JP2001011764A - Hydrophilic non-woven fabric, battery separator using the same and battery - Google Patents
Hydrophilic non-woven fabric, battery separator using the same and batteryInfo
- Publication number
- JP2001011764A JP2001011764A JP11179992A JP17999299A JP2001011764A JP 2001011764 A JP2001011764 A JP 2001011764A JP 11179992 A JP11179992 A JP 11179992A JP 17999299 A JP17999299 A JP 17999299A JP 2001011764 A JP2001011764 A JP 2001011764A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- nonwoven fabric
- metallocene catalyst
- battery
- molecular weight
- 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、衛生材料、ワイパ
ー、フィルター、ニッケル−カドミウム電池、ニッケル
−亜鉛電池、ニッケル−水素電池等のアルカリ蓄電池な
どに好適な親水性不織布に関するものである。The present invention relates to a hydrophilic nonwoven fabric suitable for sanitary materials, wipers, filters, alkaline storage batteries such as nickel-cadmium batteries, nickel-zinc batteries and nickel-hydrogen batteries.
【０００２】[0002]
【従来の技術】従来から、ポリオレフィン系繊維からな
る不織布は疎水性であり、例えば、電池セパレータに用
いたときの濡れ性に劣るため、ポリオレフィン系繊維か
らなる不織布を親水化処理する様々な方法が提案されて
いる。親水化処理方法としては、スルホン化処理、フッ
素化処理、コロナ放電処理、またはビニルモノマーのグ
ラフト重合処理などが挙げられるが、特に二次電池の自
己放電性の改良において、スルホン化処理が有用であ
り、様々な方法が提案されている。例えば、特開平１−
１３２０４２号公報および特開平１−１３２０４４号公
報には、ポリプロピレン繊維を開繊し分散させた後、ポ
リエチレンを分散させた有機溶媒中に均一にふりかけて
ポリプロピレン繊維同士に結着性を付与させ、さらに熱
ロール間を通過させることにより各繊維同士を熱融着さ
せて、内部がポリプロピレン、表面層付近がポリエチレ
ンである不織布とし、スルホン化処理によってポリエチ
レン部分をスルホン化した電池セパレータが開示されて
いる。また、特開平７−２７８９６３号公報には、易ス
ルホン化繊維としてガラス転移温度が５℃以上低下した
シンジオタクチックスチレン系重合成分を用い、濃硫酸
溶液中に浸漬しスルホン化した電池用セパレータが提案
されている。さらに、特開平８−３２５９３２号公報に
は、直鎖状低密度ポリエチレンを鞘成分とし、ポリプロ
ピレンを芯成分とした鞘芯型複合繊維からなる不織布を
スルホン化処理したスルホン化不織布が提案されてい
る。2. Description of the Related Art Conventionally, nonwoven fabrics made of polyolefin fibers are hydrophobic, and, for example, have poor wettability when used for battery separators. Proposed. Examples of the hydrophilization treatment method include a sulfonation treatment, a fluorination treatment, a corona discharge treatment, and a graft polymerization treatment of a vinyl monomer.In particular, in the improvement of the self-discharge property of a secondary battery, the sulfonation treatment is useful. Yes, and various methods have been proposed. For example, Japanese Unexamined Patent Publication No.
JP-A-132042 and JP-A-1-132444 disclose that after polypropylene fibers are spread and dispersed, they are uniformly sprinkled into an organic solvent in which polyethylene is dispersed to impart a binding property between the polypropylene fibers. There is disclosed a battery separator in which fibers are thermally fused by passing between heat rolls to form a nonwoven fabric in which the interior is made of polypropylene and the surface layer is made of polyethylene, and the polyethylene portion is sulfonated by a sulfonation treatment. Japanese Patent Application Laid-Open No. Hei 7-278963 discloses a battery separator which is obtained by using a syndiotactic styrene-based polymer component having a glass transition temperature lowered by 5 ° C. or more as an easily sulfonated fiber and immersing it in a concentrated sulfuric acid solution to sulfonate it. Proposed. Further, JP-A-8-325932 proposes a sulfonated nonwoven fabric obtained by sulfonating a nonwoven fabric made of a sheath-core composite fiber having linear low-density polyethylene as a sheath component and polypropylene as a core component. .
【０００３】また、ヒートシール性等接着強度の優れた
ポリエチレンとして、特開平９−４１２５５号公報、特
開平１０−２９８８２７号公報にはメタロセン触媒を用
いて重合されたポリエチレンを用いた不織布が開示され
ている。Further, as polyethylene having excellent adhesive strength such as heat sealability, JP-A-9-41255 and JP-A-10-298927 disclose non-woven fabrics using polyethylene polymerized using a metallocene catalyst. ing.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
電池用セパレータには以下の問題点がある。例えば、特
開平１−１３２０４２号公報、特開平１−１３２０４４
号公報、および特開平８−３２５９３２号公報では、高
密度ポリエチレン、中密度ポリエチレン、低密度ポリエ
チレン、直鎖状低密度ポリエチレンの易スルホン化性に
ついて種々の実験が試みられるているが、高密度ポリエ
チレンは接着強力に優れているものの、スルホン化反応
速度が遅く、直鎖状低密度ポリエチレンはスルホン化反
応速度に優れているものの、接着強力が弱く、例えば、
電池セパレータに使用するには、スルホン化度と接着強
力の面で十分に両立しているとはいえない。また、特開
平７−２７８９６３号公報では、シンジオタクチックポ
リスチレン系繊維は一般に紡糸性が悪く、細繊度化する
ことは困難であり、たとえ細繊度化が可能であったとし
ても、生産性に劣り、コスト高となる。However, the above-described battery separator has the following problems. For example, Japanese Patent Application Laid-Open Nos. 1-132042 and 1-132044
In Japanese Unexamined Patent Application Publication No. H8-325932, various experiments have been attempted on the sulfonation properties of high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene. Has excellent adhesion strength, but the sulfonation reaction rate is slow, while linear low-density polyethylene has an excellent sulfonation reaction rate, but weak adhesion strength, for example,
For use as a battery separator, it cannot be said that both the degree of sulfonation and the adhesive strength are sufficiently compatible. Further, in JP-A-7-278963, syndiotactic polystyrene fibers generally have poor spinnability and are difficult to finely fine, and even if fineness is possible, productivity is poor. , Resulting in high costs.
【０００５】また、特開平９−４１２５５号公報、特開
平１０−２９８８２７号公報においては、接着強力には
優れているものの、メタロセン触媒を用いて重合された
ポリエチレン繊維について親水性付与等の検討が未だな
されていない。In Japanese Patent Application Laid-Open Nos. 9-41255 and 10-298827, studies have been made on imparting hydrophilicity to polyethylene fibers polymerized using a metallocene catalyst, although the adhesive strength is excellent. Not yet done.
【０００６】本発明はこれらの実情に鑑み、優れた接着
強度および親水性を有する親水性不織布、さらに緩いス
ルホン化処理条件においても高度にスルホン化するスル
ホン化不織布を提供し、特に、電池寿命を低下させるこ
となく電池容量の向上に寄与しうる、生産性の優れた電
池セパレータを得ることを目的としてなされたものであ
る。In view of these circumstances, the present invention provides a hydrophilic nonwoven fabric having excellent adhesive strength and hydrophilicity, and a sulfonated nonwoven fabric which is highly sulfonated even under mild sulfonation treatment conditions. An object of the present invention is to obtain a battery separator having excellent productivity which can contribute to an improvement in battery capacity without lowering the battery capacity.
【０００７】[0007]
【課題を解決するための手段】本発明において、様々な
構成からなるポリエチレンの中から下記範囲を満たすポ
リエチレンを選択して採用することにより、優れた接着
強度および親水性を有する親水性不織布、特にスルホン
化処理においてスルホン化反応速度が速いスルホン化不
織布が得られることが判り、本発明に至った。すなわち
本発明の親水性不織布は、繊維表面の少なくとも一部に
メタロセン触媒を用いて重合されたポリエチレンが露出
している熱可塑性合成繊維を少なくとも５重量％含有す
る繊維集合体であって、前記繊維集合体が親水化処理さ
れていることを特徴とする。In the present invention, a hydrophilic non-woven fabric having excellent adhesive strength and hydrophilicity, especially a hydrophilic non-woven fabric having excellent adhesive strength and hydrophilicity is selected from the polyethylenes having various constitutions which satisfy the following range. It was found that a sulfonated nonwoven fabric having a high sulfonation reaction rate was obtained in the sulfonation treatment, and the present invention was reached. That is, the hydrophilic nonwoven fabric of the present invention is a fiber aggregate containing at least 5% by weight of a thermoplastic synthetic fiber in which polyethylene polymerized using a metallocene catalyst is exposed on at least a part of the fiber surface. The aggregate is subjected to a hydrophilic treatment.
【０００８】メタロセン触媒を用いて重合されたポリエ
チレンが下記の範囲を満たすと、特に低温接着性に優
れ、スルホン化処理におけるスルホン化反応速度が速い
親水性不織布が得られ、好ましい。 （１）密度：０．８７〜０．９３g/cm3 （２）融点：７０〜１２５℃ （３）分子量分布（重量平均分子量／数平均分子量）：
１．５〜３．５ さらに、熱可塑性合成繊維がメタロセン触媒を用いて重
合されたポリエチレンを少なくとも３０重量％と他のポ
リオレフィン系重合体との混合体を含有すると、熱接着
時の加工温度領域が広く、接着強度に優れ、好ましい。[0008] When the polyethylene polymerized using the metallocene catalyst satisfies the following range, a hydrophilic nonwoven fabric having particularly excellent low-temperature adhesiveness and a high sulfonation reaction rate in the sulfonation treatment can be obtained, which is preferable. (1) Density: 0.87 to 0.93 g / cm 3 (2) Melting point: 70 to 125 ° C. (3) Molecular weight distribution (weight average molecular weight / number average molecular weight):
1.5 to 3.5 Further, when the thermoplastic synthetic fiber contains a mixture of at least 30% by weight of polyethylene polymerized by using a metallocene catalyst and another polyolefin-based polymer, Is wide and has excellent adhesive strength, which is preferable.
【０００９】熱可塑性合成繊維が、鞘成分をメタロセン
触媒を用いて重合されたポリエチレンとし、芯成分をポ
リオレフィン系重合体とした鞘芯型複合繊維であると、
繊維表面が選択的に親水化され、不織布強力を維持でき
る点で好ましい。When the thermoplastic synthetic fiber is a sheath-core composite fiber in which the sheath component is polyethylene polymerized using a metallocene catalyst and the core component is a polyolefin polymer,
This is preferable because the fiber surface is selectively hydrophilized and the strength of the nonwoven fabric can be maintained.
【００１０】そして、親水化処理がスルホン化処理であ
ると、他のポリエチレンに比して、スルホン化反応速度
に優れ、ポリエチレン以外の素材にダメージを与えるこ
となく親水化処理を施すことができ、不織布強力や親水
性において有利である点で好ましい。[0010] When the hydrophilization treatment is a sulfonation treatment, the sulfonation reaction rate is excellent as compared with other polyethylenes, and the hydrophilization treatment can be performed without damaging materials other than polyethylene. The nonwoven fabric is preferable in terms of strength and hydrophilicity.
【００１１】前記親水性不織布からなる電池セパレータ
は、緩やかな親水化処理条件でも親水性に優れ、低コス
トであり、自己放電特性の改良に寄与するだけでなく、
電池に組み込む際の注液性や卷回性に優れる点で好まし
い。The battery separator made of the hydrophilic nonwoven fabric has excellent hydrophilicity even under mild hydrophilization treatment conditions, is low in cost, and contributes to improvement of self-discharge characteristics.
It is preferable because it has excellent liquid pouring properties and winding properties when incorporated into a battery.
【００１２】前記電池セパレータを組み込んだ電池は、
電池寿命および電池容量に優れ、好ましい。A battery incorporating the battery separator is as follows:
Excellent in battery life and battery capacity, preferred.
【００１３】[0013]
【発明の実施の形態】本発明の親水性不織布は、繊維表
面の少なくとも一部にメタロセン触媒を用いて重合され
たポリエチレンが露出してなる熱可塑性合成繊維を少な
くとも５重量％含有する繊維集合体である。メタロセン
触媒を用いて重合されたポリエチレンとしては、密度が
０．８７〜０．９７g/cm3 であるポリエチレンまたはエ
チレンと炭素数３以上のα−オレフィンとの共重合体か
らなる構造であり、炭素数３以上のα−オレフィン成分
としては、プロピレン、１−ブテン、１−ペンテン、１
−ヘキセン、１−オクテン、４−メチル−１−ペンテン
などが挙げられる。特に、下記の構造を満たすポリエチ
レンは、低温接着性に優れた親水性不織布が得られる点
で好ましく、特に、親水化処理がスルホン化処理である
とき、スルホン化反応速度が速い点で好ましい。 （１）密度：０．８７〜０．９３g/cm3 （２）融点：７０〜１２５℃ （３）分子量分布（重量平均分子量／数平均分子量）：
１．５〜３．５ より好ましくは、密度が０．９１〜０．９３g/cm3 、融
点が９５〜１２０℃、分子量分布が１．８〜３．０であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic nonwoven fabric of the present invention comprises a fiber assembly containing at least 5% by weight of a thermoplastic synthetic fiber in which polyethylene polymerized by using a metallocene catalyst is exposed on at least a part of the fiber surface. It is. Polyethylene polymerized using a metallocene catalyst has a structure of polyethylene having a density of 0.87 to 0.97 g / cm 3 or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms. As the α-olefin component having the number of 3 or more, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-octene, 4-methyl-1-pentene and the like. In particular, polyethylene satisfying the following structure is preferable in that a hydrophilic nonwoven fabric having excellent low-temperature adhesion can be obtained. In particular, when the hydrophilization treatment is a sulfonation treatment, it is preferable in that the sulfonation reaction speed is high. (1) Density: 0.87 to 0.93 g / cm 3 (2) Melting point: 70 to 125 ° C. (3) Molecular weight distribution (weight average molecular weight / number average molecular weight):
1.5 to 3.5 More preferably, the density is 0.91 to 0.93 g / cm 3 , the melting point is 95 to 120 ° C, and the molecular weight distribution is 1.8 to 3.0.
【００１４】密度が０．８７g/cm3未満であると、繊維
強力が著しく低下し、０．９３g/cm3を超えると、低温
接着性が低下するからである。融点が７０℃未満である
と、例えば電池セパレータなど耐熱性を必要とする分野
に不向きであり、１２５℃を超えると、低温接着性が有
効に利用できないからである。また、分子量分布（重量
平均分子量／数平均分子量）が１．５未満であると、繊
維加工性に劣り、３．５を超えると、低温接着性が劣る
だけでなく、スルホン化反応速度が遅くなるため、スル
ホン化処理時に処理時間を長くする、または硫酸濃度を
高くする必要があり、繊維同士の接着強力が著しく減少
するため、好ましくない。If the density is less than 0.87 g / cm 3 , the fiber strength is remarkably reduced, and if the density is more than 0.93 g / cm 3 , the low-temperature adhesiveness is reduced. If the melting point is less than 70 ° C., it is unsuitable for a field requiring heat resistance such as a battery separator, and if it exceeds 125 ° C., low-temperature adhesion cannot be effectively used. When the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 1.5, the fiber processability is inferior, and when it exceeds 3.5, not only the low temperature adhesiveness is inferior, but also the sulfonation reaction speed is slow. Therefore, it is necessary to lengthen the treatment time or increase the sulfuric acid concentration during the sulfonation treatment, which is not preferable because the adhesive strength between fibers is significantly reduced.
【００１５】また、熱可塑性合成繊維中にメタロセン触
媒を用いて重合されたポリエチレン以外の他のポリオレ
フィン系重合体を混合してもよい。このときメタロセン
触媒を用いて重合されたポリエチレンは、少なくとも３
０重量％含有することが好ましい。メタロセン触媒を用
いて重合されたポリエチレンの含有量が３０重量％未満
であると、十分なスルホン化反応速度と接着強力の両立
ができないからである。混合される他のポリオレフィン
系重合体としては、高密度ポリエチレン、ポリプロピレ
ン、エチレン−プロピレン共重合体、ポリメチルペンテ
ンなどメタロセン触媒を用いて重合されたポリエチレン
より融点の高いものが、熱接着時の加工温度領域が広い
点で好ましい。Further, a polyolefin polymer other than polyethylene polymerized by using a metallocene catalyst may be mixed in the thermoplastic synthetic fiber. At this time, the polyethylene polymerized using the metallocene catalyst has at least 3
It is preferably contained at 0% by weight. If the content of the polyethylene polymerized using the metallocene catalyst is less than 30% by weight, it is impossible to achieve both a sufficient sulfonation reaction rate and a sufficient adhesive strength. Other polyolefin polymers to be mixed, such as high-density polyethylene, polypropylene, ethylene-propylene copolymer, and polymethylpentene, which have a higher melting point than polyethylene polymerized using a metallocene catalyst, are processed during thermal bonding. This is preferable because the temperature range is wide.
【００１６】そして、メタロセン触媒を用いて重合され
たポリエチレンは、繊維表面の少なくとも一部に露出し
た繊維形態となす。このような繊維形態としては、例え
ば、単一繊維、鞘芯型複合繊維、偏心鞘芯型複合繊維、
並列型複合繊維、分割型複合繊維、海島型複合繊維など
円形または異形断面を有する繊維を任意に使用すること
ができる。なかでも、メタロセン触媒を用いて重合され
たポリエチレンを鞘成分とした鞘芯型複合繊維が、繊維
表面が選択的に親水化され、不織布強力を維持できる点
で好ましい。芯成分に用いられる熱可塑性重合体として
は特に限定はされないが、その融点がメタロセン触媒を
用いて重合されたポリエチレンの融点より１０℃以上高
い重合体が好ましい。例えば、ポリエチレンテレフタレ
ート、ポリブチレンテレフタレート等のポリエステル系
重合体、ナイロン６、ナイロン６６等のポリアミド系重
合体、ポリプロピレン、ポリメチルペンテン等のポリオ
レフィン系重合体等のホモポリマーまたは共重合体、三
元共重合体から任意に一または二以上選択して使用する
ことができる。なかでも、ポリプロピレンまたはポリメ
チルペンテンからなるポリオレフィン系重合体が加工性
において好ましい。[0016] The polyethylene polymerized using the metallocene catalyst is in a fiber form exposed on at least a part of the fiber surface. As such a fiber form, for example, a single fiber, a sheath-core composite fiber, an eccentric sheath-core composite fiber,
Fibers having a circular or irregular cross-section such as side-by-side composite fibers, split-type composite fibers, and sea-island type composite fibers can be used arbitrarily. Among them, sheath-core type composite fibers containing polyethylene polymerized using a metallocene catalyst as a sheath component are preferable because the fiber surface is selectively hydrophilized and the strength of the nonwoven fabric can be maintained. The thermoplastic polymer used for the core component is not particularly limited, but a polymer having a melting point higher than that of polyethylene polymerized by using a metallocene catalyst by 10 ° C. or more is preferable. For example, homopolymers or copolymers such as polyester polymers such as polyethylene terephthalate and polybutylene terephthalate, polyamide polymers such as nylon 6 and nylon 66, polyolefin polymers such as polypropylene and polymethylpentene, and terpolymers One or two or more polymers can be arbitrarily selected and used. Among them, a polyolefin-based polymer composed of polypropylene or polymethylpentene is preferred in terms of processability.
【００１７】例えば、メタロセン触媒を用いて重合され
たポリエチレンを鞘芯型複合繊維に用いた場合、鞘成分
と芯成分との複合比（体積比）は、３０／７０〜７０／
３０であることが好ましい。鞘成分が３０％未満である
と、接着強力に劣るとともに十分な親水化がなされず、
７０％を超えると、繊維自体の強力が低下し、工程性に
劣るからである。For example, when polyethylene polymerized using a metallocene catalyst is used for the sheath-core composite fiber, the composite ratio (volume ratio) of the sheath component and the core component is 30/70 to 70/70.
It is preferably 30. When the sheath component is less than 30%, the adhesive strength is inferior and sufficient hydrophilization is not performed,
If it exceeds 70%, the strength of the fiber itself is reduced, and the processability is poor.
【００１８】また、メタロセン触媒を用いて重合された
ポリエチレンからなる熱可塑性合成繊維の繊度は、０．
０１〜５dtexが好ましい。０．０１dtex未満であると、
不織布作製時の工程性、品質面に劣り、５dtexを超える
と、不織布における空隙の大きさが大きくなり過ぎ、例
えば、電池セパレータに使用した場合、電池組立時に短
絡の原因となり好ましくない。The fineness of a thermoplastic synthetic fiber made of polyethylene polymerized by using a metallocene catalyst is 0.1%.
01-5 dtex is preferred. If it is less than 0.01 dtex,
Inferior in processability and quality in fabricating the nonwoven fabric, if it exceeds 5 dtex, the size of the void in the nonwoven fabric becomes too large. For example, when used as a battery separator, it causes a short circuit during battery assembly, which is not preferable.
【００１９】そして、前記メタロセン触媒を用いて重合
されたポリエチレンからなる熱可塑性合成繊維は、公知
の溶融紡糸機を用い、単一ノズルまたは複合ノズルから
溶融紡糸される。紡糸温度は、メタロセン触媒を用いて
重合されたポリエチレンが変質しない温度で実施され、
紡糸温度２００〜３００℃で重合体を押し出し、所定の
繊度の紡糸フィラメントを作製する。紡糸フィラメント
は、必要に応じて延伸される。延伸は、繊維表面の少な
くとも一部に露出したメタロセン触媒を用いて重合され
たポリエチレンが融着しない温度で実施され、例えば、
延伸温度５０〜１２０℃、延伸倍率２倍以上で処理する
と、繊維強力が向上するので好ましい。得られたフィラ
メントには、繊維処理剤を付着させてもよい。親水性の
繊維処理剤を付着させると、不織布製造工程性に優れる
ので好ましい。そして、必要に応じて、捲縮付与装置で
捲縮を与え、所定の長さに切断されてメタロセン触媒を
用いて重合されたポリエチレンからなる熱可塑性合成繊
維を得る。The thermoplastic synthetic fiber made of polyethylene polymerized using the metallocene catalyst is melt-spun from a single nozzle or a composite nozzle using a known melt spinning machine. The spinning temperature is a temperature at which the polyethylene polymerized using the metallocene catalyst does not deteriorate,
The polymer is extruded at a spinning temperature of 200 to 300 ° C. to produce a spun filament having a predetermined fineness. The spun filament is drawn as needed. The stretching is performed at a temperature at which the polyethylene polymerized using the metallocene catalyst exposed on at least a part of the fiber surface does not fuse, for example,
It is preferable to perform the treatment at a stretching temperature of 50 to 120 ° C. and a stretching ratio of 2 or more, because the fiber strength is improved. A fiber treatment agent may be attached to the obtained filament. It is preferable to attach a hydrophilic fiber treatment agent because the processability of the nonwoven fabric manufacturing process is excellent. Then, if necessary, crimping is performed by a crimping device, and a thermoplastic synthetic fiber made of polyethylene cut into a predetermined length and polymerized using a metallocene catalyst is obtained.
【００２０】本発明の繊維集合体は、メタロセン触媒を
用いて重合されたポリエチレンからなる熱可塑性合成繊
維を少なくとも５重量％含有するものである。より好ま
しくは、１５〜６０重量％である。熱可塑性合成繊維が
５重量％未満であると、低温接着性に劣るだけでなく、
不織布全体の親水性が小さくなり、例えば、電池セパレ
ータとして用いた場合、目標とする電池容量が得られな
いからである。The fiber aggregate of the present invention contains at least 5% by weight of thermoplastic synthetic fibers made of polyethylene polymerized using a metallocene catalyst. More preferably, it is 15 to 60% by weight. When the amount of the thermoplastic synthetic fiber is less than 5% by weight, not only is the low-temperature adhesion inferior, but also
This is because the hydrophilicity of the entire nonwoven fabric becomes small and, for example, when used as a battery separator, a target battery capacity cannot be obtained.
【００２１】本発明の繊維集合体において、他に用いら
れる繊維としては、特に限定はされないが、メタロセン
触媒を用いて重合されたポリエチレンからなる熱可塑性
合成繊維の融点より１０℃以上高い融点、または分解点
を有する繊維で構成すると、メタロセン触媒を用いて重
合されたポリエチレンの熱接着性を有効に利用できる点
で好ましい。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、
ポリエチレンテレフタレート、ポリブチレンテレフタレ
ート等のポリエステル系繊維、ナイロン６、ナイロン６
６等のポリアミド系繊維、ポリプロピレン、ポリメチル
ペンテン等のポリオレフィン系繊維などが用いられる。In the fiber aggregate of the present invention, the other fibers used are not particularly limited, but have a melting point higher by at least 10 ° C. than the melting point of a thermoplastic synthetic fiber made of polyethylene polymerized by using a metallocene catalyst, or It is preferable to use a fiber having a decomposition point because the thermal adhesiveness of polyethylene polymerized using a metallocene catalyst can be effectively used. For example, cotton, silk, natural fibers such as wool, recycled fibers such as rayon, acrylic fibers,
Polyester fiber such as polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 6
For example, polyamide fibers such as No. 6 and polyolefin fibers such as polypropylene and polymethylpentene are used.
【００２２】本発明においては、特に繊度０．５dtex以
下の極細繊維を少なくとも１０重量％含有すると、吸液
性や保液性が向上する点で好ましい。繊度０．５dtex以
下の極細繊維は、いずれの形状であってもよいが、好ま
しくは２種類以上の重合体成分からなる分割型複合繊維
を各々の成分に分割した２種類以上の極細繊維である。
２種類以上の重合体成分からなる分割型複合繊維として
は、例えば、放射状に分割したもの、層状に分割したも
のなどが挙げられ、その分割数も３以上であればよい。
そして、前記分割型複合繊維に用いられる熱可塑性重合
体の組合せとしては、ポリエステル系重合体／ポリアミ
ド系重合体、ポリオレフィン系重合体／ポリエステル系
重合体、ポリオレフィン系重合体／ポリアミド系重合
体、またはポリプロピレン／エチレンビニルアルコール
共重合体、ポリプロピレン／ポリメチルペンテン、ポリ
プロピレン／ポリエチレン、ポリメチルペンテン／ポリ
エチレン等のポリオレフィン系重合体同士などが挙げら
れ、三種類の重合体を用いる場合としては、上記重合体
をそれぞれ異なる成分で構成すればよい。得られた分割
型複合繊維は、後述する高圧水流処理等によって分割さ
れ、極細繊維を形成する。In the present invention, it is particularly preferable to contain at least 10% by weight of ultrafine fibers having a fineness of 0.5 dtex or less, since the liquid absorbing property and the liquid retaining property are improved. The ultrafine fibers having a fineness of 0.5 dtex or less may have any shape, but are preferably two or more types of ultrafine fibers obtained by dividing a splittable conjugate fiber composed of two or more types of polymer components into each component. .
Examples of the splittable conjugate fiber composed of two or more types of polymer components include those split radially and those split into layers, and the number of splits may be three or more.
And, as the combination of the thermoplastic polymer used for the splittable conjugate fiber, a polyester-based polymer / polyamide-based polymer, a polyolefin-based polymer / a polyester-based polymer, a polyolefin-based polymer / a polyamide-based polymer, or Polyolefin-based polymers such as polypropylene / ethylene vinyl alcohol copolymer, polypropylene / polymethylpentene, polypropylene / polyethylene, and polymethylpentene / polyethylene, and the like. Examples of using three types of polymers include the above polymers. May be composed of different components. The obtained splittable conjugate fiber is split by a high-pressure water flow treatment or the like described below to form an ultrafine fiber.
【００２３】例えば、電池セパレータであれば、他に用
いられる繊維としては、ポリオレフィン系重合体からな
る単一繊維、鞘芯型複合繊維、偏心鞘芯型複合繊維、並
列型複合繊維、分割型複合繊維、海島型複合繊維など円
形または異形断面を有する繊維を用いると、耐アルカリ
性の点で好ましい。特に、繊度０．５dtex以下の極細繊
維として、ポリオレフィン系分割型複合繊維を用いる
と、吸液性や保液性が向上し、電池組み立て時の工程性
が上がる点で好ましい。For example, in the case of a battery separator, other fibers used include a single fiber made of a polyolefin polymer, a sheath-core composite fiber, an eccentric sheath-core composite fiber, a parallel composite fiber, and a split composite fiber. It is preferable to use fibers having a circular or irregular cross-section such as fibers and sea-island composite fibers in terms of alkali resistance. In particular, the use of a polyolefin-based splittable conjugate fiber as an ultrafine fiber having a fineness of 0.5 dtex or less is preferable in that the liquid absorbing property and liquid retaining property are improved and the processability during battery assembly is increased.
【００２４】次に、本発明の親水性不織布の製造方法に
ついて説明する。Next, a method for producing the hydrophilic nonwoven fabric of the present invention will be described.
【００２５】上述したメタロセン触媒を用いて重合され
たポリエチレンからなる熱可塑性合成繊維を含有してな
る繊維集合体の形態は、カード法、エアレイ法などによ
り得た乾式ウェブ、湿式法により得た湿式ウェブ、また
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
得た繊維ウェブを単独、またはこれらを少なくとも１層
含み２層以上に積層したものが用いられる。繊維集合体
の目付は、繊維の量によって調節しうるが、通常２０〜
２００g/m2にすることが望ましい。特に電池セパレータ
においては、３０〜１００g/m2が好ましい。３０g/m2未
満では不織布の強力が低くなるため、正極と負極の間で
短絡が生じ易くなり、１００g/m2を超えると通気性等が
低下するからである。The form of the fiber aggregate containing the thermoplastic synthetic fiber made of polyethylene polymerized using the metallocene catalyst described above may be a dry web obtained by a card method, an air lay method, or the like, or a wet web obtained by a wet method. A web or a fibrous web obtained by a direct method such as a melt blow method or a spun bond method is used alone, or a web obtained by laminating two or more layers including at least one layer thereof is used. The basis weight of the fiber assembly can be adjusted by the amount of the fiber, but is usually 20 to
Desirably, it is 200 g / m 2 . Particularly, in the case of a battery separator, 30 to 100 g / m 2 is preferable. If it is less than 30 g / m 2 , the strength of the nonwoven fabric is low, so that a short circuit is likely to occur between the positive electrode and the negative electrode, and if it exceeds 100 g / m 2 , the air permeability and the like are reduced.
【００２６】次いで、繊維集合体は、ニードルパンチ法
またはスパンレース法などによる機械的絡合処理、熱ロ
ール法、熱風接着法、超音波接合法などの熱接合処理、
またはそれらの組み合わせにより一体化される。本発明
においては、メタロセン触媒を用いて重合されたポリエ
チレンからなる熱可塑性合成繊維を溶融させて用いる熱
接合法が最も有効である。例えば、前記分割型複合繊維
を含有させる場合は、繊維ウェブにスパンレース処理を
施し、分割型複合繊維を分割させて繊度０．５dtex以下
の極細繊維を形成させるとともに繊維間を交絡させると
よい。Next, the fiber assembly is subjected to a mechanical entanglement treatment such as a needle punch method or a spunlace method, a heat roll method, a hot air bonding method, a heat bonding treatment such as an ultrasonic bonding method, or the like.
Or they are integrated by a combination thereof. In the present invention, the most effective method is a thermal bonding method in which thermoplastic synthetic fibers made of polyethylene polymerized using a metallocene catalyst are melted and used. For example, when the splittable conjugate fiber is contained, the fiber web is preferably spunlaced to split the splittable conjugate fiber to form an ultrafine fiber having a fineness of 0.5 dtex or less and to entangle the fibers.
【００２７】そして、上記の繊維集合体は、公知の親水
化処理方法、例えば、スルホン化処理、フッ素化処理、
コロナ放電やグロー放電等のプラズマ処理、またはビニ
ルモノマーのグラフト重合処理などで処理し、親水化不
織布とする。本発明においては特に、発煙硫酸、クロル
硫酸、濃硫酸、または無水硫酸など公知のスルホン化処
理法を用いてスルホン化処理することが好ましい。スル
ホン化度は、少なくとも０．４重量％であることが好ま
しい。より好ましくは、少なくとも０．６重量％であ
る。スルホン化度が０．４重量％未満であると、電池の
自己放電を十分に抑制できないからである。またスルホ
ン化を促進させるために、紫外線または放射線により不
織布表面を活性化させた後、スルホン化処理を施しても
よい。さらに、得られた不織布に、浸漬法、スプレー
法、ロールタッチ法等により親水性界面活性剤を均一に
付着させたり、他の親水化処理法を併用すると、初期親
水性が向上する点で好ましい。The above-mentioned fiber aggregate is subjected to a known hydrophilic treatment method, for example, a sulfonation treatment, a fluorination treatment,
Plasma treatment such as corona discharge and glow discharge, or graft polymerization treatment of a vinyl monomer is performed to obtain a hydrophilic nonwoven fabric. In the present invention, it is particularly preferable to perform sulfonation using a known sulfonation method such as fuming sulfuric acid, chlorosulfuric acid, concentrated sulfuric acid, or sulfuric anhydride. Preferably, the degree of sulfonation is at least 0.4% by weight. More preferably, it is at least 0.6% by weight. If the sulfonation degree is less than 0.4% by weight, self-discharge of the battery cannot be sufficiently suppressed. In order to promote the sulfonation, the surface of the nonwoven fabric may be activated with ultraviolet rays or radiation, and then subjected to a sulfonation treatment. Furthermore, it is preferable that a hydrophilic surfactant is uniformly attached to the obtained nonwoven fabric by a dipping method, a spray method, a roll touch method, or the like, or that another hydrophilic treatment method is used in combination, since the initial hydrophilicity is improved. .
【００２８】このようにして得られた親水性不織布にお
ける少なくとも一方向の引張強力は、３０N/5cm以上で
あることが好ましい。特に電池セパレータにおいては、
５０N/5cm以上であることが好ましい。引張強力が３０N
/5cm未満であると、電池組み込み時の卷回性に劣るから
である。The tensile strength in at least one direction of the hydrophilic non-woven fabric thus obtained is preferably 30 N / 5 cm or more. Especially in battery separators,
It is preferably 50 N / 5 cm or more. 30N tensile strength
If it is less than / 5 cm, the winding property at the time of assembling the battery is inferior.
【００２９】[0029]
【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、密度、融点、分子量分布、スルホン化率、引
張強力、保液率、容量保存率およびショート率は、以下
の方法により測定した。 ［密度］ＪＩＳ Ｋ ６７６０に準拠し、測定した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described with reference to embodiments. The density, melting point, molecular weight distribution, sulfonation rate, tensile strength, liquid retention rate, capacity storage rate, and short-circuit rate were measured by the following methods. [Density] Measured according to JIS K 6760.
【００３０】［融点］ＪＩＳ Ｋ ７１７２に準拠し、
ＤＳＣ法により測定した。[Melting point] According to JIS K7172,
It was measured by the DSC method.
【００３１】［分子量分布］ゲル・パーミエーション・
クロマトグラフィー（ＧＰＣ法）により測定した。 ［スルホン化度］ （１）試料の調整 試料より５ｃｍ×５ｃｍの試験片を採取し、１３重量％
ＫＯＨ水溶液に３０分間浸漬した。その後、水道水で３
０分間洗浄し、さらに純水で３０分間洗浄した試料を６
０℃にて１時間乾燥させた。 （２）スルホン化度の測定 蛍光Ｘ線測定装置を用いて、不織布中の硫黄元素濃度を
測定し、全元素濃度で除して１００倍したものをスルホ
ン化度とした。 ［引張強力］ＪＩＳ Ｌ １０９６に準じ、幅５cm、長
さ１５cmの試料片をつかみ間隔１０cmで把持し、定速伸
長型引張試験機を用いて引張速度３０cm／分で伸長し、
切断時の荷重値を引張強力とした。 ［保液率］試験片の水分平衡状態の重量（Ｗ）を１mgま
で測定する。次に比重１．３０のＫＯＨ溶液中に試験片
を浸漬し、ＫＯＨ溶液を１時間吸収させたのち液中から
引き上げて１０分間放置した後、試験片の重量（Ｗ1)を
測定し、保液率（％）＝（（Ｗ1−Ｗ）／Ｗ）×１００
の式より保液率（重量％）を算出した。 ［容量保存率］電池セパレータを、通常のニッケル極と
水素吸蔵合金負極の間に挟み込み、電解液として比重
１．３のＫＯＨ溶液を含浸させＳＡクラスのＮｉ−ＭＨ
電池を同一条件で初期の活性化を行った後充電を行い、
容量２０００ｍＡｈとした。この電池を４５℃の条件で
２週間放置した後に再度容量を測定した。この時の容量
の残存率を容量保存率とした。 ［ショート率］ＳＡクラスのＮｉ−ＭＨ電池を１００個
組み立てたときに、短絡が起きた割合をショート率とし
た。 ［繊維の準備］ （繊維１） 鞘成分を密度０．９１５g/cm3 、融点１０
８℃、分子量分布（重量平均分子量／数平均分子量）
２．９のメタロセン触媒を用いて重合されたポリエチレ
ン（宇部興産（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）とした複合比
が５０／５０、繊度１．７dtex、繊維長１０mmの同心円
鞘芯型複合繊維。 （繊維２） 鞘成分を密度０．９１５g/cm3 、融点１０
８℃、分子量分布（重量平均分子量／数平均分子量）
２．９のメタロセン触媒を用いて重合されたポリエチレ
ン（宇部興産（株）製）５０重量％と、密度０．９５g/
cm3 、融点１３２℃、分子量分布（重量平均分子量／数
平均分子量）５．０のチーグラー−ナッタ触媒を用いて
重合された高密度ポリエチレン（日本ポリケム（株）
製）５０重量％の混合体とし、芯成分を融点１６３℃の
ポリプロピレン（日本ポリケム（株）製）とした複合比
が５０／５０、繊度１．７dtex、繊維長１０mmの同心円
鞘芯型複合繊維。 （繊維３） 鞘成分を密度０．９５g/cm3 、融点１３２
℃、分子量分布（重量平均分子量／数平均分子量）５．
０のチーグラー−ナッタ触媒を用いて重合された高密度
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）とした複合比が５０／５０、繊度１．７dtex、繊維
長１０mmの同心円鞘芯型複合繊維。 （繊維４） 第１成分を融点２４０℃のポリメチルペン
テン（三井化学（株）製）とし、第２成分を融点１６３
℃のポリプロピレン（日本ポリケム（株）製）とした複
合比が５０／５０、２つの成分が放射状に８分割された
繊維断面を有する繊度２．３dtex、繊維長６mmの分割型
複合繊維。 （繊維５） 融点１３２℃の高密度ポリエチレン（日本
ポリケム（株）製）からなる繊度２．３dtex、繊維長１
０mmのポリエチレン単一繊維。 （繊維６） 鞘成分を密度０．９１８g/cm3 、融点１０
５℃、分子量分布（重量平均分子量／数平均分子量）
５．０のチーグラー−ナッタ触媒を用いて重合された低
密度ポリエチレン（日本ポリケム（株）製）とし、芯成
分を融点１６３℃のポリプロピレン（日本ポリケム
（株）製）とした複合比が５０／５０、繊度１．７dte
x、繊維長１０mmの同心円鞘芯型複合繊維。[Molecular weight distribution] Gel permeation
It was measured by chromatography (GPC method). [Sulfonation degree] (1) Preparation of sample A test piece of 5 cm x 5 cm was collected from the sample, and 13 wt%
It was immersed in a KOH aqueous solution for 30 minutes. Then, tap water 3
The sample was washed for 0 minutes and further washed with pure water for 30 minutes.
Dry at 0 ° C. for 1 hour. (2) Measurement of Sulfonation Degree The sulfur element concentration in the nonwoven fabric was measured using a fluorescent X-ray measuring apparatus, and the result was divided by the total element concentration and multiplied by 100 to obtain the sulfonation degree. [Tensile strength] According to JIS L 1096, a sample piece having a width of 5 cm and a length of 15 cm is gripped at an interval of 10 cm and stretched at a tensile speed of 30 cm / min using a constant-speed stretching type tensile tester.
The load value at the time of cutting was defined as tensile strength. [Liquid retention ratio] The weight (W) of the test piece in a water equilibrium state is measured up to 1 mg. Next, the test piece was immersed in a KOH solution having a specific gravity of 1.30, and after absorbing the KOH solution for one hour, withdrawn from the solution and allowed to stand for 10 minutes, the weight (W 1 ) of the test piece was measured and retained. Liquid ratio (%) = ((W 1 −W) / W) × 100
The liquid retention rate (% by weight) was calculated from the equation. [Capacity preservation ratio] A battery separator is sandwiched between a normal nickel electrode and a hydrogen-absorbing alloy negative electrode, and impregnated with a KOH solution having a specific gravity of 1.3 as an electrolytic solution, to thereby obtain a SA-class Ni-MH.
After performing the initial activation of the battery under the same conditions, charge the battery,
The capacity was set to 2000 mAh. After the battery was left at 45 ° C. for 2 weeks, the capacity was measured again. The remaining rate of the capacity at this time was defined as the capacity storage rate. [Short Ratio] When 100 SA-class Ni-MH batteries were assembled, the ratio of occurrence of short circuits was defined as the short ratio. [Preparation of Fiber] (Fiber 1) The sheath component was made to have a density of 0.915 g / cm 3 and a melting point of 10.
8 ° C, molecular weight distribution (weight average molecular weight / number average molecular weight)
A composite ratio of 50/50 and a fineness of 1 was obtained by using polyethylene (manufactured by Ube Industries, Ltd.) polymerized using a 2.9 metallocene catalyst, and using polypropylene (manufactured by Nippon Polychem Co., Ltd.) having a melting point of 163 ° C. as a core component. 0.7dtex, concentric sheath-core composite fiber having a fiber length of 10 mm. (Fiber 2) A sheath component having a density of 0.915 g / cm 3 and a melting point of 10
8 ° C, molecular weight distribution (weight average molecular weight / number average molecular weight)
50% by weight of polyethylene (manufactured by Ube Industries, Ltd.) polymerized using a 2.9 metallocene catalyst, and a density of 0.95 g /
High-density polyethylene (Nippon Polychem Co., Ltd.) polymerized using a Ziegler-Natta catalyst having a cm 3 , a melting point of 132 ° C., and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 5.0.
Concentric sheath-core composite fiber with a composite ratio of 50/50, a fineness of 1.7 dtex, and a fiber length of 10 mm, which is a mixture of 50% by weight and a core component of polypropylene having a melting point of 163 ° C. (manufactured by Nippon Polychem Co., Ltd.) . (Fiber 3) A sheath component having a density of 0.95 g / cm 3 and a melting point of 132
4.degree. C., molecular weight distribution (weight average molecular weight / number average molecular weight) 5.
High-density polyethylene (manufactured by Nippon Polychem Co., Ltd.) polymerized using a Ziegler-Natta catalyst having a melting point of 163 ° C. polypropylene (Nippon Polychem Co., Ltd.)
And a composite ratio of 50/50, a fineness of 1.7 dtex and a fiber length of 10 mm. (Fiber 4) The first component was polymethylpentene having a melting point of 240 ° C. (manufactured by Mitsui Chemicals, Inc.), and the second component was melting point 163.
Polypropylene (manufactured by Nippon Polychem Co., Ltd.) having a conjugate ratio of 50/50, a splittable conjugate fiber having a fineness of 2.3 dtex and a fiber length of 6 mm having a fiber cross section in which two components are radially divided into eight. (Fiber 5) Fineness 2.3 dtex, fiber length 1 made of high-density polyethylene (manufactured by Nippon Polychem Co., Ltd.) having a melting point of 132 ° C.
0 mm polyethylene single fiber. (Fiber 6) A sheath component having a density of 0.918 g / cm 3 and a melting point of 10
5 ° C, molecular weight distribution (weight average molecular weight / number average molecular weight)
A low density polyethylene (manufactured by Nippon Polychem Co., Ltd.) polymerized using a Ziegler-Natta catalyst of 5.0 and a core component of polypropylene having a melting point of 163 ° C. (manufactured by Nippon Polychem Co., Ltd.) have a composite ratio of 50 /. 50, fineness 1.7 dte
x, a concentric sheath-core composite fiber having a fiber length of 10 mm.
【００３２】［実施例１、２、比較例１］繊維１〜繊維
３をそれぞれ準備し、０．５％の濃度になるようにスラ
リーを調製し、湿式抄紙して目付６５g/m2 の原紙を得
た。さらに、鞘成分の融点より１０℃低い温度に調整し
た熱板プレスを用い、５ＭＰａで３０秒間加圧し、不織
布を得た。得られた不織布を三酸化イオウガス中で３０
秒間および６０秒間反応さた後に、中和・洗浄・乾燥工
程を経てそれぞれ実施例１、実施例２、比較例１の親水
性不織布を得た。それぞれのスルホン化度を表１に示
す。[Examples 1, 2 and Comparative Example 1] Fibers 1 to 3 were prepared, slurries were prepared so as to have a concentration of 0.5%, wet papermaking was performed, and base paper having a basis weight of 65 g / m 2 was prepared. I got Further, a hot plate press adjusted to a temperature lower by 10 ° C. than the melting point of the sheath component was used and pressed at 5 MPa for 30 seconds to obtain a nonwoven fabric. The obtained nonwoven fabric is put in sulfur trioxide gas for 30 minutes.
After reacting for 2 seconds and 60 seconds, the hydrophilic nonwoven fabrics of Example 1, Example 2, and Comparative Example 1 were obtained through neutralization, washing, and drying steps, respectively. Table 1 shows the respective sulfonation degrees.
【００３３】[0033]
【表１】 表１に示すとおり、鞘成分をメタロセン触媒を用いて重
合されたポリエチレンとした鞘芯型複合繊維を用いたも
のは、スルホン化反応速度が速く、スルホン化処理効率
に優れることが判明した。[Table 1] As shown in Table 1, it was found that the one using the sheath-core composite fiber in which the sheath component was polyethylene polymerized using a metallocene catalyst had a high sulfonation reaction rate and excellent sulfonation treatment efficiency.
【００３４】［実施例３］繊維４を８０重量％と繊維１
を２０重量％とを混合して０．５％の濃度になるように
スラリーを調製し、湿式抄紙して目付６５g/m2 の原紙
を得た。そして原紙の表裏面より８Mpaの圧力で高圧柱
状水流を噴射することにより、繊維４を分割させて繊度
約０．３dtexの２種類の極細繊維を形成させるとともに
繊維間を交絡させ、１３０℃で乾燥と同時に熱融着させ
不織布を得た。Example 3 80% by weight of fiber 4 and fiber 1
Was mixed with 20% by weight to prepare a slurry so as to have a concentration of 0.5%, followed by wet papermaking to obtain a base paper having a basis weight of 65 g / m 2 . By jetting a high-pressure columnar water stream from the front and back surfaces of the base paper at a pressure of 8 MPa, the fibers 4 are divided to form two types of ultrafine fibers having a fineness of about 0.3 dtex, and the fibers are entangled and dried at 130 ° C. At the same time, heat bonding was performed to obtain a nonwoven fabric.
【００３５】得られた不織布を三酸化イオウのガス中で
３０秒間反応さた後に、中和・洗浄・乾燥工程を経て親
水性不織布とした後、熱カレンダー処理を施して、目付
６５g/m2 、厚み０．１７mmの親水性不織布を得た。After reacting the obtained nonwoven fabric in a sulfur trioxide gas for 30 seconds, a neutralizing, washing, and drying process is performed to obtain a hydrophilic nonwoven fabric, which is then subjected to a heat calendering treatment to give a basis weight of 65 g / m 2. Thus, a hydrophilic nonwoven fabric having a thickness of 0.17 mm was obtained.
【００３６】［実施例４］繊維４を８０重量％と繊維２
を２０重量％とを混合して０．５％の濃度になるように
スラリーを調製し、湿式抄紙して目付６５g/m2 の原紙
を得た。そして原紙の表裏面より８Mpaの圧力で高圧柱
状水流を噴射することにより、繊維４を分割させて繊度
約０．３dtexの２種類の極細繊維を形成させるとともに
繊維間を交絡させ、１３０℃で乾燥と同時に熱融着させ
不織布を得た。以下、実施例３と同様の方法で目付６５
g/m2 、厚み０．１７mmの親水性不織布を得た。Example 4 80% by weight of fiber 4 and fiber 2
Was mixed with 20% by weight to prepare a slurry so as to have a concentration of 0.5%, followed by wet papermaking to obtain a base paper having a basis weight of 65 g / m 2 . By jetting a high-pressure columnar water stream from the front and back surfaces of the base paper at a pressure of 8 MPa, the fibers 4 are divided to form two types of ultrafine fibers having a fineness of about 0.3 dtex, and the fibers are entangled and dried at 130 ° C. At the same time, heat bonding was performed to obtain a nonwoven fabric. Thereafter, a basis weight of 65 was obtained in the same manner as in Example 3.
A hydrophilic nonwoven fabric having a g / m 2 and a thickness of 0.17 mm was obtained.
【００３７】［比較例２］繊維４を８０重量％と繊維３
を２０重量％とを混合して０．５％の濃度になるように
スラリーを調製し、湿式抄紙して目付６５g/m2 の原紙
を得た。そして原紙の表裏面より８Mpaの圧力で高圧柱
状水流を噴射することにより、繊維４を分割させて繊度
約０．３dtexの２種類の極細繊維を形成させるとともに
繊維間を交絡させ、１３５℃で乾燥と同時に熱融着させ
不織布を得た。以下、実施例３と同様の方法で目付６５
g/m2 、厚み０．１７mmの親水性不織布を得た。Comparative Example 2 80% by weight of fiber 4 and fiber 3
Was mixed with 20% by weight to prepare a slurry so as to have a concentration of 0.5%, followed by wet papermaking to obtain a base paper having a basis weight of 65 g / m 2 . By injecting a high-pressure columnar water stream at a pressure of 8 MPa from the front and back surfaces of the base paper, the fibers 4 are divided to form two types of ultrafine fibers having a fineness of about 0.3 dtex, and the fibers are entangled and dried at 135 ° C. At the same time, heat bonding was performed to obtain a nonwoven fabric. Thereafter, a basis weight of 65 was obtained in the same manner as in Example 3.
A hydrophilic nonwoven fabric having a g / m 2 and a thickness of 0.17 mm was obtained.
【００３８】［比較例３］繊維３の代わりに繊維５を用
いた以外、比較例２と同様の方法で目付６５g/m2、厚み
０．１７mmの親水性不織布を得た。Comparative Example 3 A hydrophilic nonwoven fabric having a basis weight of 65 g / m 2 and a thickness of 0.17 mm was obtained in the same manner as in Comparative Example 2 except that the fiber 5 was used instead of the fiber 3.
【００３９】［比較例４］比較例２の不織布を三酸化イ
オウのガス中で５分間反応さた後に、中和・洗浄・乾燥
工程を経て親水性不織布とした後、熱カレンダー処理を
施して、目付６５g/m2、厚み０．１７mmの親水性不織布
を得た。[Comparative Example 4] The nonwoven fabric of Comparative Example 2 was reacted in a sulfur trioxide gas for 5 minutes, and then subjected to a neutralizing, washing and drying process to obtain a hydrophilic nonwoven fabric, and then subjected to a heat calendering treatment. Thus, a hydrophilic nonwoven fabric having a basis weight of 65 g / m 2 and a thickness of 0.17 mm was obtained.
【００４０】実施例３、４、および比較例２〜４の保液
率、および電池セパレータとして用いたときの電池性能
を表２に示す。Table 2 shows the liquid retention ratios of Examples 3 and 4 and Comparative Examples 2 to 4, and the battery performance when used as a battery separator.
【００４１】[0041]
【表２】 実施例３、４においては、引張強力を５０N/5cm以上に
維持しつつ、高度にスルホン化されているので、保液率
および容量保存率に優れていた。一方、比較例２、３に
おいては、引張強力は維持されているものの、スルホン
化度が不十分であり、保液性および電池特性が不十分で
あった。比較例４においては、スルホン化処理時間を長
くし、スルホン化を促進させたので、容量保存率は実施
例と同等のものとなったが、引張強力が低く、電池に組
み込む際の卷回性など取り扱い性に劣っていただけでな
く、ショート率も増加していた。[Table 2] In Examples 3 and 4, it was highly sulfonated while maintaining the tensile strength at 50 N / 5 cm or more, so that the liquid retention rate and the volume storage rate were excellent. On the other hand, in Comparative Examples 2 and 3, although the tensile strength was maintained, the degree of sulfonation was insufficient, and the liquid retention properties and battery characteristics were insufficient. In Comparative Example 4, since the sulfonation treatment time was lengthened and the sulfonation was promoted, the capacity retention was equivalent to that of the example, but the tensile strength was low and the winding property when incorporated into the battery was low. Not only was it inferior in handling, but also the short circuit rate was increasing.
【００４２】［実施例５］実施例３において、スルホン
化処理の代わりに、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６５g/m2、
厚み０．１７mmの親水性不織布を得た。[Example 5] In Example 3, instead of the sulfonation treatment, both sides of the nonwoven fabric were each applied four times.
Corona discharge treatment was performed so that the total discharge amount was 0.462 kW · min / m 2 , heat calendering was performed, and the basis weight was 65 g / m 2 ,
A hydrophilic nonwoven fabric having a thickness of 0.17 mm was obtained.
【００４３】［比較例５］繊維４を８０重量％と繊維６
を２０重量％とを混合した以外は、実施例５と同様の方
法で目付６５g/m2 、厚み０．１７mmの親水性不織布を
得た。[Comparative Example 5] 80% by weight of fiber 4 and fiber 6
And a hydrophilic nonwoven fabric having a basis weight of 65 g / m 2 and a thickness of 0.17 mm was obtained in the same manner as in Example 5 except that the above was mixed with 20% by weight.
【００４４】実施例５および比較例５の保液率、および
電池セパレータとして用いたときの電池性能を表２に示
す。Table 2 shows the liquid retention ratio of Example 5 and Comparative Example 5, and the battery performance when used as a battery separator.
【００４５】[0045]
【表３】 実施例５においては、接着成分として、メタロセン触媒
を用いて重合されたポリエチレンを使用しているため、
比較例５と同じ加工条件ながら、より高強力となってお
り、生産性の優れたセパレータを得ることができた。[Table 3] In Example 5, since polyethylene polymerized using a metallocene catalyst was used as the adhesive component,
Despite the same processing conditions as in Comparative Example 5, a higher strength was obtained, and a separator with excellent productivity was obtained.
【００４６】[0046]
【発明の効果】本発明の親水性不織布は、繊維表面の少
なくとも一部にメタロセン触媒を用いて重合されたポリ
エチレンが露出してなる熱可塑性合成繊維を少なくとも
５重量％含有する繊維集合体を親水化処理することによ
り、優れた接着強度および親水性を有する親水性不織布
が得られる。特に、親水化処理がスルホン化処理である
と、メタロセン触媒を用いて重合されたポリエチレンが
他のポリエチレンに比して、スルホン化反応速度が格段
に速く、他の素材にダメージを与えることなく処理する
ことができる。さらに、メタロセン触媒を用いて重合さ
れたポリエチレンのうち、密度が０．８７〜０．９３g/
cm3 、融点が７０〜１２５℃、および分子量分布（重量
平均分子量／数平均分子量）が１．５〜３．５の範囲を
満たすポリエチレンは、スルホン化反応速度が速く、低
温接着性に優れる点で有利である。The hydrophilic nonwoven fabric according to the present invention is characterized in that a fiber aggregate containing at least 5% by weight of thermoplastic synthetic fibers having at least a part of the fiber surface exposed to polyethylene polymerized using a metallocene catalyst is hydrophilic. By performing the hydrophobizing treatment, a hydrophilic nonwoven fabric having excellent adhesive strength and hydrophilicity can be obtained. In particular, when the hydrophilization treatment is a sulfonation treatment, the polyethylene polymerized using a metallocene catalyst has a much higher sulfonation reaction rate than other polyethylenes, and is treated without damaging other materials. can do. Further, among polyethylenes polymerized using the metallocene catalyst, the density is 0.87 to 0.93 g /
Polyethylene satisfying cm 3 , melting point of 70 to 125 ° C., and molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.5 to 3.5 has a high sulfonation reaction rate and excellent low-temperature adhesion. Is advantageous.
【００４７】そして、本発明の親水性不織布は、衛生材
料、ワイパー、フィルター、ニッケル−カドミウム電
池、ニッケル−亜鉛電池、ニッケル−水素電池等のアル
カリ蓄電池などに好適であり、特に、本発明の親水性不
織布からなる電池セパレータは、低コストであり、親水
性に優れ、自己放電特性の改良に寄与するだけでなく、
電池に組み込む際の注液性や卷回性に優れており、その
電池セパレータを組み込んだ電池は、電池寿命および電
池容量に優れる。The hydrophilic nonwoven fabric of the present invention is suitable for sanitary materials, wipers, filters, alkaline storage batteries such as nickel-cadmium batteries, nickel-zinc batteries, nickel-hydrogen batteries and the like. Battery separators made of conductive nonwoven fabrics are low-cost, have excellent hydrophilicity, and contribute to the improvement of self-discharge characteristics.
It is excellent in liquid injection property and winding property when incorporated in a battery, and a battery incorporating the battery separator is excellent in battery life and battery capacity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀 修二 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 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） 4L035 DD19 EE05 FF01 FF05 GG02 LA02 4L041 BA02 BA05 BA21 BA49 BC01 BC02 BD03 BD06 BD07 BD11 BD20 CA36 CA37 CA38 CA39 CA62 DD01 DD03 DD05 DD14 4L047 AA14 AA27 AA28 AB08 BB09 CA19 CB01 CB10 CC12 DA00 5H021 BB09 CC01 CC02 EE04 EE23 HH01 HH03 HH05 HH06 HH07 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuji Hori 877 Komiya, Harima-cho, Kako-gun, Hyogo Daiwa Bowpolitec Co., Ltd. (72) Tomofumi Tanaka 877 Furumiya, Harima-cho, Kako-gun, Hyogo Daiwa Boupolitec Harima Research Laboratory Co., Ltd. BD06 BD07 BD11 BD20 CA36 CA37 CA38 CA39 CA62 DD01 DD03 DD05 DD14 4L047 AA14 AA27 AA28 AB08 BB09 CA19 CB01 CB10 CC12 DA00 5H021 BB09 CC01 CC02 EE04 EE23 HH01 HH03 HH05 HH06 HH07
Claims (8)
触媒を用いて重合されたポリエチレンが露出してなる熱
可塑性合成繊維を少なくとも５重量％含有する繊維集合
体であって、前記繊維集合体が親水化処理されているこ
とを特徴とする親水性不織布。1. A fiber assembly containing at least 5% by weight of a thermoplastic synthetic fiber in which polyethylene polymerized using a metallocene catalyst is exposed on at least a part of the fiber surface, wherein the fiber assembly is hydrophilic. A hydrophilic nonwoven fabric, which has been subjected to a chemical conversion treatment.
エチレンが、下記の性質を満たすことを特徴とする請求
項１記載の親水性不織布。 （１）密度：０．８７〜０．９３g/cm3 （２）融点：７０〜１２５℃ （３）分子量分布（重量平均分子量／数平均分子量）：
１．５〜３．５2. The hydrophilic nonwoven fabric according to claim 1, wherein the polyethylene polymerized using the metallocene catalyst satisfies the following properties. (1) Density: 0.87 to 0.93 g / cm 3 (2) Melting point: 70 to 125 ° C. (3) Molecular weight distribution (weight average molecular weight / number average molecular weight):
1.5-3.5
いて重合されたポリエチレンを少なくとも３０重量％と
他のポリオレフィン系重合体との混合体を含有すること
を特徴とする請求項１または２に記載の親水性不織布。3. The thermoplastic synthetic fiber according to claim 1, wherein the thermoplastic synthetic fiber contains a mixture of at least 30% by weight of polyethylene polymerized by using a metallocene catalyst and another polyolefin-based polymer. Hydrophilic nonwoven fabric.
触媒を用いて重合されたポリエチレンとし、芯成分をポ
リオレフィン系重合体とした鞘芯型複合繊維であること
を特徴とする請求項１〜３のいずれかに記載の親水性不
織布。4. The thermoplastic synthetic fiber is a sheath-core composite fiber having a sheath component made of polyethylene polymerized by using a metallocene catalyst and a core component made of a polyolefin-based polymer. The hydrophilic nonwoven fabric according to any one of the above.
繊維を少なくとも１０重量％含有することを特徴とする
請求項１〜４のいずれかに記載の親水性不織布。5. The hydrophilic nonwoven fabric according to claim 1, wherein the fiber aggregate contains at least 10% by weight of ultrafine fibers having a fineness of 0.5 dtex or less.
を特徴とする請求項１記載の親水性不織布。6. The hydrophilic nonwoven fabric according to claim 1, wherein the hydrophilic treatment is a sulfonation treatment.
不織布からなる電池セパレータ。7. A battery separator comprising the hydrophilic nonwoven fabric according to claim 1.
電池。8. A battery incorporating the battery separator according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17999299A JP3510156B2 (en) | 1999-06-25 | 1999-06-25 | Battery separator and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17999299A JP3510156B2 (en) | 1999-06-25 | 1999-06-25 | Battery separator and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001011764A true JP2001011764A (en) | 2001-01-16 |
| JP3510156B2 JP3510156B2 (en) | 2004-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17999299A Expired - Fee Related JP3510156B2 (en) | 1999-06-25 | 1999-06-25 | Battery separator and battery |
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| Country | Link |
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| JP (1) | JP3510156B2 (en) |
Cited By (3)
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| JP2001307710A (en) * | 2000-04-18 | 2001-11-02 | Daiwabo Co Ltd | Separator for battery and its manufacturing method and battery |
| WO2011122657A1 (en) * | 2010-03-30 | 2011-10-06 | ダイワボウホールディングス株式会社 | Polyolefin-based split-type conjugate fibre, fibrous mass and cell separator using same, and production method for same |
| EP2604646A4 (en) * | 2010-08-12 | 2014-06-18 | Toray Battery Separator Film | Microporous film, process for production of the film, and use of the film |
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| EP2604646A4 (en) * | 2010-08-12 | 2014-06-18 | Toray Battery Separator Film | Microporous film, process for production of the film, and use of the film |
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| Publication number | Publication date |
|---|---|
| JP3510156B2 (en) | 2004-03-22 |
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