JP2001076703A - Introducing method of sulfur-containing functional group, method of manufacturing for separator for battery, and separator for battery - Google Patents

Introducing method of sulfur-containing functional group, method of manufacturing for separator for battery, and separator for battery

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Publication number
JP2001076703A
JP2001076703A JP25236399A JP25236399A JP2001076703A JP 2001076703 A JP2001076703 A JP 2001076703A JP 25236399 A JP25236399 A JP 25236399A JP 25236399 A JP25236399 A JP 25236399A JP 2001076703 A JP2001076703 A JP 2001076703A
Authority
JP
Japan
Prior art keywords
sulfur
separator
battery
gas
functional group
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
Application number
JP25236399A
Other languages
Japanese (ja)
Other versions
JP4065630B2 (en
Inventor
Masanao Tanaka
政尚 田中
Toshiaki Takase
俊明 高瀬
Hiroaki Yamazaki
洋昭 山崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Vilene Co Ltd
Original Assignee
Japan Vilene Co Ltd
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Filing date
Publication date
Application filed by Japan Vilene Co Ltd filed Critical Japan Vilene Co Ltd
Priority to JP25236399A priority Critical patent/JP4065630B2/en
Publication of JP2001076703A publication Critical patent/JP2001076703A/en
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Publication of JP4065630B2 publication Critical patent/JP4065630B2/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Cell Separators (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently introducing a sulfur-containing functional group, with high reactivity, the manufacturing method of a separator for a battery, and a separator for a battery. SOLUTION: The introducing method of the sulfur-containing functional group comprises contacting an objective material having moisture with a mixed gas containing fluorine gas and sulfur-containing compound gas. The manufacturing method of the separator for the battery comprises contacting a fiber sheet having moisture with the mixture gas containing fluorine gas and sulfur- containing compound gas. The separator for the battery comprises the sheet manufactured by the above process.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は硫黄含有官能基の導
入方法、電池用セパレータの製造方法、及び電池用セパ
レータに関する。
The present invention relates to a method for introducing a sulfur-containing functional group, a method for producing a battery separator, and a battery separator.

【0002】[0002]

【従来の技術】例えば、ポリオレフィン系繊維からなる
不織布は耐アルカリ性に優れているため、ニッケル−水
素電池やニッケル−カドミウム電池などアルカリ電池の
セパレータとして好適に使用することができる。しかし
ながら、ポリオレフィン系繊維は電解液との親和性が低
く、ポリオレフィン系繊維からなる不織布をセパレータ
として使用したアルカリ電池は、起電反応をスムーズに
生じることができないため、ポリオレフィン系繊維と電
解液との親和性を付与するために、様々な表面処理が実
施されている。
2. Description of the Related Art For example, nonwoven fabrics made of polyolefin fibers have excellent alkali resistance, and can be suitably used as separators for alkaline batteries such as nickel-hydrogen batteries and nickel-cadmium batteries. However, polyolefin-based fibers have low affinity for the electrolytic solution, and an alkaline battery using a nonwoven fabric made of polyolefin-based fibers as a separator cannot generate an electromotive reaction smoothly. Various surface treatments have been implemented to impart affinity.

【0003】この表面処理方法の1つとして、ポリオレフィ
ン系繊維からなる不織布をフッ素ガスと硫黄含有化合物
ガスとを含む混合ガスと接触させる方法がある。この方
法によれば、硫黄含有官能基(例えば、スルホフルオラ
イド基など)をポリオレフィン系繊維に導入できるた
め、ポリオレフィン系繊維と電解液との親和性を付与す
ることができる。しかしながら、工業的な観点から、更
に反応性が高く、効率的に硫黄含有官能基を導入できる
方法が待ち望まれていた。
[0003] As one of the surface treatment methods, there is a method in which a nonwoven fabric made of a polyolefin fiber is brought into contact with a mixed gas containing a fluorine gas and a sulfur-containing compound gas. According to this method, since a sulfur-containing functional group (for example, a sulfofluoride group) can be introduced into the polyolefin-based fiber, the affinity between the polyolefin-based fiber and the electrolytic solution can be imparted. However, from an industrial point of view, there has been a long-awaited need for a method having a higher reactivity and capable of efficiently introducing a sulfur-containing functional group.

【0004】他方、電池用セパレータ以外の分野、例えば、
イオン吸収性、アンモニア吸着性或いは生体適合性を必
要とする分野においても、電池用セパレータの場合と同
様に、工業的な観点から、更に反応性が高く、効率的に
硫黄含有官能基を導入できる方法が待ち望まれていた。
On the other hand, fields other than battery separators, for example,
Even in the field where ion absorption, ammonia adsorption or biocompatibility is required, from the industrial point of view, the reactivity is higher and the sulfur-containing functional group can be introduced efficiently from the industrial viewpoint as in the case of the battery separator. The way was long-awaited.

【0005】[0005]

【発明が解決しようとする課題】本発明は上記の問題点
を解決するためになされたものであり、反応性が高く、
効率的に硫黄含有官能基を導入できる方法、電池用セパ
レータの製造方法、及び電池用セパレータを提供するこ
とを目的とする。
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has high reactivity.
It is an object of the present invention to provide a method for efficiently introducing a sulfur-containing functional group, a method for producing a battery separator, and a battery separator.

【0006】[0006]

【課題を解決するための手段】本発明の硫黄含有官能基
の導入方法は、水分を保有する被処理体を、フッ素ガス
と硫黄含有化合物ガスとを含む混合ガスと接触させる方
法である。このように、水分を保有する被処理体をフッ
素ガスと硫黄含有化合物ガスとを含む混合ガスと接触さ
せると、反応性が高く、効率的に硫黄含有官能基を導入
できることを見い出したのである。
The method for introducing a sulfur-containing functional group according to the present invention is a method in which an object to be treated having moisture is brought into contact with a mixed gas containing a fluorine gas and a sulfur-containing compound gas. As described above, it has been found that, when an object to be treated having moisture is brought into contact with a mixed gas containing a fluorine gas and a sulfur-containing compound gas, reactivity is high and a sulfur-containing functional group can be efficiently introduced.

【0007】本発明の電池用セパレータの製造方法は、水分
を保有する繊維シートを含むシートを、フッ素ガスと硫
黄含有化合物ガスとを含む混合ガスと接触させる方法で
ある。このように、水分を保有する繊維シートを含むシ
ートをフッ素ガスと硫黄含有化合物ガスとを含む混合ガ
スと接触させると、反応性が高く、効率的に硫黄含有官
能基を導入でき、親水性に優れる電池用セパレータを製
造できることを見い出したのである。
[0007] The method for producing a battery separator of the present invention is a method in which a sheet containing a fiber sheet having moisture is brought into contact with a mixed gas containing a fluorine gas and a sulfur-containing compound gas. Thus, when the sheet containing the fiber sheet having moisture is brought into contact with the mixed gas containing the fluorine gas and the sulfur-containing compound gas, the reactivity is high, the sulfur-containing functional group can be efficiently introduced, and the hydrophilicity is improved. They found that they could produce excellent battery separators.

【0008】本発明の電池用セパレータは上記のような方法
により製造されたシートからなるため、効率的に製造で
き、親水性にも優れるものである。
[0008] Since the battery separator of the present invention comprises a sheet manufactured by the above-described method, it can be efficiently manufactured and has excellent hydrophilicity.

【0009】[0009]

【発明の実施の形態】本発明において硫黄含有官能基を
導入できる被処理体としては、特に限定されるものでは
ないが、例えば、繊維、糸、フィルム、多孔質膜、織
物、編物、不織布、ネット或いはこれらの複合体である
ことができる。なお、被処理体がシート状のもの(例え
ば、フィルム、多孔質膜、織物、編物、不織布、ネット
或いはこれらの複合体)であると、屈曲性に優れてお
り、ロール状に巻くことができるため、巻き出した後に
硫黄含有官能基を導入し、その後巻き取ることができ、
製造上好適である。また、被処理体を構成する樹脂成分
も特に限定されるものではないが、例えば、ポリエチレ
ンやポリプロピレンなどのポリオレフィン、ポリエステ
ル、ポリアミド、ポリイミド、ポリフェニレンサルファ
イド、シリコーン樹脂、含フッ素樹脂などを挙げること
ができる。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The object to be treated in the present invention into which a sulfur-containing functional group can be introduced is not particularly limited. Examples thereof include fibers, yarns, films, porous membranes, woven fabrics, knitted fabrics, non-woven fabrics, and the like. It can be a net or a composite of these. When the object to be processed is a sheet-shaped object (for example, a film, a porous film, a woven fabric, a knitted fabric, a nonwoven fabric, a net, or a composite thereof), the object has excellent flexibility and can be wound into a roll. Therefore, after unwinding, a sulfur-containing functional group can be introduced, and then can be wound up,
It is suitable for manufacturing. Further, the resin component constituting the object to be treated is not particularly limited, but examples thereof include polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyimides, polyphenylene sulfides, silicone resins, and fluorine-containing resins. .

【0010】なお、電池用セパレータを製造する場合、被処
理体は電解液の保持性に優れるように、織物、編物或い
は不織布などの繊維シートを含んでいるのが好ましく、
不織布を含んでいるのがより好ましく、不織布と微孔フ
ィルムからなるのが特に好ましい。また、繊維シートを
構成する繊維及び微孔フィルムを構成する樹脂成分も特
に限定されるものではないが、耐アルカリ性や耐酸化性
に優れているように、ポリオレフィン系樹脂を含んでい
るのが好ましく、ポリオレフィン系樹脂のみから構成さ
れているのがより好ましい。より具体的には、ポリエチ
レン(例えば、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な
ど)、エチレン系共重合体、ポリプロピレン、プロピレ
ン系共重合体、ポリメチルペンテン、メチルペンテン系
共重合体などから構成されているのが好ましい。
[0010] When the battery separator is manufactured, the object to be treated preferably contains a fiber sheet such as a woven fabric, a knitted fabric, or a nonwoven fabric so as to have excellent electrolyte retention.
More preferably, it comprises a nonwoven fabric, and particularly preferably it comprises a nonwoven fabric and a microporous film. Further, the fibers constituting the fiber sheet and the resin component constituting the microporous film are not particularly limited, but preferably contain a polyolefin-based resin so as to be excellent in alkali resistance and oxidation resistance. More preferably, it is composed of only a polyolefin resin. More specifically, polyethylene (for example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, etc.), ethylene-based copolymer, polypropylene, propylene-based copolymer, polymethylpentene, methyl It is preferably composed of a pentene copolymer or the like.

【0011】このような被処理体は水分を保有する状態で、
フッ素ガスと硫黄含有化合物ガスとを含む混合ガスと接
触させる。この被処理体の水分保有量は少なすぎると反
応性があまり向上せず、効率的に硫黄含有官能基を導入
できず、多すぎると、被処理体全体に均一に硫黄含有官
能基を導入できない傾向があるため、被処理体の水分保
有量は被処理体質量の0.5〜50%であるのが好まし
く、0.5〜40%であるのがより好ましい。なお、被
処理体の面密度は通常10〜300g/m 2程度である
ため、水分保有量は0.05〜150g/m2であるの
が好ましく、0.05〜120g/m2であるのがより
好ましい。特に、不織布を含むシートから電池用セパレ
ータを製造する場合、水分保有量はシートの質量の0.
5〜40%であるのが好ましく、0.5〜30%である
のがより好ましい。なお、電池用セパレータの面密度は
通常30〜100g/m2程度であるため、水分保有量
は0.15〜40g/m2であるのが好ましく、0.1
5〜30g/m2であるのがより好ましい。なお、この
「水分保有量」は、被処理体を温度105〜110℃で
一定質量となるまで乾燥した時の質量との質量差をい
う。
[0011] Such an object to be processed retains moisture,
Contact with mixed gas containing fluorine gas and sulfur-containing compound gas
Touch. If the water content of the object is too small,
Effective introduction of sulfur-containing functional groups without significant improvement in responsiveness
If it is not possible, if too much, the sulfur
Since there is a tendency that no functional groups can be introduced,
The weight is preferably 0.5 to 50% of the mass of the object to be treated.
And more preferably 0.5 to 40%. In addition,
The surface density of the treated body is usually 10 to 300 g / m. TwoIs about
Therefore, the water content is 0.05 to 150 g / mTwoIs
Is preferred, and 0.05 to 120 g / mTwoIs more
preferable. In particular, separation of batteries for non-woven fabric
When producing a sheet, the water content is 0.1% of the sheet mass.
It is preferably from 5 to 40%, and from 0.5 to 30%.
Is more preferred. The surface density of the battery separator is
Usually 30-100g / mTwoWater content
Is 0.15 to 40 g / mTwoAnd preferably 0.1
5 to 30 g / mTwoIs more preferable. Note that this
"Water content" means that the object to be treated is heated at a temperature of 105 to 110C.
What is the difference in mass from the mass when dried to a constant mass?
U.

【0012】前述のような被処理体(電池用セパレータとし
て好適である繊維シートを含むシートを含む、以下同
様)が水分を保有していない場合には、被処理体に対し
て水分を付与する。この被処理体への水分の付与方法と
しては、例えば、被処理体を水中に浸漬する方法、被処
理体に水を塗布する方法、被処理体に水を散布する方
法、などがある。なお、電池用セパレータのように、ポ
リオレフィン系樹脂からなる繊維や微孔フィルムに対し
て水分を付与する場合、ポリオレフィン系樹脂は疎水性
であり、水分が馴染みにくい場合がある。このような場
合には、被処理体を予め放電処理(例えば、コロナ放電
処理、プラズマ処理、グロー放電処理又は電子線処理な
ど)などによって被処理体を改質した後に、水分を付与
するのが好ましい。また、水に界面活性剤を添加して、
被処理体との馴染みを向上させても良いし、前記のよう
な方法により水分を付与した後に、被処理体をフィルム
で挟み込んだり、一対のロール間を通すなどして、強制
的に水分を付与しても良い。
When the object to be processed (including a sheet including a fiber sheet suitable as a battery separator, the same applies hereinafter) does not have moisture, the object to be processed is provided with moisture. . Examples of a method of applying moisture to the object include a method of immersing the object in water, a method of applying water to the object, and a method of spraying water on the object. When water is imparted to a fiber or a microporous film made of a polyolefin resin, as in a battery separator, the polyolefin resin is hydrophobic, and the water may be difficult to adapt. In such a case, it is preferable that the object be modified in advance by a discharge treatment (for example, a corona discharge treatment, a plasma treatment, a glow discharge treatment, an electron beam treatment, or the like) and then water be provided. preferable. Also, add a surfactant to the water,
It is possible to improve the familiarity with the object to be processed, or after applying the water by the method described above, forcibly remove the water by sandwiching the object to be processed with a film or passing between a pair of rolls. You may give.

【0013】次いで、水分を保有する被処理体をフッ素ガス
と硫黄含有化合物ガスとを含む混合ガスと接触させて、
被処理体に硫黄含有官能基を導入する。この硫黄含有化
合物ガスとしては、例えば、一酸化硫黄ガス、二酸化硫
黄ガスなどがある。なお、本発明においてはフッ素ガス
や硫黄含有化合物ガス以外のガス、例えば、酸素含有化
合物ガス(例えば、酸素ガス、一酸化炭素ガス、二酸化
炭素ガスなど)を含んでいても良い。また、フッ素ガス
は反応性が非常に高いため、窒素ガスや希ガス(例え
ば、ヘリウム、アルゴンなど)を混合して、フッ素ガス
を希釈するのが好ましい。このように窒素ガスや希ガス
を含む場合の体積比率は、(フッ素ガス、F):(硫黄
含有化合物ガス(場合により酸素含有化合物ガスも含
む)、R):(窒素ガスや希ガス、D)=0.1〜2
0:0.1〜20:99.8〜60であるのが好まし
い。
Next, the object to be treated having moisture is brought into contact with a mixed gas containing a fluorine gas and a sulfur-containing compound gas,
A sulfur-containing functional group is introduced into the object. Examples of the sulfur-containing compound gas include a sulfur monoxide gas and a sulfur dioxide gas. In the present invention, a gas other than the fluorine gas and the sulfur-containing compound gas, for example, an oxygen-containing compound gas (for example, an oxygen gas, a carbon monoxide gas, a carbon dioxide gas, or the like) may be included. Further, since fluorine gas has extremely high reactivity, it is preferable to dilute the fluorine gas by mixing a nitrogen gas or a rare gas (for example, helium, argon, or the like). As described above, the volume ratio when a nitrogen gas or a rare gas is contained is as follows: (fluorine gas, F) :( sulfur-containing compound gas (including oxygen-containing compound gas in some cases), R) :( nitrogen gas, rare gas, D ) = 0.1-2
The ratio is preferably 0: 0.1-20: 99.8-60.

【0014】なお、水分を保有する被処理体と混合ガスとの
接触は室温下で実施することもできるし、硫黄含有官能
基を導入しやすいように、被処理体と混合ガスとを接触
させる前、接触させる際或いは接触させた後に、被処理
体を加熱しても良い。なお、被処理体の混合ガスとの接
触温度は10〜80℃程度であるのが好ましい。
The contact between the object to be treated having water and the mixed gas can be carried out at room temperature, and the object to be treated and the mixed gas are brought into contact so that a sulfur-containing functional group can be easily introduced. The object to be processed may be heated before, during, or after the contact. Note that the contact temperature of the object to be processed with the mixed gas is preferably about 10 to 80 ° C.

【0015】また、被処理体の混合ガスとの接触時間も特に
限定するものではないが、硫黄含有官能基を十分に導入
できるように、10秒以上接触させるのが好ましい。な
お、前記混合ガスは反応性が非常に高く危険であるた
め、被処理体と混合ガスとの接触は密閉された容器内で
実施したり、被処理体の入口部分と出口部分とを窒素ガ
スなどによりシール可能な容器内で実施するのが好まし
い。
The contact time of the object to be treated with the mixed gas is not particularly limited, but it is preferable that the object be contacted for 10 seconds or more so that the sulfur-containing functional group can be sufficiently introduced. Since the mixed gas has a very high reactivity and is dangerous, the contact between the object to be processed and the mixed gas is performed in a closed container, or the inlet and outlet of the object to be processed are filled with nitrogen gas. It is preferably carried out in a container that can be sealed by such as.

【0016】このように水分を保有する被処理体を混合ガス
と接触させることによって、硫黄含有官能基を導入する
ことができるが、混合ガス中にフッ素ガスが含まれてい
るため、フッ素原子を含む官能基(例えば、スルホフル
オライド基など)も導入されるため、更に親水性を必要
とする場合(例えば、電池用セパレータに使用する場
合)、混合ガスと接触させた後に被処理体を水やアルコ
ールなどに浸漬して、フッ素原子を水素原子で置換する
のが好ましい。
[0016] By bringing the object to be treated having moisture into contact with the mixed gas as described above, a sulfur-containing functional group can be introduced. However, since fluorine gas is contained in the mixed gas, fluorine atoms can be introduced. Since a functional group (for example, a sulfofluoride group) is also introduced, when further hydrophilicity is required (for example, when used for a battery separator), the object to be treated is brought into contact with a mixed gas before being treated with water. It is preferable to replace the fluorine atom with a hydrogen atom by immersion in water or alcohol.

【0017】このように硫黄含有官能基を導入した被処理体
は、親水性、吸水性、保水性、接着性、染色性、印刷特
性、イオン交換性、イオン吸収性、アンモニア吸着性、
或いは生体適合性が付与又は向上したものであるため、
これらの特性を必要とする用途に好適に使用することが
できる。特に、前述のような方法により硫黄含有官能基
を導入して親水化した繊維シート(特にポリオレフィン
系繊維からなる繊維シート)を含むシートを、電池用セ
パレータ(特に、ニッケル−カドニウム電池、ニッケル
−水素電池)として使用すると、電池製造時において電
解液を容易にセパレータ全体に注液することができ、し
かも長期間における電解液の保持性にも優れているた
め、使用寿命の長い電池を製造することができる。
The object to which the sulfur-containing functional group is introduced as described above is hydrophilic, water-absorbing, water-retaining, adhesive, dyeing, printing, ion-exchange, ion-absorbing, ammonia-adsorbing,
Or because the biocompatibility is given or improved,
It can be suitably used for applications requiring these characteristics. In particular, a sheet including a fiber sheet (particularly a fiber sheet made of polyolefin fiber) which has been hydrophilized by introducing a sulfur-containing functional group by the above-mentioned method is used for a battery separator (in particular, a nickel-cadmium battery, a nickel-hydrogen battery). When used as a battery, it is possible to easily inject the electrolyte into the entire separator during battery manufacture, and it is also excellent in the retention of the electrolyte over a long period of time. Can be.

【0018】以下に、本発明の実施例を記載するが、本発明
は以下の実施例に限定されるものではない。
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

【0019】[0019]

【実施例】(不織布の作成)芯成分がポリプロピレン
(融点:160℃)からなり、鞘成分(融着成分)が低
密度ポリエチレン(融点:115℃)からなる、繊度2
デニール、繊維長10mmの芯鞘型熱融着性繊維25m
ass%、図1に示すような、ポリプロピレン成分(図
中記号12、円形状で繊度0.02デニールのポリプロ
ピレン極細繊維(融点:160℃)1本と、三角形状で
繊度0.08デニールのポリプロピレン極細繊維(融
点:160℃)8本とを発生可能)と、高密度ポリエチ
レン成分(図中記号11、繊度0.08デニールの高密
度ポリエチレン極細繊維(融点:125℃)8本を発生
可能)とからなる、オレンジ状断面を有する、繊度1.
3デニール、繊維長15mmの分割性繊維40mass
%、及び引張り強さが9g/d(デニール)で、繊度2
デニール、繊維長10mmの高強度ポリプロピレン繊維
(融点:168℃)35mass%とを混合分散させた
スラリーを、傾斜ワイヤー型短網方式により抄造して繊
維ウエブを形成した。
EXAMPLES (Preparation of nonwoven fabric) Fineness 2 having a core component of polypropylene (melting point: 160 ° C.) and a sheath component (fusing component) of low density polyethylene (melting point: 115 ° C.)
Denier, core-sheath type heat-fusible fiber with a fiber length of 10 mm 25 m
as%, as shown in FIG. 1, a polypropylene component (symbol 12 in the figure, one circular ultrafine polypropylene fiber having a fineness of 0.02 denier (melting point: 160 ° C.) and a triangular polypropylene having a fineness of 0.08 denier Eight ultra-fine fibers (melting point: 160 ° C) can be generated and eight high-density polyethylene components (symbol 11 in the figure, eight high-density polyethylene ultra-fine fibers having a fineness of 0.08 denier (melting point: 125 ° C) can be generated) Having an orange cross section and a fineness of 1.
3 denier, splittable fiber 40 mass having a fiber length of 15 mm
% And tensile strength 9 g / d (denier), fineness 2
A slurry obtained by mixing and dispersing denier and 35 mass% of high-strength polypropylene fiber having a fiber length of 10 mm (melting point: 168 ° C.) was formed by a slant wire short net method to form a fiber web.

【0020】次いで、この繊維ウエブを温度120℃に設定
された熱風循環式ドライヤーにより、繊維ウエブの乾燥
と同時に芯鞘型熱融着性繊維の鞘成分を融着させ、融着
繊維ウエブを製造した。次いで、この融着繊維ウエブを
100メッシュのネット上に載置し、ノズル径0.15
mm、ノズルピッチ0.8mmで一列にノズルを配置し
たノズルプレートから内圧12MPaの水流を、この融
着繊維ウエブに対して両面交互に2回づつ噴出して、絡
合させると同時に分割性繊維を分割した。次いで、この
水流を作用させた融着繊維ウエブを温度120℃に設定
された熱風循環式ドライヤーにより乾燥すると同時に芯
鞘型熱融着性繊維の鞘成分を融着させて、面密度60g
/m2、厚さ0.15mmの不織布を製造した。
Next, the fiber web is dried by a hot air circulation dryer set at a temperature of 120 ° C., and simultaneously with the drying of the fiber web, the sheath component of the core-sheath type heat-fusible fiber is fused to produce a fused fiber web. did. Next, the fused fiber web was placed on a 100 mesh net, and the nozzle diameter was 0.15.
mm, a water stream with an internal pressure of 12 MPa is jetted from the nozzle plate in which nozzles are arranged in a line at a nozzle pitch of 0.8 mm to the fused fiber web alternately on both sides alternately twice, so as to be entangled and at the same time splittable fibers. Divided. Next, the fused fiber web to which the water flow was applied was dried by a hot air circulation dryer set at a temperature of 120 ° C., and at the same time, the sheath component of the core-sheath type heat-fusible fiber was fused to obtain a surface density of 60 g.
/ M 2 and a non-woven fabric having a thickness of 0.15 mm.

【0021】(実施例1)前述のようにして得た不織布に対
して水を均一に散布した後、ニップロール間を通すこと
により、不織布に水を馴染ませると同時に、水分量が不
織布質量の10%となるように調節した。次いで、フッ
素ガス(3vol%)、酸素ガス(5vol%)、二酸
化硫黄ガス(5vol%)及び窒素ガス(87vol
%)からなる混合ガスで満たされた容器内に、前記水分
を付与した不織布を供給し、不織布を前記混合ガスと1
20秒間(温度:20℃)接触させた。そして、この混
合ガスと接触させた不織布を温度80℃に設定されたド
ライヤーにより乾燥した後、線圧力9.8N/cmでカ
レンダー処理を実施して、面密度60g/m2、厚さ
0.15mmのセパレータを製造した。
(Example 1) [0021] After uniformly spraying water on the nonwoven fabric obtained as described above, water is applied to the nonwoven fabric by passing between nip rolls, and at the same time, the water content is 10% of the weight of the nonwoven fabric. %. Next, fluorine gas (3 vol%), oxygen gas (5 vol%), sulfur dioxide gas (5 vol%) and nitrogen gas (87 vol%)
%) Is supplied to the container filled with the mixed gas consisting of
The contact was performed for 20 seconds (temperature: 20 ° C.). Then, the nonwoven fabric contacted with the mixed gas is dried by a drier set at a temperature of 80 ° C., and then calendered at a linear pressure of 9.8 N / cm to have an areal density of 60 g / m 2 and a thickness of 0.1 g / m 2 . A 15 mm separator was manufactured.

【0022】(実施例2)前述のようにして得た不織布に対
して水を均一に散布した後、ニップロール間を通すこと
により、不織布に水を馴染ませると同時に、水分量が不
織布質量の25%となるように調節したことを除いて、
実施例1と同じ操作を繰り返して、面密度60g/
2、厚さ0.15mmのセパレータを製造した。
(Example 2) [0022] After uniformly spraying water on the non-woven fabric obtained as described above, water is passed between the nip rolls to make the non-woven fabric familiar with water, and at the same time, the water content is 25% of the weight of the non-woven fabric. Except that it was adjusted to be%
The same operation as in Example 1 was repeated to obtain an areal density of 60 g /
A separator having a thickness of m 2 and a thickness of 0.15 mm was produced.

【0023】(比較例)前述のようにして得た不織布に対し
て水を散布することなく、そのまま使用(水分量が不織
布質量の0%)したことを除いて、実施例1と同じ操作
を繰り返して、面密度60g/m2、厚さ0.15mm
のセパレータを製造した。
(Comparative Example) The same operation as in Example 1 was performed except that water was not sprayed on the nonwoven fabric obtained as described above, and the water was used as it was (water content was 0% of the mass of the nonwoven fabric). Repeatedly, area density 60 g / m 2 , thickness 0.15 mm
Was manufactured.

【0024】(吸液高さの測定)実施例1〜2及び比較例の
各々のセパレータを幅25mm、長さ180mmの短冊
状に裁断した後、水分平衡に至らせた。次いで、各々の
短冊状のセパレータの一端から5mmまでの領域を、温
度20℃±2℃に保たれた比重1.3の水酸化カリウム
水溶液に対して直角に浸漬し、10分後における、水酸
化カリウム水溶液の上昇した高さを測定した。この結果
は表1に示す通りであった。このように本発明のセパレ
ータは吸液速度が速く、電解液をセパレータ全体に注液
することができるため、電池を効率よく生産することが
できるものであった。
(Measurement of Liquid Absorbing Height) Each of the separators of Examples 1 and 2 and Comparative Example was cut into a rectangular shape having a width of 25 mm and a length of 180 mm, and the water was equilibrated. Next, a region from one end of each strip-shaped separator to 5 mm is immersed at right angles in an aqueous solution of potassium hydroxide having a specific gravity of 1.3 kept at a temperature of 20 ° C. ± 2 ° C., and after 10 minutes, The elevated height of the aqueous potassium oxide solution was measured. The results were as shown in Table 1. As described above, since the separator of the present invention has a high liquid absorption rate and can inject the electrolytic solution into the entire separator, the battery can be efficiently produced.

【0025】[0025]

【表1】 【table 1】

【0026】(滴下吸収速度の測定)実施例1〜2及び比較
例の各々のセパレータを水分平衡に至らせた後、各々の
セパレータの無作為に選んだ5点に対して、温度20℃
±2℃で比重1.3の水酸化カリウム水溶液30μl
(マイクロリットル)を滴下し、水酸化カリウム水溶液
がセパレータに完全に吸収されるまでに要する時間を各
々測定し、その平均時間を算出した。この結果は表1に
示す通りであった。このように本発明のセパレータは吸
収速度が速いため、電池を効率よく生産することができ
るものであった。
(Measurement of Drop Absorption Rate) After each of the separators of Examples 1 and 2 and Comparative Example was brought into water equilibrium, a temperature of 20 ° C. was measured for five randomly selected points of each separator.
30 µl of aqueous potassium hydroxide solution with a specific gravity of 1.3 at ± 2 ° C
(Microliter) was dropped, and the time required for the aqueous potassium hydroxide solution to be completely absorbed by the separator was measured, and the average time was calculated. The results were as shown in Table 1. As described above, since the separator of the present invention has a high absorption rate, a battery can be efficiently produced.

【0027】[0027]

【発明の効果】本発明の硫黄含有官能基の導入方法は、
反応性が高く、効率的に硫黄含有官能基を導入できる方
法である。
According to the method for introducing a sulfur-containing functional group of the present invention,
This method has high reactivity and can efficiently introduce a sulfur-containing functional group.

【0028】本発明の電池用セパレータの製造方法は、反応
性が高く、効率的に硫黄含有官能基を導入でき、親水性
に優れる電池用セパレータを製造できる方法である。
The method for producing a battery separator according to the present invention is a method for producing a battery separator having high reactivity, capable of efficiently introducing a sulfur-containing functional group, and having excellent hydrophilicity.

【0029】本発明の電池用セパレータは効率的に製造で
き、親水性にも優れるものである。
The battery separator of the present invention can be manufactured efficiently and has excellent hydrophilicity.

【図面の簡単な説明】[Brief description of the drawings]

【図1】 分割性繊維の模式的断面図FIG. 1 is a schematic sectional view of a splittable fiber.

【符号の説明】[Explanation of symbols]

1 分割性繊維 11 高密度ポリエチレン成分 12 ポリプロピレン成分 Reference Signs List 1 splittable fiber 11 high-density polyethylene component 12 polypropylene component

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4F073 AA01 BA07 BA08 BA23 BA29 BA31 BB01 BB04 DA04 DA06 DA09 4L031 AA14 AB09 AB10 AB34 BA07 BA17 CA08 DA08 DA09 DA21 5H021 BB09 CC02 EE02 EE04 EE07 EE08 EE10 EE23 EE34 HH01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F073 AA01 BA07 BA08 BA23 BA29 BA31 BB01 BB04 DA04 DA06 DA09 4L031 AA14 AB09 AB10 AB34 BA07 BA17 CA08 DA08 DA09 DA21 5H021 BB09 CC02 EE02 EE04 EE07 EE08 EE10 EE23 EE34

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】 水分を保有する被処理体を、フッ素ガス
と硫黄含有化合物ガスとを含む混合ガスと接触させるこ
とを特徴とする、硫黄含有官能基の導入方法。
1. A method for introducing a sulfur-containing functional group, comprising contacting an object to be treated having moisture with a mixed gas containing a fluorine gas and a sulfur-containing compound gas.
【請求項2】 被処理体の水分保有量が、被処理体質量
の0.5〜50%であることを特徴とする、請求項1に
記載の硫黄含有官能基の導入方法。
2. The method for introducing a sulfur-containing functional group according to claim 1, wherein the water content of the object to be treated is 0.5 to 50% of the mass of the object to be treated.
【請求項3】 水分を保有する繊維シートを含むシート
を、フッ素ガスと硫黄含有化合物ガスとを含む混合ガス
と接触させることを特徴とする、電池用セパレータの製
造方法。
3. A method for producing a battery separator, comprising contacting a sheet containing a fiber sheet holding moisture with a mixed gas containing a fluorine gas and a sulfur-containing compound gas.
【請求項4】 繊維シートを含むシートの水分保有量
が、シート質量の0.5〜40%であることを特徴とす
る、請求項3に記載の電池用セパレータの製造方法。
4. The method for producing a battery separator according to claim 3, wherein the moisture content of the sheet including the fiber sheet is 0.5 to 40% of the sheet mass.
【請求項5】 請求項3又は請求項4に記載の方法によ
り製造されたシートからなることを特徴とする電池用セ
パレータ。
A separator for a battery, comprising a sheet manufactured by the method according to claim 3 or 4.
JP25236399A 1999-09-07 1999-09-07 Method for introducing sulfur-containing functional group, method for producing battery separator, and battery separator Expired - Lifetime JP4065630B2 (en)

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JP4065630B2 JP4065630B2 (en) 2008-03-26

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