JPH06231746A - Separator paper for alkaline dry battery - Google Patents
Separator paper for alkaline dry batteryInfo
- Publication number
- JPH06231746A JPH06231746A JP5041841A JP4184193A JPH06231746A JP H06231746 A JPH06231746 A JP H06231746A JP 5041841 A JP5041841 A JP 5041841A JP 4184193 A JP4184193 A JP 4184193A JP H06231746 A JPH06231746 A JP H06231746A
- Authority
- JP
- Japan
- Prior art keywords
- separator paper
- fiber
- weight
- paper
- organic solvent
- 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
Landscapes
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルカリマンガン乾電池
等の各種アルカリ電池における陽極活物質と陰極活物質
とを隔離するために用いるセパレータ紙に関し、特には
内部短絡を防止するとともに、セパレータ紙に要求され
る耐アルカリ性、緻密性、保液性、電気特性等の諸特性
を高いレベルで同時に充足するセパレータ紙に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a separator paper used to separate an anode active material and a cathode active material in various alkaline batteries such as alkaline manganese dry batteries, and particularly to prevent an internal short circuit and require separator paper. The present invention relates to a separator paper which simultaneously satisfies various characteristics such as alkali resistance, denseness, liquid retention, and electrical characteristics at a high level.
【０００２】[0002]
【従来の技術】通常アルカリ乾電池には、陽極活物質と
陰極活物質を隔離するためのセパレータ紙が用いられて
いるが、このセパレータ紙として要求される特性は前記
陽極活物質と陰極活物質の接触による内部短絡を防止
し、水酸化カリウム等の電解液や二酸化マンガン等の減
極剤に対して収縮や変質を起さない優れた耐久性を有
し、かつ、起電反応を生ずるために必要にして充分な量
の電解液を保持するとともに、イオンの伝導を妨げずに
内部抵抗を小さくでき、かつ、電池内部に組み込まれた
場合の占有容積が小さく、両極活物質の量を増やすこと
ができることである。2. Description of the Related Art Normally, an alkaline dry battery uses a separator paper for separating an anode active material and a cathode active material. The characteristics required of this separator paper are that of the anode active material and the cathode active material. In order to prevent internal short circuit due to contact, it has excellent durability that does not cause contraction or deterioration with respect to electrolytes such as potassium hydroxide and depolarizers such as manganese dioxide, and to cause an electromotive reaction. It is necessary to hold a sufficient amount of electrolytic solution as necessary, to reduce the internal resistance without hindering the conduction of ions, and to occupy a small volume when incorporated in the battery, and to increase the amount of the bipolar active material. Is possible.
【０００３】従来セパレータ紙としては、耐アルカリ性
合成繊維のビニロン繊維を主体とし、耐アルカリ性セル
ロース繊維であるビスコースレーヨン繊維、α−セルロ
ース成分９８％以上のリンターパルプ、マーセル化クラ
フトパルプ等を配合し、バインダーとしてポリビニルア
ルコール繊維を添加した合成繊維とセルロース繊維の混
抄紙が使用されている。The conventional separator paper is mainly composed of vinylon fiber which is an alkali resistant synthetic fiber, and is blended with viscose rayon fiber which is an alkali resistant cellulose fiber, linter pulp containing 98% or more of α-cellulose component, mercerized kraft pulp and the like. As the binder, a mixed paper of synthetic fiber and cellulose fiber to which polyvinyl alcohol fiber is added is used.
【０００４】例えば、出願人は特公昭５７−９６５０号
によりマーセル化木材クラフトパルプ（叩解品）を単独
で又は合成繊維と混抄したセパレータ紙を提供し、更に
特開平２−１１９０４９号により叩解可能な耐アルカリ
性セルロース繊維（マーセル化木材パルプ、エスパルト
パルプ、マニラ麻パルプ、ポリノジックレーヨン）と合
成繊維を混抄したセパレータ紙を提供している。また特
開昭６２−１５４５５９号には、前記セパレータ紙を構
成する繊維の一部又は全部を従来の繊度１〜３デニール
の太い繊維に代えて、繊度０．８デニール以下の合成繊
維としたアルカリ乾電池用セパレータ紙、及び上記合成
繊維とセルロース繊維（レーヨン、リンターパルプ、木
材パルプ等の未叩解品）を重量比が１５：８５〜８５：
１５で混抄したセパレータ紙の構成が開示されている。For example, the applicant provides separator paper in which mercerized wood kraft pulp (beaten product) is used alone or mixed with synthetic fibers according to Japanese Patent Publication No. 57-9650, and can be beaten according to JP-A No. 2-119049. Provided is separator paper obtained by mixing alkali-resistant cellulose fibers (mercerized wood pulp, esparto pulp, manila hemp pulp, polynosic rayon) and synthetic fibers. Further, in Japanese Patent Laid-Open No. 62-154559, a part or all of the fibers constituting the separator paper is replaced with conventional thick fibers having a fineness of 1 to 3 denier, and synthetic fibers having a fineness of 0.8 denier or less are used. The weight ratio of the separator paper for dry batteries, and the above synthetic fibers and cellulose fibers (unbeaten products such as rayon, linter pulp, wood pulp) is 15: 85-85:
The composition of separator paper mixed in No. 15 is disclosed.
【０００５】これらはビニロン繊維だけでは電解液によ
る湿潤性が不十分であるため、湿潤性の良い耐アルカリ
性セルロース系材料を配合したものであり、又緻密性の
要求されることに関しては耐アルカリ性合成繊維の繊維
径の小さいものを用いることや電解液による湿潤性を向
上させる目的で配合された耐アルカリ性セルロース系材
料のリンターパルプやマーセル化クラフトパルプを叩解
することによって繊維のフィブリル化を行い、細かい繊
維に砕いて緻密性の向上を図っているものである。Since vinylon fibers alone do not have sufficient wettability with an electrolytic solution, they are blended with an alkali-resistant cellulosic material having good wettability, and regarding the requirement of compactness, an alkali-resistant synthetic material is used. Fibrillation of fibers is performed by beating linter pulp or mercerized kraft pulp of alkali-resistant cellulosic material that has been blended for the purpose of improving wettability with an electrolyte or using a fiber having a small fiber diameter. It is crushed into fibers to improve the compactness.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記耐
アルカリ性セルロース系材料を高い配合割合としたセパ
レータ紙は保液性は向上するが、強アルカリ性電解液に
よる寸法収縮を起こし、近時セパレータ紙に要求される
基準に照らせばアルカリ乾電池用セパレータ紙として実
用的でない。即ち、上記特公昭５７−９６５０号によれ
ば、緻密で保液性が高く電気特性の良いセパレータ紙を
得ることができるが、面積収縮率（４０％−ＫＯＨ×７
０℃×２４Ｈ）が５〜１０％と大きくなり耐アルカリ性
に欠ける。また、特開平２−１１９０４９号によれば、
電気特性は良好であるが、保液性を近時の要求である５
００％以上に高めるためにはマーセル化パルプを３５重
量％以上配合することが必要となり、そうすると面積収
縮率が５〜１０％と大きくなり、逆に３５重量％以下の
配合では面積収縮率は５％以内となるが、保液性が不足
し、緻密性も欠け、現実問題として満足なアルカリ乾電
池用セパレータ紙を供与するに至っていない。However, the separator paper containing the alkali-resistant cellulosic material in a high blending ratio has improved liquid retention, but dimensional shrinkage due to the strong alkaline electrolyte causes a recent demand for separator paper. According to the standard, it is not practical as a separator paper for alkaline batteries. That is, according to the above Japanese Patent Publication No. 57-9650, it is possible to obtain a separator paper which is dense and has a high liquid retention and good electric characteristics, but the area shrinkage ratio (40% -KOH × 7).
(0 ° C x 24H) is as large as 5 to 10% and lacks alkali resistance. Further, according to Japanese Patent Application Laid-Open No. 2-119049,
Electrical properties are good, but liquid retention is a recent requirement 5
In order to increase the amount to more than 00%, it is necessary to blend 35% by weight or more of mercerized pulp, which results in a large area shrinkage ratio of 5 to 10%. However, as a practical matter, a satisfactory separator sheet for alkaline dry batteries has not been provided yet.
【０００７】一方、亜鉛を陰極活物質とするアルカリ乾
電池にあっては、従来放電反応を円滑に行うため、亜鉛
粒子の表面を水銀でアマルガム化して活物質とする手段
が用いられてきたが、近時水銀による環境汚染を防止す
る観点から水銀を使用しない無水銀化が前提となってい
る。この無水銀化されたアルカリ乾電池は陰極亜鉛粒同
士の物理的接触が弱くなり陰極領域での導電性が不安定
になることによって電池寿命が短くなる傾向にある。一
方において例えばアルカリマンガン乾電池は陰極の無水
銀化を伴いながら携帯用電源として多様化し、益々その
用途は広がっており、貯蔵後の連続放電や間欠放電の放
電維持時間の延長等の電池性能の向上が期待されてい
る。On the other hand, in the alkaline dry battery using zinc as the cathode active material, conventionally, in order to smoothly carry out the discharge reaction, a means of amalgamating the surface of zinc particles with mercury to obtain an active material has been used. From the viewpoint of preventing environmental pollution due to mercury in recent years, it has been premised on mercury-free conversion to mercury-free. In this silver-free alkaline dry battery, physical contact between cathode zinc particles is weakened and the conductivity in the cathode region becomes unstable, so that the battery life tends to be shortened. On the other hand, for example, alkaline manganese dry batteries have been diversified as portable power sources with the use of anhydrous silver as the cathode, and their applications are expanding, and improvements in battery performance such as extended discharge maintenance time for continuous discharge after storage and intermittent discharge. Is expected.
【０００８】かかる電池性能を向上させる方法の一つに
セパレータ紙に多くの電解液を与え、陰極の亜鉛イオン
の拡散を助けて伝導性を妨げず、電気抵抗を低くするこ
とがある。乾電池内のセパレータ紙に注入された電解液
の一部は陽極活物質壁への移行と放電途中の陰極側への
移行を伴い、セパレータ層は残された電解液によって起
電反応を起こすために必要にして十分な電解液量をセパ
レータ紙の繊維質に保持していなければならない。即
ち、セパレータ紙の材料（繊維）はイオン拡散性を妨げ
ないだけの電解液を保持し得る湿潤性を持ち備えた繊維
素材でなければならない。物理的には電解液の一時的な
保液性はよりポーラスに設計されたセパレータ紙が有利
と言える。しかしながら、一方では両極間の隔離性にお
いて短絡防止のためにはより緻密性であることが要求さ
れている。一般に緻密性が増せば電気抵抗が大きくなり
乾電池の放電特性は悪化する。よって、近時のセパレー
タ紙に要求される諸特性を同時に充足するセパレータ紙
は従来提供されていないのが実情である。One of the methods for improving the battery performance is to provide a large amount of electrolytic solution to the separator paper to assist the diffusion of zinc ions in the cathode and not hinder the conductivity, thereby lowering the electric resistance. A part of the electrolytic solution injected into the separator paper in the dry battery is accompanied by the migration to the anode active material wall and the migration to the cathode side during discharge, and the separator layer causes an electromotive reaction by the remaining electrolytic solution. The required and sufficient amount of electrolyte must be retained in the fibrous material of the separator paper. That is, the material (fiber) of the separator paper must be a fibrous material having a wettability capable of holding an electrolytic solution that does not hinder the ionic diffusivity. Physically, it can be said that the separator paper, which is designed more porous, has an advantage in temporarily retaining the electrolyte. However, on the other hand, the isolation between the electrodes is required to be more dense in order to prevent a short circuit. Generally, as the compactness increases, the electric resistance increases and the discharge characteristics of the dry battery deteriorate. Therefore, in reality, no separator paper has hitherto been provided that simultaneously satisfies various characteristics required of separator paper.
【０００９】そこで、本発明は内部短絡を防止するとと
もに、セパレータ紙に要求される耐アルカリ性、緻密
性、保液性、電気特性等の諸特性を高いレベルで同時に
充足するアルカリ乾電池用セパレータ紙、具体的には耐
アルカリ性として面積収縮率５％以下、緻密性として気
密度３．０秒／１００ｍｌ以上、保液性として保液率５
００％以上、電気特性としてＥＳＲ２０ｍΩ以下のアル
カリ乾電池用セパレータ紙を提供することを課題とす
る。Therefore, the present invention prevents the occurrence of internal short circuit, and at the same time, achieves a high level of various characteristics such as alkali resistance, compactness, liquid retention, and electrical characteristics required for separator paper, and a separator paper for alkaline dry batteries, Specifically, the area shrinkage rate is 5% or less as alkali resistance, the airtightness is 3.0 seconds / 100 ml or more as the denseness, and the liquid retention rate is 5 as the liquid retention property.
It is an object of the present invention to provide a separator paper for an alkaline dry battery having an electric property of 00% or more and an ESR of 20 mΩ or less.
【００１０】[0010]
【課題を解決するための手段】本発明は上記課題を達成
するために、アルカリ乾電池における陽極活物質と陰極
活物質とを隔離するためのセパレータ紙において、前記
セパレータ紙は原料として耐アルカリ性を有するととも
に叩解可能な精製セルロース繊維の有機溶剤紡糸レーヨ
ン繊維を２０重量％〜９０重量％の範囲で含有し、か
つ、該有機溶剤紡糸レーヨン繊維の叩解の程度がＣＳＦ
の値で５００ｍｌ〜０ｍｌの範囲であるアルカリ乾電池
用セパレータ紙の構成を提供する。また、耐アルカリ性
合成繊維を混抄してなり、耐アルカリ性合成繊維がビニ
ロン繊維である構成、耐アルカリ性の再生セルロース繊
維を混抄してなり、耐アルカリ性の再生セルロース繊維
がポリノジックレーヨン繊維である構成、有機溶剤紡糸
レーヨン繊維の一部をα−セルロース成分９８％以上の
リンターパルプ又はマーセル化クラフトパルプから選択
された一種又は複数のものに３０重量％以下の配合範囲
で代替した構成、及び溶解性ポリビニルアルコール繊維
をバインダーとして５重量％〜２０重量％配合した構成
を提供する。To achieve the above object, the present invention provides a separator paper for separating an anode active material and a cathode active material in an alkaline dry battery, wherein the separator paper has alkali resistance as a raw material. The organic solvent-spun rayon fiber of refined cellulose fiber capable of beating together with the organic solvent-spun rayon fiber is contained in the range of 20% by weight to 90% by weight, and the degree of beating of the organic solvent-spun rayon fiber is CSF.
The composition of the separator paper for alkaline batteries has a value in the range of 500 ml to 0 ml. Further, it is made by mixing the alkali-resistant synthetic fibers, the alkali-resistant synthetic fibers are vinylon fibers, the alkali-resistant regenerated cellulose fibers are mixed, the alkali-resistant regenerated cellulose fibers are polynosic rayon fibers, organic A composition in which a part of the solvent-spun rayon fiber is replaced with one or more selected from linter pulp or mercerized kraft pulp having an α-cellulose component of 98% or more in a compounding range of 30% by weight or less, and soluble polyvinyl alcohol Provided is a composition in which 5% by weight to 20% by weight of fibers are mixed as a binder.
【００１１】[0011]
【作用】上記構成の本発明によれば、得られたセパレー
タ紙はフィブリル化した極細なセルロース繊維がセパレ
ータ紙中に含有されるものであり、緻密性に優れた気密
度が高いものであって、アルカリ乾電池のセパレータ紙
として使用した場合に両極活物質の接触による内部短絡
や無水銀化に伴う内部短絡の防止効果が大きく、かつ、
電気抵抗の小さな、更に活物質の充填量を増加すること
のできるセパレータ紙を得ることができる。即ち、本発
明にかかるセパレータ紙は電解液による厚みの膨潤性が
あって陽極壁への沿いも良く、耐アルカリ性セルロース
系繊維が増量されたことにより高い保液性を持ち備えて
いると同時に湿潤性が著しく強く、電極間に十分な電解
液を保持していることによって電気抵抗をより低下させ
放電途中においても陽極亜鉛粒の間隙に電解液を補給し
うる性能を持つものである。また、叩解によってフィブ
リル化された極細な枝別れ繊維によって緻密な紙層形成
がされ、従来品に比べより細孔性を有することから両極
のより十分な隔離性を備え陰極生成物の陽極への貫通を
防止し、高い保液性と併せて乾電池の保存性を向上させ
ることができる。よって、内部短絡を防止するととも
に、セパレータ紙に要求される耐アルカリ性、緻密性、
保液性、電気特性等の諸特性を高いレベルで同時に充足
することができる。According to the present invention having the above-mentioned constitution, the obtained separator paper is one in which fibrillated ultrafine cellulose fibers are contained in the separator paper, which is excellent in denseness and high in airtightness. , When used as separator paper for alkaline batteries, the effect of preventing internal short circuit due to contact of both electrode active materials and internal short circuit due to silver-free conversion is large, and
It is possible to obtain a separator paper having a low electric resistance and capable of increasing the filling amount of the active material. That is, the separator paper according to the present invention has a swelling property in thickness due to the electrolytic solution and is good along the anode wall, and has high liquid retention property due to the increased amount of the alkali-resistant cellulosic fibers, and at the same time wet. It has a remarkably strong property, and by holding a sufficient electrolytic solution between the electrodes, the electrical resistance is further lowered, and the electrolytic solution can be replenished to the gap between the anode zinc particles during discharging. In addition, a fine paper layer is formed by the ultrafine branching fibers fibrillated by beating, and since it has more porosity than the conventional product, it has more sufficient isolation between the two electrodes and the cathode product to the anode. Penetration can be prevented, and the storage stability of the dry battery can be improved together with high liquid retention. Therefore, while preventing internal short circuit, alkali resistance, denseness, required for separator paper,
It is possible to simultaneously satisfy various characteristics such as liquid retention and electrical characteristics at a high level.
【００１２】[0012]
【実施例】以下、本発明にかかるアルカリ乾電池用セパ
レータ紙の各種実施例を説明する。本発明はセパレータ
紙の原料として耐アルカリ性を有するとともに叩解可能
な精製セルロース繊維の有機溶剤紡糸レーヨン繊維を使
用することに特徴を有する。EXAMPLES Various examples of separator sheets for alkaline dry batteries according to the present invention will be described below. The present invention is characterized by using an organic solvent-spun rayon fiber of refined cellulose fiber which has alkali resistance and can be beaten as a raw material of separator paper.
【００１３】有機溶剤紡糸レーヨン繊維の４０％−ＫＯ
Ｈ水溶液の７０℃×１００時間の分解率は僅かに１．５
％であり、同一条件における一般のビスコースレーヨン
繊維の分解率が１２％で有るのに比べ、大幅に耐アルカ
リ性に優れている。このことは高濃度のアルカリ電解液
を使用するアルカリ乾電池のセパレータ紙として電解液
による収縮が極めて少ないことを示しており、収縮防止
には最適の材料である。また、有機溶剤紡糸レーヨン繊
維はビスコースレーヨン繊維と同じように電解液による
濡れ性があり、繊維の膨潤作用を伴った保液性にも優
れ、リンターパルプやマーセル化クラフトパルプと同じ
ようにリファイナー等で叩解し、簡単にフィブリル化し
た極細繊維を作り出すことができる。40% of organic solvent-spun rayon fiber-KO
The decomposition rate of H aqueous solution at 70 ° C for 100 hours is only 1.5.
%, Which is much better in alkali resistance than the general viscose rayon fiber decomposition rate of 12% under the same conditions. This indicates that the separator paper of an alkaline dry battery using a high-concentration alkaline electrolyte has very little shrinkage due to the electrolyte, and is an optimum material for preventing shrinkage. In addition, organic solvent-spun rayon fibers have the same wettability with electrolyte as viscose rayon fibers, and also have excellent liquid retention with swelling action of the fibers, and like linter pulp and mercerized kraft pulp, refiner It can be beaten with, etc. to easily produce fibrillated ultrafine fibers.
【００１４】本発明で使用する有機溶剤紡糸レーヨン繊
維は精製セルロース繊維である。本発明で精製とは乾電
池に悪影響を及ぼす金属成分、例えば鉄，銅の含有量が
少ないもの（数ｐｐｍオーダ）であり、又α−セルロー
ス含有量が９９．８％以上であり、電解液としての４０
％−ＫＯＨ水溶液への溶出成分が殆どないことをいう。
これは有機溶剤紡糸レーヨン繊維は再生セルロースの製
造工程が有機溶剤のみであって、一般のビスコースレー
ヨンのように水酸化ナトリウム（ＮａＯＨ）や二硫化炭
素（ＣＳ2）を使用しないので、重合度の低下や使用薬
剤若しくは使用薬剤中の不純物の残留が殆どないためと
考えられる。The organic solvent-spun rayon fibers used in the present invention are purified cellulose fibers. Purification in the present invention means a metal component having a bad influence on a dry battery, for example, a substance having a small content of iron or copper (on the order of several ppm), and an α-cellulose content of 99.8% or more, which is used as an electrolytic solution. Of 40
% -KOH aqueous solution has almost no components eluted.
This is because the organic solvent-spun rayon fiber uses only an organic solvent in the production process of regenerated cellulose and does not use sodium hydroxide (NaOH) or carbon disulfide (CS 2 ) as in general viscose rayon, and therefore the degree of polymerization is It is considered that there is almost no decrease in the amount of impurities and the residual amount of the drug used or impurities in the drug used.
【００１５】そこで、本発明では精製セルロース繊維で
ある有機溶剤紡糸レーヨン繊維を叩解して、繊維をフィ
ブリル化させて極細の繊維とした後、この叩解後の有機
溶剤紡糸レーヨン繊維を原料としてセパレータ紙を抄紙
する。有機溶剤紡糸レーヨン繊維の含有量と叩解度は、
電池セパレータの要求する特性に合わせて適当な値に設
定することができるが、本発明の場合にあっては、有機
溶剤紡糸レーヨン繊維の含有量が２０重量％〜９０重量
％の範囲内であるようにしてあり、かつ、叩解度がＣＳ
Ｆ（カナダ標準形口水度、Canadian Standard Freenes
s）で５００ｍｌ〜０ｍｌの範囲であるようにしてあ
る。有機溶剤紡糸レーヨン繊維の配合割合が９０重量％
以上では保液性も限界に近付き寸法収縮が増して実用性
がなく、２０重量％以下では保液性が従来品と大差がな
く、不十分である。更に叩解度はＣＳＦ５００ｍｌ以上
を上回る場合は、叩解による繊維のフィブリル化が不充
分であり緻密性に劣り、逆にＣＳＦ０ｍｌに叩解された
材料を更に叩解すると、抄紙する際に抄紙機の抄き網か
ら流出することとなり、歩留り低下等の結果を招く。Therefore, in the present invention, the organic solvent-spun rayon fiber, which is a purified cellulose fiber, is beaten to fibrillate the fiber into an ultrafine fiber, and the beaten organic solvent-spun rayon fiber is used as a raw material for separator paper. Paper making. The content and beating degree of organic solvent spun rayon fiber are
Although it can be set to an appropriate value according to the characteristics required for the battery separator, in the case of the present invention, the content of the organic solvent spun rayon fiber is within the range of 20% by weight to 90% by weight. And the degree of beating is CS
F (Canadian Standard Freenes
In s), the range is 500 ml to 0 ml. 90% by weight of organic solvent-spun rayon fiber
In the above cases, the liquid retention becomes close to the limit and the dimensional shrinkage increases, which is not practical, and when it is 20% by weight or less, the liquid retention is not much different from the conventional product and is insufficient. Further, when the beating degree exceeds CSF 500 ml or more, the fibrillation of the fiber due to beating is insufficient and the denseness is poor, and conversely, when the material beaten to 0 ml CSF is further beaten, the paper making machine of the paper machine is used when making paper. Will result in a decrease in yield and the like.
【００１６】なお、上記叩解によりフィブリル化した有
機溶剤紡糸レーヨン繊維に、耐アルカリ性合成繊維、例
えばビニロン繊維を混抄したり、耐アルカリ性の再生セ
ルロース繊維、例えばポリノジックレーヨン繊維を混抄
することによりセパレータ紙の緻密性を高め、繊維間の
孔径を小さくして緻密性の優れたセパレータ紙を得るこ
とができる。The organic solvent-spun rayon fiber fibrillated by the above beating is mixed with an alkali resistant synthetic fiber such as vinylon fiber or an alkali resistant regenerated cellulose fiber such as polynosic rayon fiber to prepare a separator paper. It is possible to obtain a separator paper having excellent compactness by increasing the compactness and reducing the pore size between the fibers.
【００１７】また、有機溶剤紡糸レーヨン繊維の一部を
α−セルロース成分９８％以上のリンターパルプ又はマ
ーセル化クラフトパルプから選択された一種又は複数の
ものに３０重量％以下（好ましくは１５重量％〜３０重
量％）の配合範囲で代替させることでき、この代替によ
っても面積収縮の小さい耐アルカリ性セルロース繊維を
高配合としたセパレータ紙を得ることができる。このリ
ンターパルプやマーセル化クラフトパルプは経済的には
有機溶剤紡糸レーヨン繊維より安価であり、一部をこれ
らの材料で代替することは実際的メリットがある。な
お、代替の範囲が３０重量％以上では寸法収縮が大きす
ぎて所期の効果を得ることができない。Further, a part of the organic solvent-spun rayon fiber is 30% by weight or less (preferably 15% by weight or more) in one or more selected from linter pulp or mercerized kraft pulp having an α-cellulose component of 98% or more. (30% by weight) may be used as a substitute, and this substitute also makes it possible to obtain a separator paper having a high content of alkali-resistant cellulose fibers having a small area shrinkage. The linter pulp and the mercerized kraft pulp are economically cheaper than the organic solvent-spun rayon fiber, and there is a practical merit in substituting a part thereof with these materials. If the alternative range is 30% by weight or more, the dimensional shrinkage is too large to obtain the desired effect.
【００１８】更にセパレータ紙の必要とする強度に応じ
てバインダーとして溶解性ポリビニルアルコール繊維を
５重量％〜２０重量％配合させる。この溶解性ポリビニ
ルアルコール繊維は抄紙機の乾燥工程で湿紙中の水温上
昇に伴って溶解し、乾燥された後に繊維間を結着して強
度を強化する。５重量％以下の配合割合では必要な強度
が得られず、逆に２０重量％を越えると繊維間の空孔率
を低下させ電気抵抗を増大し好ましくない。Further, 5 to 20% by weight of soluble polyvinyl alcohol fiber is added as a binder depending on the required strength of the separator paper. The soluble polyvinyl alcohol fibers are dissolved in the wet process of the paper machine as the temperature of water in the wet paper increases, and after being dried, the fibers are bound to each other to strengthen the strength. If the compounding ratio is 5% by weight or less, the required strength cannot be obtained. On the contrary, if it exceeds 20% by weight, the porosity between the fibers is lowered and the electric resistance is increased, which is not preferable.
【００１９】そこで、本発明にかかるアルカリ乾電池用
セパレータ紙の製造に際し、有機溶剤紡糸レーヨン繊維
はＣＯＵＲＴＡＵＬＤＳ社のＴＥＮＣＥＬ繊維を水に分
散させ、ダブルディスクリファイナーで所定の叩解を行
い、他の繊維材料と混合して円網抄紙機で抄紙した。な
お、有機溶剤紡糸レーヨン繊維の叩解の度合がＣＳＦ５
０ｍｌ〜０ｍｌの領域の配合は長網抄紙機を用いて抄紙
した。以下に本発明にかかる具体的な各種実施例と、比
較のために製造した従来品の比較例を示す。Therefore, in the production of the separator paper for an alkaline dry battery according to the present invention, the organic solvent spun rayon fiber is prepared by dispersing TENCEL fiber manufactured by COULTAULDS in water and beaten it with a double disc refiner to a predetermined fiber material. It mixed and paper-made with the cylinder paper machine. The beating degree of the organic solvent spun rayon fiber is CSF5.
The composition in the range of 0 ml to 0 ml was made using a Fourdrinier paper machine. Hereinafter, various specific examples according to the present invention and comparative examples of conventional products manufactured for comparison will be shown.
【００２０】［実施例１］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）８０重量％をダブルディスクリフ
ァイナーでＣＳＦ５００ｍｌに叩解した後、ビニロン繊
維（１ｄ×３ｍｍ）１５重量％と溶解性ポリビニルアル
コール繊維（１ｄ×３ｍｍ）５重量％を配合して原料と
し、円網抄紙機で抄紙して厚さ１２２μｍ、坪量３９．
０ｇ／ｍ2のセパレータ紙を得た。Example 1 80 wt% of organic solvent spun rayon fiber (1.5 d × 3 mm) was beaten to CSF 500 ml with a double disc refiner, and then 15 wt% of vinylon fiber (1 d × 3 mm) and soluble polyvinyl alcohol fiber. (1d × 3 mm) 5% by weight was blended as a raw material, and paper was made by a cylinder paper machine to have a thickness of 122 μm and a basis weight of 39.
0 g / m 2 of separator paper was obtained.
【００２１】［実施例２］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）５０重量％をダブルディスクリフ
ァイナーでＣＳＦ３８０ｍｌに叩解した後、ビニロン繊
維（１ｄ×３ｍｍ）４０重量％と溶解性ポリビニルアル
コール繊維（１ｄ×３ｍｍ）１０重量％を配合して原料
とし、円網抄紙機で抄紙して厚さ１２１μｍ、坪量３
９．２ｇ／ｍ2のセパレータ紙を得た。Example 2 50% by weight of organic solvent-spun rayon fiber (1.5 d × 3 mm) was beaten to 380 ml of CSF with a double disc refiner, and then 40% by weight of vinylon fiber (1 d × 3 mm) and soluble polyvinyl alcohol fiber. (1d × 3 mm) 10% by weight was blended as a raw material, and the paper was made with a cylinder paper machine to have a thickness of 121 μm and a basis weight of 3
9.2 g / m 2 of separator paper was obtained.
【００２２】［実施例３］有機溶剤紡糸レーヨン繊維
（１．５ｄ×２ｍｍ）２５重量％をダブルディスクリフ
ァイナーでＣＳＦ１００ｍｌに叩解した後、ビニロン繊
維（１ｄ×３ｍｍ）６５重量％と溶解性ポリビニルアル
コール繊維（１ｄ×３ｍｍ）１０重量％を配合して原料
とし、円網抄紙機で抄紙して厚さ１２５μｍ、坪量３
８．０ｇ／ｍ2のセパレータ紙を得た。Example 3 25 wt% of organic solvent spun rayon fiber (1.5 d × 2 mm) was beaten to 100 ml of CSF with a double disc refiner, then 65 wt% of vinylon fiber (1 d × 3 mm) and soluble polyvinyl alcohol fiber (1d × 3 mm) 10% by weight was blended as a raw material, and the paper was made with a cylinder paper machine to have a thickness of 125 μm and a basis weight of 3
A separator paper of 8.0 g / m 2 was obtained.
【００２３】［実施例４］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）５０重量％をダブルディスクリフ
ァイナーでＣＳＦ３００ｍｌに叩解した後、ポリノジッ
クレーヨン繊維（１．５ｄ×３ｍｍ）３０重量％と溶解
性ポリビニルアルコール繊維（１ｄ×３ｍｍ）２０重量
％を配合して原料とし、円網抄紙機で抄紙して厚さ１２
８μｍ、坪量３８．２ｇ／ｍ2のセパレータ紙を得た。Example 4 50% by weight of organic solvent spun rayon fiber (1.5 d × 3 mm) was beaten to CSF 300 ml with a double disc refiner, and then dissolved with 30% by weight of polynosic rayon fiber (1.5 d × 3 mm). 20% by weight of polyvinyl alcohol fiber (1d × 3 mm) was blended as a raw material, and paper was made with a cylinder paper machine to a thickness of 12
A separator paper having a thickness of 8 μm and a basis weight of 38.2 g / m 2 was obtained.
【００２４】［実施例５］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）５０重量％をダブルディスクリフ
ァイナーでＣＳＦ３００ｍｌに叩解した後、マーセル化
クラフトパルプ２０重量％、ビニロン繊維（１ｄ×３ｍ
ｍ）２０重量％、溶解性ポリビニルアルコール繊維（１
ｄ×３ｍｍ）１０重量％を配合して原料とし、円網抄紙
機で抄紙して厚さ１２５μｍ、坪量３８．５ｇ／ｍ2の
セパレータ紙を得た。Example 5 50% by weight of organic solvent spun rayon fiber (1.5 d × 3 mm) was beaten to 300 ml of CSF with a double disc refiner, 20% by weight of mercerized kraft pulp, and vinylon fiber (1 d × 3 m).
m) 20% by weight, soluble polyvinyl alcohol fiber (1
(d × 3 mm) 10% by weight was used as a raw material, and paper was made by a cylinder paper machine to obtain a separator paper having a thickness of 125 μm and a basis weight of 38.5 g / m 2 .
【００２５】［実施例６］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）３５重量％をダブルディスクリフ
ァイナーでＣＳＦ２００ｍｌに叩解した後、リンターパ
ルプ２５重量％、ポリノジックレーヨン繊維（１．５ｄ
×３ｍｍ）２５重量％、溶解性ポリビニルアルコール繊
維（１ｄ×３ｍｍ）１５重量％を配合して原料とし、円
網抄紙機で抄紙して厚さ１２８μｍ、坪量３７．８ｇ／
ｍ2のセパレータ紙を得た。[Example 6] 35 wt% of organic solvent spun rayon fiber (1.5 d x 3 mm) was beaten to CSF 200 ml with a double disc refiner, and then 25 wt% of linter pulp and polynosic rayon fiber (1.5 d)
X3 mm) 25% by weight, soluble polyvinyl alcohol fiber (1d × 3 mm) 15% by weight as a raw material, papermaking with a cylinder paper machine, thickness 128 μm, basis weight 37.8 g /
m 2 of separator paper was obtained.
【００２６】［実施例７］有機溶剤紡糸レーヨン繊維
（１．５ｄ×３ｍｍ）９０重量％をダブルディスクリフ
ァイナーでＣＳＦ０ｍｌに叩解した後、リンターパルプ
１０重量％を配合して原料とし長網抄紙機で抄紙して厚
さ８５μｍ、坪量３９．１ｇ／ｍ2のセパレータ紙を得
た。Example 7 90% by weight of organic solvent-spun rayon fiber (1.5 d × 3 mm) was beaten to 0 ml of CSF with a double disc refiner, and then 10% by weight of linter pulp was blended and used as a raw material in a Fourdrinier paper machine. Paper was made to obtain a separator paper having a thickness of 85 μm and a basis weight of 39.1 g / m 2 .
【００２７】［比較例１］リンターパルプ３５重量％を
ダブルディスクリファイナーでＣＳＦ４００ｍｌに叩解
した後、ビニロン繊維（０．５ｄ×２ｍｍ）５５重量％
と溶解性ポリビニルアルコール繊維（１ｄ×３ｍｍ）１
０重量％を配合して原料とし、円網抄紙機で抄紙して厚
さ１２６μｍ、坪量３８．０ｇ／ｍ2のセパレータ紙を
得た。[Comparative Example 1] 35 wt% of linter pulp was beaten to 400 ml of CSF with a double disc refiner, and then 55 wt% of vinylon fiber (0.5d × 2 mm).
And soluble polyvinyl alcohol fiber (1d x 3mm) 1
0% by weight was blended as a raw material and papermaking was carried out by a cylinder paper machine to obtain a separator paper having a thickness of 126 μm and a basis weight of 38.0 g / m 2 .
【００２８】［比較例２］マーセル化パルプ３５重量％
をダブルディスクリファイナーでＣＳＦ５００ｍｌに叩
解した後、ビニロン繊維（０．５ｄ×２ｍｍ）５５重量
％と溶解性ポリビニルアルコール繊維（１ｄ×３ｍｍ）
１０重量％を配合して原料とし、円網抄紙機で抄紙して
厚さ１２７μｍ、坪量３８．４ｇ／ｍ2のセパレータ紙
を得た。Comparative Example 2 35% by weight of mercerized pulp
Was beaten to 500 ml of CSF with a double disc refiner, then 55% by weight of vinylon fiber (0.5d x 2mm) and soluble polyvinyl alcohol fiber (1d x 3mm)
10% by weight was blended as a raw material and papermaking was carried out by a cylinder paper machine to obtain a separator paper having a thickness of 127 μm and a basis weight of 38.4 g / m 2 .
【００２９】［比較例３］比較例２のマーセル化パルプ
２５重量％とビスコースレーヨン繊維（０．７ｄ×３ｍ
ｍ）２５重量％にビニロン繊維（０．５ｄ×２ｍｍ）４
０重量％と溶解性ポリビニルアルコール繊維（１ｄ×３
ｍｍ）１０重量％を配合して原料とし円網抄紙機で抄紙
して厚さ１３０μｍ、坪量３７．２ｇ／ｍ2のセパレー
タ紙を得た。Comparative Example 3 25% by weight of the mercerized pulp of Comparative Example 2 and viscose rayon fiber (0.7 d × 3 m)
m) 25% by weight of vinylon fiber (0.5d × 2mm) 4
0% by weight and soluble polyvinyl alcohol fiber (1d × 3
mm) 10% by weight was used as a raw material to make a paper with a cylinder paper machine to obtain a separator paper having a thickness of 130 μm and a basis weight of 37.2 g / m 2 .
【００３０】［比較例４］比較例１のリンターパルプ５
０重量％とビニロン繊維（０．５ｄ×２ｍｍ）４０重量
％と溶解性ポリビニルアルコール繊維（１ｄ×３ｍｍ）
１０重量％を配合して原料とし円網抄紙機で抄紙して厚
さ１３０μｍ、坪量３８．０ｇ／ｍ2のセパレータ紙を
得た。[Comparative Example 4] Linter pulp 5 of Comparative Example 1
0% by weight and vinylon fiber (0.5d × 2mm) 40% by weight and soluble polyvinyl alcohol fiber (1d × 3mm)
10% by weight was blended as a raw material to make a paper with a cylinder paper machine to obtain a separator paper having a thickness of 130 μm and a basis weight of 38.0 g / m 2 .
【００３１】上記の実施例１〜７と比較例１〜４によっ
て得られたセパレータ紙に関し、厚さ（μｍ）．坪量
（ｇ／ｍ2）．引張強度（ｋｇ／１５ｍｍ）．気密度
（秒）．保液率（％）．収縮率（％）．電気抵抗（ｍ
Ω）を測定した。尚、測定方法及び装置は次の通りであ
る。Regarding the separator papers obtained in Examples 1 to 7 and Comparative Examples 1 to 4, the thickness (μm). Basis weight (g / m 2 ). Tensile strength (kg / 15mm). Air tightness (seconds). Liquid retention rate (%). Shrinkage factor(%). Electric resistance (m
Ω) was measured. The measuring method and apparatus are as follows.
【００３２】（１）厚さ 厚さは得られたセパレータ紙の５ヶ所をダイアルシック
ネスゲージで測定し、その平均値とした。(1) Thickness The thickness was measured at 5 points on the obtained separator paper with a dial thickness gauge and taken as an average value.
【００３３】（２）坪量，引張強度 坪量はＪＩＳ Ｐ ８１２４に規定された方法を採用
し、引張強度はＪＩＳＰ ８１１３に規定されている方
法を採用した。(2) Basis Weight and Tensile Strength The basis weight was determined by the method specified in JIS P 8124, and the tensile strength was determined by the method specified in JIS P 8113.
【００３４】（３）気密度 気密度はＪＩＳ Ｐ ８１１７（紙及び板紙の透気度試
験方法）のＢ型測定器の下部試験片取り付け部分に直径
６ｍｍの円筒絞りを取り付け、絞り面にセパレータ紙を
挟み込み、セパレータ紙の直径６ｍｍ円筒面を１００ｍ
ｌの空気が通過するのに要する時間（秒／１００ｍｌ）
を測定した。(3) Airtightness Airtightness is determined by attaching a cylindrical diaphragm having a diameter of 6 mm to the lower test piece mounting portion of the B-type measuring device of JIS P 8117 (permeability test method for paper and board), and separating paper on the diaphragm surface. The separator paper with a diameter of 6 mm and a cylindrical surface of 100 m.
Time required for 1 air to pass (sec / 100ml)
Was measured.
【００３５】（４）保液率 大きさ５０×５０ｍｍの試験片を４０％−ＫＯＨ水溶液
に１０分間浸漬して４５度に傾斜したガラス板に３分間
放置した後、液滴を取り除き重量を測定し、次式によっ
て算出する。 保液率（％）＝（Ｗ２−Ｗ１）／Ｗ１×１００ Ｗ１＝浸漬前の重量，Ｗ２＝浸漬後の重量(4) Liquid retention rate A test piece having a size of 50 × 50 mm was immersed in a 40% -KOH aqueous solution for 10 minutes and left on a glass plate inclined at 45 ° for 3 minutes, and then the droplets were removed and the weight was measured. Then, it is calculated by the following formula. Liquid retention rate (%) = (W2-W1) / W1 × 100 W1 = weight before immersion, W2 = weight after immersion
【００３６】（５）収縮率 大きさ１００×１００ｍｍの試験片を４０％−ＫＯＨ水
溶液に７０℃で２４時間浸漬した後の長さを測定し、次
式によって面積の収縮率を求めた。 収縮率（％）＝（Ａ１−Ａ２）／Ａ１×１００ Ａ１＝浸漬前の面積，Ａ２＝浸漬後の面積(5) Shrinkage A test piece having a size of 100 × 100 mm was dipped in a 40% -KOH aqueous solution at 70 ° C. for 24 hours, the length was measured, and the area shrinkage was calculated by the following formula. Shrinkage (%) = (A1−A2) / A1 × 100 A1 = area before immersion, A2 = area after immersion
【００３７】（６）電気抵抗 電気抵抗は電解液に４０％−ＫＯＨ水溶液を使用して、
３ｍｍの間隔の白金電極の間にセパレータ紙を挿入し、
この挿入に伴う電極間の電気抵抗の増加分を１Ｋｚの周
波数でＥＳＲメータを用いて測定して電気抵抗とした。(6) Electric resistance Electric resistance was measured by using 40% -KOH aqueous solution as the electrolytic solution.
Insert the separator paper between the 3mm platinum electrodes,
The increase in the electric resistance between the electrodes due to this insertion was measured at a frequency of 1 Kz using an ESR meter to obtain the electric resistance.
【００３８】このような測定手段を用いて前記各実施例
及び比較例のセパレータ紙を測定した結果を表１に示
す。Table 1 shows the results of measuring the separator paper of each of the above-mentioned Examples and Comparative Examples using such measuring means.
【００３９】[0039]
【表１】 [Table 1]
【００４０】表１に示す通り、実施例１〜３は有機溶剤
紡糸レーヨン繊維８０〜２５重量％をＣＳＦ５００〜１
００ｍｌまで叩解してフィブリル化させたものである
が、略同一厚さ、坪量の比較例１〜３に比較して、緻密
性を表す気密度が従来品の１．４〜２．２秒から３．０
〜３．５秒に上がって緻密性が向上し、同時に電解液の
保液率も４１０〜４５０％から５３０〜６００％に向上
して電気抵抗が１６〜２２ｍΩから１３〜１４ｍΩに著
しく軽減されている。As shown in Table 1, in Examples 1 to 3, 80 to 25% by weight of organic solvent-spun rayon fiber was added to CSF 500 to 1
It was beaten up to 00 ml to be fibrillated, but compared with Comparative Examples 1 to 3 of approximately the same thickness and basis weight, the airtightness showing the denseness was 1.4 to 2.2 seconds of the conventional product. To 3.0
Up to 3.5 seconds to improve the compactness, and at the same time, the electrolyte retention rate is also increased from 410 to 450% to 530 to 600%, and the electric resistance is significantly reduced from 16 to 22 mΩ to 13 to 14 mΩ. There is.
【００４１】実施例４〜６は更に保液率を向上させる目
的と経済的な効果を得るため、有機溶剤紡糸レーヨン繊
維の一部を安価なα−セルロース成分９８％以上のリン
ターパルプやマーセル化クラフトパルプに代替したもの
であるが、実施例１〜３に比較しても、緻密性を表す気
密度が３．５〜４．０と同等若しくはそれ以上に緻密性
が向上し、同時に電解液の保液率も５９０〜６３０％に
向上して電気抵抗も１４〜１６ｍΩと同等に改善されて
いる。In Examples 4 to 6, in order to further improve the liquid retention rate and to obtain an economical effect, a part of the organic solvent-spun rayon fiber was made into linter pulp or mercer with an inexpensive α-cellulose component of 98% or more. Although it is a substitute for kraft pulp, even when compared with Examples 1 to 3, the airtightness showing the denseness is equal to or higher than 3.5 to 4.0, and the denseness is improved, and at the same time, the electrolytic solution is used. The liquid retention rate was improved to 590 to 630% and the electrical resistance was improved to 14 to 16 mΩ.
【００４２】実施例７では有機溶剤紡糸レーヨン繊維９
０重量％をＣＳＦ値が０ｍｌの領域まで叩解した極細繊
維を原料としたものであり、引張強度は３．０Ｋｇと実
用上問題のない強度を有しつつ、気密度が１９秒、保液
率が６６５％、電気抵抗が１１ｍΩという最良のセパレ
ータ紙を得ることができた。In Example 7, organic solvent spun rayon fiber 9
It is made from ultrafine fibers beaten 0% by weight to the region where the CSF value is 0 ml. It has a tensile strength of 3.0 Kg and practically no problem, air tightness of 19 seconds, liquid retention rate. Of 665% and an electric resistance of 11 mΩ were obtained.
【００４３】比較例４は従来の耐アルカリ性セルロース
繊維を高い配合割合にして得られるセパレータ紙の特性
を確認したものであるが、電解液（４０％−ＫＯＨ水溶
液）により収縮率が１１．２％と増大して実用のないこ
と知ることができる。Comparative Example 4 confirms the characteristics of a separator paper obtained by using a conventional alkali-resistant cellulose fiber in a high blending ratio, but the shrinkage ratio is 11.2% by the electrolytic solution (40% -KOH aqueous solution). You can know that there is no practical use.
【００４４】以上の測定結果から本発明にかかる有機溶
剤紡糸レーヨン繊維を叩解して得られるセパレータ紙は
内部短絡を防止するとともに、セパレータ紙に要求され
る耐アルカリ性、緻密性、保液性、電気特性等の諸特性
を高いレベルで同時に充足するアルカリ乾電池用セパレ
ータ紙、具体的には耐アルカリ性として面積収縮率５％
以下、緻密性として気密度３．０秒／１００ｍｌ以上、
保液性として保液率５００％以上、電気特性としてＥＳ
Ｒ２０ｍΩ以下のセパレータ紙を得ることができる。よ
って、従来の耐アルカリ性セルロース繊維を用いて得ら
れたセパレータ紙より、気密度が高く緻密性があり無水
銀化された陰極亜鉛と陽極活物質の十分な隔離機能を持
ち、叩解された微細及び極細繊維は十分な電解液を保持
することによって低い電気抵抗を示し、電池性能を向上
させる保液機能も高く、面積収縮率も小さい驚異的なセ
パレータ紙を得ることができる。From the above measurement results, the separator paper obtained by beating the organic solvent-spun rayon fiber according to the present invention prevents internal short-circuit, and also has the alkali resistance, the compactness, the liquid retention property, and the electric resistance required for the separator paper. Separator paper for alkaline batteries, which satisfies various characteristics at a high level at the same time, specifically 5% area shrinkage as alkali resistance
Hereafter, the airtightness as denseness is 3.0 seconds / 100 ml or more,
Liquid retention rate of 500% or more and electrical characteristics of ES
A separator paper having an R of 20 mΩ or less can be obtained. Therefore, compared with the separator paper obtained using the conventional alkali-resistant cellulose fiber, the airtight and dense and has a sufficient function of separating the negative electrode zinc and the anode active material that are anhydrous silverized and the beaten fine and The ultrafine fibers show a low electric resistance by holding a sufficient amount of electrolytic solution, have a high liquid retaining function for improving battery performance, and can obtain a surprising separator paper with a small area shrinkage ratio.
【００４５】次に前記実施例１〜７と比較例１〜３によ
って得られたセパレータ紙を用いて、無水銀化亜鉛を使
用したアルカリマンガン乾電池（ＬＲ６）を試作し、２
０℃において７５Ωと３９０Ωの連続放電を行い、終止
電圧（０．９Ｖ）までの電圧維持時間を試験した結果を
表２に示す。Next, using the separator papers obtained in Examples 1 to 7 and Comparative Examples 1 to 3, an alkaline manganese dry battery (LR6) using anhydrous zincated zinc was manufactured as a trial product.
Table 2 shows the results of testing the voltage maintaining time up to the final voltage (0.9 V) by continuously discharging 75Ω and 390Ω at 0 ° C.
【００４６】[0046]
【表２】 [Table 2]
【００４７】表２から明らかなように７５Ω連続放電に
おいて、従来のセパレータ紙を使用した比較例１〜３の
電池では電圧維持時間は１５１〜１５４時間であるのに
対し、本発明にかかる実施例１〜３の電池では１６１時
間以上、実施例４〜６の電池は１６６時間以上であるこ
とが確認された。３９０Ω連続放電においても比較例１
〜３の電池は７９４〜８３０時間に対し、本発明にかか
る実施例１〜３の電池では９０５時間以上、実施例４〜
６の電池は９３０時間以上であることが確認された。ま
た、実施例７の電池では７５Ω連続放電において１６２
時間、３９０Ω連続放電において９６５時間であること
が確認された。これらは電池内部の短絡が防止され、従
来の物より電池放電に十分な電解液が放電終止まで両電
極間に介在し亜鉛イオンの拡散を十分にさせ得たものと
考えられる。As is apparent from Table 2, in the case of 75Ω continuous discharge, the batteries of Comparative Examples 1 to 3 using the conventional separator paper have the voltage maintaining time of 151 to 154 hours, while the Examples according to the present invention. It was confirmed that the batteries 1 to 3 lasted 161 hours or longer, and the batteries of Examples 4 to 6 lasted 166 hours or longer. Comparative Example 1 also in 390Ω continuous discharge
3 to 793 hours, the batteries of Examples 1 to 3 according to the present invention have 905 hours or more, and the batteries of Examples 4 to
It was confirmed that the battery of No. 6 had 930 hours or more. In addition, the battery of Example 7 is 162 in 75Ω continuous discharge.
It was confirmed that the time was 965 hours in 390Ω continuous discharge. It is considered that the short circuit inside the battery was prevented, and the electrolytic solution sufficient for battery discharge was present between both electrodes until the end of discharge, and zinc ions could be sufficiently diffused as compared with the conventional products.
【００４８】[0048]
【発明の効果】以上詳細に説明した如く、本発明にかか
るアルカリ乾電池用セパレータ紙は、一般の耐アルカリ
性セルロース繊維を混合することによって高濃度アルカ
リ電解液において高い保液性は可能であるが、寸法収縮
の小さく、緻密性に優れたセパレータ紙は設計できない
という従来のアルカリ乾電池用のセパレータ紙の欠点を
解消して、従来の耐アルカリ性セルロース繊維より耐ア
ルカリ性が強く、湿潤性に優れ、高濃度アルカリ電解液
においても寸法収縮の小さい有機溶剤紡糸レーヨン繊維
を叩解して、ＣＳＦ５００ｍｌ〜０ｍｌのフィブリル化
した極細繊維を造り、耐アルカリ性合成繊維のビニロン
繊維や再生繊維のポリノジックレーヨン繊維と配合させ
ることにより耐アルカリ性セルロース系材料の高配合割
合を可能にし、従来品より電解液に対して寸法収縮が少
なく、緻密性、湿潤性、保液性に優れ、電気抵抗の低い
アルカリ乾電池用セパレータ紙を得ることできる。As described in detail above, the separator paper for alkaline dry batteries according to the present invention can have a high liquid retaining property in a high concentration alkaline electrolyte by mixing general alkaline resistant cellulose fibers. It eliminates the disadvantage of conventional separator paper for alkaline batteries, which has a small size shrinkage and cannot be designed with excellent compactness, and has stronger alkali resistance than conventional alkali resistant cellulose fibers, excellent wettability, and high concentration. By beating organic solvent-spun rayon fibers that have small dimensional shrinkage even in an alkaline electrolyte, to make fibril 500 μm to 0 ml fibrillated ultrafine fibers, and blend them with alkali resistant synthetic vinylon fibers or recycled polynosic rayon fibers. It enables a high blending ratio of alkali-resistant cellulosic materials, Less dimensional shrinkage of the electrolyte solution from the goods, denseness, wettability, excellent liquid retention can be obtained a separator paper for low electric resistance alkaline batteries.
【００４９】即ち、叩解された有機溶剤紡糸レーヨン繊
維はアルカリ乾電池の電解液による収縮を伴うことなく
繊維自体に膨潤性があり、電解液の保持力が増大してセ
パレータとしての高い保液機能を持ち、フィブリル化し
た極細枝別れ繊維の紙層構造となることによって孔径が
小さく緻密性を持ったセパレータ紙である。このことに
よりアルカリ乾電池のセパレータ紙として使用した場
合、両極活物質の接触による内部短絡の防止効果が大き
く、該セパレータ紙の積層枚数を少なくすることができ
陰極亜鉛粒の充填量を増し乾電池の電気容量を増大する
ことができる。更に、均一に緻密性が大きいため無水銀
化に伴う陰極亜鉛からの導電性生成物による内部短絡を
防止して乾電池の長期間の保存性を向上させることがで
きる。また、電解液の保持性の良い極細枝別れ繊維の紙
層構造は電気抵抗が小さくなりアルカリ乾電池の重負荷
放電性能も驚異的に向上させる利点を有している。That is, the beaten beaten organic solvent spun rayon fiber has a swelling property without contraction due to the electrolytic solution of the alkaline dry battery, the electrolytic solution holding power is increased, and a high liquid retaining function as a separator is obtained. It is a separator paper with a small pore size and a high density because it has a paper layer structure of ultrafine branching fibers that are fibrillated. Therefore, when used as separator paper for alkaline dry batteries, the effect of preventing internal short-circuiting due to contact of both electrode active materials is great, the number of laminated separator papers can be reduced, and the filling amount of cathode zinc particles can be increased to improve the electric power of dry batteries. The capacity can be increased. Furthermore, since the density is uniformly large, it is possible to prevent an internal short circuit due to a conductive product from the negative electrode zinc due to the formation of anhydrous silver, thereby improving the long-term storage stability of the dry battery. Further, the paper layer structure of the ultrafine branching fiber having a good electrolyte retaining property has an advantage that the electric resistance becomes small and the heavy load discharge performance of the alkaline dry battery is improved remarkably.
Claims (7)
極活物質とを隔離するためのセパレータ紙において、前
記セパレータ紙は原料として耐アルカリ性を有するとと
もに叩解可能な精製セルロース繊維の有機溶剤紡糸レー
ヨン繊維を２０重量％〜９０重量％の範囲で含有し、か
つ、該有機溶剤紡糸レーヨン繊維の叩解の程度がＣＳＦ
の値で５００ｍｌ〜０ｍｌの範囲であることを特徴とす
るアルカリ乾電池用セパレータ紙。1. A separator paper for separating an anode active material and a cathode active material in an alkaline dry battery, wherein the separator paper has alkali resistance as a raw material and is a beating organic solvent spun rayon fiber of refined cellulose fiber. % To 90% by weight, and the beating degree of the organic solvent spun rayon fiber is CSF.
The separator paper for alkaline batteries has a value of 500 ml to 0 ml.
求項１記載のアルカリ乾電池用セパレータ紙。2. The separator paper for an alkaline dry battery according to claim 1, which is a mixture of alkali resistant synthetic fibers.
ある請求項２記載のアルカリ乾電池用セパレータ紙。3. The separator paper for an alkaline dry battery according to claim 2, wherein the alkali-resistant synthetic fiber is vinylon fiber.
抄してなる請求項１，２，３記載のアルカリ乾電池用セ
パレータ紙。4. The separator paper for an alkaline dry battery according to claim 1, wherein the separator paper is a mixture of alkali-resistant regenerated cellulose fibers.
リノジックレーヨン繊維である請求項４記載のアルカリ
乾電池用セパレータ紙。5. The separator paper for an alkaline dry battery according to claim 4, wherein the alkali-resistant regenerated cellulose fiber is polynosic rayon fiber.
セルロース成分９８％以上のリンターパルプ又はマーセ
ル化クラフトパルプから選択された一種又は複数のもの
に３０重量％以下の配合範囲で代替した請求項１，２，
３，４，５記載のアルカリ乾電池用セパレータ紙。6. A part of the organic solvent-spun rayon fiber is α-
A method of substituting one or more selected from linter pulp or mercerized kraft pulp having a cellulose component of 98% or more with a compounding range of 30% by weight or less.
Separator paper for alkaline dry batteries described in 3, 4, 5.
ンダーとして５重量％〜２０重量％配合した請求項１，
２，３，４，５，６記載のアルカリ乾電池用セパレータ
紙。7. A composition comprising soluble polyvinyl alcohol fibers as a binder in an amount of 5% by weight to 20% by weight.
Separator paper for alkaline dry battery according to 2, 3, 4, 5, 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04184193A JP3290734B2 (en) | 1993-02-04 | 1993-02-04 | Separator paper for alkaline batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04184193A JP3290734B2 (en) | 1993-02-04 | 1993-02-04 | Separator paper for alkaline batteries |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002009371A Division JP2002251988A (en) | 2002-01-18 | 2002-01-18 | Separator paper for alkaline dry battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06231746A true JPH06231746A (en) | 1994-08-19 |
| JP3290734B2 JP3290734B2 (en) | 2002-06-10 |
Family
ID=12619487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04184193A Expired - Lifetime JP3290734B2 (en) | 1993-02-04 | 1993-02-04 | Separator paper for alkaline batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3290734B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006090790A1 (en) * | 2005-02-25 | 2006-08-31 | Kuraray Co., Ltd. | Alkaline battery separator and alkaline primery battery |
| US7544444B2 (en) | 2004-06-30 | 2009-06-09 | Panasonic Corporation | Alkaline dry battery and method for evaluating separator for use in alkaline dry battery |
| JP2010251215A (en) * | 2009-04-17 | 2010-11-04 | Nippon Kodoshi Corp | Separator for battery, and the battery |
| WO2012036025A1 (en) * | 2010-09-16 | 2012-03-22 | 株式会社クラレ | Alkaline battery separator and alkaline battery using separator |
| JP2012109268A (en) * | 2012-02-27 | 2012-06-07 | Kuraray Co Ltd | Separator for alkaline battery and alkaline primary battery |
| WO2013114949A1 (en) * | 2012-01-31 | 2013-08-08 | ニッポン高度紙工業株式会社 | Separator for alkaline battery and alkaline battery |
| JP2013179036A (en) * | 2012-01-31 | 2013-09-09 | Nippon Kodoshi Corp | Alkaline battery separator and alkaline battery |
| JP2014123443A (en) * | 2012-12-20 | 2014-07-03 | Lenzing Ag | Alkali battery separator, and alkali battery |
| JP2015518248A (en) * | 2012-04-26 | 2015-06-25 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| JP2016511511A (en) * | 2013-02-22 | 2016-04-14 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| JP2017224611A (en) * | 2017-07-06 | 2017-12-21 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| CN109155205A (en) * | 2016-05-09 | 2019-01-04 | 三菱制纸株式会社 | Electro chemical elements use spacer and use electrochemical element made of it |
| US10446820B2 (en) | 2015-09-15 | 2019-10-15 | Kuraray Co., Ltd. | Alkaline battery separator |
| WO2020137630A1 (en) | 2018-12-26 | 2020-07-02 | 株式会社クラレ | Alkaline battery separator and method for manufacturing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3480836A4 (en) | 2016-06-30 | 2020-03-11 | Kuraray Co., Ltd. | Separator for capacitor |
-
1993
- 1993-02-04 JP JP04184193A patent/JP3290734B2/en not_active Expired - Lifetime
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7544444B2 (en) | 2004-06-30 | 2009-06-09 | Panasonic Corporation | Alkaline dry battery and method for evaluating separator for use in alkaline dry battery |
| WO2006090790A1 (en) * | 2005-02-25 | 2006-08-31 | Kuraray Co., Ltd. | Alkaline battery separator and alkaline primery battery |
| JP2006236808A (en) * | 2005-02-25 | 2006-09-07 | Kuraray Co Ltd | Separator for alkaline battery and alkaline primary battery |
| US8097366B2 (en) | 2005-02-25 | 2012-01-17 | Kuraray Co., Ltd. | Alkaline battery separator comprising alkali-resistance synthetic fiber, fibrillated organic solvent-spun cellulose fiber and mercerized pulp, and alkaline primary battery |
| JP2010251215A (en) * | 2009-04-17 | 2010-11-04 | Nippon Kodoshi Corp | Separator for battery, and the battery |
| WO2012036025A1 (en) * | 2010-09-16 | 2012-03-22 | 株式会社クラレ | Alkaline battery separator and alkaline battery using separator |
| US9142816B2 (en) | 2010-09-16 | 2015-09-22 | Kuraray Co., Ltd. | Alkaline battery separator and alkaline battery using separator |
| WO2013114949A1 (en) * | 2012-01-31 | 2013-08-08 | ニッポン高度紙工業株式会社 | Separator for alkaline battery and alkaline battery |
| JP2013179036A (en) * | 2012-01-31 | 2013-09-09 | Nippon Kodoshi Corp | Alkaline battery separator and alkaline battery |
| JP2012109268A (en) * | 2012-02-27 | 2012-06-07 | Kuraray Co Ltd | Separator for alkaline battery and alkaline primary battery |
| JP2015518248A (en) * | 2012-04-26 | 2015-06-25 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| JP2017143065A (en) * | 2012-04-26 | 2017-08-17 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| JP2014123443A (en) * | 2012-12-20 | 2014-07-03 | Lenzing Ag | Alkali battery separator, and alkali battery |
| JP2016511511A (en) * | 2013-02-22 | 2016-04-14 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| US10446820B2 (en) | 2015-09-15 | 2019-10-15 | Kuraray Co., Ltd. | Alkaline battery separator |
| CN109155205A (en) * | 2016-05-09 | 2019-01-04 | 三菱制纸株式会社 | Electro chemical elements use spacer and use electrochemical element made of it |
| US10818898B2 (en) | 2016-05-09 | 2020-10-27 | Mitsubishi Paper Mills Limited | Separator for electrochemical elements and electrochemical element including separator for electrochemical elements |
| JP2017224611A (en) * | 2017-07-06 | 2017-12-21 | レンツィング アクチェンゲゼルシャフト | Battery separator |
| WO2020137630A1 (en) | 2018-12-26 | 2020-07-02 | 株式会社クラレ | Alkaline battery separator and method for manufacturing same |
| CN113228398A (en) * | 2018-12-26 | 2021-08-06 | 株式会社可乐丽 | Separator for alkaline battery and method for producing same |
| US11936067B2 (en) | 2018-12-26 | 2024-03-19 | Kuraray Co., Ltd. | Alkaline battery separator and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3290734B2 (en) | 2002-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3290734B2 (en) | Separator paper for alkaline batteries | |
| EP2104161B1 (en) | Separator for alkaline battery, method for producing the same, and battery comprising the same | |
| EP3447779B1 (en) | Separator for electrochemical element and electrochemical element | |
| US20030180622A1 (en) | Separator for electrochemical device and method for producing the same, and electrochemical device | |
| CN103081169B (en) | Alkaline battery barrier film and alkaline battery | |
| KR19980024098A (en) | Alkaline Batteries | |
| JP5844166B2 (en) | Alkaline battery separator and alkaline battery | |
| EP3425698B1 (en) | Alkaline battery separator and alkaline battery | |
| JP2014123443A (en) | Alkali battery separator, and alkali battery | |
| JP2938315B2 (en) | Alkaline battery separator | |
| JP3466206B2 (en) | Electrolytic capacitor | |
| CN108448029B (en) | AGM diaphragm for lead-carbon battery and preparation method thereof | |
| JP2000003834A (en) | Electric double-layer capacitor | |
| CN1636286A (en) | Nonwoven separator for electrochemical cell | |
| JPH0748375B2 (en) | Separator paper for alkaline batteries | |
| JP6739946B2 (en) | Alkaline battery separator and alkaline battery | |
| JPH0572063B2 (en) | ||
| JP6739947B2 (en) | Alkaline battery separator and alkaline battery | |
| US1644344A (en) | Primary cell | |
| JPH0963560A (en) | Separator and battery using same | |
| JP3310935B2 (en) | Separator paper for alkaline batteries | |
| JP2002251988A (en) | Separator paper for alkaline dry battery | |
| JP6355295B2 (en) | Alkaline battery separator and alkaline battery | |
| JPH05251274A (en) | Electrolytic capacitor | |
| CN111684558B (en) | Separator for electrochemical element and electrochemical element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080322 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110322 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110322 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130322 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term |