JP2000215876A - Battery separator and battery using the same - Google Patents
Battery separator and battery using the sameInfo
- Publication number
- JP2000215876A JP2000215876A JP11312084A JP31208499A JP2000215876A JP 2000215876 A JP2000215876 A JP 2000215876A JP 11312084 A JP11312084 A JP 11312084A JP 31208499 A JP31208499 A JP 31208499A JP 2000215876 A JP2000215876 A JP 2000215876A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- component
- nonwoven fabric
- battery
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Paper (AREA)
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケル−カドミ
ウム電池、ニッケル−亜鉛電池、ニッケル−水素電池等
のアルカリ蓄電池用に好適な電池用セパレータおよびそ
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery separator suitable for alkaline storage batteries such as nickel-cadmium batteries, nickel-zinc batteries, nickel-metal hydride batteries, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、電池用セパレータとしては、ポリ
プロピレン等のポリオレフィン系繊維からなる不織布が
好ましく使用されており、特にポリオレフィン系極細繊
維からなる不織布を親水化処理した電池用セパレータが
提案されている。例えば、本出願人において特開平５−
１８６９１１号公報および特開平５−１８６９６４号公
報には、メチルペンテン系重合体／ポリオレフィン系重
合体の組み合わせからなる分割型複合繊維にスルホン基
を導入したスルホン化ポリオレフィン系繊維を６０重量
％以上含有する繊維集合体を提案している。2. Description of the Related Art In recent years, as a battery separator, a nonwoven fabric made of a polyolefin fiber such as polypropylene has been preferably used. In particular, a battery separator obtained by hydrophilizing a nonwoven fabric made of a polyolefin ultrafine fiber has been proposed. . For example, in the present applicant,
JP-A-186911 and JP-A-5-186964 contain 60% by weight or more of a sulfonated polyolefin-based fiber obtained by introducing a sulfone group into a splittable conjugate fiber composed of a combination of a methylpentene-based polymer / polyolefin-based polymer. A fiber assembly is proposed.
【０００３】また、特開平７−１４７１５４号公報に
は、ポリオレフィン系分割型複合繊維５０重量％以上か
らなる水流絡合不織布をビニルモノマーのグラフト重
合、スルホン化処理などの親水化処理した電池用セパレ
ータが開示されている。また、特開平８−２７３６５４
号公報には、ポリオレフィン系極細繊維が５０重量％以
上からなり、極細繊維同士を部分的に融着させた水流絡
合不織布を親水化処理した電池用セパレータが開示され
ている。Japanese Patent Application Laid-Open No. 7-147154 discloses a battery separator in which a hydroentangled nonwoven fabric comprising 50% by weight or more of a polyolefin-based splittable conjugate fiber is subjected to hydrophilic treatment such as graft polymerization of vinyl monomer and sulfonation treatment. Is disclosed. Also, Japanese Patent Application Laid-Open No. 8-273654
In Japanese Patent Application Laid-Open Publication No. H11-157, a battery separator is disclosed, in which a hydroentangled nonwoven fabric comprising polyolefin-based ultrafine fibers of 50% by weight or more and where the ultrafine fibers are partially fused to each other is hydrophilized.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
電池用セパレータには以下の問題点がある。例えば、特
開平５−１８６９１１号公報および特開平５−１８６９
６４号公報の繊維集合体を電池用セパレータとして用い
ると、スルホン化処理後の不織布強力が低くなる傾向に
あり、またコスト高となり、十分とはいえない。また、
特開平７−１４７１５４号公報の電池用セパレータは、
ポリプロピレン／ポリエチレンからなる分割型複合繊維
を主体とし、ポリプロピレン／低密度ポリエチレンの組
合せからなる複合接着繊維により熱接着させているの
で、不織布強力が低く、効率的に親水化処理できないな
ど、工程性に劣る。それを解消するために検討がなされ
た特開平８−２７３６５４号公報の電池用セパレータ
は、分割型複合繊維の１成分である低融点極細繊維同士
を融着させた後、分割および絡合させているので、不織
布強力においては改善されるものの、極細繊維成分自体
を自己融着させるため、空隙の確保が困難となり、保液
性の点で不十分である。However, the above-described battery separator has the following problems. For example, JP-A-5-186911 and JP-A-5-1869
When the fiber aggregate disclosed in Japanese Patent No. 64 is used as a battery separator, the strength of the nonwoven fabric after sulfonation tends to be low, and the cost is high, which is not sufficient. Also,
JP-A-7-147154 discloses a battery separator.
Mainly made of splittable composite fiber composed of polypropylene / polyethylene and thermally bonded with composite adhesive fiber composed of a combination of polypropylene / low-density polyethylene, the nonwoven fabric has low strength and cannot be efficiently hydrophilized. Inferior. The battery separator disclosed in Japanese Patent Application Laid-Open No. 8-273654, which has been studied to solve this problem, is obtained by fusing low-melting ultrafine fibers, which are one component of splittable conjugate fibers, to each other, and then dividing and entangled. Therefore, although the strength of the nonwoven fabric is improved, it is difficult to secure a void because the ultrafine fiber component itself is self-fused, and the liquid retaining property is insufficient.
【０００５】本発明はこれらの実情に鑑み、優れた保液
性および十分な不織布強力を有し、電池寿命を低下させ
ることなく電池容量の向上に寄与しうる電池用セパレー
タ、および自己放電性の改良など優れた電池特性を有す
る電池を得ることを目的としてなされたものである。In view of these circumstances, the present invention provides a battery separator which has excellent liquid retention properties and sufficient nonwoven fabric strength, and which can contribute to an improvement in battery capacity without reducing battery life, and a self-discharge property. The purpose of the present invention is to obtain a battery having excellent battery characteristics such as improvement.
【０００６】[0006]
【課題を解決するための手段】本発明の電池用セパレー
タは、ポリ（４−メチルペンテン−１）または４−メチ
ルペンテン−１と他のオレフィンとの共重合体からなる
メチルペンテン系重合体を第１成分とし、第１成分とは
異なるポリオレフィン系重合体またはその共重合体を第
２成分とし、繊維断面において２成分が交互に隣接して
配置され、２成分のうち少なくとも１成分が２個以上に
分割されてなる分割型複合繊維と、高融点成分および低
融点成分からなるポリオレフィン系複合繊維の少なくと
も２種類の繊維を含有する不織布であって、前記分割型
複合繊維および前記ポリオレフィン系複合繊維の含有量
が６０重量％を超えない範囲であり、前記不織布が親水
化処理されていることを特徴とする。かかる構成を採る
ことにより、優れた保液性および十分な不織布強力を有
し、電池特性に優れた電池用セパレータが得られること
が判り本発明に至った。The battery separator according to the present invention comprises a poly (4-methylpentene-1) or a methylpentene-based polymer comprising a copolymer of 4-methylpentene-1 and another olefin. As a first component, a polyolefin-based polymer or a copolymer thereof different from the first component is used as a second component, and two components are alternately arranged adjacent to each other in a fiber cross section, and at least one of the two components is two A nonwoven fabric containing at least two types of split conjugate fibers divided as described above and a polyolefin-based conjugate fiber comprising a high-melting component and a low-melting component, wherein the split-type conjugate fiber and the polyolefin-based conjugate fiber Is not more than 60% by weight, and the nonwoven fabric is subjected to a hydrophilic treatment. By adopting such a configuration, it has been found that a battery separator having excellent liquid retention properties and sufficient nonwoven fabric strength and having excellent battery characteristics can be obtained.
【０００７】本発明の電池用セパレータにおいて、前記
分割型複合繊維の含有量は１５〜６０重量％、前記ポリ
オレフィン系複合繊維の含有量は２０〜６０重量％であ
ることが望ましく、他の合成繊維を４０重量％を超えな
い範囲で含有させてもよい。In the battery separator of the present invention, the content of the splittable conjugate fiber is preferably 15 to 60% by weight, the content of the polyolefin-based conjugate fiber is preferably 20 to 60% by weight, and other synthetic fibers are preferably used. May be contained in a range not exceeding 40% by weight.
【０００８】前記不織布は、分割型複合繊維を構成する
２成分において実質的に溶融することなく、ポリオレフ
ィン系複合繊維の低融点成分により熱融着されているこ
とが望ましい。It is desirable that the nonwoven fabric is heat-sealed by the low melting point component of the polyolefin-based conjugate fiber without substantially melting in the two components constituting the splittable conjugate fiber.
【０００９】また、不織布を構成する分割型複合繊維、
ポリオレフィン系複合繊維、および他の合成繊維の繊維
長が３〜２５mmであると、緻密な不織布が得られ、保液
性の点で有利である。Further, a splittable conjugate fiber constituting the nonwoven fabric,
When the fiber length of the polyolefin-based conjugate fiber and other synthetic fibers is 3 to 25 mm, a dense nonwoven fabric is obtained, which is advantageous in terms of liquid retention.
【００１０】前記不織布は、繊維長の異なる繊維ウェブ
同士を積層されてなる複合不織布であることが不織布強
力を向上させる点で望ましい。The non-woven fabric is preferably a composite non-woven fabric obtained by laminating fiber webs having different fiber lengths from the viewpoint of improving the strength of the non-woven fabric.
【００１１】本発明の電池用セパレータの好ましい形態
としては、前記不織布の少なくとも一部の層に他のシー
トを積層してなる複合シートであって、該複合シートが
親水化処理されていることが望ましく、不織布強力が向
上し、卷回性や耐ショート性の点で有利である。A preferred embodiment of the battery separator of the present invention is a composite sheet obtained by laminating another sheet on at least a part of the nonwoven fabric, wherein the composite sheet has been subjected to a hydrophilic treatment. Desirably, the strength of the nonwoven fabric is improved, which is advantageous in terms of winding property and short-circuit resistance.
【００１２】また、本発明の電池用セパレータの好まし
い別の形態としては、前記親水化処理された不織布の少
なくとも一部の層に他のシートが積層されていることが
望ましい。In another preferred embodiment of the battery separator of the present invention, it is desirable that another sheet is laminated on at least a part of the layer of the nonwoven fabric subjected to the hydrophilic treatment.
【００１３】前記分割型複合繊維は、メチルペンテン系
重合体を第１成分とし、ポリプロピレン系重合体を第２
成分とすることが望ましい。また、前記ポリオレフィン
系複合繊維は、鞘成分を高密度ポリエチレンとし、芯成
分をポリプロピレンとした鞘芯型複合繊維であることが
望ましい。The splittable conjugate fiber comprises a methylpentene polymer as a first component and a polypropylene polymer as a second component.
It is desirable to use it as a component. The polyolefin-based conjugate fiber is preferably a sheath-core conjugate fiber in which the sheath component is high-density polyethylene and the core component is polypropylene.
【００１４】そして、前記親水化処理は、スルホン化処
理であることが望ましく、スルホン化処理のうち、発煙
硫酸処理、クロロスルホン酸処理、あるいは無水硫酸処
理のいずれか１つを用いると、電池の自己放電性を改良
できる点で有利である。また、スルホン化度は、０．４
〜２重量％であることが望ましい。The hydrophilization treatment is desirably a sulfonation treatment. When any one of the fuming sulfuric acid treatment, chlorosulfonic acid treatment, and sulfuric anhydride treatment is used, the battery can be treated as a sulfonation treatment. This is advantageous in that the self-discharge property can be improved. The sulfonation degree is 0.4
It is desirably about 2% by weight.
【００１５】前記のうち、いずれかの電池用セパレータ
を組み込んだ電池は、自己放電性を改良し、特に電気自
動車（ＰＥＶ）やハイブリッド車（ＨＥＶ）用に好適で
ある。以下、本発明の内容を具体的に説明する。Among the above, batteries incorporating any of the battery separators have improved self-discharge properties and are particularly suitable for electric vehicles (PEV) and hybrid vehicles (HEV). Hereinafter, the contents of the present invention will be specifically described.
【００１６】[0016]
【発明の実施の形態】本発明に用いる分割型複合繊維
は、ポリ（４−メチルペンテン−１）または４−メチル
ペンテン−１と他のオレフィンとの共重合体からなるメ
チルペンテン系重合体を第１成分とし、第１成分とは異
なるポリオレフィン系重合体またはその共重合体を第２
成分とし、繊維断面において２成分が交互に隣接して配
置され、２成分のうち少なくとも１成分が２個以上に分
割されてなり、その構成単位は長さ方向に連続し、全構
成単位の一部は必ず繊維表面に露出している断面形状を
有するものである。具体的には、第１成分および第２成
分が図１〜図３のように配列されたものを好ましく使用
することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The splittable conjugate fiber used in the present invention is a poly (4-methylpentene-1) or a methylpentene-based polymer comprising a copolymer of 4-methylpentene-1 and another olefin. As the first component, a polyolefin polymer different from the first component or a copolymer thereof is used as the second component.
In the fiber cross-section, two components are alternately arranged adjacent to each other, and at least one component of the two components is divided into two or more components. The part has a sectional shape that is always exposed on the fiber surface. Specifically, those in which the first component and the second component are arranged as shown in FIGS. 1 to 3 can be preferably used.
【００１７】前記分割型複合繊維の第１成分であるメチ
ルペンテン系重合体としては、ポリ（４−メチルペンテ
ン−１）または４−メチルペンテン−１と他のオレフィ
ンとの共重合体が挙げられ、共重合する他のオレフィン
としては、例えばエチレン、プロピレン、１−ブテン、
１−ペンテン、１−ヘキセン、３−メチル−１−ブテン
などが挙げられる。Examples of the methylpentene polymer as the first component of the splittable conjugate fiber include poly (4-methylpentene-1) or a copolymer of 4-methylpentene-1 and another olefin. As other olefins to be copolymerized, for example, ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene and the like.
【００１８】前記分割型複合繊維の第２成分としては、
ポリエチレン、ポリプロピレン、ポリブテン−１などの
第１成分とは異なるポリオレフィン系重合体またはその
共重合体が用いられ、なかでも融点（Ｄ2m）が１３０℃
以上、より好ましくは１５０℃以上のポリオレフィン系
重合体またはその共重合体を使用するとよい。前記第１
成分および第２成分からなる組み合わせの分割型複合繊
維は、耐熱性に優れ、電池内での過激な反応にも、十分
対応が可能である。なかでも、メチルペンテン系重合体
を第１成分とし、ポリプロピレン系重合体を第２成分と
する組み合わせが最も効果的である。As the second component of the splittable conjugate fiber,
Polyolefin polymers different from the first component such as polyethylene, polypropylene and polybutene-1 or copolymers thereof are used, and the melting point (D 2m ) is 130 ° C.
As described above, it is more preferable to use a polyolefin-based polymer or a copolymer thereof at 150 ° C. or higher. The first
The splittable conjugate fiber comprising the combination of the component and the second component is excellent in heat resistance and can sufficiently cope with a severe reaction in the battery. Of these, a combination of a methylpentene polymer as the first component and a polypropylene polymer as the second component is most effective.
【００１９】前記分割型複合繊維における両成分の分割
数は、５〜２０が好ましく、両成分の複合比は紡糸工程
の容易性の点から第１成分：第２成分が３０：７０〜７
０：３０程度が好ましい。また、分割型複合繊維の繊度
は、分割後の各構成単位の繊度が０．１〜０．５dtexと
なるように、分割数や複合比を調整して適宜決定すると
よい。分割後の各構成単位の繊度が０．１dtex未満であ
ると、発煙硫酸やクロロスルホン酸での処理を行った場
合に急激な劣化を起こし、不織布強力が低下し好ましく
ない。０．５dtexを超えると、後述する複合繊維あるい
は合成繊維との繊度の差が少なくなり、緻密な空隙が確
保できないからである。The number of splits of both components in the splittable conjugate fiber is preferably 5 to 20, and the composite ratio of both components is 30:70 to 7 for the first component: the second component from the viewpoint of easiness of the spinning process.
About 0:30 is preferable. Further, the fineness of the splittable conjugate fiber may be appropriately determined by adjusting the number of splits and the composite ratio so that the fineness of each constituent unit after splitting is 0.1 to 0.5 dtex. If the fineness of each structural unit after division is less than 0.1 dtex, the treatment with fuming sulfuric acid or chlorosulfonic acid causes rapid deterioration, and the strength of the nonwoven fabric is undesirably reduced. If it exceeds 0.5 dtex, the difference in fineness from the later-described conjugate fiber or synthetic fiber becomes smaller, and a dense void cannot be secured.
【００２０】前記分割型複合繊維が本発明の電池用セパ
レータに占める割合は、６０重量％を超えない範囲であ
り、１５〜６０重量％であることが好ましい。より好ま
しくは、２０〜６０重量％である。分割型複合繊維の含
有量が少なすぎると、メチルペンテン系重合体の比率が
少なすぎるため、強い親水化条件でないと十分な親水基
の導入ができなくなり、不織布強力の低下を招いたり、
コスト高となる。６０重量％を超えると、親水化処理後
の不織布強力が低くなる傾向にあり、またコスト高とな
るからである。The proportion of the splittable conjugate fiber in the battery separator of the present invention does not exceed 60% by weight, preferably 15 to 60% by weight. More preferably, it is 20 to 60% by weight. If the content of the splittable conjugate fiber is too small, the ratio of the methylpentene polymer is too small, so that it is not possible to introduce a sufficient hydrophilic group unless strong hydrophilization conditions are caused, or the nonwoven fabric strength is reduced,
The cost is high. If it exceeds 60% by weight, the strength of the nonwoven fabric after the hydrophilic treatment tends to be low, and the cost is high.
【００２１】次に、本発明に用いる高融点成分および低
融点成分からなるポリオレフィン系複合繊維は、ポリエ
チレン、ポリプロピレン、ポリブテン−１、ポリ−４−
メチルペンテン−１、エチレン−ビニルアルコール共重
合体などのポリオレフィン系重合体またはその共重合体
が用いられる。高融点成分の融点をＢ1m、低融点成分の
融点をＢ2mとすると、低融点成分は以下の関係を満たす
ことが好ましい。 （１）Ｂ1m＞Ｂ2m （２）１２０℃＜Ｂ2m＜Ｄ2m 上記の関係を満たすポリオレフィン系複合繊維として
は、例えば、高密度ポリエチレン／ポリプロピレン、エ
チレン−プロピレン共重合体／ポリプロピレンなどが挙
げられ、これらを用いると、繊維強力にも優れ、２成分
樹脂間の層間剥離も少なく、十分な融着強力が得られる
点で好ましい。Next, the polyolefin-based composite fibers comprising the high melting point component and the low melting point component used in the present invention are polyethylene, polypropylene, polybutene-1, poly-4-.
Polyolefin-based polymers such as methylpentene-1 and ethylene-vinyl alcohol copolymer or copolymers thereof are used. Assuming that the melting point of the high melting point component is B 1m and the melting point of the low melting point component is B 2m , the low melting point component preferably satisfies the following relationship. (1) B1m > B2m (2) 120.degree. C. < B2m < D2m Examples of polyolefin-based composite fibers satisfying the above relationship include high-density polyethylene / polypropylene and ethylene-propylene copolymer / polypropylene. The use of these is preferred in that the fiber strength is excellent, the delamination between the two-component resins is small, and sufficient fusion strength is obtained.
【００２２】複合繊維の繊維形態は特に限定されず、同
心円または偏心の鞘芯型複合繊維、並列型複合繊維、あ
るいは前記素材が２種類以上混合されてなる単一繊維が
挙げられ、断面形状も円形、異形などいずれであっても
よい。The fiber form of the conjugate fiber is not particularly limited, and examples thereof include concentric or eccentric sheath-core conjugate fibers, side-by-side conjugate fibers, and single fibers obtained by mixing two or more kinds of the above-mentioned materials. Any shape such as a circle and an irregular shape may be used.
【００２３】本発明においては、特に、高密度ポリエチ
レン／ポリプロピレンの組み合わせからなる同心円鞘芯
型複合繊維が、不織布の熱処理時における加工温度領域
が広く、得られた不織布の強力が大きく、耐薬品性、耐
酸化劣化に優れている点で好ましい。In the present invention, in particular, a concentric sheath-core composite fiber comprising a combination of high-density polyethylene / polypropylene has a wide processing temperature range at the time of heat treatment of the nonwoven fabric, the obtained nonwoven fabric has high strength, and has high chemical resistance. It is preferable because it is excellent in oxidation resistance deterioration.
【００２４】そして、前記ポリオレフィン系複合繊維
は、６０重量％を超えない範囲であり、２０〜６０重量
％含有することが好ましい。より好ましくは、４０〜６
０重量％である。ポリオレフィン系複合繊維の含有量が
少なすぎると、十分な不織布強力が得られず、６０重量
％を超えると、空隙の確保が困難となり、保液性の点で
不十分であるからである。The polyolefin-based conjugate fiber is contained in an amount not exceeding 60% by weight, preferably 20 to 60% by weight. More preferably, 40 to 6
0% by weight. If the content of the polyolefin-based conjugate fiber is too small, sufficient nonwoven fabric strength cannot be obtained, and if it exceeds 60% by weight, it is difficult to secure voids, and the liquid retaining property is insufficient.
【００２５】さらに、本発明の電池用セパレータには、
他の合成繊維を４０重量％を超えない範囲で混合しても
よい。より好ましくは、２０〜４０重量％である。他の
合成繊維の含有量が４０重量％を超えると、親水化処理
の効果が少なくなり必要な性能が得られないからであ
る。例えば、繊維間で形成される空隙を確保するためで
あれば、分割型複合繊維の分割により形成される分割後
の各構成単位の繊度よりも大きく、ポリオレフィン系複
合繊維の繊度と同じまたは小さい合成繊維を使用すれば
よく、また親水性をさらに向上させるのであれば、親水
化剤等を樹脂中に予め混合させた合成繊維を使用しても
よい。そして、他の合成繊維は、ポリオレフィン系複合
繊維の溶融する温度では実質的に溶融しないものから選
ばれ、ポリプロピレン、ポリエステル、ナイロン等、汎
用されている合成繊維を使用することができる。なかで
も繊度が０．５〜５dtex、繊維強度が６〜１５cN/dtex
からなるポリプロピレン繊維が耐薬品性が高い点で好ま
しい。Further, the battery separator of the present invention includes:
Other synthetic fibers may be mixed within a range not exceeding 40% by weight. More preferably, it is 20 to 40% by weight. If the content of the other synthetic fibers exceeds 40% by weight, the effect of the hydrophilic treatment is reduced, and the required performance cannot be obtained. For example, in order to secure voids formed between fibers, the composite size is larger than the fineness of each constituent unit after division formed by division of the splittable conjugate fiber, and is equal to or smaller than the fineness of the polyolefin-based composite fiber. A fiber may be used, and if the hydrophilicity is further improved, a synthetic fiber in which a hydrophilizing agent or the like is previously mixed in a resin may be used. The other synthetic fibers are selected from those which do not substantially melt at the temperature at which the polyolefin-based conjugate fibers melt, and synthetic fibers commonly used such as polypropylene, polyester, and nylon can be used. Above all, fineness is 0.5-5 dtex, fiber strength is 6-15 cN / dtex
Is preferred because of its high chemical resistance.
【００２６】前記構成繊維を含有してなる繊維ウェブの
形態は、カード法、エアレイ法などにより得た乾式ウェ
ブ、湿式法により得た湿式ウェブ、あるいはメルトブロ
ー法やスパンボンド法などの直接法により得た長繊維ウ
ェブが用いられる。なかでも前記構成繊維の繊維長が３
〜２５mmからなる湿式ウェブが均質なウェブを得る点で
好ましい。より好ましい繊維長は５〜１５mmである。繊
維長が３mm未満では後述する高圧水流処理時に繊維が飛
散し、繊維間の交絡が不十分となり、工程上好ましくな
く、２５mmを超えると特に湿式抄紙法によって不織布を
製造する場合、スラリー中における繊維の分散性が悪く
なり均一な不織布を得ることができないからである。The form of the fiber web containing the constituent fibers can be obtained by a dry web obtained by a card method, an air lay method, a wet web obtained by a wet method, or a direct method such as a melt blow method or a spun bond method. Long fiber webs are used. In particular, the fiber length of the constituent fibers is 3
Wet webs of up to 25 mm are preferred in order to obtain a homogeneous web. A more preferred fiber length is 5 to 15 mm. If the fiber length is less than 3 mm, the fibers are scattered during high-pressure water flow treatment to be described later, and the entanglement between the fibers becomes insufficient, which is not preferable in the process. If the fiber length exceeds 25 mm, especially when a nonwoven fabric is produced by a wet papermaking method, the fibers in the slurry This is because the dispersibility of the nonwoven fabric deteriorates, and a uniform nonwoven fabric cannot be obtained.
【００２７】これらの繊維ウェブは、熱カレンダー処
理、熱風加工処理、高圧水流処理等の方法により処理さ
れる。このとき、少なくとも分割型複合繊維を構成する
２成分において実質的に溶融することなく、ポリオレフ
ィン系複合繊維の低融点成分により熱融着されているこ
とが好ましい。ここでいう、実質的に溶融するとは、熱
圧着などにより軟化して扁平し、繊維同士が密着したよ
うなものではなく、完全に繊維の一部が溶融したものを
指す。構成繊維同士がポリオレフィン系複合繊維の低融
点成分のみの熱融着であると、分割型複合繊維が分割し
て得られた極細繊維および他の合成繊維が空隙を確保し
つつ、複合繊維の高融点成分が繊維強力を維持して融着
させるので、不織布強力のばらつきが少なく、緻密な空
隙が確保できる。These fibrous webs are processed by a method such as a hot calendering treatment, a hot air processing treatment, a high-pressure water jet treatment and the like. At this time, it is preferable that at least the two components constituting the splittable conjugate fiber are not substantially melted but are thermally fused by the low melting point component of the polyolefin-based conjugate fiber. The term “substantially melted” as used herein refers to a material that is softened and flattened by thermocompression bonding or the like, and is not a material in which fibers are in close contact with each other, but a material in which a part of fibers is completely melted. When the constituent fibers are heat-sealed only with the low melting point component of the polyolefin-based conjugate fiber, the ultrafine fibers and other synthetic fibers obtained by splitting the splittable conjugate fiber maintain the voids while maintaining the height of the conjugate fiber. Since the melting point component fuses while maintaining the fiber strength, there is little variation in the strength of the nonwoven fabric and a dense void can be secured.
【００２８】そして、他の不織布の形態としては、上記
構成繊維の範囲内で混合率を適宜変更して積層させた、
あるいは繊維長の異なる繊維ウェブ同士を積層させた複
合不織布であってもよい。例えば、後者であれば、前記
繊維長３〜２５mmの構成繊維からなる湿式抄紙法による
繊維ウェブに、繊維長２５mmを超えるステープル繊維か
らなる繊維ウェブ、あるいは長繊維ウェブを少なくとも
一方の面に積層することができる。繊維長の異なる繊維
ウェブ同士を積層させると、繊維長の短い繊維ウェブが
緻密性に寄与し、繊維長の長い繊維ウェブが不織布強力
が向上に寄与して、電池組み込み時の生産性に優れるの
で都合がよい。これらの繊維ウェブは、カードウェブな
どの未結合ウェブ、構成繊維の一部を接着剤や自己接着
などで結合させた結合不織布、あるいはニードルパンチ
や高圧水流処理により交絡させた不織布などいずれの形
態であってもよい。積層方法としては、未結合ウェブ同
士を積層した後に繊維同士を交絡させてもよいし、少な
くとも一方の繊維ウェブを予め上記の結合または交絡方
法で不織布化したものを積層した後に繊維同士を交絡さ
せてもよい。As another form of the nonwoven fabric, the nonwoven fabric was laminated by appropriately changing the mixing ratio within the range of the constituent fibers.
Alternatively, it may be a composite nonwoven fabric in which fiber webs having different fiber lengths are laminated. For example, in the case of the latter, a fiber web made of staple fibers having a fiber length of more than 25 mm or a long fiber web is laminated on at least one surface on a fiber web made of the constituent fibers having a fiber length of 3 to 25 mm by a wet papermaking method. be able to. When fiber webs with different fiber lengths are laminated, a fiber web with a short fiber length contributes to the denseness, and a fiber web with a long fiber length contributes to the improvement of the strength of the non-woven fabric, and is excellent in productivity when incorporated in a battery. convenient. These fiber webs are in any form such as an unbonded web such as a card web, a bonded nonwoven fabric in which a part of the constituent fibers are bonded by an adhesive or self-adhesion, or a nonwoven fabric entangled by needle punching or high pressure water flow treatment. There may be. As a lamination method, the fibers may be entangled after laminating the unbonded webs, or the fibers may be entangled after laminating at least one of the fibrous webs previously formed into a nonwoven fabric by the bonding or entanglement method. You may.
【００２９】さらに、別の不織布の形態としては、前記
不織布の少なくとも一部の層に他のシートを積層させて
もよい。ここでは、前記不織布の少なくとも一部の層に
他のシートを積層して予め複合シートを作製しておいた
後、親水化処理を施したものであってもよいし、前記不
織布を予め親水化処理しておいた後、少なくとも一部の
層に他のシートを積層されたものであってもよい。ここ
でいう他のシートとは、繊維長が３〜２５mmの繊維から
なる湿式不織布、繊維長が２５mmを超える繊維からなる
構成繊維の一部を接着剤や自己接着などで結合させた結
合不織布、ニードルパンチや高圧水流処理により交絡さ
せた不織布、あるいは多孔性フィルムなどを指す。前記
他のシートのうち繊維長が３〜２５mmの繊維からなる湿
式不織布を用いると、低目付でありながら貫通孔の発生
する割合が少ない不織布が得られ、電池におけるショー
ト率を軽減させることができる。また、繊維長が２５mm
を超える繊維あるいは多孔性フィルムを用いれば、さら
に不織布強力を向上させることができる。As another form of the nonwoven fabric, another sheet may be laminated on at least a part of the layer of the nonwoven fabric. Here, another sheet may be laminated on at least a part of the layer of the nonwoven fabric to prepare a composite sheet in advance and then subjected to a hydrophilization treatment, or the nonwoven fabric may be hydrophilized in advance. After the treatment, another sheet may be laminated on at least a part of the layers. The other sheet referred to here is a wet nonwoven fabric made of a fiber having a fiber length of 3 to 25 mm, a bonded nonwoven fabric obtained by bonding a part of constituent fibers made of a fiber having a fiber length of more than 25 mm with an adhesive or self-adhesive, It refers to a nonwoven fabric or a porous film entangled by needle punch or high-pressure water flow treatment. When a wet nonwoven fabric having a fiber length of 3 to 25 mm among the other sheets is used, a nonwoven fabric having a low basis weight and a low rate of occurrence of through holes is obtained, and a short circuit rate in a battery can be reduced. . The fiber length is 25mm
If a fiber or a porous film exceeding the above is used, the strength of the nonwoven fabric can be further improved.
【００３０】前記他のシートの素材としては特に限定さ
れず、ポリオレフィン系樹脂、ポリアミド系樹脂、ある
いはポリエステル系樹脂などいずれであってもよい。ま
た、積層方法も少なくとも一部の層に他のシートが積層
されていれば特に限定されず、本発明の不織布の片面、
あるいは両面に他のシートを積層してもよいし、前記不
織布の間に他のシートを挿入しておいてもよい。さらに
上記積層体を２層以上に積層してもよい。そして、上記
積層体における各層間の結合方法についても特に限定さ
れず、例えば、高圧水流処理により本発明の不織布を予
め作製しておき、他のシートと積層させた後、熱風や熱
ロールなどの熱処理により結合してもよいし、本発明を
構成する繊維ウェブと他のシートを予め積層させた後、
高圧水流処理により結合させてもよい。The material of the other sheet is not particularly limited, and may be any of a polyolefin resin, a polyamide resin, and a polyester resin. Further, the lamination method is not particularly limited as long as another sheet is laminated on at least a part of the layers, and one side of the nonwoven fabric of the present invention,
Alternatively, another sheet may be laminated on both sides, or another sheet may be inserted between the nonwoven fabrics. Further, the laminate may be laminated in two or more layers. The method of bonding between the layers in the laminate is not particularly limited. For example, the nonwoven fabric of the present invention is prepared in advance by high-pressure water flow treatment, and after being laminated with another sheet, hot air or a hot roll. It may be bonded by heat treatment, or after previously laminating the fiber web and other sheets constituting the present invention,
You may combine by high-pressure water flow process.
【００３１】前記不織布あるいは複合シートの目付は、
繊維の量によって調節しうるが３０〜１００g/m2にする
ことが望ましい。３０g/m2未満では不織布の強力が低く
なるため、正極と負極の間でショートが発生しやすくな
り、１００g/m2を超えると通気性等が低下するからであ
る。The basis weight of the nonwoven fabric or composite sheet is as follows:
Although it can be adjusted depending on the amount of the fiber, it is desirably 30 to 100 g / m 2 . If it is less than 30 g / m 2 , the strength of the nonwoven fabric is low, so that a short circuit is likely to occur between the positive electrode and the negative electrode, and if it exceeds 100 g / m 2 , air permeability and the like are reduced.
【００３２】そして、前述した不織布あるいは複合シー
トは、親水化処理されていることが好ましい。親水化処
理としては、ビニルモノマーのグラフト共重合処理、フ
ッ素ガス処理、スルホン化処理、コロナ放電処理、プラ
ズマ処理などが挙げられるが、なかでもスルホン化処理
が電池の自己放電性を改良する点で優れており、スルホ
ン化処理としては、濃硫酸処理、発煙硫酸処理、クロロ
スルホン酸処理、無水硫酸処理などが挙げられ、スルホ
ン化処理のうち、発煙硫酸処理、クロロスルホン酸処
理、あるいは無水硫酸処理が反応性が高く、比較的容易
にスルホン化処理できるので好ましい。また、スルホン
化度は、０．４〜２重量％であることが好ましく、０．
７〜１．５重量％がさらに好ましい。スルホン化度が
０．４重量％未満であると、電池の自己放電性の改良が
不十分であり、２重量％を超えると、処理コストの増大
を招くだけでなく、不織布の強力低下に繋がるからであ
る。親水化処理は、不織布形成後に行うのが生産性の面
で好ましいが、不織布が積層体の場合、少なくとも分割
型複合繊維を含有する不織布が親水化処理されていれば
よい。Preferably, the nonwoven fabric or composite sheet described above has been subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include a graft copolymerization treatment of a vinyl monomer, a fluorine gas treatment, a sulfonation treatment, a corona discharge treatment, and a plasma treatment. Among them, the sulfonation treatment improves the self-discharge property of the battery. Excellent sulfonation treatments include concentrated sulfuric acid treatment, fuming sulfuric acid treatment, chlorosulfonic acid treatment, sulfuric anhydride treatment, etc. Among the sulfonation treatments, fuming sulfuric acid treatment, chlorosulfonic acid treatment, or sulfuric anhydride treatment Is preferred because it has high reactivity and can be relatively easily sulfonated. Further, the degree of sulfonation is preferably 0.4 to 2% by weight,
7 to 1.5% by weight is more preferred. If the degree of sulfonation is less than 0.4% by weight, the self-discharging property of the battery is not sufficiently improved, and if it exceeds 2% by weight, not only does the processing cost increase, but also the strength of the nonwoven fabric decreases. Because. The hydrophilization treatment is preferably performed after the formation of the nonwoven fabric in terms of productivity. However, when the nonwoven fabric is a laminate, it is sufficient that at least the nonwoven fabric containing the splittable conjugate fiber has been subjected to the hydrophilic treatment.
【００３３】次に本発明の電池用セパレータの製造方法
の一例について説明する。本発明のセパレータの基材と
なる不織布の製造方法としては湿式抄紙法が望ましく、
湿式抄紙は通常の方法で行えばよい。まず分割型複合繊
維１５〜６０重量％と、ポリオレフィン系複合繊維２０
〜６０重量％と、４０重量％を超えない範囲で他の合成
繊維を混合して、０．０１〜０．６％の濃度になるよう
に水に分散させ、スラリーを調製する。このとき少量の
分散剤を加えてもよい。スラリーは短網式、円網式、あ
るいは両者を組み合わせた抄紙機等を用いて抄紙され
る。次いで、ポリオレフィン系複合繊維を溶融させて繊
維間を軽く結合させておくと、不織布の取り扱い性がよ
いので好ましい。ポリオレフィン系複合繊維の溶融は、
抄紙工程における乾燥処理の際に乾燥と同時に行っても
よく、また一旦、湿式不織布としたのち加熱処理して行
ってもよい。Next, an example of a method for producing the battery separator of the present invention will be described. As a method for producing a nonwoven fabric serving as a base material of the separator of the present invention, a wet papermaking method is desirable,
The wet papermaking may be performed by a usual method. First, 15-60% by weight of splittable conjugate fiber and polyolefin-based conjugate fiber 20
６０60% by weight and other synthetic fibers within a range not exceeding 40% by weight are mixed and dispersed in water to a concentration of 0.01 to 0.6% to prepare a slurry. At this time, a small amount of a dispersant may be added. The slurry is made using a short net type, a circular net type, or a paper machine combining the both. Next, it is preferable to melt the polyolefin-based conjugate fibers and lightly bond the fibers, since the handleability of the nonwoven fabric is good. The melting of polyolefin-based composite fibers
The drying may be performed at the same time as the drying in the paper making process, or may be performed after the wet non-woven fabric is once formed and then heated.
【００３４】そして、ポリオレフィン系複合繊維の溶融
により繊維間を軽く結合させ、形態を安定化させた状態
にしてから、高圧水流処理を施し、分割型複合繊維を分
割させて極細繊維を形成させるとともに繊維間を交絡さ
せるとよい。高圧水流処理は孔径０．０５〜０．５mmの
オリフィスが０．５〜１．５mmの間隔で設けられたノズ
ルから、水圧５〜２０MPa の柱状水流を不織布の表裏に
それぞれ１回以上噴射するとよい。得られた交絡不織布
は、１２０〜Ｄ2m℃、好ましくは１３０〜１４５℃で乾
燥と同時にポリオレフィン系複合繊維の低融点成分で構
成繊維同士を熱融着させるとよい。Then, the fibers are lightly bonded by melting the polyolefin-based conjugate fibers to form a stabilized state, and then subjected to high-pressure water flow treatment to split the split-type conjugate fibers to form ultrafine fibers. It is good to entangle the fibers. In the high pressure water flow treatment, a columnar water flow having a water pressure of 5 to 20 MPa is preferably jetted at least once on each of the front and back surfaces of the nonwoven fabric from a nozzle having orifices having a hole diameter of 0.05 to 0.5 mm provided at intervals of 0.5 to 1.5 mm. . The resulting entangled nonwoven fabric, 120~D 2m ℃, may preferably thermally fusing the constituent fibers to each other at a low melting point component at the same time polyolefin composite fibers and dried at 130 to 145 ° C..
【００３５】しかるのちに不織布は、発煙硫酸反応槽、
クロロスルホン酸反応槽、あるいは無水硫酸反応槽に浸
漬され、スルホン基が導入される。スルホン化処理条件
は、スルホン化度が０．４〜２重量％となるように適宜
設定すればよく、例えば、無水硫酸処理であれば、三酸
化イオウのガス濃度が１０〜８０体積％、反応温度が１
０〜９０℃、反応時間が１０〜６００秒で処理するとよ
い。このとき、スルホン化を促進させるために、紫外線
または放射線により不織布表面を活性化させた後、スル
ホン化処理を施してもよい。Thereafter, the nonwoven fabric is used in a fuming sulfuric acid reaction tank,
It is immersed in a chlorosulfonic acid reactor or a sulfuric anhydride reactor to introduce a sulfone group. Sulfonation treatment conditions may be appropriately set so that the degree of sulfonation is 0.4 to 2% by weight. For example, in the case of sulfuric anhydride treatment, the gas concentration of sulfur trioxide is 10 to 80% by volume, Temperature 1
The treatment is preferably performed at 0 to 90 ° C. for a reaction time of 10 to 600 seconds. At this time, in order to promote the sulfonation, the surface of the nonwoven fabric may be activated with ultraviolet rays or radiation, and then subjected to a sulfonation treatment.
【００３６】さらに、不織布に親水化処理を施した後、
浸漬法、スプレー法、ロールタッチ法等により親水性界
面活性剤を均一に付着させてもよいし、他の親水化処理
法を組み合わせてもよい。しかるのち熱カレンダー処理
して、所定の厚みに調整され、本発明の電池用セパレー
タが得られる。Further, after subjecting the nonwoven fabric to a hydrophilic treatment,
A hydrophilic surfactant may be uniformly attached by an immersion method, a spray method, a roll touch method, or the like, or another hydrophilic treatment method may be combined. Thereafter, the calendering treatment is performed to adjust the thickness to a predetermined value, thereby obtaining the battery separator of the present invention.
【００３７】[0037]
【実施例】以下、本発明の内容を実施例を挙げて説明す
る。なお、引張強力、保液率、ショート率、容量保存
率、サイクル寿命、およびスルホン化度は、以下の方法
により測定した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described with reference to embodiments. In addition, tensile strength, liquid retention rate, short-circuit rate, capacity preservation rate, cycle life, and sulfonation degree were measured by the following methods.
【００３８】（１）タテ引張強力 ＪＩＳ Ｌ １０９６に準じ、不織布のタテ方向に対し
て、幅５cm、長さ１５cmの試料片をつかみ間隔１０cmで
把持し、定速伸長型引張試験機を用いて引張速度３０cm
／分で伸長し、切断時の荷重値を引張強力とした。(1) Vertical Tensile Strength According to JIS L 1096, a sample piece having a width of 5 cm and a length of 15 cm is gripped at an interval of 10 cm with respect to the vertical direction of the nonwoven fabric, and a constant-speed elongation type tensile tester is used. Tensile speed 30cm
/ Min, and the load value at the time of cutting was defined as tensile strength.
【００３９】（２）保液率 試験片の水分平衡状態の重量（Ｗ）を１mgまで測定す
る。次に比重１．３０のＫＯＨ溶液中に試験片を浸漬
し、ＫＯＨ溶液を１時間吸収させたのち液中から引き上
げて１０分間放置した後、試験片の重量（Ｗ1) を測定
し、保液率（％）＝（（Ｗ1 −Ｗ）／Ｗ）×１００の式
より保液率を算出した。(2) Liquid Retention Rate The weight (W) of the test piece in a water equilibrium state is measured up to 1 mg. Next, the test piece is immersed in a KOH solution having a specific gravity of 1.30, and after absorbing the KOH solution for one hour, withdrawn from the solution and left for 10 minutes, the weight (W 1 ) of the test piece is measured and maintained. The liquid retention rate was calculated from the formula of liquid rate (%) = ((W 1 −W) / W) × 100.
【００４０】（３）円筒形密閉ニッケル水素電池 負極は、水素吸蔵合金、カルボニルニッケル、カルボキ
シメチルセルロース（ＣＭＣ）、ポリテトラフルオロエ
チレン（ＰＴＦＥ）に水を加え混練りしスラリーを調整
した。このスラリーをニッケルメッキしたパンチングメ
タルに浸漬塗りした後８０℃で乾燥し、加圧成型して水
素吸蔵合金負極を作成した。、正極は、公知の焼結式ニ
ッケル極を使用した。上記の負極、正極の間に各セパレ
ーターを挟み電槽缶に挿入し、電解液を注液すること
で、円筒形密閉ニッケル水素電池を作製した。(3) Cylindrical sealed nickel-metal hydride battery The negative electrode was prepared by adding water to a hydrogen storage alloy, carbonyl nickel, carboxymethyl cellulose (CMC), and polytetrafluoroethylene (PTFE) and kneading the mixture to prepare a slurry. This slurry was dip-coated on a nickel-plated punching metal, dried at 80 ° C., and molded under pressure to prepare a hydrogen storage alloy negative electrode. For the positive electrode, a known sintered nickel electrode was used. Each of the separators was sandwiched between the negative electrode and the positive electrode, inserted into a battery case, and an electrolytic solution was injected to produce a cylindrical sealed nickel-metal hydride battery.
【００４１】（４）容量保存率 前記作製した円筒形密閉ニッケル水素電池を、充電０．
１Ｃ率で１２時間、休止０．５時間、放電０．１Ｃ率で
終止電圧１．０Ｖとし、１０サイクル充放電を繰り返
し、電池初期活性を行った。そして、初期活性を行った
後、充電０．１Ｃ率で１２時間、休止０．５時間、放電
０．１Ｃ率で終止電圧１．０Ｖとし、５サイクル繰り返
した後の放電容量に対し、同条件（０．１Ｃ率）で充電
後、４５℃下で１４日間放置したときの残存容量（０．
１Ｃ率放電、終止電圧１．０Ｖ）の比を自己放電後の容
量保存率とした。充放電は２５℃で行った。(4) Capacity Conservation Rate The cylindrical sealed nickel-metal hydride battery prepared above was charged at 0.
The charge / discharge was repeated for 10 cycles at a rate of 1 C for 12 hours, a pause of 0.5 hour, a discharge of 0.1 C at a cutoff voltage of 1.0 V, and the battery was initially activated. After the initial activation, the charge capacity was changed to 12 hours at a rate of 0.1 C, the rest time was set to 0.5 V, the discharge voltage was set to 1.0 V at a rate of 0.1 C, and the discharge capacity after 5 cycles was repeated. (0.1 C rate), and then left at 45 ° C. for 14 days to obtain a remaining capacity (0.1%).
The ratio of the 1C rate discharge and the final voltage of 1.0 V) was defined as the capacity retention after self-discharge. Charge and discharge were performed at 25 ° C.
【００４２】（５）ショート率 円筒形密閉ニッケル水素電池を１００個組み立てたとき
に、短絡が起きた割合をショート率とした。(5) Short-Circuit Ratio When 100 cylindrical sealed nickel-metal hydride batteries were assembled, the ratio of short-circuits was defined as the short-circuit ratio.
【００４３】（６）サイクル寿命 初期活性を行った円筒形密閉ニッケル水素電池を、充電
０．１Ｃ率で、１０時間、休止時間０．５時間、放電
０．１Ｃ率（終止電圧１．０Ｖ）で理論容量に対する利
用率が９０％以下になったときのサイクル数を求めた。
充放電は２５℃で行った。(6) Cycle Life Cylindrical sealed nickel-metal hydride battery that had been initially activated was charged at a rate of 0.1 C for 10 hours, paused for 0.5 hour, and discharged at a rate of 0.1 C (final voltage 1.0 V). The number of cycles when the utilization rate with respect to the theoretical capacity became 90% or less was determined.
Charge and discharge were performed at 25 ° C.
【００４４】（７）スルホン化度 試料より５ｃｍ×５ｃｍの試験片を採取し、１３％ＫＯ
Ｈ水溶液に３０分間浸漬した。その後、水道水で３０分
間洗浄し、さらに純水で３０分間洗浄した試料を６０℃
にて１時間乾燥させて試料を調整した。そして、蛍光Ｘ
線測定装置を用いて、不織布中の硫黄元素濃度を測定
し、全元素濃度で除して１００倍したものをスルホン化
度とした。(7) Degree of sulfonation A test piece of 5 cm x 5 cm was sampled from the sample and was subjected to 13% KO.
It was immersed in an H aqueous solution for 30 minutes. Thereafter, the sample was washed with tap water for 30 minutes, and further washed with pure water for 30 minutes.
For 1 hour to prepare a sample. And fluorescent X
The sulfur element concentration in the nonwoven fabric was measured using a line measuring device, and the result was divided by the total element concentration and multiplied by 100 to obtain the sulfonation degree.
【００４５】（８）繊維の準備 原料として、以下の繊維を準備した。 ［繊維１］ 第１成分を融点（Ｄ1m）２４０℃のメチル
ペンテン系共重合体（三井化学（株）製）とし、第２成
分を融点（Ｄ2m）１６３℃のポリプロピレン（日本ポリ
ケム（株）製）として、複合比が５０：５０、図１に示
す繊維断面を有する繊度２．３dtex、繊維長６mmの分割
型複合繊維。(8) Preparation of Fiber The following fibers were prepared as raw materials. [Fiber 1] The first component is a methylpentene copolymer having a melting point (D 1m ) of 240 ° C. (manufactured by Mitsui Chemicals, Inc.), and the second component is polypropylene having a melting point (D 2m ) of 163 ° C. (Nippon Polychem Co., Ltd.) )), A splittable conjugate fiber having a conjugate ratio of 50:50, a fineness of 2.3 dtex having a fiber cross section shown in FIG. 1 and a fiber length of 6 mm.
【００４６】［繊維２］ 第１成分を融点（Ｄ1m）２４
０℃のメチルペンテン系共重合体（三井化学（株）製）
とし、第２成分を融点（Ｄ2m）１６３℃のポリプロピレ
ン（日本ポリケム（株）製）として、複合比が５０：５
０、図１に示す繊維断面を有する繊度２．３dtex、繊維
長４５mmの分割型複合繊維。[Fiber 2] Melting point (D 1m ) 24 of first component
0 ° C methylpentene copolymer (Mitsui Chemicals, Inc.)
The second component is polypropylene having a melting point (D 2m ) of 163 ° C. (manufactured by Nippon Polychem Co., Ltd.), and the composite ratio is 50: 5.
0, a splittable conjugate fiber having a fineness of 2.3 dtex and a fiber length of 45 mm having a fiber cross section shown in FIG.
【００４７】［繊維３］ 鞘成分を融点（Ｂ2m）１３２
℃の高密度ポリエチレン（日本ポリケム（株）製）と
し、芯成分を融点（Ｂ1m）１６３℃のポリプロピレン
（日本ポリケム（株）製）として、複合比が５０：５
０、繊度１．７dtex、繊維長１０mmの同心円鞘芯型複合
繊維。[Fiber 3] The sheath component was melted at a melting point (B 2m ) of 132.
And ° C. of high-density polyethylene (manufactured by Japan Polychem Corporation), the core component as the melting point (B 1 m) 163 ° C. of polypropylene (manufactured by Japan Polychem Corporation), the composite ratio of 50: 5
0, a concentric sheath-core composite fiber with a fineness of 1.7 dtex and a fiber length of 10 mm.
【００４８】［繊維４］ 鞘成分を融点（Ｂ2m）１０５
℃の低密度ポリエチレン（日本ポリケム（株）製）と
し、芯成分を融点（Ｂ1m）１６３℃のポリプロピレン
（日本ポリケム（株）製）として、複合比が５０：５
０、繊度１．７dtex、繊維長１０mmの同心円鞘芯型複合
繊維。[Fiber 4] Melting point (B 2m ) 105 of sheath component
° C low-density polyethylene (manufactured by Nippon Polychem Co., Ltd.), and the core component was polypropylene (manufactured by Nippon Polychem Co., Ltd.) having a melting point (B 1m ) of 163 ° C, and the composite ratio was 50: 5.
0, a concentric sheath-core composite fiber with a fineness of 1.7 dtex and a fiber length of 10 mm.
【００４９】［繊維５］ 鞘成分を融点（Ｂ2m）１３２
℃の高密度ポリエチレン（日本ポリケム（株）製）と
し、芯成分を融点（Ｂ1m）１６３℃のポリプロピレン
（日本ポリケム（株）製）として、複合比が５０：５
０、繊度１．７dtex、繊維長５１mmの同心円鞘芯型複合
繊維。[Fiber 5] Melting point (B 2m ) 132 of sheath component
And ° C. of high-density polyethylene (manufactured by Japan Polychem Corporation), the core component as the melting point (B 1 m) 163 ° C. of polypropylene (manufactured by Japan Polychem Corporation), the composite ratio of 50: 5
0, concentric sheath-core composite fiber with a fineness of 1.7 dtex and a fiber length of 51 mm.
【００５０】［繊維６］ 融点１６３℃のポリプロピレ
ン（日本ポリケム（株）製）からなり、繊度０．８dte
x、繊維長１０mmのポリプロピレン繊維。[Fiber 6] Polypropylene having a melting point of 163 ° C. (manufactured by Nippon Polychem Co., Ltd.) and a fineness of 0.8 dte
x, polypropylene fiber with a fiber length of 10 mm.
【００５１】［繊維７］ 融点１６３℃のポリプロピレ
ン（日本ポリケム（株）製）からなり、繊度０．８dte
x、繊維長５１mmのポリプロピレン繊維。[Fiber 7] Polypropylene having a melting point of 163 ° C. (manufactured by Nippon Polychem Co., Ltd.) and a fineness of 0.8 dte
x, polypropylene fiber with a fiber length of 51 mm.
【００５２】［繊維８］ 第１成分をエチレン−ビニル
アルコール共重合体（エチレン含有量３８モル％）と
し、第２成分をポリプロピレンとして、複合比が５０：
５０、図２に示す繊維断面を有する繊度３．３dtex、繊
維長６mmの分割型複合繊維。[Fiber 8] The first component was an ethylene-vinyl alcohol copolymer (ethylene content 38 mol%), the second component was polypropylene, and the composite ratio was 50:
50, a splittable conjugate fiber having a fineness of 3.3 dtex and a fiber length of 6 mm having a fiber cross section shown in FIG.
【００５３】［実施例１］繊維１を４０重量％、繊維３
を４０重量％、繊維６を２０重量％を混合して０．５％
の濃度になるようにスラリーを調製し、湿式抄紙して目
付８０g/m2の原紙を得た。そして原紙の表裏面より１０
MPaの圧力で高圧柱状水流を噴射することにより、繊維
１を分割させて極細繊維を形成させるとともに繊維間を
交絡させ、１３５℃で乾燥と同時に熱融着させ不織布を
得た。Example 1 40% by weight of fiber 1 and fiber 3
40% by weight and fiber 6 mixed with 20% by weight to form 0.5%
The slurry was prepared so as to have a concentration of 0.1 g / m 2 and wet-laid to obtain a base paper having a basis weight of 80 g / m 2 . And 10 from the front and back of the base paper
By injecting a high-pressure columnar water stream at a pressure of MPa, the fibers 1 were divided to form ultrafine fibers, and the fibers were entangled. The fibers were dried at 135 ° C. and simultaneously heat-fused to obtain a nonwoven fabric.
【００５４】得られた不織布をクロロスルホン酸５０重
量％、濃硫酸５０重量％を混合した液温４０℃の処理浴
で１時間浸漬処理し、その後希硫酸中に１０分間浸漬後
ＫＯＨ溶液に１時間浸漬して中和を行った。その後水洗
・乾燥させた後、熱カレンダー処理を施して、目付６５
g/m2、厚み０．１５mmの電池用セパレータを得た。The obtained nonwoven fabric was immersed in a treatment bath containing 50% by weight of chlorosulfonic acid and 50% by weight of concentrated sulfuric acid at a liquid temperature of 40 ° C. for 1 hour, then immersed in dilute sulfuric acid for 10 minutes, and then immersed in a KOH solution. Neutralization was performed by soaking for a period of time. Then, after washing with water and drying, a heat calendering treatment is performed to obtain a basis weight of 65%.
A battery separator having a g / m 2 and a thickness of 0.15 mm was obtained.
【００５５】［実施例２］処理液としてクロロスルホン
酸１００％を用いた以外は、実施例１と同じ方法で目付
６５g/m2、厚み０．１５mmの電池用セパレータを得た。Example 2 A battery separator having a basis weight of 65 g / m 2 and a thickness of 0.15 mm was obtained in the same manner as in Example 1, except that 100% chlorosulfonic acid was used as the treatment liquid.
【００５６】［実施例３］処理液として、発煙硫酸２０
重量％、濃硫酸８０重量％の混合液とした以外は、実施
例１と同じ方法で目付６５g/m2、厚み０．１５mmの電池
用セパレータを得た[Example 3] Fuming sulfuric acid 20 was used as the treatment liquid.
A battery separator having a basis weight of 65 g / m 2 and a thickness of 0.15 mm was obtained in the same manner as in Example 1 except that a mixed solution of 80% by weight of concentrated sulfuric acid was used.
【００５７】［実施例４］繊維１を４０重量％、繊維３
を４０重量％、繊維６を２０重量％を混合して０．５％
の濃度になるようにスラリーを調製し、湿式抄紙して目
付５５g/m2の原紙を得た。そして原紙の表裏面より１０
MPaの圧力で高圧柱状水流を噴射することにより、繊維
１を分割させて極細繊維を形成させるとともに繊維間を
交絡させ、１３５℃で乾燥と同時に熱融着させ不織布を
得た。Example 4 Fiber 1 was 40% by weight, fiber 3
40% by weight and fiber 6 mixed with 20% by weight to form 0.5%
The slurry was prepared so as to have a concentration of 5%, and wet papermaking was performed to obtain a base paper having a basis weight of 55 g / m 2 . And 10 from the front and back of the base paper
By injecting a high-pressure columnar water stream at a pressure of MPa, the fibers 1 were divided to form ultrafine fibers, and the fibers were entangled. The fibers were dried at 135 ° C. and simultaneously heat-fused to obtain a nonwoven fabric.
【００５８】得られた不織布を、アクリル酸水溶液に浸
漬した後、紫外線を照射してアクリル酸モノマーをグラ
フト共重合させた。この不織布を洗浄して未反応のアク
リル酸を除去した後、乾燥して熱カレンダー処理を施し
て、目付６５g/m2、厚み０．１５mmの電池用セパレータ
を得た。After the obtained nonwoven fabric was immersed in an aqueous solution of acrylic acid, it was irradiated with ultraviolet rays to graft copolymerize the acrylic acid monomer. The nonwoven fabric was washed to remove unreacted acrylic acid, dried, and subjected to a heat calendering treatment to obtain a battery separator having a basis weight of 65 g / m 2 and a thickness of 0.15 mm.
【００５９】［実施例５］繊維２を４０重量％、繊維４
を４０重量％、繊維７を２０重量％を混合してセミラン
ダムカード機を用いて目付３０g/m2の繊維ウェブを作製
した。そして、前記繊維ウェブの表裏面より５MPaの圧
力で高圧柱状水流を噴射することにより、繊維２を分割
させて極細繊維を形成させるとともに繊維間を交絡さ
せ、１３５℃で乾燥と同時に熱融着させ目付３０g/m2の
乾式不織布を得た。Example 5 Fiber 2 was 40% by weight, fiber 4
Was mixed with 40% by weight of the fiber and 20% by weight of the fiber 7, to prepare a fiber web having a basis weight of 30 g / m 2 using a semi-random card machine. Then, by jetting a high-pressure columnar water stream at a pressure of 5 MPa from the front and back surfaces of the fiber web, the fibers 2 are divided to form ultrafine fibers, and the fibers are entangled with each other. A dry nonwoven fabric having a basis weight of 30 g / m 2 was obtained.
【００６０】次に、湿式抄紙機において、ヤンキードラ
イヤーの入り口側に前記不織布を設置し、実施例１の構
成繊維からなる０．５％濃度のスラリーを調整し、目付
が５０g/m2となるように湿式抄紙しながら、予め設置し
た乾式不織布を積層し、１３５℃のヤンキードライヤー
で熱処理を施し、両層の熱融着性繊維を融着させて複合
不織布を得た。Next, in a wet paper machine, the nonwoven fabric was placed at the entrance side of the Yankee dryer, and a 0.5% concentration slurry composed of the constituent fibers of Example 1 was adjusted to have a basis weight of 50 g / m 2. While wet papermaking was performed as described above, the previously set dry nonwoven fabric was laminated, and heat-treated with a Yankee dryer at 135 ° C. to fuse the heat-fusible fibers of both layers to obtain a composite nonwoven fabric.
【００６１】得られた不織布をクロロスルホン酸５０重
量％、濃硫酸５０重量％を混合した液温４０℃の処理浴
で１時間浸漬処理し、その後希硫酸中に１０分間浸漬後
ＫＯＨ溶液に１時間浸漬して中和を行った。その後水洗
・乾燥させた後、熱カレンダー処理を施して、目付６５
g/m2、厚み０．１５mmの電池用セパレータを得た。The obtained nonwoven fabric is immersed in a treatment bath containing a mixture of 50% by weight of chlorosulfonic acid and 50% by weight of concentrated sulfuric acid at a liquid temperature of 40 ° C. for 1 hour, then immersed in dilute sulfuric acid for 10 minutes, and then immersed in a KOH solution. Neutralization was performed by soaking for a period of time. Then, after washing with water and drying, a heat calendering treatment is performed to obtain a basis weight of 65%.
A battery separator having a g / m 2 and a thickness of 0.15 mm was obtained.
【００６２】［実施例６］原料として繊維３の代わりに
繊維４を使用した以外は、実施例１と同じ方法で目付６
５g/m2、厚み０．１５mmの電池用セパレータを得た。Example 6 A basis weight was obtained in the same manner as in Example 1 except that the fiber 4 was used instead of the fiber 3 as a raw material.
A battery separator of 5 g / m 2 and a thickness of 0.15 mm was obtained.
【００６３】［実施例７］繊維の混合割合を、繊維１を
１０重量％、繊維３を５０重量％、繊維６を４０重量％
とした以外は、実施例１と同じ方法で目付６５g/m2、厚
み０．１５mmの電池用セパレータを得た。Example 7 The mixing ratio of the fibers was 10% by weight of fiber 1, 50% by weight of fiber 3, and 40% by weight of fiber 6.
A separator for batteries with a basis weight of 65 g / m 2 and a thickness of 0.15 mm was obtained in the same manner as in Example 1 except that the above conditions were adopted.
【００６４】［実施例８］実施例１の不織布を三酸化イ
オウガス中で３０秒間処理した後、水酸化ナトリウムで
中和しイオン交換水で洗浄した後、６０℃で乾燥させ
た。熱カレンダー処理を施して、目付６５g/m2、厚み
０．１５mmの電池用セパレータを得た。Example 8 The nonwoven fabric of Example 1 was treated in sulfur trioxide gas for 30 seconds, neutralized with sodium hydroxide, washed with ion-exchanged water, and dried at 60 ° C. Heat calendering was performed to obtain a battery separator having a basis weight of 65 g / m 2 and a thickness of 0.15 mm.
【００６５】［比較例１］原料として繊維１の代わりに
繊維８を使用した以外は、実施例１と同じ方法で目付６
５g/m2、厚み０．１５mmの電池用セパレータを得た。以
下、実施例１〜８、比較例１の物性を表１に示す。Comparative Example 1 A basis weight of 6 was obtained in the same manner as in Example 1 except that fiber 8 was used instead of fiber 1 as a raw material.
A battery separator of 5 g / m 2 and a thickness of 0.15 mm was obtained. Table 1 below shows the physical properties of Examples 1 to 8 and Comparative Example 1.
【００６６】[0066]
【表１】 [Table 1]
【００６７】実施例４は、スルホン基を有しないため、
サイクル寿命がやや短く、実施例７は、メチルペンテン
系重合体とポリオレフィン系重合体からなる分割型複合
繊維の混合量が少ないため、親水基の導入量が少ないだ
けでなく、セパレータの緻密性に欠き、容量保存率およ
びサイクル寿命がやや低くなったものの、実施例１〜
３、５、６、８においては、親水化処理の後でも十分な
強力を保持し、かつ電池に組み込んだ際の容量保存率も
８０％近くを保持し、自己放電性の改良に寄与してい
た。一方、比較例１は、スルホン化処理のような過酷な
親水化処理によって、必要以上に繊維が損傷し、タテ方
向の引張強力が極端に低下して組み立て時に破損が生
じ、ショート率が高くなり生産性が著しく低下した。Example 4 has no sulfone group.
The cycle life was rather short, and Example 7 was not only low in the amount of the hydrophilic group introduced, but also in the compactness of the separator, because the mixing amount of the splittable conjugate fiber composed of the methylpentene polymer and the polyolefin polymer was small. Chipping, capacity retention and cycle life were slightly lower, but
In Nos. 3, 5, 6, and 8, a sufficient strength was maintained even after the hydrophilization treatment, and a capacity preservation rate when incorporated in the battery was maintained at nearly 80%, contributing to improvement in self-discharge performance. Was. On the other hand, in Comparative Example 1, the fibers were damaged more than necessary due to severe hydrophilization treatment such as sulfonation treatment, the tensile strength in the vertical direction was extremely reduced, breakage occurred during assembly, and the short circuit rate increased. Productivity dropped significantly.
【００６８】[0068]
【発明の効果】本発明の電池用セパレータは、メチルペ
ンテン系重合体とポリオレフィン系重合体からなる分割
型複合繊維、および高融点成分および低融点成分からな
るポリオレフィン系複合繊維を主体とし、親水化処理を
施すことにより、耐熱性を有するとともに、優れた保液
性および十分な不織布強力を有し、電池寿命を低下させ
ることなく電池容量を向上させることができる。親水化
処理がスルホン化処理であると、特に自己放電性の改良
に寄与する。The battery separator of the present invention is mainly composed of a splittable conjugate fiber composed of a methylpentene polymer and a polyolefin polymer and a polyolefin conjugate fiber composed of a high melting point component and a low melting point component. By performing the treatment, it has heat resistance, excellent liquid retention properties and sufficient nonwoven fabric strength, and can improve the battery capacity without reducing the battery life. When the hydrophilization treatment is a sulfonation treatment, it particularly contributes to improvement of self-discharge property.
【００６９】そして、前記電池用セパレータを組み込ん
だ電池は、自己放電性が改良され、特に電気自動車（Ｐ
ＥＶ）やハイブリッド車（ＨＥＶ）用に好適である。The battery incorporating the battery separator has improved self-discharge properties, and is particularly suitable for electric vehicles (P
It is suitable for EVs and hybrid vehicles (HEV).
【図１】本発明に使用する分割型複合繊維の繊維断面図
の一例を示す。FIG. 1 shows an example of a fiber sectional view of a splittable conjugate fiber used in the present invention.
【図２】本発明に使用する分割型複合繊維の繊維断面図
の一例を示す。FIG. 2 shows an example of a fiber sectional view of a splittable conjugate fiber used in the present invention.
【図３】本発明に使用する分割型複合繊維の繊維断面図
の一例を示す。FIG. 3 shows an example of a fiber sectional view of a splittable conjugate fiber used in the present invention.
１．第１成分 ２．第２成分 1. First component 2. Second component
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｄ０６Ｍ 101:20 (72)発明者 田中 智文 兵庫県加古郡播磨町古宮877番地 ダイワ ボウポリテック株式会社播磨研究所内 (72)発明者 木田 達宣 兵庫県加古郡播磨町古宮877番地 ダイワ ボウポリテック株式会社播磨研究所内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // D06M 101: 20 (72) Inventor Tomofumi Tanaka 877 Komiya, Harima-cho, Kako-gun, Hyogo Daiwa Boupolitec Co., Ltd. Harima Research Laboratory (72) Inventor Tatsunobu Kida 877 Komiya, Harima-cho, Kako-gun, Hyogo Prefecture Harima Research Laboratory, Daiwa Boupolitec Co., Ltd.
Claims (14)
４−メチルペンテン−１と他のオレフィンとの共重合体
からなるメチルペンテン系重合体を第１成分とし、第１
成分とは異なるポリオレフィン系重合体またはその共重
合体を第２成分とし、繊維断面において２成分が交互に
隣接して配置され、２成分のうち少なくとも１成分が２
個以上に分割されてなる分割型複合繊維と、高融点成分
および低融点成分からなるポリオレフィン系複合繊維の
少なくとも２種類の繊維を含有する不織布であって、該
分割型複合繊維および該ポリオレフィン系複合繊維の含
有量が６０重量％を超えない範囲であり、該不織布が親
水化処理されていることを特徴とする電池用セパレー
タ。A first component is a methylpentene polymer comprising poly (4-methylpentene-1) or a copolymer of 4-methylpentene-1 and another olefin,
The second component is a polyolefin-based polymer or a copolymer thereof different from the components, and two components are alternately arranged adjacent to each other in a fiber cross section, and at least one component of the two components is 2
A nonwoven fabric containing at least two types of fibers, a splittable conjugate fiber divided into two or more pieces and a polyolefin-based conjugate fiber comprising a high-melting component and a low-melting component, wherein the splittable conjugate fiber and the polyolefin-based conjugate A separator for a battery, wherein the content of the fiber does not exceed 60% by weight, and the nonwoven fabric has been subjected to a hydrophilic treatment.
量％、ポリオレフィン系複合繊維の含有量が２０〜６０
重量％であることを特徴とする請求項１記載の電池用セ
パレータ。2. The split conjugate fiber content is 15 to 60% by weight, and the polyolefin conjugate fiber content is 20 to 60%.
The battery separator according to claim 1, wherein the weight is% by weight.
囲で含有していることを特徴とする請求項１または２に
記載の電池用セパレータ。3. The battery separator according to claim 1, wherein another synthetic fiber is contained in an amount not exceeding 40% by weight.
成分において実質的に溶融することなく、ポリオレフィ
ン系複合繊維の低融点成分により熱融着されていること
を特徴とする請求項１〜３のいずれかに記載の電池用セ
パレータ。4. The nonwoven fabric comprising a splittable conjugate fiber 2
The battery separator according to any one of claims 1 to 3, wherein the component is thermally fused by a low melting point component of the polyolefin-based conjugate fiber without being substantially melted.
繊維、および他の合成繊維の繊維長が、３〜２５mmであ
ることを特徴とする請求項１〜４のいずれかに記載の電
池用セパレータ。5. The battery separator according to claim 1, wherein the splittable conjugate fiber, the polyolefin-based conjugate fiber, and the other synthetic fiber have a fiber length of 3 to 25 mm.
士を積層されてなる複合不織布であることを特徴とする
請求項１〜５のいずれかに記載の電池用セパレータ。6. The battery separator according to claim 1, wherein the nonwoven fabric is a composite nonwoven fabric obtained by laminating fiber webs having different fiber lengths.
の少なくとも一部の層に他のシートを積層してなる複合
シートであって、該複合シートが親水化処理されている
ことを特徴とする電池用セパレータ。7. A composite sheet obtained by laminating another sheet on at least a part of the layer of the nonwoven fabric according to claim 1, wherein the composite sheet has been subjected to a hydrophilic treatment. Characteristic battery separator.
処理された不織布の少なくとも一部の層に他のシートが
積層されていることを特徴とする電池用セパレータ。8. A battery separator, characterized in that another sheet is laminated on at least a part of the layer of the nonwoven fabric subjected to the hydrophilic treatment according to any one of claims 1 to 6.
合体を第１成分とし、ポリプロピレン系重合体を第２成
分とすることを特徴とする請求項１〜８のいずれかに記
載の電池用セパレータ。9. The battery according to claim 1, wherein the splittable conjugate fiber has a methylpentene polymer as a first component and a polypropylene polymer as a second component. Separator.
を高密度ポリエチレンとし、芯成分をポリプロピレンと
した鞘芯型複合繊維であることを特徴とする請求項１〜
８のいずれかに記載の電池用セパレータ。10. The composite fiber according to claim 1, wherein the polyolefin-based composite fiber is a sheath-core type composite fiber having a sheath component of high-density polyethylene and a core component of polypropylene.
9. The battery separator according to any one of 8.
ことを特徴とする請求項１記載の電池用セパレータ。11. The battery separator according to claim 1, wherein the hydrophilic treatment is a sulfonation treatment.
ロロスルホン酸処理、あるいは無水硫酸処理のいずれか
１つであることを特徴とする請求項１１記載の電池用セ
パレータ。12. The battery separator according to claim 11, wherein the sulfonation treatment is any one of a fuming sulfuric acid treatment, a chlorosulfonic acid treatment, and a sulfuric anhydride treatment.
あることを特徴とする請求項１〜１２のいずれかに記載
の電池用セパレータ。13. The battery separator according to claim 1, wherein the degree of sulfonation is from 0.4 to 2% by weight.
池用セパレータを組み込んだ電池。14. A battery incorporating the battery separator according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31208499A JP3678081B2 (en) | 1998-11-16 | 1999-11-02 | Battery separator and battery using the same |
| TW089107538A TW466795B (en) | 1999-11-02 | 2000-04-21 | Battery separator and battery using the same |
| CNB001085700A CN1160812C (en) | 1999-11-02 | 2000-05-15 | Battery diaphragm and battery using same |
| HK01106355A HK1035961A1 (en) | 1999-11-02 | 2001-09-12 | A septum for battery and the battery using the same. |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32485798 | 1998-11-16 | ||
| JP10-324857 | 1998-11-16 | ||
| JP31208499A JP3678081B2 (en) | 1998-11-16 | 1999-11-02 | Battery separator and battery using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005089185A Division JP4291794B2 (en) | 1998-11-16 | 2005-03-25 | Battery separator and battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000215876A true JP2000215876A (en) | 2000-08-04 |
| JP3678081B2 JP3678081B2 (en) | 2005-08-03 |
Family
ID=26567027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31208499A Expired - Fee Related JP3678081B2 (en) | 1998-11-16 | 1999-11-02 | Battery separator and battery using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3678081B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003020524A (en) * | 2001-07-10 | 2003-01-24 | Kuraray Co Ltd | Joining-type conjugated staple fiber |
| CN100346505C (en) * | 2003-01-23 | 2007-10-31 | 大和纺织株式会社 | Separator material and method of producing the same, and alkali secondary battery separator |
| CN100403581C (en) * | 2005-12-23 | 2008-07-16 | 范亢俊 | Lithium cell, safety diaphragm of lithium ion cell and mfg. method |
| JP2012216427A (en) * | 2011-03-31 | 2012-11-08 | Daiwabo Holdings Co Ltd | Separator material, and battery comprising the same |
| CN104088154A (en) * | 2014-06-25 | 2014-10-08 | 中国第一汽车股份有限公司 | Composite modification method of non-woven fabric diaphragm |
| CN111279026A (en) * | 2017-10-03 | 2020-06-12 | 博爱德国有限公司 | Nonwoven fabric and process for forming the same |
| CN111640903A (en) * | 2019-03-01 | 2020-09-08 | 麻省固能控股有限公司 | Separator including ion flow control layer thermally activated and electrochemical device incorporating same |
| CN112803117A (en) * | 2021-01-05 | 2021-05-14 | 北京金羽新能科技有限公司 | Hydrophilic diaphragm and battery containing same |
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1999
- 1999-11-02 JP JP31208499A patent/JP3678081B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003020524A (en) * | 2001-07-10 | 2003-01-24 | Kuraray Co Ltd | Joining-type conjugated staple fiber |
| CN100346505C (en) * | 2003-01-23 | 2007-10-31 | 大和纺织株式会社 | Separator material and method of producing the same, and alkali secondary battery separator |
| CN100403581C (en) * | 2005-12-23 | 2008-07-16 | 范亢俊 | Lithium cell, safety diaphragm of lithium ion cell and mfg. method |
| JP2012216427A (en) * | 2011-03-31 | 2012-11-08 | Daiwabo Holdings Co Ltd | Separator material, and battery comprising the same |
| CN104088154A (en) * | 2014-06-25 | 2014-10-08 | 中国第一汽车股份有限公司 | Composite modification method of non-woven fabric diaphragm |
| CN111279026A (en) * | 2017-10-03 | 2020-06-12 | 博爱德国有限公司 | Nonwoven fabric and process for forming the same |
| CN111640903A (en) * | 2019-03-01 | 2020-09-08 | 麻省固能控股有限公司 | Separator including ion flow control layer thermally activated and electrochemical device incorporating same |
| CN112803117A (en) * | 2021-01-05 | 2021-05-14 | 北京金羽新能科技有限公司 | Hydrophilic diaphragm and battery containing same |
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