JPH01128351A - Manufacture of separator - Google Patents
Manufacture of separatorInfo
- Publication number
- JPH01128351A JPH01128351A JP62286231A JP28623187A JPH01128351A JP H01128351 A JPH01128351 A JP H01128351A JP 62286231 A JP62286231 A JP 62286231A JP 28623187 A JP28623187 A JP 28623187A JP H01128351 A JPH01128351 A JP H01128351A
- Authority
- JP
- Japan
- Prior art keywords
- graft
- acrylic acid
- meth
- separator
- water
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
Description
【発明の詳細な説明】
及」Ｌ反里匁里
本発明はセパレータの製造方法に関し、さらに詳しくは
、酸化銀電池などの電池内で銀イオンなどの陽極活物質
の透過阻止に優れた能力を発揮するようなセパレータの
製造方法に関する。[Detailed Description of the Invention] The present invention relates to a method for manufacturing a separator, and more specifically, to a method for manufacturing a separator that has excellent ability to block the permeation of anode active materials such as silver ions in a battery such as a silver oxide battery. This invention relates to a method for manufacturing a separator that exhibits the following properties.
の技Ｗ的背景ならびにその４題１、
一般に、電池用セパレータとしては、電気抵抗が小さく
均一であることが求められている。そこで従来、特公昭
５８−４６３号公報あるいは特開昭５５−１０５９６３
号公報などに記載されているように、電池用セパレータ
として、アクリル酸等の親水性モノマーをグラフト重合
したポリオレフィン膜が知られている。Technical Background and its 4 Problems 1 Generally, battery separators are required to have low and uniform electrical resistance. Therefore, conventionally, Japanese Patent Publication No. 58-463 or Japanese Patent Application Laid-Open No. 55-105963
As described in the above publications, polyolefin membranes in which hydrophilic monomers such as acrylic acid are graft-polymerized are known as battery separators.
ところが特公昭５８−４６３号公報あるいは特開昭５５
−１０５９６３号公報に開示されているような、ポリオ
レフィン膜にアクリル酸などの親水性モノマーをグラフ
ト重合させるセパレータの製造方法では、グラフト率を
高めるため、グラフト重合に非常に長い時間を必要とす
るという製造上の問題点があった。However, Japanese Patent Publication No. 58-463 or Japanese Unexamined Patent Publication No. 55
In the separator production method disclosed in Japanese Patent No. 105963, in which a hydrophilic monomer such as acrylic acid is graft-polymerized onto a polyolefin membrane, a very long time is required for the graft polymerization in order to increase the grafting ratio. There were manufacturing problems.
一方、特開昭５２−９６３２８号公報あるいは特開昭５
５−１２１２６７号公報などには、基材としてエチレン
−（メタ）アクリル酸共重合体を用い、これにアクリル
酸等をグラフト重合する電池用セパレータの製造方法が
開示されている。この電池用セパレータの製造方法では
、−旦フイルム状に成形したエチレン−（メタ）アクリ
ル酸共重合体に、放射線を照射して活性化させ、別のメ
タアクリル酸をグラフト重合している。このようにする
と、グラフト重合を行なう七ツマ−の低減化が図られ、
グラフト重合時間が短くなる。On the other hand, JP-A No. 52-96328 or JP-A No. 5
No. 5-121267 and the like disclose a method for producing a battery separator using an ethylene-(meth)acrylic acid copolymer as a base material and graft-polymerizing acrylic acid or the like onto the copolymer. In this method of manufacturing a battery separator, an ethylene-(meth)acrylic acid copolymer that has been formed into a film is activated by irradiation with radiation, and then another methacrylic acid is graft-polymerized. In this way, it is possible to reduce the number of 7mers that perform graft polymerization,
Graft polymerization time becomes shorter.
しかしながらこのようにして得られたグラフト膜は、電
池内の水酸化アルカリ電解液に接触すると膨潤し、寸法
変化をきたすという大きな問題点があった。もし電池用
セパレータにこのような寸法変化がめると、電池の組立
作業が困難となり、しかも使用中に電池内で漏液が起こ
り、電池の寿命が短くなるという問題点が生じてしまう
。However, the graft membrane thus obtained has a major problem in that it swells when it comes into contact with the alkaline hydroxide electrolyte in the battery, causing dimensional changes. If the battery separator undergoes such a dimensional change, it becomes difficult to assemble the battery, and moreover, liquid leaks within the battery during use, resulting in a shortened battery life.
このような問題点を解決するため、本出願人らは特願昭
６２−２２１４５５号において、エチレン−（メタ）ア
クリル酸共重合体膜を基材とし、このエチレン−（メタ
）アクリル酸共重合体膜に（メタ）アクリル酸をグラフ
ト重合した後、このグラフト膜がセパレータとして装着
されるアルカリ電池の電解液としての水酸化アルカリ水
溶液濃度をα重量％とした場合に、このグラフト膜をα
±５重量％の水酸化アルカリ水溶液で処理することを特
徴とするアルカリ電池用セパレータの製造方法を提案し
た。In order to solve these problems, the present applicants proposed a method using an ethylene-(meth)acrylic acid copolymer film as a base material in Japanese Patent Application No. 62-221455. After graft polymerizing (meth)acrylic acid to the combined membrane, if the concentration of alkali hydroxide aqueous solution as the electrolyte of an alkaline battery to which this graft membrane is installed as a separator is α% by weight, then this graft membrane is α
We proposed a method for manufacturing a separator for alkaline batteries, which is characterized by treatment with an aqueous alkali hydroxide solution of ±5% by weight.
本出願人が提案した上記アルカリ電池用セパレータの製
造方法によれば、電池内の水酸化アルカリ電解液に接触
すると膨潤し、寸法変化をきたすという問題点は解決さ
れる。しかしながら、上記特願昭６２−２２１４５５号
において提案されているアルカリ電池用セパレータの製
造方法によっても、溶解された銀イオンなどの陽極活物
質の透過を充分には阻止しえないことを見出し、鋭意検
討したところ、グラフト重合により得られたグラフト膜
を水、酸化アルカリ水溶液で中和処理した後、特定の水
溶性有機溶媒と水との混合液で洗浄すると、銀イオン粒
子の透過阻止に優れた能力を有するセパレータが１ｑら
れることを兄出し、本発明を完成させた。According to the method of manufacturing a separator for an alkaline battery proposed by the present applicant, the problem of swelling and dimensional change when it comes into contact with the alkaline hydroxide electrolyte in the battery can be solved. However, it was discovered that even the method for manufacturing a separator for alkaline batteries proposed in the above-mentioned Japanese Patent Application No. 62-221455 could not sufficiently prevent the permeation of anode active materials such as dissolved silver ions. As a result of our investigation, we found that if the graft membrane obtained by graft polymerization was neutralized with water or an aqueous alkali oxide solution and then washed with a mixture of a specific water-soluble organic solvent and water, it was excellent in blocking the permeation of silver ion particles. The present invention was completed by discovering that a separator with this ability can be produced in 1q.
発明の目的
本発明は、上記のような従来技術に伴う問題点を解決し
ようとするものであって、銀イオンなどの陽極活物質の
透過阻止を必要とするたとえば酸化銀電池などのような
電池内で、銀イオンなどの陽極活物質の透過阻止に優れ
た能力を発揮しうるようなセパレータの製造方法を提供
することを目的としている。Purpose of the Invention The present invention is intended to solve the problems associated with the prior art as described above, and is intended to solve the problems associated with the prior art as described above. The object of the present invention is to provide a method for producing a separator that can exhibit excellent ability to block the permeation of anode active materials such as silver ions.
発明の概要
本発明に係るセパレータの製造方法は、エチレン−（メ
タ）アクリル酸共重合体膜を基材とし、このエチレン−
（メタ）アクリル酸共重合体膜に（メタ）アクリル酸を
グラフト重合し、得られたグラフト膜を水酸化アルカリ
水溶液で中和し、水と水溶性有機溶媒との混合液で洗浄
することを特徴としている。Summary of the Invention The method for producing a separator according to the present invention uses an ethylene-(meth)acrylic acid copolymer film as a base material,
(meth)acrylic acid is graft-polymerized onto a (meth)acrylic acid copolymer film, the resulting graft film is neutralized with an aqueous alkali hydroxide solution, and then washed with a mixture of water and a water-soluble organic solvent. It is a feature.
本発明に係るセパレータの製造方法では、エチレン−（
メタ）アクリル酸共重合体膜を基材とし、このエチレン
−（メタ）アクリル酸共重合体膜に（メタ）アクリル酸
をグラフト重合し、得られたグラフト膜を水酸化アルカ
リ水溶液で中和し、水と水溶性有機溶媒との混合液で洗
浄しているため、たとえば酸化銀電池などのような電池
内で、銀イオンなど陽極活物質の透過阻止に優れた能力
を発揮するようなセパレータが得られる。In the method for manufacturing a separator according to the present invention, ethylene-(
Using a meth)acrylic acid copolymer film as a base material, (meth)acrylic acid is graft-polymerized onto this ethylene-(meth)acrylic acid copolymer film, and the resulting graft film is neutralized with an aqueous alkali hydroxide solution. Because it is cleaned with a mixture of water and a water-soluble organic solvent, it can be used as a separator that exhibits excellent ability to block the permeation of anode active materials such as silver ions in batteries such as silver oxide batteries. can get.
及用五且隻煎碧ｊ
以下本発明に係る電池用セパレータの製造方法について
具体的に説明する。The method for manufacturing a battery separator according to the present invention will be specifically described below.
本発明では、エチレン−（メタ）アクリル酸共重合体膜
を基材フィルムとして用いている。基材フィルムとして
のエチレン−（メタ）アクリル酸共重合体膜は、その膜
厚変動が平均膜厚値に対し、±８％以内にあることが好
ましい。このようなエチレン−（メタ）アクリル酸共重
合体膜は（メタ）アクリル酸含量が３〜１２重但％であ
るエチレン−（メタ）アクリル酸共重合体から得ること
ができる。エチレン−（メタ）アクリル酸共重合体の（
メタ）アクリル酸含量が３〜１２重量％であると、この
共重合体はメルトインデックスが小さくなり、均一な膜
厚を有するフィルムを容易に成形することができるよう
になる。もし膜厚変動が平均膜厚値に対し、±、８％を
超えるような不均一な基材を用い、この膜厚不均一な基
材フィルムに（メタ）アクリル酸をグラフト重合すると
、グラフト率をむらが生じ、均一な膜抵抗値を有するア
ルカリ電池用セパレータを得ることができないため好ま
しくない。In the present invention, an ethylene-(meth)acrylic acid copolymer film is used as the base film. The ethylene-(meth)acrylic acid copolymer film used as the base film preferably has a variation in film thickness within ±8% with respect to the average film thickness value. Such an ethylene-(meth)acrylic acid copolymer film can be obtained from an ethylene-(meth)acrylic acid copolymer having a (meth)acrylic acid content of 3 to 12% by weight. Ethylene-(meth)acrylic acid copolymer (
When the meth)acrylic acid content is 3 to 12% by weight, the copolymer has a small melt index and can be easily formed into a film having a uniform thickness. If a non-uniform base material with film thickness variation exceeding ±8% of the average film thickness value is used, and (meth)acrylic acid is graft-polymerized onto this base film with non-uniform film thickness, the grafting rate This is not preferable because it causes unevenness and makes it impossible to obtain a separator for alkaline batteries having a uniform membrane resistance value.
本発明で用いられる（メタ）アクリル酸共重合体膜は、
１０〜１００μｍ好ましくは２０〜４０μｍ程度の膜厚
を有していることが好ましい。The (meth)acrylic acid copolymer membrane used in the present invention is
It is preferable to have a film thickness of about 10 to 100 μm, preferably about 20 to 40 μm.
基材としてのエチレン−（メタ）アクリル酸共重合体膜
に（メタ）アクリル酸をグラフト重合するには、エチレ
ン−（メタ）アクリル酸共重合体膜に１〜３０Ｍｒａｄ
の電子線を照射した俊、充分に脱気された１０〜５０重
量％アクリル酸水溶液中に、電子線照射されたエチレン
−（メタ）アクリル酸共重合体を４０’Ｃで５〜６０分
間浸漬すればよい。In order to graft-polymerize (meth)acrylic acid onto an ethylene-(meth)acrylic acid copolymer film as a base material, 1 to 30 Mrad is added to the ethylene-(meth)acrylic acid copolymer film.
The ethylene-(meth)acrylic acid copolymer irradiated with the electron beam was immersed in a sufficiently degassed 10-50% by weight aqueous acrylic acid solution at 40'C for 5-60 minutes. do it.
次にこのようにして得られたエチレン−（メタ）アクリ
ル酸共重合体のグラフト膜を水酸化アルカリ水溶液で中
和処理するが、この処理はセパレータとして装着される
アルカリ電池の電解液としての水酸化アルカリ水溶液濃
度をα重量％とした場合にα±５重但％以内のアルカリ
水溶液に、上記で得られた（メタ）アクリル酸をグラフ
ト膜を浸漬することにより行なうことができる。このよ
うなグラフト膜を中和処理するための水酸化アルカリ水
溶液としては、装着される電池電解液としての水酸化カ
リウムの濃度が４０重間％でおる場合には、好ましくは
４０±５重量％の水酸化カリウム溶液を用いることが望
ましい。グラフト膜のアルカリ水溶液による中和処理は
、室温から７０℃までの温度で、１０〜６０分間行なう
ことが好ましい。Next, the graft membrane of the ethylene-(meth)acrylic acid copolymer obtained in this way is neutralized with an aqueous alkali hydroxide solution. This can be carried out by immersing the grafted membrane with the (meth)acrylic acid obtained above in an alkaline aqueous solution having a concentration of α±5% by weight, where the concentration of the alkali oxide aqueous solution is α% by weight. The aqueous alkali hydroxide solution for neutralizing such a graft membrane is preferably 40±5% by weight when the concentration of potassium hydroxide as the electrolyte for the battery to be installed is 40% by weight. It is preferable to use a potassium hydroxide solution. The neutralization treatment of the graft membrane with an alkaline aqueous solution is preferably carried out at a temperature from room temperature to 70° C. for 10 to 60 minutes.
次に、このようにして水酸化アルカリ水溶液により中和
処理されたグラフト膜を、水と水溶性有機溶媒との混合
液で洗浄する。このような水溶性有機溶媒としては、ア
ルコール系、ケトン系およびカルボン酸系などの有機溶
媒を挙げることができる。これらの有機溶媒の中でもメ
タノール、エタノール、エチレングリコールなどのアル
コール系有機溶媒およびアセトンなどのケトン系有機溶
媒が好ましい。このような有機溶媒は、単独でおるいは
２種以上混合して用いられるが、特にエチレングリコー
ルとメタノールと水との混合液が好ましい。Next, the graft membrane thus neutralized with the aqueous alkali hydroxide solution is washed with a mixed solution of water and a water-soluble organic solvent. Examples of such water-soluble organic solvents include alcohol-based, ketone-based, and carboxylic acid-based organic solvents. Among these organic solvents, alcohol-based organic solvents such as methanol, ethanol, and ethylene glycol, and ketone-based organic solvents such as acetone are preferred. Such organic solvents may be used alone or in combination of two or more, and a mixture of ethylene glycol, methanol, and water is particularly preferred.
本発明で用いられる水溶性有機溶媒は、２０’Ｃにおけ
る水に対する溶解鮮度が１体積％以上、好ましくは１０
体積％以上、より好ましくは２０体積％以上であること
が望ましく、特に完全相溶性の有機溶媒であることが望
ましい。The water-soluble organic solvent used in the present invention has a freshness of solubility in water at 20'C of 1% by volume or more, preferably 10% by volume or more.
It is desirable that the amount is at least 20% by volume, more preferably at least 20% by volume, and it is particularly desirable that the organic solvent be completely compatible with the organic solvent.
本発明で用いられる水と水溶性有機溶媒との混合物にお
ける水と水溶性有機溶媒との混合比は、重量比で５：９
５〜９５：５、好ましくは２０：８０〜８０：２０．特
に好ましくは３０ ： ７０〜７０：３０であることが
望ましい。The mixing ratio of water and water-soluble organic solvent in the mixture of water and water-soluble organic solvent used in the present invention is 5:9 by weight.
5-95:5, preferably 20:80-80:20. Particularly preferably, the ratio is 30:70 to 70:30.
上記のような水と水溶性有機溶媒との混合液によりグラ
フト膜を洗浄する際の洗浄温度は５〜７０℃、好ましく
は室温以上、５０℃未満が望ましい。洗浄時間は１〜６
０分間、好ましくは２〜５分間が望ましい。The cleaning temperature when cleaning the graft membrane with the above-mentioned mixture of water and a water-soluble organic solvent is preferably 5 to 70°C, preferably room temperature or higher and lower than 50°C. Washing time is 1-6
0 minutes, preferably 2 to 5 minutes.
上記のような水と水溶性有機溶媒との混合液によりグラ
フト膜を洗浄するには、たとえば該グラフト膜を上記の
ような混合液に浸漬すればよい。In order to wash the graft membrane with the mixture of water and a water-soluble organic solvent as described above, for example, the graft membrane may be immersed in the mixture as described above.
発明の効果
本発明に係るセパレータの製造方法では、エチレン−（
メタ）アクリル酸共重合体膜を基材とし、このエチレン
−（メタ）アクリル酸共重合体膜に（メタ）アクリル酸
をグラフト重合し、得られたグラフト膜を水酸化アルカ
リ水溶液で中和し、次いで水と水溶性有機溶媒との混合
液で洗浄しているため、銀イオンなどの陽極活物質の透
過を阻止しつるような電池用セパレータが得られ、セパ
レータ自体の寿命が延びるとともにこの電池用セパレー
タが装着された電池の寿命も延びる。Effects of the Invention In the method for manufacturing a separator according to the present invention, ethylene-(
Using a meth)acrylic acid copolymer film as a base material, (meth)acrylic acid is graft-polymerized onto this ethylene-(meth)acrylic acid copolymer film, and the resulting graft film is neutralized with an aqueous alkali hydroxide solution. This is then washed with a mixture of water and a water-soluble organic solvent, resulting in a durable battery separator that blocks the permeation of positive electrode active materials such as silver ions, extending the life of the separator itself, and improving battery life. The lifespan of batteries equipped with separators will also be extended.
以下本発明を実施例により説明するが、本発明はこれら
実施例に限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
メタアクリル酸含旦が８．５重足％であり、膜厚が３０
±２μｍでおるエチレン−メタアクリル酸共重合体膜に
、電子線照射装置を用いて１０Ｍ ｒａｄ、の電子線を
窒素雰囲気下で冷却しながら照射した。ついで電子線の
照射されたこのエチレン−メタアクリル酸共重合体膜を
、予め充分に脱気され、モール塩が０．２５’ｆｆ１ｆ
ｆ１％添加された４０℃の３５重量％アクリル酸水溶液
中に、１０分間浸漬してグラフト重合させ、グラフト膜
を得た。Example 1 Methacrylic acid content is 8.5%, film thickness is 30%
An ethylene-methacrylic acid copolymer film having a thickness of ±2 μm was irradiated with an electron beam of 10 M rad using an electron beam irradiation device while being cooled under a nitrogen atmosphere. Next, this ethylene-methacrylic acid copolymer film irradiated with an electron beam was thoroughly degassed in advance, and Mohr's salt was added to 0.25'ff1f.
Graft polymerization was carried out by immersion in a 35% by weight aqueous acrylic acid solution at 40° C. to which f1% was added for 10 minutes to obtain a grafted film.
得られたグラフト膜のグラフト率は５７％であった。The grafting rate of the obtained graft membrane was 57%.
次にこのようにアクリル酸水溶液に浸漬して得られたグ
ラフト膜（Ｉ＞を、４０％ＫＯＨ水溶液に７０℃の温度
で６０分間浸漬して中和処理し、次いでエチレングリコ
ールとメタノールと水との混合比が１：５：４である水
溶液を用い、室温で３０分間洗浄し、次いで乾燥し、セ
パレータ（Ｉ）を得た。Next, the graft membrane (I) obtained by immersing it in an acrylic acid aqueous solution was neutralized by immersing it in a 40% KOH aqueous solution at a temperature of 70°C for 60 minutes, and then it was soaked in ethylene glycol, methanol, and water. Using an aqueous solution having a mixing ratio of 1:5:4, the product was washed at room temperature for 30 minutes, and then dried to obtain a separator (I).
次に、セパレータ（Ｉ）を酸化亜鉛ＺｎＯ，飽和の３０
％ＫＯＨ水溶液に含浸してセパレータ（ｎ）を得た。次
いでセパレータ（Ｉ＞とセパレータ（■）７枚とを、セ
パレータ（Ｉ＞が最上部にくるように積層してセパレー
タ積層体を得た。Next, the separator (I) was made of zinc oxide ZnO, saturated at 30%
% KOH aqueous solution to obtain a separator (n). Next, the separator (I>) and seven separators (■) were stacked so that the separator (I> was on the top) to obtain a separator laminate.
このセパレータ積層体を第１図に示すような銀透過試験
セルに装着して、各セパレータを透過した銀イオンの量
を調べた。This separator laminate was installed in a silver permeation test cell as shown in FIG. 1, and the amount of silver ions permeated through each separator was examined.
なお第１図に示す銀透過試験セルにおいて、１はガラス
板であり、２はセパレータ積層体であり、３は壁面であ
り、４はシール部材であり、５はＡｇ２Ｏであり、６は
３０％水酸化カリウム水溶液であり、７は空気抜きであ
る。In the silver permeation test cell shown in FIG. 1, 1 is a glass plate, 2 is a separator laminate, 3 is a wall surface, 4 is a sealing member, 5 is Ag2O, and 6 is 30% It is a potassium hydroxide aqueous solution, and 7 is an air vent.
このようにして形成した銀透過試験セルを７０°Ｃで２
４時間静置した（麦、セパレータ積層体２を取り出し、
各セパレータにおける銀の浸透状態を観察したところ、
１枚目だけ銀が浸透していたが２〜８枚目には銀は認め
られなかった。The silver permeation test cell thus formed was heated at 70°C for 2 hours.
Leave it to stand for 4 hours (wheat, remove the separator laminate 2,
When we observed the state of silver penetration in each separator, we found that
Silver had penetrated into only the first sheet, but no silver was observed in the second to eighth sheets.
また各セパレータの銀の保持足をＩＣＰ発光分析で調べ
たところ、１枚目７１３５μび、２枚目３３μび、３枚
目７μ９の銀が検知され、４枚目以俊には、銀が検知さ
れなかった。In addition, when the silver holding feet of each separator were examined by ICP emission analysis, 7135μ of silver was detected in the first sheet, 33μ in the second sheet, 7μ9 in the third sheet, and silver was detected in the fourth sheet. It wasn't done.
ル校■ユ
実施例１で得られたグラフト膜を純粋で水洗した後、乾
燥してセパレータ（ＩＩＩ）を得た。このセパレータ（
ｎｌ）に実施例１と同様の試験を施したところ、銀は７
枚目まで観察された。The graft membrane obtained in Example 1 was washed with pure water and dried to obtain a separator (III). This separator (
nl) was subjected to the same test as in Example 1, and silver was 7
Observed up to the first page.
また実施例１と同様に各セパレータの銀の保持量を調べ
たところ、１枚目２３２μ７．２枚目７５μｙ、３枚目
４３μ９．４枚目６７μ９．５枚目２７μ３．６枚目２
０μ９．７枚目２４μり、８枚目２０μ９の銀が検知さ
れた。Similarly to Example 1, we investigated the amount of silver retained in each separator, and found that the first sheet was 232μ7. The second sheet was 75μy, the third sheet was 43μ9.
0μ9.24μ of silver was detected on the 7th sheet, and 20μ9 of silver was detected on the 8th sheet.
第１図は実施例において、銀透過試験に用いた銀透過試
験用セルの断面図である。
１・・・ガラス板 ２・・・セパレータ積層体３・
・・壁面
代理人 弁理士 鈴 木 俊一部
第 １ 図FIG. 1 is a cross-sectional view of a silver permeation test cell used in the silver permeation test in Examples. 1...Glass plate 2...Separator laminate 3.
...Wall Representative Patent Attorney Shunichi Suzuki Figure 1
Claims (1)
、このエチレン−（メタ）アクリル酸共重合体膜に（メ
タ）アクリル酸をグラフト重合し、得られたグラフト膜
を水酸化アルカリ水溶液で中和し、次いで水と水溶性有
機溶媒との混合液で洗浄することを特徴とするセパレー
タの製造方法。Using an ethylene-(meth)acrylic acid copolymer film as a base material, (meth)acrylic acid is graft-polymerized onto this ethylene-(meth)acrylic acid copolymer film, and the resulting graft film is treated with an aqueous alkali hydroxide solution. A method for producing a separator, which comprises neutralizing and then washing with a mixed solution of water and a water-soluble organic solvent.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62286231A JP2539860B2 (en) | 1987-11-12 | 1987-11-12 | Method for producing separator for alkaline battery having excellent performance of inhibiting silver ion permeation of anode active material |
| EP88308105A EP0306310A1 (en) | 1987-09-04 | 1988-09-01 | Process for preparing battery separators |
| KR1019880011370A KR890005183A (en) | 1987-09-04 | 1988-09-03 | How to make a stand diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62286231A JP2539860B2 (en) | 1987-11-12 | 1987-11-12 | Method for producing separator for alkaline battery having excellent performance of inhibiting silver ion permeation of anode active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01128351A true JPH01128351A (en) | 1989-05-22 |
| JP2539860B2 JP2539860B2 (en) | 1996-10-02 |
Family
ID=17701670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62286231A Expired - Lifetime JP2539860B2 (en) | 1987-09-04 | 1987-11-12 | Method for producing separator for alkaline battery having excellent performance of inhibiting silver ion permeation of anode active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2539860B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294558A (en) * | 2001-03-30 | 2002-10-09 | Japan Vilene Co Ltd | Ion-exchangeable fiber sheet and method for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55105966A (en) * | 1979-02-05 | 1980-08-14 | Japan Atom Energy Res Inst | Manufacturing method of diaphragm for cell having high dimensional stability |
| JPS55121267A (en) * | 1979-03-12 | 1980-09-18 | Matsushita Electric Ind Co Ltd | Manufacturing method of separator for battery |
-
1987
- 1987-11-12 JP JP62286231A patent/JP2539860B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55105966A (en) * | 1979-02-05 | 1980-08-14 | Japan Atom Energy Res Inst | Manufacturing method of diaphragm for cell having high dimensional stability |
| JPS55121267A (en) * | 1979-03-12 | 1980-09-18 | Matsushita Electric Ind Co Ltd | Manufacturing method of separator for battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294558A (en) * | 2001-03-30 | 2002-10-09 | Japan Vilene Co Ltd | Ion-exchangeable fiber sheet and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2539860B2 (en) | 1996-10-02 |
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