が小さいキャパシタを得ることができる。 The basis weight of the separator for the capacitor is preferably 5.0~15.0g / m 2, more preferably 5.0~10.0g / m 2, more preferably 5.0~8.0g / m 2. If it is less than 5.0 g / m 2 , sufficient mechanical strength may not be obtained, insulation between the positive electrode and the negative electrode may be insufficient, and the internal short circuit failure rate and leakage current of the capacitor may deteriorate. . If it exceeds 15.0 g / m 2 , the internal resistance of the capacitor may increase or the discharge characteristics may decrease. The basis weight of the separator of the present invention is a value measured in accordance with JIS P8124. In the present invention, the blended amount of the solvent-spun cellulose fiber is increased to 50% by mass or more by using the fibrillated solvent-spun cellulose fiber that has been beaten until the maximum fiber diameter of the trunk portion is less than 9.0 μm. However, the thickness of the separator can be adjusted to less than 9.0 μm. Further, the solvent-spun cellulose fiber and the synthetic fiber are entangled, and the mechanical strength such as tensile strength can be increased while having a low basis weight and a low thickness. As a result, the handling property as a separator and the effect of suppressing internal short circuit failure can be dramatically improved. Furthermore, since the capacitor separator can be made denser and thinner, the internal resistance of the capacitor can be kept low, and a capacitor with low discharge characteristics and leakage current can be obtained.
キャパシタ用セパレータの厚さは、6.0〜20.0μmが好ましく、7.0〜15.0μmがより好ましく、7.0〜10.0μmが更に好ましい。6.0μm未満では、十分な機械強度が得られなかったり、正極と負極との間の絶縁性が不十分で、キャパシタの内部短絡不良率や漏れ電流が悪くなったりする場合がある。20.0μmより厚いと、キャパシタの内部抵抗が高くなり、放電特性が低くなる場合がある。なお、本発明のセパレータの厚さはJIS B7502に規定された方法により測定した値、つまり、5N荷重時の外側マイクロメーターにより測定された値を意味する。 The thickness of the capacitor separator is preferably 6.0 to 20.0 μm, more preferably 7.0 to 15.0 μm, still more preferably 7.0 to 10.0 μm. If the thickness is less than 6.0 μm, sufficient mechanical strength may not be obtained, or insulation between the positive electrode and the negative electrode may be insufficient, and the internal short circuit failure rate and leakage current of the capacitor may deteriorate. If it is thicker than 20.0 μm, the internal resistance of the capacitor may increase and the discharge characteristics may decrease. The thickness of the separator of the present invention means a value measured by a method defined in JIS B7502, that is, a value measured by an outer micrometer at a load of 5N.
キャパシタ用セパレータの引張強度は、250N/m以上であることが好ましく、300N/m以上であることがより好ましく、400N/m以上であることが更に好ましい。引張強度が250N/m未満では、捲回作業時において内部短絡不良が発生しやすくなる。引張強度は高いほど好ましいが、坪量が5.0〜8.0g/m2の場合、フィブリル化した溶剤紡糸セルロース繊維と合成繊維とフィブリル化天然セルロールとが均一に絡み合ってネットワーク構造を形成しても、引張強度が500N/mを超える可能性は少ない。 The tensile strength of the capacitor separator is preferably 250 N / m or more, more preferably 300 N / m or more, and still more preferably 400 N / m or more. If the tensile strength is less than 250 N / m, an internal short circuit failure is likely to occur during the winding operation. Higher tensile strength is preferable, but when the basis weight is 5.0 to 8.0 g / m 2 , the fibrillated solvent-spun cellulose fiber, the synthetic fiber, and the fibrillated natural cellulose are uniformly entangled to form a network structure. However, there is little possibility that the tensile strength exceeds 500 N / m.
キャパシタ用セパレータのインピーダンスは、キャパシタを組んだ際の内部抵抗と相関があり、0.50Ω以下であることが好ましく、0.45Ω以下であることがより好ましく、0.40Ω以下であることが更に好ましい。セパレータのインピーダンスが0.40Ω以下であれば、放電特性やサイクル特性に優れるキャパシタを得ることができる。キャパシタのインピーダンスが0.50Ωを超えた場合、キャパシタの内部抵抗が高くなり、放電特性やサイクル特性が低下する場合がある。 The impedance of the capacitor separator has a correlation with the internal resistance when the capacitor is assembled, and is preferably 0.50Ω or less, more preferably 0.45Ω or less, and further preferably 0.40Ω or less. preferable. When the impedance of the separator is 0.40Ω or less, a capacitor having excellent discharge characteristics and cycle characteristics can be obtained. When the impedance of the capacitor exceeds 0.50Ω, the internal resistance of the capacitor increases, and the discharge characteristics and the cycle characteristics may deteriorate.
以下、実施例により本発明を更に詳しく説明するが、本発明は実施例に限定されるものではない。なお、実施例1は参考例である。
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to an Example. Example 1 is a reference example.
実施例1
リファイナーを用いて、1.4dtex(平均繊維径11.0μm)、繊維長4mmの溶剤紡糸セルロース繊維を処理し、幹部分の最大繊維径が8.8μmになるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化ポリエチレンテレフタレート(PET)短繊維を25質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%を一緒に混合し、パルパーの水中で離解させ、アジテーターによる撹拌のもと、均一な原料スラリー(0.3質量%濃度)を調製した。この原料スラリーから、傾斜型短網抄紙機を用いて、湿潤シートを得て、ヤンキードライヤー温度130℃で乾燥した後、金属ロールと弾性ロールによるカレンダー処理を施して、坪量6.3g/m2、厚さ9.2μmのキャパシタ用セパレータを得た。
Example 1
Using refiner, solvent-spun cellulose fiber with 1.4 dtex (average fiber diameter of 11.0 μm) and fiber length of 4 mm was processed, and the fibrillated solvent was advanced until the maximum fiber diameter of the trunk portion was 8.8 μm. Fibrilized natural cellulose 5 with 70% by mass of spun cellulose fiber, 25% by mass of oriented crystallized polyethylene terephthalate (PET) short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and a linter refined using a high-pressure homogenizer The mass% was mixed together, disaggregated in the water of the pulper, and a uniform raw material slurry (0.3 mass% concentration) was prepared under stirring by an agitator. From this raw material slurry, a wet sheet is obtained using an inclined short paper machine, dried at a Yankee dryer temperature of 130 ° C., and then calendered with a metal roll and an elastic roll to obtain a basis weight of 6.3 g / m. 2. A capacitor separator having a thickness of 9.2 μm was obtained.
実施例2
リファイナーを用いて、1.25dtex(平均繊維径9.5μm)、繊維長4mmの溶剤紡糸セルロース繊維を処理し、幹部分の最大繊維径が7.8μmになるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を使用した以外は、実施例1と同様な方法で、坪量6.1g/m2、厚さ8.2μmのキャパシタ用セパレータを得た。
Example 2
Using a refiner, a solvent-spun cellulose fiber having a fiber length of 1.25 dtex (average fiber diameter of 9.5 μm) and a fiber length of 4 mm was processed, and beating was performed until the maximum fiber diameter of the trunk portion reached 7.8 μm. A capacitor separator having a basis weight of 6.1 g / m 2 and a thickness of 8.2 μm was obtained in the same manner as in Example 1 except that spun cellulose fibers were used.
実施例3
リファイナーを用いて、1.25dtex(平均繊維径9.5μm)、繊維長4mmの溶剤紡糸セルロース繊維を処理し、幹部分の最大繊維径が6.8μmになるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を使用した以外は、実施例1と同様な方法で、坪量5.0g/m2、厚さ7.2μmのキャパシタ用セパレータを得た。
Example 3
Using a refiner, a solvent-spun cellulose fiber having a fiber length of 1.25 dtex (average fiber diameter of 9.5 μm) and a fiber length of 4 mm was processed, and beating was performed until the maximum fiber diameter of the trunk portion reached 6.8 μm. A capacitor separator having a basis weight of 5.0 g / m 2 and a thickness of 7.2 μm was obtained in the same manner as in Example 1 except that spun cellulose fibers were used.
実施例4
フィブリル化した溶剤紡糸セルロース繊維を50質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を40質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロースを10質量%とした以外は、実施例2と同様な方法で、坪量6.2g/m2、厚さ8.4μmのキャパシタ用セパレータを得た。
Example 4
50% by mass of a fibrillated solvent-spun cellulose fiber, 40% by mass of an oriented crystallized PET short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and a fibrillated natural cellulose obtained by refining a linter using a high-pressure homogenizer A capacitor separator having a basis weight of 6.2 g / m 2 and a thickness of 8.4 μm was obtained in the same manner as in Example 2 except that the content was 10% by mass.
実施例5
フィブリル化した溶剤紡糸セルロース繊維を90質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を5質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%とした以外は、実施例2と同様な方法で、坪量6.3g/m2、厚さ8.1μmのキャパシタ用セパレータを得た。
Example 5
90% by mass of fibrillated solvent-spun cellulose fiber, 5% by mass of oriented crystallized PET short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and fibrillated natural cellulose 5 with a linter refined using a high-pressure homogenizer A capacitor separator having a basis weight of 6.3 g / m 2 and a thickness of 8.1 μm was obtained in the same manner as in Example 2 except that the mass% was used.
実施例6
フィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を25質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%とした以外は、実施例3と同様な方法で、坪量4.8g/m2、厚さ6.8μmのキャパシタ用セパレータを得た。
Example 6
70% by mass of fibrillated solvent-spun cellulose fibers, 25% by mass of oriented crystallized PET short fibers with an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and fibrillated natural cellulose 5 with a linter refined using a high-pressure homogenizer A capacitor separator having a basis weight of 4.8 g / m 2 and a thickness of 6.8 μm was obtained in the same manner as in Example 3 except that the mass% was used.
実施例7
フィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を25質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%とした以外は、実施例2と同様な方法で、坪量7.8g/m2、厚さ10.0μmのキャパシタ用セパレータを得た。
Example 7
70% by mass of fibrillated solvent-spun cellulose fibers, 25% by mass of oriented crystallized PET short fibers with an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and fibrillated natural cellulose 5 with a linter refined using a high-pressure homogenizer A separator for capacitors having a basis weight of 7.8 g / m 2 and a thickness of 10.0 μm was obtained in the same manner as in Example 2 except that the mass% was used.
実施例8
フィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を25質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%とした以外は、実施例2と同様な方法で、坪量8.2g/m2、厚さ11.0μmのキャパシタ用セパレータを得た。
Example 8
70% by mass of fibrillated solvent-spun cellulose fibers, 25% by mass of oriented crystallized PET short fibers with an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and fibrillated natural cellulose 5 with a linter refined using a high-pressure homogenizer A separator for capacitors having a basis weight of 8.2 g / m 2 and a thickness of 11.0 μm was obtained in the same manner as in Example 2 except that the mass% was used.
実施例9
フィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径1.5μm、繊維長1.5mmのPET短繊維を25質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース5質量%とした以外は、実施例2と同様な方法で、坪量6.7g/m2、厚さ8.9μmのキャパシタ用セパレータを得た。
Example 9
70% by mass of fibrillated solvent-spun cellulose fiber, 25% by mass of PET short fiber having an average fiber diameter of 1.5 μm and a fiber length of 1.5 mm, and 5% of fibrillated natural cellulose obtained by refining the linter using a high-pressure homogenizer %, A capacitor separator having a basis weight of 6.7 g / m 2 and a thickness of 8.9 μm was obtained in the same manner as in Example 2.
比較例1
リファイナーを用いて、1.7dtex(平均繊維径11.5μm)、繊維長4mmの溶剤紡糸セルロース繊維を処理し、幹部分の最大繊維径が9.5μmになるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を使用した以外は、実施例1と同様な方法で、坪量6.1g/m2、厚さ10.1μmのキャパシタ用セパレータを得た。
Comparative Example 1
Using a refiner, a solvent-spun cellulose fiber having a length of 1.7 dtex (average fiber diameter of 11.5 μm) and a fiber length of 4 mm was processed, and the fibrillated solvent was advanced to beating until the maximum fiber diameter of the trunk portion was 9.5 μm. A separator for capacitors having a basis weight of 6.1 g / m 2 and a thickness of 10.1 μm was obtained in the same manner as in Example 1 except that spun cellulose fibers were used.
比較例2
リファイナーを用いて、1.7dtex(平均繊維径11.5μm)、繊維長4mmの溶剤紡糸セルロース繊維を処理し、幹部分の最大繊維径が9.1μmになるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を使用した以外は、実施例4と同様な方法で、坪量6.2g/m2、厚さ9.5μmのキャパシタ用セパレータを得た。
Comparative Example 2
Using a refiner, a solvent-spun cellulose fiber having a length of 1.7 dtex (average fiber diameter of 11.5 μm) and a fiber length of 4 mm was processed, and the fibrillated solvent was advanced to beating until the maximum fiber diameter of the trunk portion was 9.1 μm. A capacitor separator having a basis weight of 6.2 g / m 2 and a thickness of 9.5 μm was obtained in the same manner as in Example 4 except that spun cellulose fibers were used.
比較例3
繊維配合を、比較例2で用いたフィブリル化した溶剤紡糸セルロース繊維を30質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を50質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロース20質量%とした以外は、実施例1と同様な方法で、坪量5.3g/m2、厚さ6.4μmのキャパシタ用セパレータを得た。
Comparative Example 3
The fiber blend was 30% by mass of the fibrillated solvent-spun cellulose fiber used in Comparative Example 2, 50% by mass of oriented crystallized PET short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and a linter using a high-pressure homogenizer. A separator for a capacitor having a basis weight of 5.3 g / m 2 and a thickness of 6.4 μm was obtained in the same manner as in Example 1 except that 20% by mass of the fibrillated natural cellulose was refined.
比較例4
繊維配合を、比較例2で用いたフィブリル化した溶剤紡糸セルロース繊維を100質量%とした以外は、実施例1と同様な方法で、坪量6.3g/m2、厚さ9.4μmのキャパシタ用セパレータを得た。
Comparative Example 4
The basis weight is 6.3 g / m 2 and the thickness is 9.4 μm, in the same manner as in Example 1, except that the fiber blend is 100% by mass of the fibrillated solvent-spun cellulose fiber used in Comparative Example 2. A capacitor separator was obtained.
比較例5
繊維配合を、実施例1で用いたフィブリル化した溶剤紡糸セルロース繊維を45質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を50質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロースを5質量%とした以外は、実施例1と同様な方法で、坪量6.2g/m2、厚さ9.3μmのキャパシタ用セパレータを得た。
Comparative Example 5
The fiber blend was 45% by mass of the fibrillated solvent-spun cellulose fiber used in Example 1, 50% by mass of oriented crystallized PET short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm, and a linter using a high-pressure homogenizer. A separator for capacitors having a basis weight of 6.2 g / m 2 and a thickness of 9.3 μm was obtained in the same manner as in Example 1 except that the amount of fibrillated natural cellulose obtained by refining was changed to 5% by mass.
比較例6
繊維配合を、実施例1で用いたフィブリル化した溶剤紡糸セルロース繊維を70質量%、平均繊維径2.4μm、繊維長3mmの配向結晶化PET短繊維を30質量%とした以外は、実施例1と同様な方法で、坪量6.1g/m2、厚さ9.5μmのキャパシタ用セパレータを得た。
Comparative Example 6
The fiber blending was carried out in the same manner as in Example 1 except that 70% by mass of the fibrillated solvent-spun cellulose fiber used in Example 1 and 30% by mass of oriented crystallized PET short fiber having an average fiber diameter of 2.4 μm and a fiber length of 3 mm 1 was used to obtain a capacitor separator having a basis weight of 6.1 g / m 2 and a thickness of 9.5 μm.
比較例7
繊維配合を、実施例1で用いたフィブリル化した溶剤紡糸セルロース繊維を90質量%、高圧ホモジナイザーを用いてリンターを微細化処理したフィブリル化天然セルロースを10質量%とした以外は、実施例1と同様な方法で、坪量6.2g/m2、厚さ8.8μmのキャパシタ用セパレータを得た。
Comparative Example 7
Example 1 except that the fiber blend was 90% by mass of the fibrillated solvent-spun cellulose fiber used in Example 1, and 10% by mass of fibrillated natural cellulose whose linter was refined using a high-pressure homogenizer. In the same manner, a capacitor separator having a basis weight of 6.2 g / m 2 and a thickness of 8.8 μm was obtained.
フィブリル化した溶剤紡糸セルロース繊維変法濾水度及び長さ加重平均繊維長を下記方法によって測定した。 Modified fibrillated solvent-spun cellulose fiber The freeness and length-weighted average fiber length were measured by the following methods.
[変法濾水度]
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0.1%にした以外はJIS P8121に準拠して濾水度を測定し、これを変法濾水度とした。
[Modified freeness]
An 80 mesh wire net having a wire diameter of 0.14 mm and an aperture of 0.18 mm was used as a sieve plate, and the freeness was measured in accordance with JIS P8121, except that the sample concentration was 0.1%. Degree.
[長さ加重平均繊維長]
フィブリル化した溶剤紡糸セルロース繊維の長さ加重平均繊維長は、繊維長測定装置(品名:Fiber Lab、Metso Automation K.K製)で測定した。
[Length-weighted average fiber length]
The length-weighted average fiber length of the fibrillated solvent-spun cellulose fibers was measured with a fiber length measuring device (product name: Fiber Lab, manufactured by Metso Automation KK).
<キャパシタの作製>
電極活物質として平均粒径6μmの活性炭85質量%、導電材としてカーボンブラック7質量%、結着材としてポリテトラフルオロエチレン8質量%を混錬して厚み0.2mmのシート状電極を作製した。これを厚み50μmのアルミニウム箔の両面に導電性接着剤を用いて接着させ、圧延して有効電極面積105mm巾、19.9m長の電極を作製した。この電極を正極及び負極として用いた。キャパシタ用セパレータを110mm巾、20m長にスリットし、これを負極と正極の間に介して積層し、巻回機を用いて渦巻き型に巻回して渦巻き型素子を作製した。正極側及び負極側の最外層にはいずれもセパレータを配した。この渦巻き型素子をアルミニウム製ケースに収納した。ケースに取り付けられた正極端子及び負極端子に正極リード及び負極リードを溶接した後、電解液注液口を残してケースを封口した。この素子を収納したケースごと200℃に5時間加熱し乾燥処理をした。これを室温まで放冷した後、このケース内に電解液を注入し、注液口を密栓してキャパシタを製作し、これをキャパシタとした。電解液には、プロピレンカーボネートに1.5mol/lになるように(C2H5)3(CH3)NBF4を溶解させたものを用いた。
<Production of capacitor>
A sheet-like electrode having a thickness of 0.2 mm was prepared by kneading 85% by mass of activated carbon having an average particle size of 6 μm as an electrode active material, 7% by mass of carbon black as a conductive material, and 8% by mass of polytetrafluoroethylene as a binder. . This was adhered to both surfaces of a 50 μm thick aluminum foil using a conductive adhesive, and rolled to produce an electrode having an effective electrode area width of 105 mm and a length of 19.9 m. This electrode was used as a positive electrode and a negative electrode. A capacitor separator was slit into a width of 110 mm and a length of 20 m, and this was laminated between a negative electrode and a positive electrode, and was wound in a spiral shape using a winding machine to produce a spiral element. Separators were arranged on both the positive electrode side and the negative electrode side outermost layer. This spiral element was housed in an aluminum case. The positive electrode lead and the negative electrode lead were welded to the positive electrode terminal and the negative electrode terminal attached to the case, and then the case was sealed leaving the electrolyte injection port. The case containing this element was heated to 200 ° C. for 5 hours for drying treatment. After allowing this to cool to room temperature, an electrolyte was poured into the case, and the liquid inlet was sealed to produce a capacitor, which was used as the capacitor. As the electrolytic solution, a solution obtained by dissolving (C 2 H 5 ) 3 (CH 3 ) NBF 4 in propylene carbonate so as to have a concentration of 1.5 mol / l was used.
実施例及び比較例のセパレータについて、下記評価を行い、結果を表1に示した。 The separators of Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 1.
[坪量]
JIS P8124に準拠して坪量を測定した。
[Basis weight]
The basis weight was measured in accordance with JIS P8124.
[厚さ]
JIS B7502に規定された方法、つまり、5N荷重時の外側マイクロメーターにより、厚さを測定した。
[thickness]
The thickness was measured by the method defined in JIS B7502, that is, by an outer micrometer at 5N load.
[引張強度]
作製したセパレータについて、卓上型材料試験機(株式会社オリエンテック製、商品名STA−1150)を用いて、JIS P8113に準じて縦方向の引張強さを測定した。試験片のサイズは、縦方向250mm、幅50mmとし、2個のつかみ具の間隔を100mm、引張速度を300mm/minとした。
[Tensile strength]
About the produced separator, the tensile strength of the vertical direction was measured according to JISP8113 using the desktop type | mold material testing machine (Orientec Co., Ltd. make, brand name STA-1150). The size of the test piece was 250 mm in the vertical direction, 50 mm in width, the interval between the two grippers was 100 mm, and the tensile speed was 300 mm / min.
[インピーダンス]
作製したセパレータについて、電解液(プロピレンカーボネートに1.5mol/lになるように(C2H5)3(CH3)NBF4を溶解させたもの)に浸した後、2つの略円筒形アルミ電極に挟み、LCRメーター(Instec社製、装置名:LCR−821)を使用して、振幅100mVで100kHzにおける交流インピーダンスの抵抗成分を測定した。
[Impedance]
The separator was prepared, was immersed in the electrolyte (to be 1.5 mol / l in propylene carbonate (C 2 H 5) 3 ( CH 3) NBF 4 obtained by dissolving a), two substantially cylindrical aluminum A resistance component of AC impedance at 100 kHz with an amplitude of 100 mV was measured using an LCR meter (manufactured by Instec, apparatus name: LCR-821).
[内部短絡不良率]
作製したキャパシタに2.5Vの直流電圧を72時間印加した後、2.5Vまで充電し、充電直後の漏れ電流を測定し、10mA以上の漏れ電流が観測されたものを内部短絡不良と見なし、100個あたりの内部短絡不良率を求め、内部短絡不良率とした。
[Internal short-circuit failure rate]
After applying a DC voltage of 2.5V to the fabricated capacitor for 72 hours, charging it to 2.5V, measuring the leakage current immediately after charging, and assuming that a leakage current of 10 mA or more was observed as an internal short circuit failure, The internal short circuit failure rate per 100 pieces was determined and used as the internal short circuit failure rate.
[漏れ電流]
キャパシタを2.5Vで定電圧放電し、24時間保持した時に計測される電流値を漏れ電流(mA)とした。漏れ電流が小さいほど、好ましい。
[Leak current]
A current value measured when the capacitor was discharged at a constant voltage of 2.5 V and held for 24 hours was defined as a leakage current (mA). The smaller the leakage current, the better.
表1に示した通り、実施例1〜9のキャパシタ用セパレータは、幹部分の最大繊維径が9.0μm未満になるまで叩解を進めたフィブリル化した溶剤紡糸セルロース繊維を50質量%以上含有しているため、低坪量で、しかも低厚みでありながらも、機械強度が強く、キャパシタの内部短絡不良率が少ない。また、抵抗成分を表すインピーダンスが低かった。さらに、キャパシタ用セパレータの厚みは、フィブリル化した溶剤紡糸セルロース繊維の幹部分の最大繊維径に近い厚さにまで容易に潰すことが可能であった。 As shown in Table 1, the capacitor separators of Examples 1 to 9 contain 50% by mass or more of fibrillated solvent-spun cellulose fibers that have been beaten until the maximum fiber diameter of the trunk portion is less than 9.0 μm. Therefore, the mechanical strength is strong and the internal short-circuit defect rate of the capacitor is small although the basis weight is low and the thickness is low. Also, the impedance representing the resistance component was low. Furthermore, the thickness of the capacitor separator could be easily crushed to a thickness close to the maximum fiber diameter of the trunk portion of the fibrillated solvent-spun cellulose fiber.
坪量が5.0g/m2未満で、厚みが7.0μm未満の低坪量、低厚みのセパレータである実施例6のキャパシタ用セパレータと比較して、坪量が5.0g/m2以上で、厚みが7.0μm以上である実施例1〜5、7〜9のキャパシタ用セパレータは、引張強度が高く、キャパシタの内部短絡不良率が低く、漏れ電流も小さかった。 Basis weight is less than 5.0 g / m 2, a low basis weight of less than thickness 7.0 .mu.m, as compared to the capacitor separator of Example 6 is a separator of a low thickness, basis weight of 5.0 g / m 2 As described above, the capacitor separators of Examples 1 to 5 and 7 to 9 having a thickness of 7.0 μm or more had high tensile strength, a low internal short-circuit failure rate, and a small leakage current.
坪量が8.0g/m2を超え、厚みが10.0μmを超えている実施例8のキャパシタ用セパレータと比較して、実施例1〜7及び9のキャパシタ用セパレータは、抵抗成分を表すインピーダンスが低かった。 Compared with the capacitor separator of Example 8 in which the basis weight exceeds 8.0 g / m 2 and the thickness exceeds 10.0 μm, the capacitor separators in Examples 1 to 7 and 9 represent resistance components. The impedance was low.
実施例2と実施例9の比較から、合成繊維であるポリエステル繊維の平均繊維径が1.5μmである実施例9のキャパシタ用セパレータは、該平均繊維径が2.4μmである実施例2のキャパシタ用セパレータと比較して、引張強度が高く、インピーダンスも低く抑えられ、キャパシタの漏れ電流も小さかった。 From the comparison between Example 2 and Example 9, the capacitor separator of Example 9 in which the average fiber diameter of the polyester fiber, which is a synthetic fiber, is 1.5 μm is the same as that of Example 2 in which the average fiber diameter is 2.4 μm. Compared with the capacitor separator, the tensile strength was high, the impedance was kept low, and the leakage current of the capacitor was also small.
一方、幹部分の最大繊維径が9.0μmを超えたフィブリル化した溶剤紡糸セルロース繊維を使用した比較例1のキャパシタ用セパレータは、加工速度5m/分、線圧を200kN/m、ヒートロール(金属ロール)温度100℃の条件でカレンダー処理しても、セパレータの厚さが10.0μmを下回ることができなかった。また、フィブリル化天然セルロース繊維と合成繊維とフィブリル化天然セルロースの配合比率が同じであり、同坪量である実施例2のセパレータと比較して、引張強度も低く、キャパシタの内部短絡不良率と漏れ電流が悪化した。 On the other hand, the capacitor separator of Comparative Example 1 using fibrillated solvent-spun cellulose fibers having a trunk portion having a maximum fiber diameter exceeding 9.0 μm has a processing speed of 5 m / min, a linear pressure of 200 kN / m, a heat roll ( (Metal roll) Even when the calendar treatment was performed at a temperature of 100 ° C., the thickness of the separator could not fall below 10.0 μm. In addition, the blending ratio of the fibrillated natural cellulose fiber, the synthetic fiber, and the fibrillated natural cellulose is the same, and compared with the separator of Example 2 having the same basis weight, the tensile strength is low, and the internal short circuit failure rate of the capacitor The leakage current deteriorated.
幹部分の最大繊維径が9.0μmを超えたフィブリル化した溶剤紡糸セルロース繊維を使用した比較例2のキャパシタ用セパレータは、フィブリル化天然セルロース繊維と合成繊維とフィブリル化天然セルロースの配合比率が同じであり、同坪量である実施例4のセパレータと比較して、引張強度が低く、キャパシタの内部短絡不良率と漏れ電流が悪化し、セパレータも厚くなった。 The capacitor separator of Comparative Example 2 using the fibrillated solvent-spun cellulose fiber having the maximum fiber diameter of the trunk portion exceeding 9.0 μm has the same blending ratio of the fibrillated natural cellulose fiber, the synthetic fiber, and the fibrillated natural cellulose. Compared with the separator of Example 4 having the same basis weight, the tensile strength was low, the internal short-circuit defect rate and the leakage current of the capacitor were deteriorated, and the separator was also thickened.
幹部分の最大繊維径が9.0μmを超えたフィブリル化した溶剤紡糸セルロース繊維の配合量を30質量%に抑えた比較例3のキャパシタ用セパレータは、セパレータを薄くすることができているが、引張強度の低下が著しく、キャパシタの内部短絡不良率が悪化し、抵抗成分のインピーダンスが上昇し、キャパシタの漏れ電流が悪化した。 The capacitor separator of Comparative Example 3 in which the blending amount of the fibrillated solvent-spun cellulose fiber having a maximum fiber diameter of the trunk portion exceeding 9.0 μm was suppressed to 30% by mass was able to make the separator thin. The drop in tensile strength was remarkable, the internal short circuit defect rate of the capacitor was deteriorated, the impedance of the resistance component was increased, and the leakage current of the capacitor was deteriorated.
比較例4のキャパシタ用セパレータは、幹部分の最大繊維径が9.0μmを超えたフィブリル化した溶剤紡糸セルロース繊維のみで構成したセパレータであるが、引張強度が低下し、キャパシタの内部短絡不良率と漏れ電流が悪化し、インピーダンスが上昇した。 The capacitor separator of Comparative Example 4 is a separator composed only of fibrillated solvent-spun cellulose fibers having a trunk portion having a maximum fiber diameter exceeding 9.0 μm. However, the tensile strength is reduced and the internal short-circuit defect rate of the capacitor is reduced. The leakage current worsened and the impedance increased.
比較例5のキャパシタ用セパレータは、幹部分の最大繊維径が9.0μm未満のフィブリル化した溶剤紡糸セルロース繊維の含有量が50質量%未満の場合であるが、引張強度が低下し、キャパシタの内部短絡不良率と漏れ電流が悪化し、電解液の保液性が低下するため、インピーダンスが上昇した。 The capacitor separator of Comparative Example 5 is a case where the content of the fibrillated solvent-spun cellulose fiber having a maximum fiber diameter of the trunk portion of less than 9.0 μm is less than 50% by mass, but the tensile strength is lowered, Impedance increased because the internal short circuit failure rate and leakage current deteriorated and the electrolyte retention decreased.
比較例6のキャパシタ用セパレータは、フィブリル化天然セルロースを含まず、幹部分の最大繊維径が9.0μm未満のフィブリル化した溶剤紡糸セルロース繊維と合成繊維で構成したセパレータであるが、引張強度が低下し、キャパシタの内部短絡不良率が悪化した。 The capacitor separator of Comparative Example 6 is a separator composed of fibrillated solvent-spun cellulose fibers and synthetic fibers that do not contain fibrillated natural cellulose and the trunk has a maximum fiber diameter of less than 9.0 μm. The internal short circuit failure rate of the capacitor deteriorated.
比較例7のキャパシタ用セパレータは、合成繊維を含まず、幹部分の最大繊維径が9.0μm未満のフィブリル化した溶剤紡糸セルロース繊維とフィブリル化天然セルロースで構成したセパレータであるが、厚みが薄いにもかかわらず、インピーダンスが上昇した。 The capacitor separator of Comparative Example 7 is a separator composed of fibrillated solvent-spun cellulose fibers and a fibrillated natural cellulose that do not contain synthetic fibers and have a trunk portion with a maximum fiber diameter of less than 9.0 μm, but is thin. Nevertheless, the impedance increased.
実施例と比較例で用いたフィブリル化溶剤紡糸セルロース繊維を比較すると、変法濾水度や加重平均繊維長がほぼ同じでも、幹部分の最大繊維径が異なるフィブリル化状態が得られ、セパレータの厚みは幹部分の最大繊維径に依存することがわかる。 Comparing the fibrillated solvent-spun cellulose fibers used in the examples and comparative examples, even if the modified freeness and the weighted average fiber length are almost the same, a fibrillated state in which the maximum fiber diameter of the trunk portion is different is obtained, and the separator It can be seen that the thickness depends on the maximum fiber diameter of the trunk portion.
本発明の活用例としては、キャパシタ用セパレータが好適である。 As an application example of the present invention, a capacitor separator is suitable.
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