JP2000113870A - Manufacture of battery separator and battery separator - Google Patents
Manufacture of battery separator and battery separatorInfo
- Publication number
- JP2000113870A JP2000113870A JP10283998A JP28399898A JP2000113870A JP 2000113870 A JP2000113870 A JP 2000113870A JP 10283998 A JP10283998 A JP 10283998A JP 28399898 A JP28399898 A JP 28399898A JP 2000113870 A JP2000113870 A JP 2000113870A
- Authority
- JP
- Japan
- Prior art keywords
- component
- sea
- island
- fiber
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電池用セパレータ、
特にニッケルーカドミウム電池、ニッケルー亜鉛電池、
ニッケルー水素電池及び鉛電池等の二次電池に好適な電
池用セパレータの製造方法及び電池用セパレータに関す
る。The present invention relates to a battery separator,
Especially nickel-cadmium batteries, nickel-zinc batteries,
The present invention relates to a method for manufacturing a battery separator suitable for a secondary battery such as a nickel-metal hydride battery and a lead battery, and a battery separator.
【０００２】[0002]
【従来の技術】近年、二次電池等の電池は電子機器の軽
量化、小型化にともないセパレータの「小型化」及び
「高容量化」が進んでおり、さらなる低密度化・電解液
保液量の増加が求められている。しかしながらセパレー
タは低密度になると電解液保液量が増加する反面、デン
ドライト（放電時に電解液に溶けだした金属イオンが充
電時に金属電極の表面に生じる針状物）が成長して内部
短絡防止性が不十分となり、特に過充電時にはこの傾向
は顕著となる。2. Description of the Related Art In recent years, as batteries such as secondary batteries have become lighter and smaller in electronic equipment, separators have become smaller and have higher capacities. Increases in volume are required. However, as the density of the separator decreases, the amount of electrolyte retained increases, but on the other hand, dendrites (needle-like substances generated on the surface of the metal electrode during charging due to metal ions dissolved in the electrolyte during discharging) grow, preventing internal short-circuiting. In particular, this tendency becomes remarkable at the time of overcharging.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、高吸
液性でありながら内部短絡防止性、シャットダウン機構
発現性、機械的性能等の諸性能に優れた電池用セパレー
タの製造方法及び電池用セパレータを提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a battery separator and a battery having excellent liquid absorbing properties and excellent in various properties such as internal short-circuit prevention property, shutdown mechanism development property and mechanical performance. It is an object of the present invention to provide a separator.
【０００４】[0004]
【問題を解決するための手段】本発明は、（１） 島成
分がオレフィン系樹脂（Ａ成分）、海成分が易アルカリ
減量性ポリエステル樹脂（Ｂ成分）から構成された海島
繊維を含む不織布を製造し、該不織布からＢ成分を除去
する電池用セパレータの製造方法、（２） 島成分がオ
レフィン系樹脂（Ａ成分）、海成分が易アルカリ減量性
ポリエステル樹脂（Ｂ成分）から構成された海島繊維を
含むウエブを製造し、該ウエブに水流絡合処理を施して
不織布を製造し、該不織布からＢ成分を除去する電池用
セパレータの製造方法、（３） 島成分がオレフィン系
樹脂（Ａ成分）、海成分が易アルカリ減量性ポリエステ
ル樹脂（Ｂ成分）から構成された海島繊維及びオレフィ
ン系繊維状バインダーを含む不織布を製造し、該不織布
からＢ成分を除去する電池用セパレータの製造方法、
（４） オレフィン系繊維状バインダーが融点の異なる
２種以上のオレフィン系ポリマーから構成され、かつ該
ポリマーの融点の差が１０℃以上あり、繊維状バインダ
ー表面の少なくとも一部に低融点オレフィン系ポリマー
が存在することを特徴とする（３）に記載の電池用セパ
レータ、（５） 島成分がオレフィン系樹脂（Ａ成
分）、海成分が易アルカリ減量性ポリエステル樹脂（Ｂ
成分）から構成された海島繊維を含む不織布を製造し、
該不織布からＢ成分を除去して得られる電池用セパレー
タ、に関する。Means for Solving the Problems The present invention relates to (1) a nonwoven fabric containing sea-island fibers, wherein the island component is composed of an olefin resin (component A) and the sea component is composed of an alkali-reducible polyester resin (component B). A method for producing a battery separator for producing and removing the B component from the nonwoven fabric, (2) a sea island comprising an olefin resin (A component) as an island component and an alkali-reducible polyester resin (B component) as a sea component A method of producing a web containing fibers, subjecting the web to a hydroentanglement treatment to produce a nonwoven fabric, and removing a B component from the nonwoven fabric, a method for producing a battery separator, and (3) an island component comprising an olefin resin (A component). ), A non-woven fabric containing sea-island fibers and an olefin-based fibrous binder in which the sea component is composed of an alkali-reducible polyester resin (B component), and the B component is removed from the non-woven fabric. A method of manufacturing a pond separator,
(4) The olefin-based fibrous binder is composed of two or more olefin-based polymers having different melting points, and the difference in the melting points of the polymers is 10 ° C. or more, and at least a part of the surface of the fibrous binder has a low-melting-point olefin-based polymer. (5) The battery component according to (3), wherein the island component is an olefin-based resin (A component), and the sea component is an alkali-reducible polyester resin (B).
Component) to produce non-woven fabric containing sea-island fibers,
A battery separator obtained by removing the component B from the nonwoven fabric.
【０００５】[0005]
【発明の実施の形態】本発明は、島成分がオレフィン系
樹脂（Ａ成分）、海成分が易アルカリ減量性ポリエステ
ル樹脂（Ｂ成分）から構成された海島繊維を含む不織布
を製造し、該不織布からＢ成分を除去して電池用セパレ
ータを製造するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a non-woven fabric containing sea-island fibers in which the island component is composed of an olefin-based resin (component A) and the sea component is composed of an alkali-reducible polyester resin (component B). To produce a battery separator by removing the B component from the product.
【０００６】本発明において島成分を構成するオレフィ
ン系樹脂は特に限定されず、たとえばポリエチレン、ポ
リプロピレン、ポリメチルペンテン、４―メチルー１―
ヘキセン、４，４−ジメチルー１―ヘキセン、５―メチ
ルー２―ヘキセン、アリルシクロペンタン、アリルシク
ロヘキサン、アリルベンゼン、３―シクロヘキシルー１
―ブテン、ビニルシクロプロパン、ビニルシクロヘキサ
ン及びビニルシクロ［２，２，１］−ヘプタン等の重合
体、あるいはそれらの共重合体が挙げられる。なかでも
耐薬品性、耐熱性等に優れていることからプロピレン系
樹脂を用いるのが好ましい。紡糸性等の点から重量平均
分子量８万以上１５万以下、特に１０万以上１２万以下
のプロピレン系樹脂を用いるのがより好ましい。勿論、
２種以上の樹脂が併用されていてもよく、電池用セパレ
ータとして用いた際に電池性能に悪影響を及ぼさない範
囲で顔料、酸化防止剤、紫外線吸収剤、光安定剤等の添
加剤を含んでいてもよい。In the present invention, the olefin resin constituting the island component is not particularly limited. For example, polyethylene, polypropylene, polymethylpentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 5-methyl-2-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1
Polymers such as butene, vinylcyclopropane, vinylcyclohexane, and vinylcyclo [2,2,1] -heptane, and copolymers thereof; Among them, it is preferable to use a propylene-based resin because of its excellent chemical resistance and heat resistance. From the viewpoint of spinnability and the like, it is more preferable to use a propylene-based resin having a weight average molecular weight of 80,000 to 150,000, particularly 100,000 to 120,000. Of course,
Two or more resins may be used in combination, and include additives such as pigments, antioxidants, ultraviolet absorbers, and light stabilizers as long as they do not adversely affect battery performance when used as a battery separator. May be.
【０００７】本発明においては海成分として易アルカリ
減量性ポリエステルを用いる必要がある。該ポリエステ
ルはオレフィン系樹脂との紡糸性がよく、所望の海島繊
維を製造することができる。具体的なポリエステルの種
類は特に限定されず、アルカリにより分解及び/又は溶
解するポリエステルを用いればよい。工程性等の点から
は、島成分（オレフィン系樹脂）とのアルカリ溶解速度
比が３倍以上、特に１０倍以上、さらに１００倍以上の
易アルカリ減量性ポリステルを用いるのが好ましい。な
おここでいうアルカリ溶解速度とは、試料を９８℃、２
０ｇ／リットルの水酸化ナトリウム水溶液中に各測定サ
ンプルを浴比１：５００の条件で浸漬し、攪拌しながら
サンプルを溶解させたとき、下記式に示されたアルカリ
溶解速度定数Ｋにより示される値である。サンプルとし
ては同一条件で紡糸した直径１ｍｍのストランドを用い
るのが好ましい。In the present invention, it is necessary to use an alkali-reducible polyester as a sea component. The polyester has good spinnability with an olefin resin and can produce a desired sea-island fiber. The type of the specific polyester is not particularly limited, and a polyester which is decomposed and / or dissolved by an alkali may be used. From the viewpoint of processability and the like, it is preferable to use an alkali-reducible polyester having an alkali dissolution rate ratio of 3 times or more, particularly 10 times or more, and more preferably 100 times or more with the island component (olefin resin). The term “alkali dissolution rate” as used herein means that a sample is heated at 98 ° C., 2
When each measurement sample was immersed in a 0 g / liter aqueous solution of sodium hydroxide at a bath ratio of 1: 500 and the sample was dissolved with stirring, a value represented by an alkali dissolution rate constant K represented by the following formula: It is. It is preferable to use a strand having a diameter of 1 mm spun under the same conditions as a sample.
【０００８】[0008]
【数１】 (Equation 1)
【０００９】易アルカリ減量性ポリエステルは特に限定
されないが、ジカルボン酸、ジオール、ヒドロキシカル
ボン酸等からなるポリエステルが用いられ、共重合ポリ
エステルがより好適に使用できる。好適な易アルカリ減
量性ポリエステルとしては、下記の構成単位Ｉ〜IIIを
含む共重合ポリエステルが挙げられる。Although the alkali-reducible polyester is not particularly limited, a polyester comprising a dicarboxylic acid, a diol, a hydroxycarboxylic acid or the like is used, and a copolymerized polyester can be more preferably used. Suitable alkali-reducible polyesters include copolymerized polyesters containing the following structural units I to III.
【００１０】[0010]
【化１】 Embedded image
【００１１】紡糸性、アルカリ減量性の点から、ポリエ
ステルを構成する全酸成分の０．５〜１０モル％が構成
単位Iであり、かつ構成単位II及びIIIをそれぞれ１重量
％以上含む共重合ポリエステルが特に好ましい。特にポ
リエステルを構成する全酸成分の１〜７モル％が構成単
位Iであり、構成単位II及びIIIの合計含有率が全ポリエ
ステルの２〜５０重量％（さらに５〜３０重量％）であ
る共重合ポリエステルがより好ましい。From the viewpoint of spinnability and alkali weight loss, a copolymer containing 0.5 to 10 mol% of all the acid components constituting the polyester is the constitutional unit I and contains 1% by weight or more of each of the constitutional units II and III. Polyesters are particularly preferred. In particular, 1 to 7 mol% of the total acid component constituting the polyester is the structural unit I, and the total content of the structural units II and III is 2 to 50% by weight (further 5 to 30% by weight) of the total polyester. Polymerized polyesters are more preferred.
【００１２】ジカルボン酸単位Ｉ中の３価の芳香族基
（Ａｒ）としては、ベンゼントリイル基、ナフタレント
リイル基等が挙げられ、金属原子Ｍとしてはナトリウ
ム、カリウム、リチウム等のアルカリ金属原子が好適に
挙げられる。共重合ポリエステルを構成する他のカルボ
ン酸単位は特に限定されないが、全酸成分単位の７０モ
ル％以上が芳香族ジカルボン酸単位、特にテレフタル酸
単位であるのが好ましい。Examples of the trivalent aromatic group (Ar) in the dicarboxylic acid unit I include a benzenetriyl group and a naphthalenetriyl group. The metal atom M is an alkali metal atom such as sodium, potassium and lithium. Are preferred. The other carboxylic acid units constituting the copolymerized polyester are not particularly limited, but it is preferred that 70 mol% or more of all the acid component units are aromatic dicarboxylic acid units, particularly terephthalic acid units.
【００１３】ジオール単位II中のＲ1は、アルカリ溶解
性の点から炭素数２〜４のアルキレン基、特にエチレン
基であるのが好ましく、同じ理由から重合度ｍは１０〜
１００、特に２０〜２８であるのが好ましい。また側鎖
単位III中のＲ2は、紡糸性、アルカリ溶解性の点から炭
素数２〜４のアルキレン基、特にエチレン基であるのが
好ましく、Ｒ3は炭素数１〜１５の直鎖数１〜１５の直
鎖又は分岐状アルキル基、炭素数３〜１８のシクロアル
キル基、炭素数６〜１８のアリール基であるのが好まし
く、重合度ｎは２０〜８０であるのがより好ましい。ま
た共重合ポリエステルには他のジオール単位を有してい
るのが好ましく、炭素数２〜６の直鎖状アルキレングリ
コールから誘導された単位を含んでいるのが好ましい。R 1 in the diol unit II is preferably an alkylene group having 2 to 4 carbon atoms, particularly an ethylene group, from the viewpoint of alkali solubility. For the same reason, the polymerization degree m is 10 to 10.
It is preferably 100, especially 20 to 28. Further, R 2 in the side chain unit III is preferably an alkylene group having 2 to 4 carbon atoms, particularly an ethylene group from the viewpoint of spinnability and alkali solubility, and R 3 is a linear number having 1 to 15 carbon atoms. It is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and the degree of polymerization n is more preferably 20 to 80. The copolymerized polyester preferably has another diol unit, and preferably contains a unit derived from a linear alkylene glycol having 2 to 6 carbon atoms.
【００１４】かかるＡ成分及びＢ成分を混合紡糸してＡ
成分を島成分、Ｂ成分を海成分とする海島繊維を製造す
ればよい。Ａ成分及びＢ成分の配合割合等は適宜変更す
ればよいが、コスト、繊維径等の点からＡ成分：Ｂ成分
＝７０：３０〜５：９７，特に６０：４０〜３０：７０
（重量比）とするのが好ましい。このとき、不織布の孔
径及び通気度の点からは、海島繊維の繊度は１〜１２ｄ
程度であるのが好ましく、またＢ成分除去前の繊維（海
島繊維）の繊度は、Ｂ成分除去後の繊維（島成分）の繊
度の１０倍以上、特に５０倍以上であるのが好ましく、
１５００倍以下、特に５００倍以下であるのが好まし
い。島成分の直径、数等は、口金仕様、両ポリマーの混
練割合、紡糸温度、射出剪断速度、ドラフト、溶融粘度
等を調節することによりかえることができる。The component A and the component B are mixed and spun.
A sea-island fiber having an island component as the component and a sea component as the B component may be produced. The mixing ratio of the A component and the B component may be appropriately changed, but from the viewpoint of cost, fiber diameter, etc., the A component: B component = 70: 30 to 5:97, particularly 60:40 to 30:70.
(Weight ratio). At this time, the fineness of the sea-island fiber is 1 to 12 d in terms of the pore size and the air permeability of the nonwoven fabric.
It is preferable that the fineness of the fiber (sea-island fiber) before the removal of the B component is 10 times or more, particularly 50 times or more, the fineness of the fiber (island component) after the removal of the B component.
It is preferably 1500 times or less, particularly preferably 500 times or less. The diameter, number, etc. of the island components can be changed by adjusting the die specifications, kneading ratio of both polymers, spinning temperature, injection shear rate, draft, melt viscosity, and the like.
【００１５】なお本発明にいう海島繊維とは、繊維の横
断面においてマトリックスとなる海成分中に数個から数
万、好ましくは数十から数千個程度の島（Ａ成分：オレ
フィン系樹脂）が存在する繊維をいう。該海島繊維は押
出により成形され、かつ島成分が繊維軸方向にある程度
連続しているものであればよく、海島繊維の直径や断面
形状は特に限定されない。具体的には繊維状、ストラン
ド状等のものが挙げられる。The term "island-in-the-sea fiber" as used in the present invention means that several to several tens, preferably several tens to thousands, of islands (component A: olefin resin) are included in the sea component serving as a matrix in the cross section of the fiber. Refers to a fiber in which The sea-island fibers are formed by extrusion and the island components are continuous to some extent in the fiber axis direction, and the diameter and cross-sectional shape of the sea-island fibers are not particularly limited. Specific examples include those in the form of fibers and strands.
【００１６】かかる海島繊維を用いて不織布を製造すれ
ばよいが、セパレート性、保液性等の点からカットファ
イバーの形態で用いるのが好ましく繊維長１〜１５０ｍ
ｍ程度，特に２０〜１００ｍｍのものが広く適用でき
る。該オレフィン系繊維の配合割合は２０重量％以上／
不織布重量、特に３０重量％以上／不織布重量であるの
が好ましい。A nonwoven fabric may be produced using such sea-island fibers, but is preferably used in the form of cut fibers in terms of separation properties, liquid retention properties, etc., and a fiber length of 1 to 150 m.
m, especially 20 to 100 mm can be widely applied. The compounding ratio of the olefin fiber is 20% by weight or more /
The weight of the nonwoven fabric is preferably 30% by weight or more / the weight of the nonwoven fabric.
【００１７】不織布の機械的性能、寸法安定性等の点か
らはバインダー（樹脂状、繊維状）を配合するのが好ま
しく、バインダー能、耐薬品性等の点からオレフィン系
バインダーを用いるのが好ましい。主体繊維（島成分）
及びバインダーの配合重量比は主体繊維／バインダー＝
３０／７０〜９５／５であるのが好ましい。電気抵抗の
上昇を抑制する点からは繊維状バインダーを配合するの
が好ましく、バインダー能の点からは、繊維状バインダ
ーの表面に存在するポリマーの融点が島成分を構成する
オレフィン系樹脂の融点のー１０℃以下、特にー２０℃
以下であるのが好ましく、島成分を構成するオレフィン
系樹脂の融点のー４０℃以上であるのが好ましい。この
場合、主体繊維を実質的に溶融させることなく繊維間を
固定できることから、機械的性能、電気抵抗上昇抑制等
の点で一層優れた効果が得られる。繊維状バインダーの
単繊維繊度は特に限定されないが、不織布製造工程性、
最大孔径等の点からは０．５〜５デニールのものが好ま
しく、横断面形状はたとえば丸型、偏平型、繭型、中空
型、Ｔ字型等の形状のものを使用すればよい。It is preferable to incorporate a binder (resin-like or fibrous) from the viewpoints of mechanical performance and dimensional stability of the nonwoven fabric, and it is preferable to use an olefin-based binder from the viewpoints of binder ability, chemical resistance and the like. . Main fiber (island component)
And the blending weight ratio of the binder and the main fiber / binder =
It is preferably 30/70 to 95/5. It is preferable to blend a fibrous binder from the viewpoint of suppressing an increase in electric resistance, and from the viewpoint of the binder ability, the melting point of the polymer present on the surface of the fibrous binder is the melting point of the olefin resin constituting the island component. -10 ° C or less, especially -20 ° C
The melting point is preferably not higher than -40 ° C., which is the melting point of the olefin resin constituting the island component. In this case, since the fibers can be fixed between the fibers without substantially melting the main fibers, more excellent effects can be obtained in terms of mechanical performance, suppression of an increase in electric resistance, and the like. The single fiber fineness of the fibrous binder is not particularly limited, but nonwoven fabric manufacturing processability,
From the viewpoint of the maximum pore diameter and the like, those having a denier of 0.5 to 5 are preferable, and the cross-sectional shape may be, for example, a round, flat, cocoon, hollow, or T-shaped.
【００１８】勿論、２種類以上のポリマーにより構成さ
れた混合紡糸繊維や複合繊維（鞘型、サイドバイサイド
型、層状分割型、放射状分割型）を用いてもよく、融点
の異なる２種以上のポリマーから構成されたものを用い
るのが好ましい。なかでも両ポリマーの融点の差が１０
℃以上、好ましくは２０℃以上４０℃以下であり、繊維
状バインダー表面の少なくとも一部に低融点ポリマーが
存在する繊維状バインダーを用いるのが好ましい。この
場合、表面の低融点ポリマーが溶融してバインダー効果
を発現すると同時に、高融点ポリマーがバインダーの機
械的性能を維持できることから形態安定性等の点で優れ
た効果が得られる。Of course, a mixed spun fiber or a composite fiber (sheath type, side-by-side type, laminar split type, radial split type) composed of two or more polymers may be used. It is preferable to use the configured one. In particular, the difference between the melting points of both polymers is 10
It is preferable to use a fibrous binder having a melting point of not less than 20 ° C., preferably not less than 20 ° C. and not more than 40 ° C. and having a low melting point polymer on at least a part of the surface of the fibrous binder. In this case, the low melting point polymer on the surface melts to exhibit the binder effect, and at the same time, the high melting point polymer can maintain the mechanical performance of the binder, so that excellent effects such as morphological stability can be obtained.
【００１９】なかでも芯鞘型複合繊維がより好適に使用
され、芯成分が高融点ポリマー、鞘成分が低融点ポリマ
ー、特に主体繊維との接着性、耐薬品性等の点から芯成
分がプロピレン系ポリマー、鞘成分がエチレン系ポリマ
ーからなる芯鞘型複合繊維を用いるのが好ましい。Among them, core-sheath type composite fibers are more preferably used, and the core component is a high melting point polymer, and the sheath component is a low melting point polymer. In particular, the core component is propylene from the viewpoints of adhesiveness to the main fiber and chemical resistance. It is preferable to use a core-sheath type composite fiber in which the sheath polymer and the sheath component are composed of an ethylene polymer.
【００２０】勿論、本発明の効果を損なわない範囲であ
ればオレフィン系繊維及びオレフィン系繊維状バインダ
ー以外の成分が含まれていてもかまわない。たとえばポ
リアミド系繊維、アラミド系繊維（メタ系、パラ系）、
ポリエステル系繊維（全芳香族ポリエステル繊維を含
む）、ポリビニルアルコール系繊維や種々の添加剤等が
挙げられる。耐薬品性、シャットダウン機能等の点から
はポリオレフィン系繊維及びポリオレフィン系バインダ
ー以外の成分が３０重量％以下、特に１０重量％以下、
さらに５重量％以下であるのが好ましい。Of course, as long as the effects of the present invention are not impaired, components other than the olefin fiber and the olefin fibrous binder may be contained. For example, polyamide-based fibers, aramid-based fibers (meta-based, para-based),
Examples include polyester fibers (including wholly aromatic polyester fibers), polyvinyl alcohol fibers, and various additives. From the viewpoints of chemical resistance, shutdown function, etc., components other than the polyolefin fiber and the polyolefin binder are 30% by weight or less, particularly 10% by weight or less,
Further, it is preferably at most 5% by weight.
【００２１】不織布の製造方法は特に限定されず、その
形態はランダムウエブであってもクロスウエブであって
もかまわない。繊維を均一に配置させ、より緻密なシー
ト構造を形成させる点からは湿式抄造法により不織布を
製造するのが好ましい。また吸液性が高い不織布を得る
点からは乾式法により不織布を製造するのが好ましく、
具体的にはローラーカード、クロスラッパー、ランダム
ウエバー等によりクロスウエブ又はランダムウエブを製
造すればよい。The method for producing the nonwoven fabric is not particularly limited, and the form may be a random web or a cross web. From the viewpoint of uniformly disposing the fibers and forming a more dense sheet structure, it is preferable to produce the nonwoven fabric by a wet papermaking method. In addition, from the viewpoint of obtaining a nonwoven fabric having a high liquid absorbing property, it is preferable to manufacture the nonwoven fabric by a dry method,
Specifically, a cross web or a random web may be manufactured using a roller card, a cross wrapper, a random weber, or the like.
【００２２】このときニードルパンチや水流絡合等の絡
合処理を行ってもかまわない。絡合処理を行うとＢ成分
を除去した後のシートの機械的性能が高まるために好適
に実施される。ニードルパンチ処理を行う場合には、最
大孔径の点からニードルの径を必要以上に大きくしない
のが好ましい。また水流絡合処理を行う場合には、たと
えばノズル径０．０３〜０．３ｍｍ（特に０．０９〜
０．２ｍｍと）、ピッチ０．１５〜５ｍｍ（特に０．５
〜１．５ｍｍ）のノズルを1〜３列に配列したノズルプ
レートを用いるのが好ましく、水圧１０〜５００ｋｇ／
ｃｍ2の水流で１回又は複数回処理する方法が好適に挙
げられる。At this time, an entanglement process such as needle punching or water entanglement may be performed. When the entanglement process is performed, the mechanical performance of the sheet after removing the B component is enhanced, so that the entanglement process is suitably performed. When performing the needle punching process, it is preferable that the diameter of the needle is not increased more than necessary from the point of the maximum hole diameter. When the water entanglement process is performed, for example, the nozzle diameter is 0.03 to 0.3 mm (particularly 0.09 to 0.3 mm).
0.2 mm), pitch 0.15-5 mm (especially 0.5 mm)
It is preferable to use a nozzle plate having 1 to 3 rows of nozzles having a water pressure of 10 to 500 kg /
A method in which treatment is carried out once or multiple times with a water stream of cm 2 is preferably mentioned.
【００２３】得られた不織布にアルカリ処理を施して海
島繊維の海成分を除去することにより、所望の電池用セ
パレータを得ることができる。オレフィン系樹脂は耐ア
ルカリ性に優れているため海成分除去処理によっても実
質的に性能が劣化せず、しかもアルカリ処理は工業的に
容易に行うことができることから、優れた効果が得られ
る。アルカリ処理の方法は特に限定されずが、たとえば
所定の濃度、温度のアルカリ性溶液に浸漬すればよい。
アルカリ性溶液は水酸化ナトリウム、水酸化カルシウ
ム、リン酸三ナトリウム等の強アルカリ溶液が好まし
く、工程性等の点から２０〜１００℃、２〜６０ｇ／リ
ットルのＮａＯＨ水溶液等に数分〜数時間浸漬する方法
が好適に挙げられる。弱アルカリ物質、分解促進剤、界
面活性剤等を併用することも可能である。海成分を除去
した後、島成分を分繊する目的で再度水流絡合するのが
好ましい。By subjecting the obtained nonwoven fabric to an alkali treatment to remove the sea component of the sea-island fiber, a desired battery separator can be obtained. Since the olefin resin has excellent alkali resistance, its performance is not substantially deteriorated even by the sea component removal treatment, and the alkali treatment can be easily carried out industrially, so that excellent effects can be obtained. The method of the alkali treatment is not particularly limited, but may be, for example, immersion in an alkaline solution having a predetermined concentration and temperature.
The alkaline solution is preferably a strong alkaline solution such as sodium hydroxide, calcium hydroxide, trisodium phosphate, etc., and immersed in a 20 to 100 ° C., 2 to 60 g / L NaOH aqueous solution for several minutes to several hours from the viewpoint of processability and the like. A suitable method is mentioned. It is also possible to use a weak alkali substance, a decomposition accelerator, a surfactant and the like in combination. After removing the sea component, it is preferable to carry out hydroentanglement again for the purpose of separating the island component.
【００２４】次いでＢ成分を除去した後に加熱して不織
布の機械的性能を高めるのが好ましい。なかでも芯成分
が高融点ポリマー、鞘成分が低融点ポリマーからなる芯
鞘型繊維状バインダーを配合している場合には、繊維状
バインダーの機械的性能等を損なうことなく強固に繊維
間を固定できることから、機械的性能、電気抵抗上昇抑
制等の点で一層優れた効果が得られる。このときの温度
は適宜設定すればよいが、主体繊維の性能が損なわれな
い範囲で熱処理を施すのが好ましい。熱処理の温度、圧
力、時間等は適宜設定すればよい。Next, it is preferable to increase the mechanical performance of the nonwoven fabric by heating after removing the component B. Above all, when a core-in-sheath type fibrous binder consisting of a high-melting polymer and a low-melting polymer is mixed in the core component, the fibers are firmly fixed without impairing the mechanical performance of the fibrous binder. As a result, more excellent effects can be obtained in terms of mechanical performance, suppression of increase in electric resistance, and the like. The temperature at this time may be appropriately set, but it is preferable to perform heat treatment within a range where the performance of the main fiber is not impaired. The temperature, pressure, time, and the like of the heat treatment may be set as appropriate.
【００２５】電池用セパレータを構成する主体繊維の単
繊維繊度は、セパレート性、機械的性能、充放電時、電
池内温度が異常に上昇した際の安全対策としてのシャッ
トダウン機能発現性の点から０．０１〜０．１デニー
ル、特に０．０４〜０．０８デニールとするのが好まし
い。極細繊維を用いて通常の方法で不織布化すると密度
が高く通気度が低いものとなるが、本発明の方法により
得られる不織布は、極細繊維により構成されているにも
かかわらずかかる問題は生じない。また通常の紡糸方法
では１デニール以下の繊維を工業的に製造することは困
難であるが、かかる方法によれば極細繊維から構成され
た不織布を効率的に製造できる。The single fiber fineness of the main fibers constituting the battery separator is 0 from the viewpoint of the separation property, the mechanical performance, and the manifestation of a shutdown function as a safety measure when the temperature inside the battery rises abnormally during charging and discharging. It is preferably 0.01 to 0.1 denier, particularly preferably 0.04 to 0.08 denier. When the nonwoven fabric is formed into a nonwoven fabric by a normal method using ultrafine fibers, the density is high and the air permeability is low.However, the nonwoven fabric obtained by the method of the present invention does not cause such a problem even though the nonwoven fabric is constituted by the ultrafine fibers. . In addition, it is difficult to industrially produce fibers having a denier of 1 denier or less by a normal spinning method. However, according to such a method, a nonwoven fabric composed of ultrafine fibers can be efficiently produced.
【００２６】同様の点から、不織布表面の最大孔径２５
〜１５０μｍ、通気度０．５〜１５ｃｍ3／ｃｍ2／ｓｅ
ｃ、さらに最大孔径４０〜１２０μｍ、通気度０．８〜
１０ｃｍ3／ｃｍ2／ｓｅｃ、特に最大孔径４０〜１００
μｍ、通気度１〜７ｃｍ3／ｃｍ2／ｓｅｃとするのが好
ましい。From the same point, the maximum pore size 25
１５０150 μm, air permeability 0.5-15 cm 3 / cm 2 / se
c, furthermore, maximum pore diameter of 40 to 120 μm, air permeability of 0.8 to
10 cm 3 / cm 2 / sec, especially the maximum pore size 40 to 100
[mu] m, preferably with air permeability 1~7cm 3 / cm 2 / sec.
【００２７】保液性、小型化の点からは不織布の密度を
０．６ｇ／ｃｍ3以下、特に０．５８ｇ／ｃｍ3以下とす
るのが好ましく、機械的性能の点からは密度０．２０ｇ
／ｃｍ3以上とするのが好ましい。また同様の理由から
厚さ０．０５〜０．５０ｍｍ程度、坪量２０〜８０ｇ／
ｍ2程度であるのが好ましい。不織布の裂断長は寸法安
定性等の点から４ｋｍ以上、特に５ｋｍ以上、さらに
５．５ｋｍ以上であるのが好ましい。また本発明によれ
ば吸液性に優れたセパレータを得ることができ、具体的
には吸液量３．５ｇ／ｇ以上、特に４ｇ／ｇ以上、さら
に５ｇ／ｇ以上のセパレータが得られる。It is preferable that the density of the nonwoven fabric be 0.6 g / cm 3 or less, particularly 0.58 g / cm 3 or less from the viewpoint of liquid retention and miniaturization, and from the viewpoint of mechanical performance, the density is 0.20 g / cm 3.
/ Cm 3 or more. For the same reason, the thickness is about 0.05 to 0.50 mm and the basis weight is 20 to 80 g /
It is preferably about m 2 . The breaking length of the nonwoven fabric is preferably 4 km or more, particularly 5 km or more, and more preferably 5.5 km or more from the viewpoint of dimensional stability and the like. Further, according to the present invention, a separator having excellent liquid absorbing properties can be obtained, and specifically, a separator having a liquid absorbing amount of 3.5 g / g or more, particularly 4 g / g or more, and more preferably 5 g / g or more can be obtained.
【００２８】またセパレータに対する電解液の吸液性を
高める点から親水性を高めるための処理を施すのが好ま
しい。具体的には、界面活性剤の塗布、スルホン化処
理、プラズマ処理、スパッタリング処理等の処理が挙げ
られ、これらの２つ以上の処理を併用してもかまわな
い。なかでも親水耐久性の向上の点から、少なくともス
ルホン化処理を施すのが好ましい。特に親水性化等の点
から硫黄濃度が１０ｐｐｍ以上、工程性及びコスト等の
点からは１００００ｐｐｍ以下、特に８０００ｐｐｍ以
下となるようにスルホン化するのが好ましい。スルホン
化の方法は特に限定されないが、たとえば発煙硫酸、硫
酸、クロロ硫酸、塩化スルフリル等を含むスルホン化溶
液で処理する方法が挙げられる。なかでも発煙硫酸は反
応性が高く比較的容易にスルホン化できるため好適に使
用できる。スルホン化処理後は希釈したスルホン化溶
液、水の順で不織布を洗浄し、乾燥するのが理想的であ
る。勿論スルホン化処理を行う前又は後に他の親水化処
理を施してもかまわない。親水化処理後の吸液速度は６
００ｓ／２５ｍｍ以下、特に１００ｓ／２５ｍｍ以下で
あるのが好ましい。かかる親水化処理は不織布化後に施
すのが好ましく、Ｂ成分を除去した後に親水化処理を行
うのがより好ましい。It is preferable to perform a treatment for increasing the hydrophilicity from the viewpoint of increasing the liquid absorbing property of the electrolytic solution to the separator. Specific examples include a surfactant application, a sulfonation treatment, a plasma treatment, and a sputtering treatment. Two or more of these treatments may be used in combination. Above all, it is preferable to perform at least a sulfonation treatment from the viewpoint of improving the hydrophilic durability. In particular, sulfonation is preferably performed so that the sulfur concentration is 10 ppm or more from the viewpoint of hydrophilicity and the like, and 10000 ppm or less, particularly 8000 ppm or less from the viewpoint of processability and cost. The sulfonation method is not particularly limited, and examples thereof include a method of treating with a sulfonation solution containing fuming sulfuric acid, sulfuric acid, chlorosulfuric acid, sulfuryl chloride and the like. Among them, fuming sulfuric acid is preferably used because it has high reactivity and can be sulfonated relatively easily. Ideally, after the sulfonation treatment, the nonwoven fabric is washed and dried in the order of the diluted sulfonation solution and water. Of course, another hydrophilic treatment may be performed before or after the sulfonation treatment. Liquid absorption rate after hydrophilization treatment is 6
It is preferably at most 00 s / 25 mm, particularly preferably at most 100 s / 25 mm. Such a hydrophilization treatment is preferably performed after forming the nonwoven fabric, and more preferably, the hydrophilization treatment is performed after the B component is removed.
【００２９】本発明により得られる電池用セパレータは
諸性能に優れたものであり、広範囲に適用できるもので
あるが、なかでもニッケルーカドミウム電池、ニッケル
ー亜鉛電池、ニッケルー水素電池及び鉛電池等の二次電
池用の電池用セパレータとして用いた場合により優れた
効果が得られる。また本発明の効果を損なわない範囲で
あれば、該不織布の両面又は片面に他の層（布帛層、微
多孔フィルム層）を積層してもかまわない。The battery separator obtained according to the present invention is excellent in various performances and can be applied to a wide range. Among them, there are two types such as nickel-cadmium battery, nickel-zinc battery, nickel-hydrogen battery and lead battery. When used as a battery separator for a secondary battery, more excellent effects can be obtained. Further, another layer (a fabric layer or a microporous film layer) may be laminated on both sides or one side of the nonwoven fabric as long as the effects of the present invention are not impaired.
【００３０】[0030]
【実施例】以下に実施例により本発明を説明するが、本
実施例により何等限定されるものではない。 ［重量平均分子量、数平均分子量］ＧＰＣ法により測定
した。 ［最大孔径 μｍ］コールター・エレクトロニクス社
製：ｃｏｌｔｅｒ ＰＯＲＯＭＥＴＥＲIIにより測定し
た。 ［坪量 ｇ／ｍ2］ＪＩＳ Ｐ ８１２４「紙のメート
ル坪量測定方法」に準じて測定した。 ［厚さ ｍｍ 密度 ｇ／ｃｍ3］ＪＩＳ Ｐ ８１１
８「紙及び板紙の厚さと密度の試験方法」に準じて測定
した。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. [Weight average molecular weight, number average molecular weight] Measured by GPC method. [Maximum pore size: μm] Measured by coulter electronics manufactured by Coulter POROMETER II. [Basic weight g / m 2 ] Measured according to JIS P 8124 “Measurement of metric basis weight of paper”. [Thickness mm Density g / cm 3 ] JIS P 811
8 Measured according to “Test method for thickness and density of paper and paperboard”.
【００３１】［裂断長 ｋｍ］ＪＩＳ Ｐ ８１１３
「紙及び板紙の引張強さ試験方法」に準じて測定した。 ［通気度 ｃｍ3／ｃｍ2／ｓｅｃ］ＪＩＳ Ｌ １０９
６―１９９６「一般織物試験方法」の通気性測定方法に
準じ、株式会社東洋精機製作所製ブラジール型通気度試
験機により測定した。[Kiss length] JIS P 8113
The measurement was carried out according to "Testing method for tensile strength of paper and paperboard". [Air permeability: cm 3 / cm 2 / sec] JIS L109
The measurement was carried out using a Brasil-type air permeability tester manufactured by Toyo Seiki Seisaku-Sho, Ltd. in accordance with the air permeability measurement method described in 6-1996 “Test Method for General Fabrics”.
【００３２】［吸液量 ｇ／ｇ］５０ｍｍ×５０ｍｍの
試料を３５％ＫＯＨ液に３０秒間浸漬した後の保液量を
測定した。 ［吸液速度 秒］試料の端部を３５％ＫＯＨ液に浸漬
し、３５％ＫＯＨ液が高さ２５ｍｍまで吸い上げるまで
に要した時間により吸液速度を評価した。 ［硫黄濃度 ｐｐｍ］酸素燃焼フラスコ法により試料の
硫黄吸収させた吸収液をイオンクロマトアナライザー
（横河電気社製）により求めた。[Liquid absorption g / g] A 50 mm × 50 mm sample was immersed in a 35% KOH solution for 30 seconds, and the amount of liquid retained was measured. [Liquid Absorption Speed] The end of the sample was immersed in a 35% KOH solution, and the absorption speed was evaluated based on the time required for the 35% KOH solution to suck up to a height of 25 mm. [Sulfur Concentration ppm] The absorption liquid in which the sample was subjected to sulfur absorption by the oxyfuel combustion flask method was determined using an ion chromatography analyzer (manufactured by Yokogawa Electric Corporation).
【００３３】［Ｂ成分］５―ナトリウムスルホイソフタ
ル酸（Ｉ’）が共重合ポリエステルを構成する全酸成分
の２．５モル％、分子量２０００のポリエチレングリコ
ール（II’）及び化２で示されるポリオキシエチレング
リシジルエーテル（III’）から得られる構成単位Ｉ〜I
Iが全共重合ポリエステルのそれぞれ１０重量％を占
め、残部がテレフタル酸及びエチレングリコールから得
られる構成単位により構成された共重合ポリエステル
（固有粘度０．５８ｄｌ／ｇ）を用いた。なお、該共重
合ポリエステルは、以下の実施例及び比較例で用いたＡ
成分（オレフィン系樹脂）とのアルカリ溶解速比が１０
０倍以上のものであった。[Component B] 5-sodium sulfoisophthalic acid (I ') is 2.5 mol% of the total acid components constituting the copolymerized polyester, polyethylene glycol (II') having a molecular weight of 2,000, and poly (2) Structural units I to I obtained from oxyethylene glycidyl ether (III ')
A copolymer polyester (intrinsic viscosity: 0.58 dl / g) was used, in which I occupied 10% by weight of the total copolymerized polyester and the remainder was constituted by constituent units obtained from terephthalic acid and ethylene glycol. In addition, the copolymer polyester was used in the following Examples and Comparative Examples.
The alkali dissolution rate ratio of the component (olefin resin) is 10
It was more than 0 times.
【００３４】[0034]
【化２】 Embedded image
【００３５】［実施例１］重量平均分子量１０５２０
０、融点１６６℃のポリプロピレン（Ａ成分）４０重量
％、易アルカリ減量性共重合ポリエステル（Ｂ成分）６
０重量％を混合紡糸して、Ａ成分が島成分、Ｂ成分が海
成分を構成した４．３デニールの海島型繊維（島成分の
直径約０．００５２デニール）を製造し、これを主体繊
維として用いた。また鞘成分がポリエチレン（融点１３
４℃）、芯成分（融点１６７℃）がポリプロピレンであ
る２．１デニールの芯鞘型複合繊維（クラレ社製「Ｎ−
７４０」）を繊維状バインダーとして用いた。該主体繊
維７０重量部及び繊維状バインダー３０重量部を混合
し、ローラーカード、クロスラッパーを用いてクロスウ
エブを製造した。次いで、ノズル径０．１ｍｍ、ピッチ
０．６ｍｍ、１列のノズルプレートを用いて、水圧３０
ｋｇ／ｃｍ2―５０ｋｇ／ｃｍ2―８０ｋｇ／ｃｍ2−１
００ｋｇ／ｃｍ2の水流で表裏各１回水流絡合処理を行
った。Example 1 Weight average molecular weight 10520
0, 40% by weight of polypropylene (component A) having a melting point of 166 ° C., alkali-reducible copolyester (component B) 6
0% by weight is mixed and spun to produce 4.3 denier sea-island type fiber (island component having a diameter of about 0.0052 denier) in which component A is an island component and component B is a sea component. Used as The sheath component is polyethylene (melting point 13
4 ° C.), and a 2.1-denier core-sheath type composite fiber (“N-
740 ") was used as the fibrous binder. 70 parts by weight of the main fiber and 30 parts by weight of the fibrous binder were mixed, and a cross web was manufactured using a roller card and a cross wrapper. Then, using a nozzle plate having a nozzle diameter of 0.1 mm and a pitch of 0.6 mm in one row, a water pressure of 30 mm was used.
kg / cm 2 -50 kg / cm 2 -80 kg / cm 2 -1
The water entanglement treatment was performed once on each of the front and back sides with a water flow of 00 kg / cm 2 .
【００３６】次いで９８℃、４０ｇ／リットルのＮａＯ
Ｈ水溶液に１時間浸漬してＢ成分を除去した後、１５０
℃×２０ｋｇ／ｃｍ×１ｍ／ｍｉｎの条件で加熱加圧処
理を行った。次いで発煙硫酸によりスルホン化し、希硫
酸、水の順で洗浄後乾燥して電池用セパレータを製造し
た。また短絡シュミレーションテストとしてニッケル電
極を用いたＡＡサイズのスパイラル型電池に交流を付加
し、電池の電流と缶温度を測定する方法でシャットダウ
ン機能を評価した結果は良好であった。結果を表1に示
す。Then, at 98 ° C., 40 g / l of NaO
After immersion in H aqueous solution for 1 hour to remove the B component, 150
The heating and pressurizing treatment was performed under the conditions of ° C × 20 kg / cm × 1 m / min. Next, the mixture was sulfonated with fuming sulfuric acid, washed with diluted sulfuric acid and water in that order, and then dried to produce a battery separator. Further, as a short circuit simulation test, an AC was applied to an AA size spiral type battery using a nickel electrode, and the shutdown function was evaluated by a method of measuring the battery current and the can temperature, and the result was good. Table 1 shows the results.
【００３７】［実施例２］重量平均分子量１４０００、
融点１６９℃のポリプロピレン（Ａ成分）５０重量％、
易アルカリ減量性共重合ポリエステル（Ｂ成分）５０重
量％を混合紡糸して、Ａ成分が島成分、Ｂ成分が海成分
を構成した９．８デニールの海島型繊維（島成分の直径
約０．００９８デニール）を製造し、これを主体繊維と
し、かつ主体繊維と繊維状バインダーの配合比（重量
比）を５０：５０にした以外は実施例１と同様に電池用
セパレータを製造した。短絡シュミレーションテストと
してニッケル電極を用いたＡＡサイズのスパイラル型電
池に交流を付加し、電池の電流と缶温度を測定する方法
でシャットダウン機能を評価したところ結果は良好であ
った。結果を表1に示す。Example 2 The weight average molecular weight was 14,000,
50% by weight of polypropylene (component A) having a melting point of 169 ° C.
A 9.8-denier sea-island type fiber in which A component constitutes an island component and B component constitutes a sea component is mixed and spun with 50% by weight of alkali-reducible copolyester (component B). (0098 denier) was manufactured, and a battery separator was manufactured in the same manner as in Example 1 except that the main fiber was used as the main fiber and the mixing ratio (weight ratio) of the main fiber and the fibrous binder was set to 50:50. As a short-circuit simulation test, an AC was applied to an AA-size spiral battery using a nickel electrode, and the shutdown function was evaluated by measuring the battery current and the can temperature. The result was good. Table 1 shows the results.
【００３８】［実施例３］重量平均分子量９５０００、
融点１６５℃のポリプロピレン（Ａ成分）３７重量％、
易アルカリ溶解性共重合ポリエステル（Ｂ成分）６３重
量％を混合紡糸して、Ａ成分が島成分、Ｂ成分が海成分
を構成した２．７デニールの海島型繊維（島成分の直径
約０．０２９デニール）を製造し、これを主体繊維と
し、かつ主体繊維と繊維状バインダーの配合比（重量
比）を８０：２０にした以外は実施例１と同様に電池用
セパレータを製造した。これを主体繊維とした以外は実
施例１と同様に電池用セパレータを製造した。短絡シュ
ミレーションテストとしてニッケル電極を用いたＡＡサ
イズのスパイラル型電池に交流を付加し、電池の電流と
缶温度を測定する方法でシャットダウン機能を評価した
ところ結果は良好であった。結果を表1に示す。Example 3 A weight average molecular weight of 95,000,
37% by weight of polypropylene (component A) having a melting point of 165 ° C.
A 2.7 denier sea-island type fiber in which A component is an island component and B component is a sea component is mixed and spun with 63% by weight of an alkali-soluble copolyester (component B). 029 denier), a battery separator was produced in the same manner as in Example 1 except that this was used as the main fiber, and the blending ratio (weight ratio) of the main fiber and the fibrous binder was 80:20. A battery separator was manufactured in the same manner as in Example 1 except that this was used as a main fiber. As a short-circuit simulation test, an AC was applied to an AA-size spiral battery using a nickel electrode, and the shutdown function was evaluated by measuring the battery current and the can temperature. The result was good. Table 1 shows the results.
【００３９】［実施例４］重量平均分子量１０５２０
０、融点１６６℃のポリプロピレン（Ａ成分）３７重量
％、易アルカリ溶解性共重合ポリエステル（Ｂ成分）６
３重量％を混合紡糸して、Ａ成分が島成分、Ｂ成分が海
成分を構成した４．０デニールの海島型繊維（島成分の
直径約０．０６５デニール）を製造し、これを主体繊維
として用い、ポリエチレン（融点１３４℃）及びポリプ
ロピレン（融点１６７℃）からなる２．２デニールのサ
イドバイサイド型複合繊維を繊維状バインダーとして用
いた以外は実施例１と同様に電池用セパレータを製造し
た。短絡シュミレーションテストとしてニッケル電極を
用いたＡＡサイズのスパイラル型電池に交流を付加し、
電池の電流と缶温度を測定する方法でシャットダウン機
能を評価したところ結果は良好であった。結果を表1に
示す。Example 4 Weight average molecular weight 10520
0, 37% by weight of polypropylene (component A) having a melting point of 166 ° C, alkali-soluble copolyester (component B) 6
3% by weight was mixed and spun to produce a 4.0 denier sea-island type fiber (island component having a diameter of about 0.065 denier) in which the component A constituted an island component and the component B constituted a sea component. And a battery separator was manufactured in the same manner as in Example 1 except that 2.2 denier side-by-side conjugate fiber composed of polyethylene (melting point 134 ° C.) and polypropylene (melting point 167 ° C.) was used as a fibrous binder. As a short-circuit simulation test, an alternating current was applied to an AA-sized spiral battery using nickel electrodes,
When the shutdown function was evaluated by measuring the battery current and the can temperature, the results were good. Table 1 shows the results.
【００４０】［比較例１］重量平均分子量９５０００、
融点１６５℃のポリプロピレン（Ａ成分）４０重量％、
易アルァリ溶解性共重合ポリエステル（Ｂ成分）６０重
量％を混合紡糸して、Ａ成分が島成分、Ｂ成分が海成分
を構成した７．０デニールの海島型繊維（島成分の直径
約０．００８デニール）を製造し、これを主体繊維とし
て用いた以外は実施例１と同様に電池用セパレータを製
造した。得られたセパレータは通気性が高く電気抵抗の
高いものであり、保液性も不十分であった。短絡シュミ
レーションテストとしてニッケル電極を用いたＡＡサイ
ズのスパイラル型電池に交流を付加し、電池の電流と缶
温度を測定する方法でシャットダウン機能を評価したと
ころ結果は不良であった。結果を表1に示す。Comparative Example 1 A weight average molecular weight of 95,000,
40% by weight of polypropylene (component A) having a melting point of 165 ° C.
A 7.0-denier sea-island type fiber in which A component is an island component and B component is a sea component is mixed and spun with 60% by weight of an easily soluble copolyester (component B). 008 denier), and a battery separator was manufactured in the same manner as in Example 1 except that this was used as a main fiber. The obtained separator had high air permeability and high electric resistance, and had insufficient liquid retention. As a short circuit simulation test, alternating current was applied to an AA-sized spiral battery using a nickel electrode, and the shutdown function was evaluated by measuring the battery current and the can temperature. The result was poor. Table 1 shows the results.
【００４１】［比較例２］主体繊維として、単繊維繊度
１．１デニールのポリプロピレン繊維を用い、アルカリ
処理を行わなかった以外は実施例１と同様に行った。得
られたセパレータは孔径が大きくセパレート性の低いも
のであり、且つ裂断長が低く低強力であるため電池用セ
パレータとして不十分なものであった。短絡シュミレー
ションテストとしてニッケル電極を用いたＡＡサイズの
スパイラル型電池に交流を付加し、電池の電流と缶温度
を測定する方法でシャットダウン機能を評価したところ
結果は不良であった。結果を表1に示す。Comparative Example 2 The procedure of Example 1 was repeated except that a polypropylene fiber having a single fiber fineness of 1.1 denier was used as the main fiber, and the alkali treatment was not performed. The obtained separator had a large pore diameter and a low separation property, and was insufficient as a battery separator because of a low breaking length and low strength. As a short circuit simulation test, alternating current was applied to an AA-sized spiral battery using a nickel electrode, and the shutdown function was evaluated by measuring the battery current and the can temperature. The result was poor. Table 1 shows the results.
【００４２】[0042]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L047 AA14 AA21 AA27 AA28 BA04 BB01 BB02 BB09 CB07 CB10 CC12 5H021 BB08 BB13 CC02 EE04 EE08 EE32 HH06 5H028 AA02 AA05 BB02 BB06 EE06 HH08 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L047 AA14 AA21 AA27 AA28 BA04 BB01 BB02 BB09 CB07 CB10 CC12 5H021 BB08 BB13 CC02 EE04 EE08 EE32 HH06 5H028 AA02 AA05 BB02 BB06 EE06 HH08
Claims (5)
海成分が易アルカリ減量性ポリエステル樹脂（Ｂ成分）
から構成された海島繊維を含む不織布を製造し、該不織
布からＢ成分を除去する電池用セパレータの製造方法。An island component is an olefin resin (A component),
Sea component is alkali-reducible polyester resin (component B)
A method for producing a battery separator for producing a nonwoven fabric containing sea-island fibers composed of the following, and removing the B component from the nonwoven fabric.
海成分が易アルカリ減量性ポリエステル樹脂（Ｂ成分）
から構成された海島繊維を含むウエブを製造し、該ウエ
ブに水流絡合処理を施して不織布を製造し、該不織布か
らＢ成分を除去する電池用セパレータの製造方法。2. The island component is an olefin resin (A component),
Sea component is alkali-reducible polyester resin (component B)
And producing a nonwoven fabric by subjecting the web to a hydroentanglement treatment, and removing the B component from the nonwoven fabric.
海成分が易アルカリ減量性ポリエステル樹脂（Ｂ成分）
から構成された海島繊維及びオレフィン系繊維状バイン
ダーを含む不織布を製造し、該不織布からＢ成分を除去
する電池用セパレータの製造方法。3. The island component is an olefin resin (A component),
Sea component is alkali-reducible polyester resin (component B)
A non-woven fabric comprising a sea-island fiber and an olefin-based fibrous binder constituted by the method described above, and the component B is removed from the non-woven fabric.
異なる２種以上のオレフィン系ポリマーから構成され、
かつ該ポリマーの融点の差が１０℃以上あり、繊維状バ
インダー表面の少なくとも一部に低融点オレフィン系ポ
リマーが存在することを特徴とする請求項３に記載の電
池用セパレータ。4. The olefin-based fibrous binder is composed of two or more olefin-based polymers having different melting points,
4. The battery separator according to claim 3, wherein the difference in the melting points of the polymers is 10 ° C. or more, and the low-melting-point olefin-based polymer is present on at least a part of the surface of the fibrous binder.
海成分が易アルカリ減量性ポリエステル樹脂（Ｂ成分）
から構成された海島繊維を含む不織布を製造し、該不織
布からＢ成分を除去して得られる電池用セパレータ。5. An island component comprising an olefin resin (component A),
Sea component is alkali-reducible polyester resin (component B)
A battery separator obtained by producing a nonwoven fabric containing sea-island fibers composed of the following, and removing the B component from the nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10283998A JP2000113870A (en) | 1998-10-06 | 1998-10-06 | Manufacture of battery separator and battery separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10283998A JP2000113870A (en) | 1998-10-06 | 1998-10-06 | Manufacture of battery separator and battery separator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000113870A true JP2000113870A (en) | 2000-04-21 |
Family
ID=17672974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10283998A Pending JP2000113870A (en) | 1998-10-06 | 1998-10-06 | Manufacture of battery separator and battery separator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000113870A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002151358A (en) * | 2000-11-15 | 2002-05-24 | Kuraray Co Ltd | Separator for capacitor and manufacturing method thereof |
| JP2003059478A (en) * | 2001-08-08 | 2003-02-28 | Japan Vilene Co Ltd | Separator for lead-acid battery |
| US7402539B2 (en) | 2000-08-10 | 2008-07-22 | Japan Vilene Co., Ltd. | Battery separator |
| JP2016121430A (en) * | 2016-02-10 | 2016-07-07 | 三井化学株式会社 | Meltblown nonwoven fabric and use thereof |
| CN109004154A (en) * | 2018-07-23 | 2018-12-14 | 广东蒙泰高新纤维股份有限公司 | A kind of method of wet process copy paper technique manufacture diaphragm of power lithium ion battery |
-
1998
- 1998-10-06 JP JP10283998A patent/JP2000113870A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7402539B2 (en) | 2000-08-10 | 2008-07-22 | Japan Vilene Co., Ltd. | Battery separator |
| JP2002151358A (en) * | 2000-11-15 | 2002-05-24 | Kuraray Co Ltd | Separator for capacitor and manufacturing method thereof |
| JP2003059478A (en) * | 2001-08-08 | 2003-02-28 | Japan Vilene Co Ltd | Separator for lead-acid battery |
| JP2016121430A (en) * | 2016-02-10 | 2016-07-07 | 三井化学株式会社 | Meltblown nonwoven fabric and use thereof |
| CN109004154A (en) * | 2018-07-23 | 2018-12-14 | 广东蒙泰高新纤维股份有限公司 | A kind of method of wet process copy paper technique manufacture diaphragm of power lithium ion battery |
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