JP2001207362A - Non-woven fabric having excellent thrust resistance, method for producing the same and separator for battery - Google Patents
Non-woven fabric having excellent thrust resistance, method for producing the same and separator for batteryInfo
- Publication number
- JP2001207362A JP2001207362A JP2000015293A JP2000015293A JP2001207362A JP 2001207362 A JP2001207362 A JP 2001207362A JP 2000015293 A JP2000015293 A JP 2000015293A JP 2000015293 A JP2000015293 A JP 2000015293A JP 2001207362 A JP2001207362 A JP 2001207362A
- Authority
- JP
- Japan
- Prior art keywords
- section
- cross
- nonwoven fabric
- fiber
- length
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、異物などが不織布
を貫通したり、突き破って破損したりするのを抑制し、
包装材、ワイパー、壁紙などの化粧シート、防草シート
などの農業用、土木用資材に好適な不織布であって、特
に、電極等のバリや充放電の繰り返しにより発生するデ
ンドライドなど異物による破損を抑制するのに好適な電
池用セパレータに関するものである。BACKGROUND OF THE INVENTION The present invention suppresses foreign matter from penetrating or breaking through a nonwoven fabric,
Non-woven fabric suitable for agricultural and civil engineering materials such as packaging materials, wipers, decorative sheets such as wallpaper, grass-proof sheets, etc., and is particularly resistant to damage by foreign matter such as burrs on electrodes and dendrites generated by repeated charge and discharge. The present invention relates to a battery separator suitable for suppression.
【０００２】[0002]
【従来の技術】従来より、包装材、ワイパー、壁紙など
の化粧シート、防草シートなどの農業用、土木用資材な
どの用途において様々な不織布が商品化されており、通
常不織布の形態として、サーマルボンドタイプ不織布、
スパンボンド不織布、あるいはスパンレース不織布が好
ましく利用されている。サーマルボンドタイプ不織布や
スパンボンド不織布は繊維同士を接着させることにより
不織布強力を維持しているが一般に空隙が大きく、容易
に異物などが不織布を貫通したり、突き破って破損した
りする。また、スパンレース不織布であっても、異物が
不織布内部に入り込み易く、異物が尖った形状のもので
あれば容易に不織布を貫通したり、突き破って破損させ
たりしてしまう。それを解消するために、不織布の密度
を高密度にする、あるいは目付や厚みを大きくする方法
が採られているが、使用できる用途が限られていた。2. Description of the Related Art Conventionally, various nonwoven fabrics have been commercialized for use in agricultural and civil engineering materials such as decorative sheets such as wrapping materials, wipers and wallpaper, and grass-proof sheets. Thermal bond type non-woven fabric,
Spunbond nonwoven fabric or spunlace nonwoven fabric is preferably used. Thermal bond type nonwoven fabrics and spunbonded nonwoven fabrics maintain the strength of the nonwoven fabric by bonding the fibers to each other, but generally have large voids, and foreign matter easily penetrates or breaks through the nonwoven fabric. Further, even with spun lace nonwoven fabric, foreign matter easily enters the nonwoven fabric, and if the foreign matter has a sharp shape, the nonwoven fabric easily penetrates or breaks through the nonwoven fabric. In order to solve this problem, a method of increasing the density of the nonwoven fabric or increasing the basis weight and thickness has been adopted, but the usable applications have been limited.
【０００３】また、電解液の保液性向上を目的として、
異形断面繊維を用いた電池用セパレータが提案されてい
る。例えば、特開昭５９−３７６４８号公報には、繊維
断面形状に凹部と凸部を有するガラス繊維を使用した電
池用セパレータが開示され、特開昭６０−６５４４９号
公報には、異形断面を有しかつ多孔性のポリプロピレン
繊維を用いた電池用セパレータが開示され、特開昭６３
−１４８５３９号公報には、厚さ方向に密度差を有する
２層以上の積層体からなり、構成繊維として異形断面繊
維を用いた電池用セパレータが開示され、特開平９−８
２３０３号公報には、平均繊維径２μm以下のガラス繊
維と繊維長２〜３０mmの異形断面繊維を含有する電池用
セパレータが開示されている。In order to improve the liquid retention of the electrolyte,
There has been proposed a battery separator using fibers having an irregular cross section. For example, Japanese Patent Application Laid-Open No. 59-37648 discloses a battery separator using glass fibers having concave and convex portions in a fiber cross-sectional shape, and Japanese Patent Application Laid-Open No. 60-65449 has an irregular cross-section. And a battery separator using a porous polypropylene fiber are disclosed in
Japanese Patent Application Laid-Open No. Hei 9-8-14839 discloses a battery separator comprising a laminate of two or more layers having a density difference in the thickness direction and using fibers having irregular cross-sections as constituent fibers.
No. 2303 discloses a battery separator containing glass fibers having an average fiber diameter of 2 μm or less and modified fibers having a fiber length of 2 to 30 mm.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
電池用セパレータは、電解液の保液性向上を目的とし、
不織布内部に空間を多くするために、表面積の大きい異
形断面繊維を採用しているが、電極等のバリや充放電の
繰り返しにより発生するデンドライドなど異物による破
損を防止することについて検討されておらず、例えば、
特開昭６０−６５４４９号公報では、発泡剤を添加して
多孔性を付与しているため、繊維強度が部分的に弱く、
突き刺し強力に劣る。特開昭５９−３７６４８号公報で
は、繊維径の細いガラス繊維を使用しておりコスト高で
ある。特開昭６３−１４８５３９号公報では、厚さ方向
に密度差を有しているため、低密度層から異物が不織布
内部に入り込み易く、短絡を生じやすい。さらに、特開
平９−８２３０３号公報でも、ガラス繊維主体であるた
めコスト高であるとともに、異形断面繊維が繊維間の空
間を作り、嵩高性を持たせる目的で用いられるため、異
物が不織布内部に入り込み易く、短絡を生じやすいとい
う問題がある。However, the above-mentioned battery separator aims at improving the liquid retention of the electrolyte,
In order to increase the space inside the non-woven fabric, a modified cross-section fiber with a large surface area is used.However, no study has been made on preventing damage from foreign matter such as burrs on electrodes or dendrites generated by repeated charge and discharge. For example,
In JP-A-60-65449, since a foaming agent is added to impart porosity, the fiber strength is partially weak,
Poor piercing power. JP-A-59-37648 uses glass fibers having a small fiber diameter, which is expensive. In Japanese Patent Application Laid-Open No. 63-148538, since there is a density difference in the thickness direction, foreign matter easily enters the inside of the nonwoven fabric from the low-density layer, and a short circuit is easily generated. Furthermore, in Japanese Patent Application Laid-Open No. 9-82303, the cost is high because the glass fiber is mainly used, and the deformed cross-section fiber is used for the purpose of creating a space between the fibers and giving the bulkiness. There is a problem that it is easy to enter and a short circuit is easily caused.
【０００５】本発明はこれらの実情に鑑み、異物などが
不織布を貫通したり、突き破って破損したりするのを抑
制し、耐突き刺し強力に優れた不織布を得ることを目的
としてなされたものである。The present invention has been made in view of the above circumstances, and has as its object to prevent a foreign material from penetrating or breaking through a nonwoven fabric and to obtain a nonwoven fabric excellent in piercing resistance and strong. .
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、繊維断面が非円形形状からなる異形断面合成繊維を
少なくとも１０mass％含有する不織布であって、前記異
形断面合成繊維の繊維断面において断面の差し渡し長さ
の最も大きい部分を長辺とし、前記長辺と直交する断面
の差し渡し長さで最も大きくなる部分を短辺としたと
き、扁平比（長辺の長さ／短辺の長さ）を少なくとも
１．２とし、かつ後述する単位不織布密度当りの突き刺
し強力を少なくとも２０Ｎ／(g/cm3)とすることによ
り、異物などが不織布を貫通したり、突き破って破損し
たりするのを抑制し、耐突き刺し強力に優れた不織布を
得ることを知り本発明に至った。In order to solve the above-mentioned problems, a non-woven fabric containing at least 10% by mass of a modified cross-section synthetic fiber having a non-circular fiber cross-section is provided. The flattening ratio (length of the long side / length of the short side) is defined assuming that the longest part is the long side and the shortest part is the longest part of the crossing length of the cross section orthogonal to the long side. Is set to at least 1.2 and the piercing strength per unit nonwoven fabric density to be described later is set to at least 20 N / (g / cm 3 ), thereby preventing foreign matter and the like from penetrating or breaking through the nonwoven fabric. Then, it was found that a nonwoven fabric excellent in piercing resistance and excellent in strength was obtained, which led to the present invention.
【０００７】前記異形断面合成繊維における長辺の長さ
は、５〜６０μmであることが望ましい。また、前記異
形断面合成繊維の繊維強度が７．０cN/dtex以上である
ことが望ましい。It is desirable that the length of the long side of the modified cross-section synthetic fiber is 5 to 60 μm. Further, it is desirable that the fiber strength of the synthetic fiber having a modified cross section is 7.0 cN / dtex or more.
【０００８】前記異形断面合成繊維は、２以上の突起部
を有していること望ましい。また、異形断面合成繊維
は、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
れてなる異形断面発生型複合繊維を各々の成分に分割し
た単繊維であることが望ましい。It is desirable that the modified synthetic fiber has two or more projections. Further, the modified cross-section synthetic fiber is obtained by dividing a composite cross-section-generating composite fiber in which two components are alternately arranged adjacent to each other in a fiber cross section and at least one of the two components is divided into two or more. It is desirable that it is a single fiber.
【０００９】前記不織布は、親水化処理を施されること
が望ましい。Preferably, the nonwoven fabric is subjected to a hydrophilic treatment.
【００１０】前記不織布は、繊維断面において断面の差
し渡し長さの最も大きい部分を長辺とし、長辺と直交す
る断面の差し渡し長さで最も大きくなる部分を短辺とし
たとき、扁平比（長辺の長さ／短辺の長さ）が少なくと
も１．２である異形断面合成繊維を全繊維に対して少な
くとも１０mass％となるように水に分散させ、スラリー
を調製し、抄紙機を用いて湿式抄紙することにより製造
できる。さらに、湿式抄紙後、最高水圧３MPa 以下で高
圧水流を噴射し、繊維の分散を向上させることができ
る。[0010] In the nonwoven fabric, when the longest portion of the cross-sectional length of the cross-section in the fiber cross-section is the long side, and the shortest side is the portion of the cross-sectional length perpendicular to the long side, the aspect ratio (length A synthetic fiber having a modified cross-section (length of side / length of short side) of at least 1.2 is dispersed in water so as to be at least 10 mass% based on all fibers, a slurry is prepared, and a slurry is prepared using a paper machine. It can be produced by wet papermaking. Furthermore, after wet papermaking, a high-pressure water stream can be jetted at a maximum water pressure of 3 MPa or less to improve the dispersion of fibers.
【００１１】また、前記不織布は、異形断面発生型複合
繊維を水に分散させるとともに全繊維に対して少なくと
も１０mass％の異形断面合成繊維となるように各々の成
分に分割してスラリーを調製し、抄紙機を用いて湿式抄
紙することにより製造できる。さらに、湿式抄紙後、最
高水圧３MPa 以下で高圧水流を噴射すると、繊維の分散
を向上させることができる。Further, the nonwoven fabric is prepared by dispersing a modified cross-section-generating conjugate fiber in water and dividing it into individual components so as to be a modified cross-section synthetic fiber of at least 10 mass% with respect to all fibers to prepare a slurry, It can be produced by wet papermaking using a paper machine. Furthermore, if a high-pressure water stream is jetted at a maximum water pressure of 3 MPa or less after wet papermaking, the dispersion of fibers can be improved.
【００１２】前記不織布を用いた電池用セパレータは、
電極等のバリや充放電の繰り返しにより発生するデンド
ライドなど異物による破損を抑制する点で望ましい。以
下、本発明の内容を具体的に説明する。[0012] The battery separator using the non-woven fabric,
It is desirable in that damage due to foreign matter such as burrs on electrodes and dendrites generated by repeated charge and discharge is suppressed. Hereinafter, the contents of the present invention will be specifically described.
【００１３】[0013]
【発明の実施の形態】本発明に用いられる異形断面合成
繊維は、繊維断面が非円形形状からなり、例えば、十字
形、Ｉ字形、Ｈ字形、Ｌ字形、Ｔ字形、Ｘ字形、Ｙ字
形、三角形以上の多角形、扇形、楕円形などの断面が用
いられ、その一例を図１に示す。なかでも、図１（ａ）
あるいは（ｂ）に示すような繊維断面の輪郭が丸みを帯
びた十字形やＨ字形など断面の差し渡し長さの最も大き
い部分を長辺としたとき、長辺から延びる２以上の突起
部４を有する異形断面合成繊維、あるいは図２に示すよ
うな繊維断面において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
れてなる異形断面発生型複合繊維を各々の成分に分割し
た単繊維を用いることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The modified cross-section synthetic fiber used in the present invention has a non-circular cross section, for example, a cross, I, H, L, T, X, Y, A cross section such as a polygon having a shape of a triangle or more, a sector, an ellipse, or the like is used, and an example thereof is shown in FIG. Above all, Figure 1 (a)
Alternatively, assuming that the longest portion is the cross-over length of the cross-section, such as a cross shape or an H-shape in which the cross-section of the fiber is round as shown in (b), two or more protrusions 4 extending from the long side are formed. A synthetic fiber having a modified cross section or a composite fiber having a modified cross section in which two components are alternately arranged adjacently in a fiber cross section as shown in FIG. 2 and at least one of the two components is divided into two or more. It is preferable to use a single fiber divided into each component.
【００１４】そして、繊維断面において断面の差し渡し
長さの最も大きい部分を長辺とし、長辺と直交する断面
の差し渡し長さで最も大きくなる部分を短辺としたと
き、扁平比（長辺の長さ／短辺の長さ）を少なくとも
１．２となる異形断面合成繊維が用いられる。より好ま
しくは、少なくとも２である。例えば、図１（ａ）〜
（ｃ）に示す異形断面合成繊維であれば、断面の差し渡
し長さの最も大きい部分が長辺２、長辺２と直交する断
面の差し渡し長さで最も大きくなる部分が短辺３とな
り、図２に示す異形断面発生型複合繊維を各々の成分に
分割した扇形断面繊維であれば、断面の差し渡し長さの
最も大きい部分が長辺２、長辺２と直交する断面の差し
渡し長さで最も大きくなる部分が短辺３となる。扁平比
が１．２未満であると、異物が不織布を突き刺したとき
に繊維が異物の押圧に対して逃げにくく、貫通するのを
抑制することができ、例えば、電池用セパレータであれ
ば、異物が対極に到達するのを防止することができるか
らである。In the fiber cross section, when the longest portion of the cross-over length of the cross section is the long side, and the shortest side is the portion of the cross-over length of the cross section orthogonal to the long side, the flatness ratio (the long side A synthetic fiber having a modified cross section having a length / length of a short side of at least 1.2 is used. More preferably, it is at least 2. For example, FIG.
In the case of the modified cross-section synthetic fiber shown in (c), the longest portion of the cross-sectional length is the long side 2 and the shortest portion of the cross-sectional length orthogonal to the long side 2 is the short side 3. 2 is a fan-shaped cross-section fiber obtained by dividing the modified cross-section generating conjugate fiber into each component, the longest portion of the cross-section length is the longest side 2 and the longest cross-section length orthogonal to the long side 2 The larger portion is the short side 3. When the aspect ratio is less than 1.2, when the foreign matter pierces the nonwoven fabric, the fiber is hard to escape against the pressure of the foreign matter and can be suppressed from penetrating. Is prevented from reaching the counter electrode.
【００１５】このとき、異形断面合成繊維における長辺
の長さは、５〜６０μmであることが好ましい。より好
ましくは８〜４０μmである。長辺の長さが５μm未満で
あると、繊維が異物の押圧に対して逃げてしまい、耐突
き刺し性の効果が十分に得られず、長辺の長さが６０μ
mを超えると、繊維間の空隙が大きくなりすぎるため、
逆に突き刺し性に劣る。At this time, it is preferable that the length of the long side of the modified cross-section synthetic fiber is 5 to 60 μm. More preferably, it is 8 to 40 μm. If the length of the long side is less than 5 μm, the fiber escapes due to the pressing of the foreign matter, the effect of piercing resistance cannot be sufficiently obtained, and the length of the long side is 60 μm.
If it exceeds m, the gap between the fibers becomes too large,
Conversely, it has poor piercing properties.
【００１６】本発明に用いる異形断面合成繊維の素材と
しては、特に限定されるものではないが、ポリエステル
系樹脂、ポリアミド系樹脂、ポリオレフィン系樹脂など
が用いられ、特に、電池用セパレータに用いるのであれ
ば、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樹脂が好まし
い。繊維形態も単一繊維のみならず、異形断面であれば
複合繊維であってもよい。The material of the modified cross-section synthetic fiber used in the present invention is not particularly limited, but polyester-based resin, polyamide-based resin, polyolefin-based resin and the like are used. For example, polyethylene, polypropylene, polybutene-1,
Polyolefin resins such as poly (4-methylpentene-1) and ethylene-vinyl alcohol copolymer are preferred. The fiber form is not limited to a single fiber, but may be a composite fiber as long as it has an irregular cross section.
【００１７】また、本発明においては、各々の成分に分
割した単繊維が異形断面繊維であれば、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異形断面発生型複合
繊維も包含される。異形断面発生型複合繊維としては、
例えば、ポリエステル系樹脂／ポリオレフィン系樹脂、
ポリエステル系樹脂／ポリアミド系樹脂、ポリオレフィ
ン系樹脂／ポリアミド系樹脂などの異族系樹脂の組み合
わせ、あるいはポリ（４−メチルペンテン−１）／ポリ
プロピレン、エチレン−ビニルアルコール共重合体／ポ
リプロピレン、ポリプロピレン／ポリエチレンなどの同
族系樹脂の組み合わせからなるものが用いられる。その
繊維形態は、分割後異形断面を有していれば特に限定は
されず、分割前は円形であってもよい。そして、異形断
面発生型複合繊維の分割数は、４〜２０であることが好
ましい。In the present invention, if the single fiber divided into each component is a fiber having a modified cross section, two components are alternately arranged adjacent to each other in the fiber cross section, and at least one of the two components is two. It is divided as described above, and its constituent units are continuous in the length direction, and a part of all the constituent units also includes modified cross-section-generating composite fibers having a cross-sectional shape that is always exposed on the fiber surface. As a modified cross-section generating composite fiber,
For example, polyester resin / polyolefin resin,
Polyester resin / polyamide resin, polyolefin resin / polyamide resin and other heterologous resin combinations, or poly (4-methylpentene-1) / polypropylene, ethylene-vinyl alcohol copolymer / polypropylene, polypropylene / polyethylene, etc. A resin comprising a combination of the above-mentioned homologous resins is used. The fiber form is not particularly limited as long as it has an irregular cross section after division, and may be circular before division. It is preferable that the number of divisions of the modified cross section-generating composite fiber is 4 to 20.
【００１８】そして、前記異形断面合成繊維は全繊維に
対して少なくとも１０mass％含有される。より好ましく
は、１０〜６０mass％である。異形断面合成繊維の含有
量が１０mass％未満であると、耐突き刺し性の効果が十
分に得られないからである。他に用いられる繊維として
は、特に限定はされず、例えば、コットン、シルク、ウ
ールなどの天然繊維、レーヨンなどの再生繊維、アクリ
ル系繊維、ポリエステル系繊維、ポリアミド系繊維、ポ
リオレフィン系繊維などの単一繊維、複合繊維が用途に
応じて適宜用いられる。特に、電池用セパレータに用い
る場合、ポリオレフィン系単一繊維、あるいは鞘成分を
ポリエチレン、エチレン−プロピレン共重合体、ポリブ
テン−１、エチレン−ビニルアルコール共重合体とし、
芯成分をポリプロピレン、ポリ（４−メチルペンテン−
１）、ポリエチレンテレフタレートなどの鞘成分の融点
より１０℃以上高い樹脂とした熱接着性鞘芯型複合繊維
を用いるとよい。このとき、熱接着性鞘芯型複合繊維は
３０〜６０mass％含有すると、各繊維間の自由度を抑制
することができ、不織布の突き刺し性がさらに向上する
ので好ましい。[0018] The modified cross-section synthetic fiber contains at least 10 mass% of all fibers. More preferably, it is 10 to 60 mass%. If the content of the modified cross-section synthetic fiber is less than 10 mass%, the effect of piercing resistance cannot be sufficiently obtained. Other fibers used are not particularly limited. For example, natural fibers such as cotton, silk, and wool, recycled fibers such as rayon, acrylic fibers, polyester fibers, polyamide fibers, and polyolefin fibers can be used. Single fibers and composite fibers are used as appropriate according to the application. In particular, when used for a battery separator, the polyolefin-based single fiber, or the sheath component is polyethylene, ethylene-propylene copolymer, polybutene-1, ethylene-vinyl alcohol copolymer,
The core component is polypropylene, poly (4-methylpentene-
1) It is preferable to use a heat-adhesive sheath-core composite fiber made of a resin higher than the melting point of the sheath component such as polyethylene terephthalate by 10 ° C. or more. At this time, it is preferable that the content of the heat-adhesive sheath-core conjugate fiber is 30 to 60% by mass because the degree of freedom between the fibers can be suppressed and the piercing property of the nonwoven fabric is further improved.
【００１９】次に、本発明の耐突き刺し性に優れた不織
布を製造方法に沿って説明する。前記異形断面合成繊維
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、湿式抄紙法により得た
湿式抄紙ウェブ、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
が、なかでも構成繊維の繊維長が３〜２５mmからなる湿
式抄紙ウェブが均質なウェブを得て、異形断面合成繊維
が繊維ウェブの長手方向（厚み方向と直交する方向）に
整列し易い点で好ましい。より好ましい繊維長は５〜１
５mmである。繊維長が３mm未満では、耐突き刺し性の効
果が十分に得られず、後述する高圧水流処理時に繊維が
飛散し、地合斑となり突き刺し強力が低下し、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。Next, the nonwoven fabric having excellent stab resistance according to the present invention will be described in accordance with a manufacturing method. The form of the fibrous web containing the modified cross-section synthetic fiber is a card method, a dry web obtained by an air lay method, a wet papermaking web obtained by a wet papermaking method, or a direct method such as a melt blow method or a spun bond method. The obtained long-fiber web is used. Among them, a wet-type papermaking web having a fiber length of 3 to 25 mm of a constituent fiber obtains a homogeneous web, and the synthetic fiber having an irregular cross-section has a longitudinal direction (perpendicular to the thickness direction) of the fibrous web. Direction). More preferred fiber length is 5-1
5 mm. If the fiber length is less than 3 mm, the effect of piercing resistance is not sufficiently obtained, fibers are scattered during high-pressure water flow treatment to be described later, and the piercing strength is reduced as formation unevenness. If the fiber length exceeds 25 mm, the nonwoven fabric is particularly produced by wet papermaking. This is because, in the case of producing, the dispersibility of the fibers in the slurry is deteriorated, and a uniform nonwoven fabric cannot be obtained.
【００２０】上記繊維ウェブは、熱カレンダー処理、熱
風加工処理、高圧水流処理等、あるいはそれらの組み合
わせの方法により処理することができる。このとき、高
圧水流処理を用いる場合、できるだけ構成繊維を厚み方
向に配向させないような条件で処理することが好まし
い。具体的には、高圧水流処理の最高水圧を３MPa 以下
で噴射すると、厚み方向への配向を抑制することができ
る。構成繊維が厚み方向に配向していると、尖った異物
が繊維を避けて不織布内部に進入し易く、例えば、電池
用セパレータの場合、電極等のバリや充放電の繰り返し
により発生するデンドライドなど異物が対極に到達した
り、または破損したりして、短絡する比率が増大するか
らである。The fibrous web can be treated by a method such as a heat calendering treatment, a hot air treatment, a high-pressure water jet treatment, or a combination thereof. At this time, when using a high-pressure water flow treatment, it is preferable to perform the treatment under such a condition that the constituent fibers are not oriented in the thickness direction as much as possible. Specifically, when the maximum water pressure in the high-pressure water flow treatment is jetted at 3 MPa or less, orientation in the thickness direction can be suppressed. When the constituent fibers are oriented in the thickness direction, sharp foreign substances are likely to enter the nonwoven fabric avoiding the fibers.For example, in the case of a battery separator, foreign substances such as burrs of electrodes and dendrites generated by repeated charge and discharge This is because the rate of short-circuiting increases due to reaching the counter electrode or breaking.
【００２１】そして、前記不織布は、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、界面活性剤
処理、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。その後必要に応じて厚み等を調整
して本発明の不織布となす。Preferably, the nonwoven fabric has been subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include a surfactant treatment, a graft copolymerization treatment of a vinyl monomer, a fluorine gas treatment, a sulfonation treatment, a corona discharge treatment, and a plasma treatment. Thereafter, the thickness and the like are adjusted as necessary to obtain the nonwoven fabric of the present invention.
【００２２】例えば、本発明の電池用セパレータの製造
方法の１例としては、まず、扁平比（長辺の長さ／短辺
の長さ）が少なくとも１．２である異形断面合成繊維を
１０mass％以上と、熱接着性鞘芯型複合繊維および／ま
たはポリオレフィン系繊維を混合して、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、熱接着性鞘芯型複合繊
維を溶融させて繊維間を接着させる。この後、必要に応
じて高圧水流処理を施してもよい。しかるのちに不織布
には、前記親水化処理が施され、親水化不織布となす。
その後、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。For example, as an example of the method for producing the battery separator of the present invention, first, a synthetic fiber having a modified cross section having an aspect ratio (length of a long side / length of a short side) of at least 1.2 is obtained by applying 10 mass % Or more and the heat-adhesive sheath-core conjugate fiber and / or the polyolefin-based fiber are mixed, and 0.01 to 0.1%.
Disperse in water to a concentration of 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, the heat-adhesive sheath-core composite fibers are melted to bond the fibers. Thereafter, high-pressure water flow treatment may be performed as necessary. Thereafter, the nonwoven fabric is subjected to the above-mentioned hydrophilic treatment to form a hydrophilic nonwoven fabric.
Then, it is subjected to a heat calendering treatment to adjust the thickness to a predetermined value, and the battery separator of the present invention is obtained.
【００２３】また、本発明の電池用セパレータの製造方
法の別の１例としては、まず異形断面発生型複合繊維
と、熱接着性鞘芯型複合繊維および／またはポリオレフ
ィン系繊維を混合して、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、水に分散させる際にパルパーでの解離時間を長くし
たり、事前に水または湯に浸漬したりして、全繊維に対
して少なくとも１０mass％の異形断面合成繊維となるよ
うに各々の成分に分割させると、後述する高圧水流処理
時の水圧を低く抑制できる点で特に好ましい。そして、
抄紙機を用いて湿式抄紙され、不織布の取り扱い性を高
めるために、熱接着性鞘芯型複合繊維を溶融させて繊維
間を軽く接着させておく。さらに、湿式抄紙後、高圧水
流を噴射し、未分割の異形断面発生型複合繊維を分割さ
せる。このとき全ての異形断面発生型複合繊維が分割し
なくても少なくとも１０mass％の異形断面合成繊維が得
られていれば、本発明の目的は達成される。前述したよ
うに湿式抄紙前に異形断面発生型複合繊維を分割させた
場合、最高水圧３MPa 以下で処理すると、厚み方向への
繊維の絡合が抑制され、突き刺し強力が向上する点で好
ましい。得られた不織布は、乾燥と同時に熱接着性鞘芯
型複合繊維の低融点成分で構成繊維同士を熱融着させ、
その後は上記方法と同様にして電池用セパレータが得ら
れる。As another example of the method for producing a battery separator of the present invention, first, a modified cross-section generating composite fiber, a heat-adhesive sheath-core composite fiber and / or a polyolefin-based fiber are mixed. Disperse in water to a concentration of 0.01 to 0.6% to prepare a slurry. At this time, when dispersing in water, the dissociation time in the pulper is lengthened, or the fiber is immersed in water or hot water in advance, so that each of the fibers has a modified cross-section synthetic fiber of at least 10 mass% with respect to all fibers. The division into components is particularly preferable in that the water pressure during the high-pressure water flow treatment described below can be suppressed low. And
In order to improve the handleability of the nonwoven fabric after wet papermaking using a paper machine, the heat-adhesive sheath-core type composite fibers are melted to lightly bond the fibers. Furthermore, after the wet papermaking, a high-pressure water stream is injected to divide the undivided modified cross section-generating composite fibers. At this time, the object of the present invention is achieved as long as at least 10 mass% of synthetic fibers having a modified cross section is obtained without splitting all of the composite fibers having a modified cross section. As described above, when the modified cross-section-generating type composite fiber is divided before wet papermaking, it is preferable to treat the composite fiber at a maximum water pressure of 3 MPa or less, since the entanglement of the fiber in the thickness direction is suppressed and the piercing strength is improved. The obtained nonwoven fabric is dried and simultaneously heat-fused the constituent fibers with the low-melting-point component of the heat-adhesive sheath-core composite fiber,
Thereafter, a battery separator is obtained in the same manner as described above.
【００２４】本発明の不織布の目付は、用途に応じて適
宜設定すればよいが、電池用セパレータに用いる場合で
あれば、３０〜１００g/m2にすることが好ましい。３０
g/m2未満であると、突き刺し強力に劣るだけでなく、不
織布の引張強力が弱すぎる為、電池の作製に問題が生
じ、１００g/m2を超えると、突き刺し強力は向上するも
のの、ガスの通過性が悪化し、寿命面で不利となるから
である。The basis weight of the nonwoven fabric of the present invention may be appropriately set according to the intended use, but is preferably 30 to 100 g / m 2 when used for a battery separator. 30
If it is less than g / m 2, not only inferior in strength piercing, because tension of the nonwoven fabric strength is too weak, there is a problem in the production of the battery, if it exceeds 100 g / m 2, although powerful is improved piercing, gas This is because the passage property of the steel deteriorates, and the life is disadvantageous.
【００２５】さらに、本発明の不織布の密度は、１７５
kPa荷重時（ＪＩＳ−Ｂ−７５０２に準じたマイクロメ
ーターによる測定）で０．６g/cm3以下あることが好ま
しい。より好ましくは、０．３〜０．５g/cm3である。
不織布密度が０．６g/cm3を超えると、ガスの通過性が
悪化し、寿命面で不利となるからである。Further, the density of the nonwoven fabric of the present invention is 175
It is preferably 0.6 g / cm 3 or less under a kPa load (measured by a micrometer according to JIS-B-7502). More preferably, it is 0.3 to 0.5 g / cm 3 .
If the density of the nonwoven fabric exceeds 0.6 g / cm 3 , the gas permeability deteriorates and the life is disadvantageous.
【００２６】このようにして、下記に示す単位不織布密
度当りの突き刺し強力が少なくとも２０Ｎ／(g/cm3)で
ある耐突き刺し性に優れた不織布が得られる。 （突き刺し強力）カトーテック（株）製「ＫＥＳ−Ｇ５
ハンディー圧縮試験機」を用いて、縦３０mm、横１０
０mmの大きさに裁断した不織布を準備し、試料の上に縦
４６mm、横８６mm、厚み７mmのアルミ板の中央部に直径
１１mmの孔を有する押さえ板を載置した後、先端部が１
mmφの球状部、軸の部分が底面直径２．２mm、高さ１
８．７mmの円錐状になった針を、２mm／秒の速度で押さ
え板の孔の中央に垂直に突き刺した時の最大荷重（Ｎ）
を測定し、１７５kPa荷重（ＪＩＳ−Ｂ−７５０２に準
じたマイクロメーターによる測定）での不織布密度で除
して突き刺し強力Ｎ／(g/cm3)とした。単位不織布密度
当りの突き刺し強力が２０Ｎ／(g/cm3)未満であると、
異物などが不織布を容易に貫通したり、突き破って破損
させたりし、特に、電池用セパレータの場合、電極等の
バリや充放電の繰り返しにより発生するデンドライドな
ど異物が対極へ容易に到達したり、破損したりして、短
絡の比率が増大してしまうからである。In this way, a non-woven fabric having excellent stab resistance and having a piercing strength per unit non-woven fabric density of at least 20 N / (g / cm 3 ) is obtained. (Piercing Power) “KES-G5” manufactured by Kato Tech Co., Ltd.
30mm long, 10mm wide using a "handy compression tester"
A nonwoven fabric cut to a size of 0 mm is prepared, and a holding plate having a hole of 11 mm in diameter at the center of an aluminum plate having a length of 46 mm, a width of 86 mm, and a thickness of 7 mm is placed on the sample.
mmφ spherical part, shaft part is bottom diameter 2.2mm, height 1
Maximum load (N) when a 8.7 mm conical needle is vertically pierced into the center of the hole of the holding plate at a speed of 2 mm / sec.
Was measured and divided by the density of the nonwoven fabric under a load of 175 kPa (measured by a micrometer according to JIS-B-7502) to determine the piercing strength N / (g / cm 3 ). When the piercing strength per unit nonwoven fabric density is less than 20 N / (g / cm 3 ),
Foreign matter easily penetrates the nonwoven fabric or breaks through the nonwoven fabric, especially in the case of battery separators, foreign matter such as burrs of electrodes and dendrites generated by repeated charge and discharge easily reach the counter electrode, This is because the ratio of short circuit increases due to breakage.
【００２７】また、得られた不織布は、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る。親水化処理を施すことによ
り、例えば、ワイパーとして用いる場合、水分のある対
象物を払拭したり、ウェットワイパーとして利用するこ
とができ、電池用セパレータとして用いる場合、容量保
存率やサイクル寿命の向上に寄与するからである。The obtained nonwoven fabric is preferably 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. The sulfonation treatment includes concentrated sulfuric acid treatment, fuming sulfuric acid treatment, chlorosulfonic acid treatment, sulfuric anhydride treatment, and the like. By performing the hydrophilization treatment, for example, when used as a wiper, it can wipe off an object with moisture or can be used as a wet wiper, and when used as a battery separator, to improve the capacity storage rate and cycle life. Because it contributes.
【００２８】[0028]
【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、繊維断面における長辺および短辺の長さ、単
繊維強度、不織布の引張強力、およびショート率は、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, the length of the long side and the short side in the fiber cross section, the single fiber strength, the tensile strength of the nonwoven fabric, and the short ratio were measured by the following methods.
【００２９】［長辺、短辺の長さ］繊維を約１０００本
に束ねて孔径０．５mmの開孔を有するアルミ板に通し、
板表面に沿うようにカットし、電子顕微鏡を用いて４０
倍に拡大し、１cm×１cm四方中に存在する異形断面合成
繊維において断面の差し渡し長さの最も大きい部分を長
辺、長辺と直交する断面の差し渡し長さで最も大きくな
る部分を短辺として長さを各々測定し、その平均値を長
辺および短辺の長さとした。[Long side, short side length] Bundled about 1000 fibers and passed through an aluminum plate having an aperture with a hole diameter of 0.5 mm.
Cut along the plate surface and use an electron microscope to cut
In the synthetic fiber of irregular cross-section present in 1 cm x 1 cm square, the longest part of the cross-over length of the cross section is the long side, and the longest part of the cross-over length of the cross section orthogonal to the long side is the short side Each length was measured, and the average value was taken as the length of the long side and the short side.
【００３０】［単繊維強度］ＪＩＳ−Ｌ−１０１５に準
じ、引張試験機を用いて、試料のつかみ間隔を２０mmと
したときの荷重値を測定し、単位繊度あたりの荷重値を
単繊維強度とした。[Single fiber strength] According to JIS-L-1015, a load value was measured using a tensile tester with a sample holding distance of 20 mm, and the load value per unit fineness was defined as the single fiber strength. did.
【００３１】［不織布の引張強力］ＪＩＳ−Ｌ−１０９
６に準じ、不織布のタテ方向に対して、幅５cm、長さ１
５cm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。[Tensile strength of nonwoven fabric] JIS-L-109
According to 6, in the vertical direction of the nonwoven fabric, width 5 cm, length 1
A 5 cm sample piece was gripped at a spacing of 10 cm, stretched at a tensile speed of 30 cm / min using a constant-speed stretching type tensile tester, and the load value at cutting was defined as tensile strength.
【００３２】［ショート率］負極を水素吸蔵合金、カル
ボニルニッケル、カルボキシメチルセルロース（ＣＭ
Ｃ）、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、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とし、正極を
公知の焼結式ニッケル極として、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。作製し
た円筒形密閉ニッケル水素電池を、充電０．１Ｃ率で１
２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。このとき、短絡が起きた割合をショー
ト率とした。[Short Ratio] The negative electrode was made of a hydrogen storage alloy, carbonyl nickel, carboxymethyl cellulose (CM
C), water was added to polytetrafluoroethylene (PTFE) and kneaded to prepare a slurry, and this slurry was dip-coated on a nickel-plated punching metal, and then 80 ° C.
And press-molded to form a hydrogen-absorbing alloy negative electrode, the positive electrode as a well-known sintered nickel electrode, inserting each separator between the negative electrode and the positive electrode into a battery case, and injecting the electrolyte. Thus, a cylindrical sealed nickel-metal hydride battery was manufactured. The fabricated cylindrical sealed nickel-metal hydride battery is charged at
The final voltage was set to 1.0 V at a discharge rate of 0.1 C for 2 hours, a pause of 0.5 hour, and a charge / discharge cycle of 10 cycles was repeated to perform the initial activation of the battery. At this time, the ratio of occurrence of the short circuit was defined as the short circuit rate.
【００３３】［実施例１］図１（ａ）に示す繊維断面を
有し、融点１６３℃のポリプロピレン（日本ポリケム
（株）製）からなる繊度２．２dtex、繊維長１０mmのポ
リプロピレン繊維を６０mass％と、鞘成分を融点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、繊度１．７
dtex、繊維長１０mmの同心円鞘芯型複合繊維を４０mass
％とを混合して、パルパーでの解離時間を１５分とし、
０．５％の濃度になるようにスラリーを調製し、湿式抄
紙したあと、ヤンキードライヤーを用い１３５℃で乾燥
と同時に鞘芯型複合繊維の鞘成分を溶融し熱融着させて
目付５０g/m2の湿式不織布を得た。Example 1 A polypropylene fiber having a fiber cross section shown in FIG. 1A and having a fineness of 2.2 dtex and a fiber length of 10 mm made of polypropylene (manufactured by Nippon Polychem Co., Ltd.) having a melting point of 163.degree. And a sheath component with a melting point of 132
° C high-density polyethylene (manufactured by Nippon Polychem Co., Ltd.) and a core component of polypropylene having a melting point of 163 ° C (manufactured by Nippon Polychem Co., Ltd.), a composite ratio of 50:50 and a fineness of 1.7.
dtex, 40mm of concentric sheath-core composite fiber with a fiber length of 10mm
% And the dissociation time in the pulper is 15 minutes,
A slurry was prepared so as to have a concentration of 0.5%, and wet-papermaking was performed. The slurry was dried at 135 ° C. using a Yankee dryer, and simultaneously, the sheath component of the sheath-core composite fiber was melted and heat-sealed to obtain a basis weight of 50 g / m 2. 2 was obtained.
【００３４】得られた湿式不織布の両面をそれぞれ４回
ずつ、総放電量が、０．４６２KW・分／m2となるように
コロナ放電処理を施し、熱カレンダー処理して、目付５
０g/m2、厚み１２０μmの電池用セパレータを得た。The obtained wet nonwoven fabric was subjected to corona discharge treatment four times each on each side so that the total discharge amount was 0.462 kW · min / m 2, and subjected to a heat calender treatment to obtain a basis weight of 5%.
A battery separator having a thickness of 0 g / m 2 and a thickness of 120 μm was obtained.
【００３５】［実施例２］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２つの突起部からなる繊維断面を有す
る繊度３．３dtex、繊維長６mmの異形断面発生型複合繊
維を５０mass％と、実施例１の同心円鞘芯型複合繊維を
３０mass％と、融点１６３℃のポリプロピレン（日本ポ
リケム（株）製）からなり、繊維断面が円形形状を有す
る繊度０．８dtex、繊維長１０mmのポリプロピレン繊維
を２０mass％とを混合して、パルパーでの解離時間を１
５分とし、０．５％の濃度になるようにスラリーを調製
し、湿式抄紙したあと、表裏面より３MPaの圧力で高圧
柱状水流を噴射することによって、異形断面発生型複合
繊維を分割させて扇形の繊維断面を有する極細繊維を形
成させるとともに繊維間を交絡させ、１３５℃で乾燥と
同時に熱融着させて目付５０g/m2の湿式不織布を得た。Example 2 The first component was an ethylene-vinyl alcohol copolymer (ethylene content 38 mol%), the second component was polypropylene, and the composite ratio was 50:
2, 50 mass% of the modified cross-section generating conjugate fiber having a fineness of 3.3 dtex and a fiber length of 6 mm having a fiber cross section composed of the two protrusions shown in FIG. 2 and 30 mass% of the concentric sheath-core conjugate fiber of Example 1. A polypropylene fiber having a melting point of 163 ° C (made by Nippon Polychem Co., Ltd.) having a circular cross section of a fineness of 0.8 dtex and a fiber length of 10 mm was mixed with 20 mass%, and the dissociation time with a pulper was determined. 1
After 5 minutes, a slurry was prepared so as to have a concentration of 0.5%, wet papermaking was performed, and then a high-pressure columnar water stream was injected from the front and back surfaces at a pressure of 3 MPa, thereby dividing the irregular cross-section generating type composite fiber. Ultrafine fibers having a fan-shaped fiber cross section were formed, and the fibers were entangled. The fibers were dried at 135 ° C. and heat-fused to obtain a wet nonwoven fabric having a basis weight of 50 g / m 2 .
【００３６】得られた湿式不織布の両面をそれぞれ４回
ずつ、総放電量が、０．４６２KW・分／m2となるように
コロナ放電処理を施し、熱カレンダー処理して、目付５
０g/m2、厚み１２０μmの電池用セパレータを得た。The wet-type nonwoven fabric was subjected to corona discharge treatment on both sides four times each so that the total discharge amount was 0.462 kW · min / m 2 , heat calendering was performed, and the basis weight was 5%.
A battery separator having a thickness of 0 g / m 2 and a thickness of 120 μm was obtained.
【００３７】［比較例１］実施例２の円形形状ポリプロ
ピレン繊維を６０mass％と、実施例１の同心円鞘芯型複
合繊維を４０mass％とした以外は、実施例１と同様の方
法で目付５０g/m2、厚み１２０μmの電池用セパレータ
を得た。Comparative Example 1 A basis weight of 50 g / m2 was obtained in the same manner as in Example 1 except that the circular polypropylene fiber of Example 2 was changed to 60 mass% and the concentric sheath-core composite fiber of Example 1 was changed to 40 mass%. An m 2 , 120 μm thick battery separator was obtained.
【００３８】［比較例２］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４５mmの異形断面発生型複合繊維を５０mass％と、
実施例１の同心円鞘芯型複合繊維を３０mass％と、融点
１６３℃のポリプロピレン（日本ポリケム（株）製）か
らなり、繊維断面が円形形状を有する繊度０．８dtex、
繊維長３８mmのポリプロピレン繊維を２０mass％とを混
合し、セミランダムカード機により繊維ウェブを作製
し、表裏面より１５MPaの圧力で高圧柱状水流を噴射す
ることによって、異形断面発生型複合繊維を分割させて
扇形の繊維断面を有する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
て目付５０g/m2の乾式不織布を得た。得られた乾式不織
布を実施例１と同様の方法で親水化処理を施し、目付５
０g/m2、厚み１２０μｍの電池用セパレータを得た。以
下、実施例１〜２、比較例１〜２の物性を表１に示す。Comparative Example 2 The first component was an ethylene-vinyl alcohol copolymer (ethylene content 38 mol%), the second component was polypropylene, and the composite ratio was 50:
2, 50 mass% of a modified cross section-generating composite fiber having a fineness of 3.3 dtex and a fiber length of 45 mm having a fiber cross section shown in FIG.
The concentric sheath-core type composite fiber of Example 1 was made of polypropylene (manufactured by Nippon Polychem Co., Ltd.) having a melting point of 163 ° C. and a fiber density of 0.8 dtex having a circular cross section.
Polypropylene fiber having a fiber length of 38 mm is mixed with 20 mass%, a fibrous web is produced by a semi-random card machine, and a high-pressure columnar water stream is jetted from the front and back surfaces at a pressure of 15 MPa, thereby dividing the composite fiber having an irregular cross section. Then, ultrafine fibers having a fan-shaped fiber cross section were formed, and the fibers were entangled. The fibers were dried at 135 ° C. and heat-fused to obtain a dry nonwoven fabric having a basis weight of 50 g / m 2 . The obtained dry nonwoven fabric was subjected to a hydrophilic treatment in the same manner as in Example 1 to obtain a basis weight of 5%.
A battery separator of 0 g / m 2 and a thickness of 120 μm was obtained. Table 1 below shows the physical properties of Examples 1 and 2 and Comparative Examples 1 and 2.
【００３９】[0039]
【表１】 [Table 1]
【００４０】実施例１〜２においては、所定の異形断面
を有しているので、突き刺し強力が大きく、得られた不
織布を電池用セパレータとして用いると、ショート率が
格段に低減され、さらに親水化処理を施したことによっ
て、電池特性に優れたニッケル水素電池を得ることがで
きた。一方、比較例１では、全てが円形形状の繊維断面
からなる繊維を用いたため、突き刺し強力が小さく、シ
ョート率が大きくなった。比較例２では、所定の異形断
面を有しているものの、異形断面発生型複合繊維を分割
させるのに、１５MPaの高圧水流で処理したため、不織
布の厚み方向に構成繊維が配向してしまっただけでな
く、水流痕も形成され密度斑が生じたため突き刺し強力
が不十分であった。In Examples 1 and 2, since they have a predetermined irregular cross-section, they have high piercing strength, and when the obtained nonwoven fabric is used as a battery separator, the short-circuit rate is remarkably reduced, and the hydrophilicity is further reduced. By performing the treatment, a nickel-metal hydride battery having excellent battery characteristics could be obtained. On the other hand, in Comparative Example 1, since fibers having a circular fiber cross section were used, the piercing strength was small and the short-circuit rate was large. In Comparative Example 2, although the fiber had a predetermined irregular cross-section, it was treated with a high-pressure water stream of 15 MPa to divide the irregular-section-generating composite fiber, so that only the constituent fibers were oriented in the thickness direction of the nonwoven fabric. However, water marks were also formed and density irregularities were generated, resulting in insufficient piercing strength.
【００４１】[0041]
【発明の効果】本発明の不織布は、繊維断面が非円形形
状からなり、所望の扁平比（長辺の長さ／短辺の長さ）
を有する異形断面合成繊維を少なくとも１０mass％含有
することにより、高い突き刺し強力を得ることができ
る。また、異形断面合成繊維が２以上の突起部を有する
繊維、あるいは繊維断面において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
に分割されてなる異形断面発生型複合繊維を各々の成分
に分割した単繊維であると、高い突き刺し強力とともに
高い保液性を得ることができる。そして、本発明の不織
布は、湿式抄紙法を用いて、あるいは湿式抄紙した後、
３MPa以下のような低水圧下での水流絡合処理法を用い
て製造することにより、所望の突き刺し強力を有する不
織布を得ることができる。本発明の耐突き刺し性に優れ
た不織布は、包装材、ワイパー、壁紙などの化粧シー
ト、防草シートなどの農業用、土木用資材に好適であ
り、特に、電極等のバリや充放電の繰り返しにより発生
するデンドライドなど異物による破損を抑制する電池用
セパレータとして好適である。The nonwoven fabric of the present invention has a non-circular fiber cross section and a desired aspect ratio (long side length / short side length).
High piercing strength can be obtained by containing at least 10 mass% of the modified cross-section synthetic fiber having the following. Further, a modified cross-section synthetic fiber is a fiber having two or more protrusions, or a modified cross-section in which two components are alternately arranged adjacent to each other in a fiber cross section and at least one of the two components is divided into two or more. When the monofilament is obtained by dividing the type composite fiber into each component, high piercing strength and high liquid retention can be obtained. And the nonwoven fabric of the present invention, using a wet papermaking method, or after wet papermaking,
A nonwoven fabric having a desired piercing strength can be obtained by manufacturing using a water entanglement treatment method under a low water pressure of 3 MPa or less. The nonwoven fabric having excellent stab resistance of the present invention is suitable for agricultural and civil engineering materials such as packaging materials, wipers, decorative sheets such as wallpaper, grass-proof sheets, and the like. It is suitable as a battery separator that suppresses damage due to foreign matter such as dendride generated by the battery.
【図１】本発明に使用する異形断面合成繊維の繊維断面
図の一例を示す。FIG. 1 shows an example of a fiber cross-sectional view of a modified cross-section synthetic fiber used in the present invention.
【図２】本発明に使用する異形断面発生型複合繊維およ
び発生後の異形断面合成繊維の繊維断面図の一例を示
す。FIG. 2 shows an example of a fiber cross-sectional view of a modified cross section-generating composite fiber used in the present invention and a modified cross section synthetic fiber after generation.
１．異形断面合成繊維 ２．長辺 ３．短辺 ４．突起部 1. 1. Synthetic fiber with irregular cross section Long side 3. Short side 4. protrusion
───────────────────────────────────────────────────── フロントページの続き (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 Ｆターム(参考） 4L047 AB02 AB09 BA21 CB07 CB10 CC10 CC12 4L055 AF16 AF17 AF21 AF39 AF46 AF47 BD06 BD07 BE02 BE20 EA07 EA16 FA11 GA02 5H021 BB08 CC01 CC02 HH00 HH01 HH03 HH06 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Tomofumi Tanaka 877 Komiya, Harima-cho, Kako-gun, Hyogo Daiwa Bow Polytech Co., Ltd. Harima Research Laboratory F-term (reference) 4L047 AB02 AB09 BA21 CB07 CB10 CC10 CC12 4L055 AF16 AF17 AF21 AF39 AF46 AF47 BD06 BD07 BE02 BE20 EA07 EA16 FA11 GA02 5H021 BB08 CC01 CC02 HH00 HH01 HH03 HH06
Claims (10)
合成繊維を少なくとも１０mass％含有する不織布であっ
て、該異形断面合成繊維の繊維断面において断面の差し
渡し長さの最も大きい部分を長辺とし、該長辺と直交す
る断面の差し渡し長さで最も大きくなる部分を短辺とし
たとき、扁平比（長辺の長さ／短辺の長さ）が少なくと
も１．２であり、かつ下記に示す単位不織布密度当りの
突き刺し強力が少なくとも２０Ｎ／(g/cm3)であること
を特徴とする耐突き刺し性に優れた不織布。 （突き刺し強力）カトーテック（株）製「ＫＥＳ−Ｇ５
ハンディー圧縮試験機」を用いて、縦３０mm、横１０
０mmの大きさに裁断した不織布を準備し、試料の上に縦
４６mm、横８６mm、厚み７mmのアルミ板の中央部に直径
１１mmの孔を有する押さえ板を載置した後、先端部が１
mmφの球状部、軸の部分が底面直径２．２mm、高さ１
８．７mmの円錐状になった針を、２mm／秒の速度で押さ
え板の孔の中央に垂直に突き刺した時の最大荷重（Ｎ）
を測定し、１７５kPa荷重（ＪＩＳ−Ｂ−７５０２に準
じたマイクロメーターによる測定）での不織布密度で除
して突き刺し強力Ｎ／(g/cm3)とした。1. A nonwoven fabric containing at least 10 mass% of a modified cross-section synthetic fiber having a non-circular fiber cross section, and a portion having the largest cross-sectional length in a fiber cross section of the modified cross-section synthetic fiber is defined as a long side. Assuming that the shortest side is the portion having the largest cross length of the cross section perpendicular to the long side, the aspect ratio (length of the long side / length of the short side) is at least 1.2, and A nonwoven fabric excellent in piercing resistance, characterized in that the piercing strength per unit nonwoven fabric density shown is at least 20 N / (g / cm 3 ). (Piercing Power) “KES-G5” manufactured by Kato Tech Co., Ltd.
30mm long, 10mm wide using a "handy compression tester"
A nonwoven fabric cut to a size of 0 mm is prepared, and a holding plate having a hole of 11 mm in diameter at the center of an aluminum plate having a length of 46 mm, a width of 86 mm, and a thickness of 7 mm is placed on the sample.
mmφ spherical part, shaft part is bottom diameter 2.2mm, height 1
Maximum load (N) when a 8.7 mm conical needle is vertically pierced into the center of the hole of the holding plate at a speed of 2 mm / sec.
Was measured and divided by the density of the nonwoven fabric under a load of 175 kPa (measured by a micrometer according to JIS-B-7502) to determine the piercing strength N / (g / cm 3 ).
５〜６０μmであることを特徴とする請求項１記載の耐
突き刺し性に優れた不織布。2. The nonwoven fabric excellent in piercing resistance according to claim 1, wherein the length of the long side of the modified cross-section synthetic fiber is 5 to 60 μm.
/dtex以上であることを特徴とする請求項１または２に
記載の耐突き刺し性に優れた不織布。3. The fiber strength of the modified cross-section synthetic fiber is 7.0 cN.
3. The nonwoven fabric having excellent stab resistance according to claim 1 or 2, wherein the nonwoven fabric has a ratio of / dtex or more.
していることを特徴とする請求項１〜３のいずれかに記
載の耐突き刺し性に優れた不織布。4. The nonwoven fabric having excellent piercing resistance according to claim 1, wherein the modified synthetic fiber has two or more projections.
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異形断面発生型複
合繊維を各々の成分に分割した単繊維であることを特徴
とする請求項１〜４のいずれかに記載の耐突き刺し性に
優れた不織布。5. The synthetic fiber having a modified cross section having a cross section of 2 in the fiber cross section.
The component is arranged alternately adjacent to each other, and is a single fiber obtained by dividing a modified cross-section generating type conjugate fiber obtained by dividing at least one of the two components into two or more components. 5. The nonwoven fabric having excellent stab resistance according to any one of 1 to 4.
に親水化処理を施すことを特徴とする耐突き刺し性に優
れた不織布。6. A nonwoven fabric excellent in piercing resistance, wherein the nonwoven fabric according to claim 1 is subjected to a hydrophilic treatment.
最も大きい部分を長辺とし、該長辺と直交する断面の差
し渡し長さで最も大きくなる部分を短辺としたとき、扁
平比（長辺の長さ／短辺の長さ）が少なくとも１．２で
ある異形断面合成繊維を全繊維に対して少なくとも１０
mass％となるように水に分散させ、スラリーを調製し、
抄紙機を用いて湿式抄紙することを特徴とする耐突き刺
し性に優れた不織布の製造方法。7. The flatness ratio (long side) of the fiber cross section, where the longest portion of the cross-over length of the cross section is the long side and the shortest side of the cross-section length of the cross section orthogonal to the long side is the short side. (Length / short side length) of at least 1.2
mass% to be dispersed in water to prepare a slurry,
A method for producing a nonwoven fabric having excellent stab resistance, characterized by performing wet papermaking using a paper machine.
るとともに全繊維に対して少なくとも１０mass％の異形
断面合成繊維となるように各々の成分に分割してスラリ
ーを調製し、抄紙機を用いて湿式抄紙することを特徴と
する耐突き刺し性に優れた不織布の製造方法。8. A modified cross-section-generating conjugate fiber is dispersed in water, and a slurry is prepared by dividing each component so as to be a synthetic fiber having a modified cross section of at least 10 mass% with respect to all fibers. A method for producing a nonwoven fabric having excellent stab resistance, characterized by wet papermaking.
水流を噴射することを特徴とする請求項７または８に記
載の耐突き刺し性に優れた不織布の製造方法。9. The method for producing a nonwoven fabric excellent in piercing resistance according to claim 7, wherein a high-pressure water stream is jetted at a maximum water pressure of 3 MPa or less after wet papermaking.
布を用いた電池用セパレータ。10. A battery separator using the nonwoven fabric according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000015293A JP4174160B2 (en) | 2000-01-25 | 2000-01-25 | Nonwoven fabric excellent in puncture resistance, method for producing the same, and battery separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000015293A JP4174160B2 (en) | 2000-01-25 | 2000-01-25 | Nonwoven fabric excellent in puncture resistance, method for producing the same, and battery separator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001207362A true JP2001207362A (en) | 2001-08-03 |
| JP4174160B2 JP4174160B2 (en) | 2008-10-29 |
Family
ID=18542615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000015293A Expired - Fee Related JP4174160B2 (en) | 2000-01-25 | 2000-01-25 | Nonwoven fabric excellent in puncture resistance, method for producing the same, and battery separator |
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| JP2003268662A (en) * | 2002-03-07 | 2003-09-25 | Mitsubishi Paper Mills Ltd | Nonwoven fabric and method for producing the same |
| JP2004308038A (en) * | 2003-04-04 | 2004-11-04 | Kuraray Co Ltd | Low-density wet type nonwoven fabric |
| JP2007186813A (en) * | 2006-01-12 | 2007-07-26 | Nippon Ester Co Ltd | Polyamide short fiber |
| JP2011099193A (en) * | 2009-10-06 | 2011-05-19 | Nippon Ester Co Ltd | Short-cut conjugate fiber for wet-laid staple fiber nonwoven fabric |
| JP2011236536A (en) * | 2009-05-25 | 2011-11-24 | Nippon Ester Co Ltd | Short-cut fiber for wet-laid staple fiber nonwoven fabric |
| JP2012017543A (en) * | 2010-07-09 | 2012-01-26 | Nippon Ester Co Ltd | Wet-laid staple fiber nonwoven fabric |
| JP2012216363A (en) * | 2011-03-31 | 2012-11-08 | Daiwabo Holdings Co Ltd | Separator material and battery comprising the same |
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| JP2003268662A (en) * | 2002-03-07 | 2003-09-25 | Mitsubishi Paper Mills Ltd | Nonwoven fabric and method for producing the same |
| JP2004308038A (en) * | 2003-04-04 | 2004-11-04 | Kuraray Co Ltd | Low-density wet type nonwoven fabric |
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| JP2011236536A (en) * | 2009-05-25 | 2011-11-24 | Nippon Ester Co Ltd | Short-cut fiber for wet-laid staple fiber nonwoven fabric |
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