JPH06187962A - Separator for alkaline battery and manufacture thereof - Google Patents
Separator for alkaline battery and manufacture thereofInfo
- Publication number
- JPH06187962A JPH06187962A JP43A JP33852292A JPH06187962A JP H06187962 A JPH06187962 A JP H06187962A JP 43 A JP43 A JP 43A JP 33852292 A JP33852292 A JP 33852292A JP H06187962 A JPH06187962 A JP H06187962A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- alkaline battery
- resin
- fiber
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケル−カドミウム
蓄電池、ニッケル−水素蓄電池、ニッケル−亜鉛電池等
の密閉型アルカリ電池に好適に用いられるアルカリ電池
用不織布セパレータおよびその製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-woven fabric separator for an alkaline battery, which is preferably used for a sealed alkaline battery such as a nickel-cadmium battery, a nickel-hydrogen battery and a nickel-zinc battery, and a method for producing the same.
【０００２】[0002]
【従来の技術】アルカリ蓄電池に用いるセパレータは、
長時間に亘る充放電のくり返しに対しアルカリ電解液を
長時間に亘って保持し、電極間の接触による短絡を防止
することが要求される。2. Description of the Related Art Separator used in alkaline storage batteries is
It is required to hold the alkaline electrolyte for a long time against repeated charging / discharging for a long time to prevent a short circuit due to contact between electrodes.
【０００３】現在、アルカリ電池セパレータ用不織布に
多用されているポリアミド系繊維は、長期間の充放電の
くり返しに於いて、耐アルカリ性、耐酸化性等の耐薬品
性が十分でない為に繊維劣化が進行し、電極間短絡によ
り電池寿命を低下させるという欠点があった。At present, polyamide-based fibers, which are widely used as non-woven fabrics for alkaline battery separators, do not have sufficient chemical resistance such as alkali resistance and oxidation resistance during repeated charging / discharging for a long period of time, so that fiber deterioration is caused. However, there is a drawback that the battery life progresses and the battery life is reduced due to a short circuit between the electrodes.
【０００４】これに対し、耐アルカリ性、耐酸化性等耐
薬品性に優れたポリオレフィン系繊維を用いたセパレー
タが提案されているが、親水性が乏しい為、電解液保持
性が極めて悪く、充放電のくり返しにより電解液がドラ
イアウトし易いという欠点があった。On the other hand, a separator using a polyolefin fiber excellent in chemical resistance such as alkali resistance and oxidation resistance has been proposed. However, since the hydrophilicity is poor, the electrolyte retention is extremely poor and the charge and discharge are poor. There was a drawback in that the electrolyte solution was easily dried out due to repetition.
【０００５】これらの欠点を解決する方法としては、界
面活性剤を付与したもの（特開昭５８−１７５２５６号
公報）、親水性の無機粉体を添加したもの（特開昭６４
−５７５６８号公報）、ポリエチレン繊維或いはポリプ
ロピレン繊維をスルフォン化処理して親水基であるスル
フォン酸基を導入したもの（特開平１−１３２０４３号
公報、特開平１−１３２０４４号公報）等が提案されて
いる。As a method for solving these drawbacks, a method in which a surfactant is added (JP-A-58-175256) and a method in which hydrophilic inorganic powder is added (JP-A-64).
No. 57568), polyethylene fibers or polypropylene fibers are sulfonated to introduce a sulfonic acid group, which is a hydrophilic group (Japanese Patent Laid-Open Nos. 1-132043 and 1-132044). There is.
【０００６】[0006]
【発明が解決しようとする課題】上記界面活性剤を付与
する方法および親水性の無機粉体を添加する方法は、電
池反応により、繊維表面から界面活性剤や無機粉体が電
解液中に脱落することが多く、いずれも長期間にわたる
安定な親水性を持続する事が困難であるという問題があ
った。The method of applying the above-mentioned surfactant and the method of adding the hydrophilic inorganic powder are such that the surface active agent and the inorganic powder fall off from the fiber surface into the electrolytic solution due to the cell reaction. In many cases, it is difficult to maintain stable hydrophilicity over a long period of time.
【０００７】又、上記スルフォン化処理に関するもの
は、α−オレフィンを発煙硫酸等でスルフォン化処理す
るものであり、スルフォン基を所定量効率良く導入する
定量コントロールが困難であり、長期間にわたる安定な
親水性を持続する事が困難であった。The above-mentioned sulfonation treatment involves sulfonation of α-olefins with fuming sulfuric acid and the like, and it is difficult to quantitatively control the introduction of a predetermined amount of sulfone groups efficiently, and stable for a long period of time. It was difficult to maintain hydrophilicity.
【０００８】本発明の目的は、長期間に亘って親水性を
持続できるとともに、耐アルカリ性、耐酸化性等の化学
的安定性にも優れたアルカリ電池用セパレータおよびそ
の製造方法を提供することである。An object of the present invention is to provide a separator for an alkaline battery which can maintain hydrophilicity for a long period of time and is also excellent in chemical stability such as alkali resistance and oxidation resistance, and a method for producing the same. is there.
【０００９】[0009]
【課題を解決するための手段】本発明は、耐薬品性繊維
から成る不織布シートの繊維交点および繊維表面の少な
くとも一部に付着したＡＳ樹脂（アクリロニトリル−ス
チレン共重合樹脂）にカルボキシル基を導入してなるも
のである。SUMMARY OF THE INVENTION According to the present invention, a carboxyl group is introduced into an AS resin (acrylonitrile-styrene copolymer resin) attached to at least a part of a fiber intersection and a fiber surface of a non-woven fabric sheet made of chemical resistant fibers. It will be.
【００１０】本発明における耐薬品性繊維とは、ポリプ
ロピレン（ＰＰ）、ポリエチレン（ＰＥ）等のポリオレ
フィン系繊維等をいうが、これらの繊維は単独で用いて
もよく、また２種以上を併用してもよい。さらに、これ
らの繊維をたとえば、芯鞘構造等の複合繊維として適宜
混合使用してもよい。The chemical resistant fibers in the present invention include polyolefin fibers such as polypropylene (PP) and polyethylene (PE). These fibers may be used alone or in combination of two or more kinds. May be. Further, these fibers may be appropriately mixed and used as, for example, a composite fiber having a core-sheath structure or the like.
【００１１】本発明に用いるＡＳ樹脂は、ディッピン
グ、コーティング等の手法により、不織布シートに被覆
させるが、特に限定されるものではない。The AS resin used in the present invention is coated on the nonwoven fabric sheet by a technique such as dipping or coating, but is not particularly limited.
【００１２】また本発明は、耐薬品性繊維に対するＡＳ
樹脂の付着割合が３〜５０重量％であることを特徴とす
る。The present invention also provides an AS for chemically resistant fibers.
It is characterized in that the resin adhesion ratio is 3 to 50% by weight.
【００１３】上記付着割合が３重量％未満では、電解液
との親和性の向上が見られず、５０重量％を超えるとア
ルカリ電池用セパレータに要求される通気性が阻害さ
れ、好ましくない。When the above-mentioned adhesion ratio is less than 3% by weight, the affinity with the electrolytic solution is not improved, and when it exceeds 50% by weight, the air permeability required for the alkaline battery separator is impaired.
【００１４】ところで、上記ＡＳ樹脂は、アクリロニト
リルの含有量が多い程加水分解による親水性の向上が大
きいが、反面、水溶化してしまうことから、５０重量％
以下の含有量であることが望ましい。また、アクリロニ
トリルの含有量が５重量％未満になると電解液との親和
性の向上が見られないため、５重量％以上であることが
望ましい。By the way, the higher the content of acrylonitrile in the AS resin, the greater the improvement in hydrophilicity due to hydrolysis, but on the other hand, since it becomes water soluble, it is 50% by weight.
The following contents are desirable. Further, when the content of acrylonitrile is less than 5% by weight, the affinity with the electrolytic solution is not improved, so that the content is preferably 5% by weight or more.
【００１５】また本発明は、耐薬品性から成る不織布シ
ートに、ＡＳ樹脂を含む結合剤を付着させた後、加水分
解処理を行なうものである。In the present invention, a hydrolytic treatment is carried out after a binder containing an AS resin is attached to a chemically resistant non-woven sheet.
【００１６】上記加水分解処理とは、ＡＳ樹脂中のニト
リル基（−ＣＮ）を、アルカリ処理等による加水分解に
より親水基であるカルボキシル基（−ＣＯＯＨ）に変成
させるものである。この反応は、下記一般式に示すよう
に二段階で進行し、ＡＳ樹脂にカルボキシル基が導入さ
れる。The above-mentioned hydrolysis treatment is to convert the nitrile group (-CN) in the AS resin into a carboxyl group (-COOH) which is a hydrophilic group by hydrolysis by an alkali treatment or the like. This reaction proceeds in two steps as shown in the following general formula, and a carboxyl group is introduced into the AS resin.
【００１７】[0017]
【化１】 [Chemical 1]
【００１８】[0018]
【作用】本発明に従えば、親水性を有するカルボキシル
基が導入されたＡＳ樹脂によって、不織布シートは親水
性に優れたものとなり、これによって長期間にわたる電
解液親和性、保液性に優れるとともに長期間にわたる充
放電の繰返しに対しても安定なアルカリ電池用セパレー
タを得ることができる。According to the present invention, the AS resin having a hydrophilic carboxyl group introduced therein makes the non-woven fabric sheet excellent in hydrophilicity, which makes it excellent in affinity for electrolyte solution and liquid retention property for a long period of time. It is possible to obtain a alkaline battery separator that is stable even after repeated charging and discharging over a long period of time.
【００１９】[0019]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。 （実施例）芯がポリプロピレン、鞘がポリエチレンによ
り構成される芯鞘型加熱接着性繊維（０．９ｄ×３８ｍ
ｍ）３０％と、レギュラーのポリプロピレン繊維（１．
５ｄ×３８ｍｍ）７０％との混合繊維よりなるウエブ
を、１３０℃に加熱した一対のカレンダーロールで加熱
圧着し、目付６５ｇ／ｍ2 、厚さ０．２０ｍｍの不織布
シートＡを得た。EXAMPLES The present invention will be described in more detail below with reference to examples. (Example) A core-sheath type heat-bondable fiber (0.9d × 38m) having a polypropylene core and a polyethylene sheath.
m) 30% and regular polypropylene fiber (1.
(5d × 38 mm) 70% of a mixed fiber web was thermocompression bonded by a pair of calender rolls heated to 130 ° C. to obtain a nonwoven fabric sheet A having a basis weight of 65 g / m 2 and a thickness of 0.20 mm.
【００２０】次に、アクリロニトリルの含有量が３５重
量％であるＡＳ樹脂を上記不織布シートＡに均一に含浸
後、乾燥、熱処理加工して、目付７０ｇ／ｍ2 の不織布
シートＢを形成した。Next, the nonwoven fabric sheet A was uniformly impregnated with the AS resin having an acrylonitrile content of 35% by weight, dried and heat-treated to form a nonwoven fabric sheet B having a basis weight of 70 g / m 2 .
【００２１】さらに該不織布シートＢを、１０％ＫＯＨ
溶液中にて９５℃、３０分間の条件により加水分解処理
を行なった後、水洗、乾燥処理を行ない、本実施例のア
ルカリ電池用セパレータを得た。Further, the nonwoven fabric sheet B is mixed with 10% KOH.
Hydrolysis treatment was performed in the solution at 95 ° C. for 30 minutes, followed by washing with water and drying to obtain an alkaline battery separator of this example.
【００２２】（比較例１）上記実施例で得た不織布シー
トＡを比較例１のアルカリ電池用セパレータとした。Comparative Example 1 The nonwoven fabric sheet A obtained in the above example was used as the alkaline battery separator of Comparative Example 1.
【００２３】（比較例２）上記実施例で得た不織布シー
トＢを比較例２のアルカリ電池用セパレータとした。Comparative Example 2 The nonwoven fabric sheet B obtained in the above example was used as the alkaline battery separator in Comparative example 2.
【００２４】（比較例３）６−ナイロン繊維（１．５ｄ
×３８ｍｍ）７０％と、芯部が６−ナイロン、鞘部が融
点１６０℃のナイロン６−１０−１２の三元共重合体で
なる芯鞘型熱融着繊維（２ｄ×３８ｍｍ）３０％との混
合繊維よりなるウエブを、１６０℃に加熱した一対のカ
レンダーロールで加熱圧着して得た目付７５ｇ／ｍ2 、
厚さ０．２０ｍｍの不織布シートを比較例３のアルカリ
電池用セパレータとした。(Comparative Example 3) 6-nylon fiber (1.5d
X38 mm) 70%, core-sheath type heat-sealing fiber (2d × 38 mm) 30% composed of a ternary copolymer of 6-nylon in the core and nylon 6-10-12 in the sheath with a melting point of 160 ° C. A weight of 75 g / m 2 obtained by thermocompressing a web composed of the mixed fibers of (1) with a pair of calender rolls heated to 160 ° C.,
A 0.20 mm thick non-woven fabric sheet was used as the alkaline battery separator of Comparative Example 3.
【００２５】以下、実施例および比較例１〜３で得たア
ルカリ電池用セパレータの諸物性の比較テストを行なっ
た結果を表１に示す。Table 1 shows the results of a comparative test of various physical properties of the alkaline battery separators obtained in Examples and Comparative Examples 1 to 3.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表中、試験項目のテスト方法は下記の通り
である。 吸液速度 ；比重１．３０の苛性カリ溶液中に試料巾
２５ｍｍのセパレータ材の一端を浸漬、３０分後の吸液
高さ。 保液率 ；比重１．３０の苛性カリ溶液中にセパレ
ータ材を浸漬し、１０分間吊り干し、水切り後の溶液吸
収率。 耐アルカリ性；比重１．３０の苛性カリ溶液中に８０℃
にて３０日間浸漬した時の重量減少率。 耐酸化性試験後の強度保持率；５％ＫＭｎＯ4 溶液２５
０ｍｌと、比重１．３０の苛性カリ溶液５０ｍｌとの混
合液中で、５０℃１時間浸漬した後のセパレータ引張強
度保持率。In the table, the test methods of the test items are as follows. Liquid absorption speed: Liquid absorption height after 30 minutes of immersion of one end of a separator material having a sample width of 25 mm in a caustic potash solution having a specific gravity of 1.30. Liquid retention rate: The solution absorption rate after immersing the separator material in a caustic potash solution having a specific gravity of 1.30, suspending it for 10 minutes, and draining it. Alkali resistance; 80 ℃ in caustic potash solution with specific gravity of 1.30
Weight reduction rate after soaking for 30 days. Strength retention after oxidation resistance test; 5% KMnO 4 solution 25
The separator tensile strength retention rate after immersion in a mixed solution of 0 ml and 50 ml of a caustic potash solution having a specific gravity of 1.30 at 50 ° C. for 1 hour.
【００２８】上記表１より明らかなように、本発明によ
るセパレータは、優れた電解液親和性を示し、比較例３
のナイロン繊維を用いたセパレータに匹敵する吸液性，
保液性を有する事が窺われる。As is clear from Table 1 above, the separator according to the present invention exhibits excellent electrolytic solution affinity, and Comparative Example 3
Liquid absorption comparable to that of nylon fiber separator,
It can be said that it has liquid retention.
【００２９】また、耐アルカリ性、耐酸化性に於いても
良好なる耐久性を有し、本実施例によるアルカリ電池セ
パレータを電池に組み込み、充放電を繰返し行なっても
長期間にわたる使用に十分耐えることを示す。Further, it has good durability in terms of alkali resistance and oxidation resistance, and has sufficient durability for long-term use even if the alkaline battery separator according to this embodiment is incorporated into a battery and repeatedly charged and discharged. Indicates.
【００３０】[0030]
【発明の効果】本発明は上記の如く構成した事により、
長期にわたり電解液との親和性を維持出来るとともに、
更に良好なる耐久性を有する為、長期間にわたる充放電
の繰返しに対しても安定であり、電池寿命を大巾に改善
することが可能なアルカリ電池用セパレータを得ること
ができる。The present invention has the above-mentioned constitution,
The affinity with the electrolyte can be maintained for a long time,
Further, since it has good durability, it is possible to obtain an alkaline battery separator that is stable against repeated charging and discharging over a long period of time and can greatly improve battery life.
Claims (3)
維交点および繊維表面の少なくとも一部に付着したＡＳ
樹脂（アクリロニトリル・スチレン共重合樹脂）に、カ
ルボキシル基を導入して成ることを特徴とするアルカリ
電池用セパレータ。1. An AS attached to at least a part of a fiber intersection and a fiber surface of a non-woven sheet made of chemically resistant fiber.
A separator for an alkaline battery, which is obtained by introducing a carboxyl group into a resin (acrylonitrile / styrene copolymer resin).
基を有するＡＳ樹脂の付着割合が３〜５０重量％である
請求項１記載のアルカリ電池用セパレータ。2. The separator for an alkaline battery according to claim 1, wherein an attachment ratio of the AS resin having a carboxyl group to the chemical resistant fiber is 3 to 50% by weight.
Ｓ樹脂を含む結合剤を付着させた後、加水分解処理を行
なうことを特徴とするアルカリ電池用セパレータの製造
方法。3. A non-woven fabric sheet made of chemical resistant fibers
A method for producing a separator for an alkaline battery, which comprises applying a binder containing an S resin and then performing a hydrolysis treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06187962A (en) | 1992-12-18 | 1992-12-18 | Separator for alkaline battery and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06187962A (en) | 1992-12-18 | 1992-12-18 | Separator for alkaline battery and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06187962A true JPH06187962A (en) | 1994-07-08 |
Family
ID=18318957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP43A Pending JPH06187962A (en) | 1992-12-18 | 1992-12-18 | Separator for alkaline battery and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06187962A (en) |
-
1992
- 1992-12-18 JP JP43A patent/JPH06187962A/en active Pending
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