JPH06163020A - Alkaline battery separator and manufacture thereof - Google Patents
Alkaline battery separator and manufacture thereofInfo
- Publication number
- JPH06163020A JPH06163020A JP43A JP30683692A JPH06163020A JP H06163020 A JPH06163020 A JP H06163020A JP 43 A JP43 A JP 43A JP 30683692 A JP30683692 A JP 30683692A JP H06163020 A JPH06163020 A JP H06163020A
- Authority
- JP
- Japan
- Prior art keywords
- nbr
- melamine
- separator
- nonwoven fabric
- resin
- 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]
【産業上の利用分野】本発明はＮｉ−Ｃｄ，Ｎｉ−Ｚ
ｎ，Ｎｉ−Ｈ電池等のアルカリ二次電池の高濃度アルカ
リ電解液に対し、優れた耐久性を有し、さらに吸液，保
液性能を増大させたアルカリ電池用セパレータおよびそ
の製造方法に関する。The present invention relates to Ni-Cd and Ni-Z.
TECHNICAL FIELD The present invention relates to an alkaline battery separator having excellent durability with respect to a high-concentration alkaline electrolyte of an alkaline secondary battery such as an n, Ni—H battery and further having enhanced liquid absorbing and retaining properties, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来からアルカリ二次電池用セパレータ
に要求される特性として、電解液との親和性が良く、吸
液速度，保液性に優れる事、長期間の充放電の繰返し使
用に耐え得る耐アルカリ性，耐酸化性等の化学的安定性
に優れる事、内部抵抗が小さく、電極から発生するガス
の通過を妨げない通気性に優れる事等、種々の性能が要
求されている。2. Description of the Related Art Conventionally, alkaline secondary battery separators have been required to have a good affinity with an electrolytic solution, an excellent liquid absorption rate, and a good liquid retention property, and can withstand repeated use for a long period of charge and discharge. Various performances are required, such as excellent chemical stability such as alkali resistance and oxidation resistance to be obtained, low internal resistance, and excellent air permeability that does not prevent passage of gas generated from the electrode.
【０００３】また、アルカリ二次電池用セパレータとし
ては従来よりポリアミド繊維の熱接着による不織布や、
ポリオレフィン系繊維の熱接着による不織布が用いられ
て来た。Further, as a separator for an alkaline secondary battery, a non-woven fabric made by heat-bonding polyamide fibers has been conventionally used,
Non-woven fabrics have been used that are the thermal bonding of polyolefin fibers.
【０００４】[0004]
【発明が解決しようとする課題】上記ポリアミド繊維か
らなる不織布は親水性に優れる為、電解液の吸液性，保
液性が高く、アルカリ電池用セパレータとして多用され
ているが、長期間の充放電の繰返し使用における化学的
耐久性に劣るという欠点があった。一方、高温度域にお
ける耐アルカリ性，耐酸化性等の化学的安定性に優れた
ポリプロピレン繊維、ポリエチレン繊維等のポリオレフ
ィン系繊維を用いた不織布から成るアルカリ電池用セパ
レータが種々提案されているが、オレフィン系繊維は親
水性に劣る為電解液保持性が極めて悪く、電解液がドラ
イアウトし易く急速充電，高率放電用途では使用出来な
いという欠点があった。Since the non-woven fabric made of the above polyamide fiber is excellent in hydrophilicity, it has a high liquid absorbing property and liquid retaining property for the electrolytic solution and is widely used as a separator for alkaline batteries, but it can be charged for a long period of time. It has a drawback that it is inferior in chemical durability in repeated use of electric discharge. On the other hand, various alkaline battery separators made of non-woven fabric using polyolefin fibers such as polypropylene fiber and polyethylene fiber, which have excellent chemical stability such as alkali resistance and oxidation resistance in a high temperature range, have been proposed. Since the system fibers are inferior in hydrophilicity, the electrolyte retention is extremely poor, and the electrolyte is liable to dry out and cannot be used for rapid charge and high rate discharge applications.
【０００５】このため、従来からかかるポリオレフィン
系繊維に親水性を持たせるために、界面活性剤にて処理
する方法、繊維表面を発泡させる等凹凸を形成して表面
積を増大させる方法、プラズマ処理等により繊維表面を
活性化して電解液との親和性を向上させる方法、電子線
照射法により繊維表面に親水性モノマーをグラフト重合
させる方法、親水性を有するビニルアルコール等をオレ
フィンと共重合させた素材を適用する方法、スルホン化
処理等化学的後処理法により親水基を導入する方法等が
提案，検討されているが、いずれも長期間にわたる安定
な親水性を付与し、かつ連続して安定なものを得る事が
困難であるという問題があった。Therefore, conventionally, in order to impart hydrophilicity to such polyolefin fibers, a method of treating with a surfactant, a method of forming irregularities such as foaming of the fiber surface to increase the surface area, plasma treatment, etc. The method of activating the fiber surface by means of improving the affinity with the electrolytic solution, the method of graft-polymerizing a hydrophilic monomer on the fiber surface by the electron beam irradiation method, the material in which hydrophilic vinyl alcohol or the like is copolymerized with an olefin Has been proposed and studied, but a method of introducing a hydrophilic group by a chemical post-treatment method such as sulfonation treatment has been proposed. There was a problem that it was difficult to get things.
【０００６】したがって本発明の目的は、アルカリ電解
液との親和性に優れるとともに長期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および
その製造方法を提供することである。Therefore, an object of the present invention is to provide an alkaline battery separator which has excellent affinity with an alkaline electrolyte and is stable even after repeated charging and discharging for a long period of time, and a method for producing the same.
【０００７】[0007]
【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ＮＢＲ（アクリロニトリル−ブタ
ジエン共重合ラバー）−メラミン架橋樹脂が、カルボキ
シル基およびスルホン酸基を有してなるものである。SUMMARY OF THE INVENTION According to the present invention, a NBR (acrylonitrile-butadiene copolymer rubber) -melamine cross-linking resin attached to at least a part of a fiber intersection and a fiber surface of a non-woven sheet made of chemically resistant fiber is a carboxyl group. It has a group and a sulfonic acid group.
【０００８】本発明における耐薬品性繊維とは、ポリア
ミド繊維，ポリプロピレン（ＰＰ），ポリエチレン（Ｐ
Ｅ）等のポリオレフィン系繊維をいうが、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 fiber in the present invention means polyamide fiber, polypropylene (PP), polyethylene (P
E) and other polyolefin fibers are used, and these fibers may be used alone or in combination of two or more. Further, these fibers may be appropriately mixed and used as, for example, a composite fiber having a core-sheath structure or the like.
【０００９】本発明に用いるＮＢＲ−メラミン架橋樹脂
とは、ＮＢＲ樹脂にトリメチロールメラミン，ヘキサメ
チロールメラミン，メトキシ化トリメチロールメラミン
等のメラミン系樹脂を架橋し、耐水性，耐薬品性を向上
させたものをいう。上記ＮＢＲ−メラミン架橋樹脂は、
ディッピング，コーティング，発泡コーティング等の手
法により、不織布シートに被覆する事が可能であり、特
に限定されるものではないが、良好なる電解液親和性及
び浸透性，保液性を付与する為には発泡コーティング法
による事が特に好ましい。The NBR-melamine crosslinked resin used in the present invention is a NBR resin crosslinked with a melamine resin such as trimethylolmelamine, hexamethylolmelamine and methoxylated trimethylolmelamine to improve water resistance and chemical resistance. Say something. The NBR-melamine crosslinked resin is
The non-woven fabric sheet can be coated by a technique such as dipping, coating, or foam coating, and is not particularly limited, but in order to impart good electrolytic solution affinity, penetrability, and liquid retention. The foam coating method is particularly preferable.
【００１０】また本発明は、耐薬品性繊維に対するＮＢ
Ｒ−メラミン架橋樹脂の付着割合が３〜５０重量％であ
ることを特徴とする。The present invention also relates to NB for chemically resistant fibers.
The R-melamine crosslinked resin is characterized by having an adhesion ratio of 3 to 50% by weight.
【００１１】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。If the adhesion ratio is less than 3% by weight, the affinity with the electrolytic solution is not improved, and if it exceeds 50% by weight, the air permeability required for the alkaline battery separator is impaired.
【００１２】ところで、上記ＮＢＲ−メラミン架橋樹脂
は、アクリロニトリルの含有量が多い程、親水性，耐薬
品性に安定なものとなる反面、樹脂が硬化して脆い性質
となる。このため、カルボキシル基導入時の加水分解の
後の強度低下をきたすことから、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１０重量％未満になると、親水性，耐薬品性の低
下が著しいため、１０重量％以上であることが望まし
い。By the way, the NBR-melamine crosslinked resin becomes more stable in hydrophilicity and chemical resistance as the content of acrylonitrile increases, but on the other hand, the resin hardens and becomes brittle. Therefore, the strength is lowered after the hydrolysis when the carboxyl group is introduced, and therefore the content is preferably 50% by weight or less. Further, when the content of acrylonitrile is less than 10% by weight, hydrophilicity and chemical resistance are remarkably deteriorated, so that the content is preferably 10% by weight or more.
【００１３】また本発明は、耐薬品性繊維から成る不織
布シートに、ＮＢＲ−メラミン架橋樹脂を含む結合剤を
付着させた後、加水分解処理，スルホン化処理をこの順
序で行なうものである。Further, according to the present invention, a binder containing an NBR-melamine cross-linking resin is adhered to a non-woven fabric sheet made of chemical resistant fibers, and then hydrolysis treatment and sulfonation treatment are carried out in this order.
【００１４】上記加水分解処理とは、ＮＢＲ−メラミン
架橋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、ＮＢＲ−メラミン
架橋樹脂にカルボキシル基が導入される。The above-mentioned hydrolysis treatment means that the nitrile group (-CN) in the NBR-melamine crosslinked resin is hydrolyzed by an alkali treatment or the like, which is a carboxyl group (-).
COOH). This reaction proceeds in two steps as shown in the following general formula, and a carboxyl group is introduced into the NBR-melamine crosslinked resin.
【００１５】[0015]
【化１】 [Chemical 1]
【００１６】また、上記スルホン化処理とは、ＳＯ3 ガ
ス、発煙硫酸、高濃度の濃硫酸等による公知の方法で行
なうものであり、下記に示すように、加水分解処理され
たＮＢＲ−メラミン架橋樹脂のカルボキシル基が結合し
た３級炭素原子に、親水基であるスルホン酸基（−ＳＯ
3 Ｈ）が導入される。The above-mentioned sulfonation treatment is carried out by a known method using SO 3 gas, fuming sulfuric acid, concentrated sulfuric acid having a high concentration and the like. As shown below, hydrolysis-treated NBR-melamine cross-linking is carried out. At the tertiary carbon atom to which the carboxyl group of the resin is bound, a sulfonic acid group (-SO
3 H) is introduced.
【００１７】[0017]
【化２】 [Chemical 2]
【００１８】[0018]
【作用】本発明に従えば、親水性を有するカルボキシル
基およびスルホン酸基が導入されたＮＢＲ−メラミン架
橋樹脂によって、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 NBR-melamine cross-linking resin into which hydrophilic carboxyl groups and sulfonic acid groups have been introduced makes the non-woven sheet excellent in hydrophilicity, and thereby has a long-term affinity with the electrolyte solution. Thus, it is possible to obtain an alkaline battery separator that has excellent liquid retention properties and is stable even after repeated charging and discharging for 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。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００２０】（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×３８ｍｍ）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０．２０ｍ
ｍの不織布シートＡを得た。(Example) A core-sheath type heat-adhesive fiber having a core of polypropylene and a sheath of polyethylene (0.
9d × 38mm) 30% and regular polypropylene fiber (1.5d × 38mm) 70% of a mixed fiber web is thermocompression bonded by a pair of calender rolls heated to 130 ° C., and a basis weight of 65 g / m 2 , 0.20m thick
A non-woven fabric sheet A having m.
【００２１】次に、アクリロニトリルの含有量が３５重
量％であるＮＢＲ樹脂１００重量部に対し、トリメチロ
ールメラミン３５重量部及びアミン系の硬化触媒３重量
部を配合した結合材を、発泡コーティング法により上記
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７１ｇ／ｍ2 の不織布シートＢを形成した。Next, 100 parts by weight of an NBR resin having an acrylonitrile content of 35% by weight was mixed with 35 parts by weight of trimethylolmelamine and 3 parts by weight of an amine-based curing catalyst to prepare a binder, which was subjected to a foam coating method. The nonwoven fabric sheet A was uniformly impregnated, dried and heat-treated to form a nonwoven fabric sheet B having a basis weight of 71 g / m 2 .
【００２２】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
し、その後洗浄処理を実施した後乾燥して、引続き該不
織布シートをＳＯ3 ガス濃度が８Ｖｏｌ％、温度６０℃
のガス雰囲気中で３０秒間の気層接触処理を行なった
後、水洗，希アンモニア水による中和処理を経て、さら
に十分に洗浄後乾燥して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.
The solution was hydrolyzed in the solution at 95 ° C. for 30 minutes, then washed and then dried, and then the nonwoven fabric sheet had an SO 3 gas concentration of 8 Vol% and a temperature of 60 ° C.
After performing the vapor layer contact treatment for 30 seconds in the gas atmosphere of No. 3, it was washed with water, neutralized with dilute ammonia water, washed sufficiently and dried to obtain an alkaline battery separator of this example.
【００２３】（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.
【００２４】（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 of Comparative Example 2.
【００２５】（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８０ｇ／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. 80 g / m 2 of a basis weight obtained by heat-pressing a web composed of the mixed fiber 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.
【００２６】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.
【００２７】[0027]
【表１】 [Table 1]
【００２８】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。 耐酸化性試験後強度保持率；５％ＫＭｎＯ4 溶液２５０
ｍｌ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力
保持率。The test methods for the test items in the table 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 rate after oxidation resistance test; 5% KMnO 4 solution 250
The tensile strength retention of the separator after immersion in a mixed solution of 50 ml of a caustic potash solution having a specific gravity of 1.30 at 50 ° C. for 1 hour.
【００２９】上記表１より明らかなように、本実施例に
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。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用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。As is clear from Table 1 above, the separator according to the present embodiment exhibits excellent affinity for the electrolytic solution, and has a liquid absorbing property and a liquid retaining property comparable to those of the separator using the nylon fiber of Comparative Example 3. Things are revealed. Also, it has good durability in alkali resistance and oxidation resistance, and the alkaline battery separator according to the present embodiment is incorporated in a battery.
It shows that it can withstand long-term use even after repeated charging and discharging.
【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ＮＢ
Ｒ（アクリロニトリル−ブタジエン共重合ラバー）−メ
ラミン架橋樹脂が、カルボキシル基およびスルホン酸基
を有してなることを特徴とするアルカリ電池用セパレー
タ。1. An NB attached to at least a part of a fiber intersection and a fiber surface of a non-woven sheet made of chemically resistant fiber.
An R- (acrylonitrile-butadiene copolymer rubber) -melamine cross-linked resin having a carboxyl group and a sulfonic acid group, an alkaline battery separator.
基およびスルホン酸基を有するＮＢＲ−メラミン架橋樹
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 alkaline battery separator according to claim 1, wherein an adhesion ratio of the NBR-melamine crosslinked resin having a carboxyl group and a sulfonic acid group to the chemical resistant fiber is 3 to 50% by weight.
ＢＲ−メラミン架橋樹脂を含む結合剤を付着させた後、
加水分解処理、スルホン化処理をこの順序で行なうこと
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 chemically resistant fiber is made of N.
After applying the binder containing the BR-melamine cross-linked resin,
A method for manufacturing an alkaline battery separator, which comprises performing a hydrolysis treatment and a sulfonation treatment in this order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30683692A JP3160655B2 (en) | 1992-11-17 | 1992-11-17 | Alkaline battery separator and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30683692A JP3160655B2 (en) | 1992-11-17 | 1992-11-17 | Alkaline battery separator and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06163020A true JPH06163020A (en) | 1994-06-10 |
| JP3160655B2 JP3160655B2 (en) | 2001-04-25 |
Family
ID=17961845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30683692A Expired - Fee Related JP3160655B2 (en) | 1992-11-17 | 1992-11-17 | Alkaline battery separator and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3160655B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065092A1 (en) * | 1998-06-09 | 1999-12-16 | Nippon Sheet Glass Co., Ltd. | Separator for enclosed cell |
| EP1286372A1 (en) * | 2001-01-22 | 2003-02-26 | Sony Corporation | Flood electric switch and method for preparation thereof |
| CN113161549A (en) * | 2021-03-25 | 2021-07-23 | 万向一二三股份公司 | Photo-crosslinking binder system, slurry composition containing photo-crosslinking binder system and application of slurry composition |
-
1992
- 1992-11-17 JP JP30683692A patent/JP3160655B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999065092A1 (en) * | 1998-06-09 | 1999-12-16 | Nippon Sheet Glass Co., Ltd. | Separator for enclosed cell |
| GB2353896B (en) * | 1998-06-09 | 2002-01-16 | Nippon Sheet Glass Co Ltd | Separator for sealed cell |
| US6528205B1 (en) | 1998-06-09 | 2003-03-04 | Yuasa Corporation | Non-woven fabric separator for sealed electrolytic cells |
| EP1286372A1 (en) * | 2001-01-22 | 2003-02-26 | Sony Corporation | Flood electric switch and method for preparation thereof |
| EP1286372A4 (en) * | 2001-01-22 | 2003-06-11 | Sony Corp | Flood electric switch and method for preparation thereof |
| CN113161549A (en) * | 2021-03-25 | 2021-07-23 | 万向一二三股份公司 | Photo-crosslinking binder system, slurry composition containing photo-crosslinking binder system and application of slurry composition |
| CN113161549B (en) * | 2021-03-25 | 2022-08-02 | 万向一二三股份公司 | Photo-crosslinking binder system, slurry composition containing photo-crosslinking binder system and application of slurry composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3160655B2 (en) | 2001-04-25 |
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