JP2002251988A - Separator paper for alkaline dry battery - Google Patents
Separator paper for alkaline dry batteryInfo
- Publication number
- JP2002251988A JP2002251988A JP2002009371A JP2002009371A JP2002251988A JP 2002251988 A JP2002251988 A JP 2002251988A JP 2002009371 A JP2002009371 A JP 2002009371A JP 2002009371 A JP2002009371 A JP 2002009371A JP 2002251988 A JP2002251988 A JP 2002251988A
- Authority
- JP
- Japan
- Prior art keywords
- separator paper
- paper
- fiber
- alkaline dry
- separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 claims abstract description 88
- 229920000297 Rayon Polymers 0.000 claims abstract description 46
- 239000002964 rayon Substances 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 18
- 239000000123 paper Substances 0.000 claims description 121
- 230000014759 maintenance of location Effects 0.000 claims description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 229920002978 Vinylon Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 229920002994 synthetic fiber Polymers 0.000 claims description 11
- 239000012209 synthetic fiber Substances 0.000 claims description 11
- 239000002655 kraft paper Substances 0.000 claims description 10
- 239000006183 anode active material Substances 0.000 claims description 8
- 239000006182 cathode active material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 14
- 238000010009 beating Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 229920001410 Microfiber Polymers 0.000 description 4
- 229920001407 Modal (textile) Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 linter pulp Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Cell Separators (AREA)
- Primary Cells (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 for separating an anode active material and a cathode active material in various alkaline batteries such as an alkaline manganese dry battery. 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 Usually, an alkaline dry battery uses a separator paper for isolating an anode active material and a cathode active material. The characteristics required for this separator paper are as follows. In order to prevent internal short circuit due to contact, to have excellent durability that does not cause shrinkage or deterioration of electrolytes such as potassium hydroxide or depolarizers such as manganese dioxide, and to generate an electromotive reaction While maintaining a necessary and sufficient amount of electrolyte, the internal resistance can be reduced without obstructing the conduction of ions, and the volume occupied when incorporated inside the battery is small, and the amount of the bipolar active material must be increased. Is what you can do.
【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。Conventionally, separator paper is mainly composed of alkali-resistant synthetic fiber vinylon fiber, alkali-resistant cellulose fiber viscose rayon fiber, linter pulp containing 98% or more α-cellulose component, mercerized kraft pulp and the like. A mixed paper of synthetic fibers and cellulose fibers to which polyvinyl alcohol fibers are added as a binder 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。[0004] For example, the applicant provides a separator paper in which mercerized wood kraft pulp (beaten product) is used alone or mixed with a synthetic fiber according to Japanese Patent Publication No. 57-9650, and can be beaten according to Japanese Patent Application Laid-Open No. 2-119049. We provide separator paper that is a mixture of alkali-resistant cellulose fibers (mercerized wood pulp, esparto pulp, manila hemp pulp, and polynosic rayon) and synthetic fibers. Japanese Unexamined Patent Publication (Kokai) No. 62-154559 discloses an alkali-based synthetic fiber having a fineness of 0.8 denier or less in place of part or all of the fibers constituting the separator paper, instead of the conventional thick fiber having a fineness of 1 to 3 denier. Separator paper for dry batteries, and the above synthetic fibers and cellulose fibers (unbeaten products such as rayon, linter pulp, and wood pulp) having a weight ratio of 15:85 to 85:
The structure of the 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。[0005] These materials contain an alkali-resistant cellulosic material having good wettability because vinylon fiber alone does not provide sufficient wettability with an electrolytic solution. Fibers are fibrillated by beating linter pulp or mercerized kraft pulp of alkali-resistant cellulosic material formulated for the purpose of improving wettability with electrolyte by using small fiber diameter of fiber It is intended to improve the compactness by crushing into fibers.
【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 above-mentioned alkali-resistant cellulose-based material in a high mixing ratio improves the liquid retaining property, but causes dimensional shrinkage due to the strong alkaline electrolyte, and has recently required a separator paper. It is not practical as a separator paper for alkaline dry batteries in light of the standards to be applied. That is, according to the above-mentioned Japanese Patent Publication No. 57-9650, it is possible to obtain a separator paper which is dense, has a high liquid retention property, and has excellent electric characteristics, but has an area shrinkage (40% -KOH × 7).
0 ° C. × 24 H), which is as large as 5 to 10%, and lacks alkali resistance. Also, according to Japanese Patent Application Laid-Open No. 2-119049,
Electrical properties are good, but liquid retention is a recent requirement.
In order to increase the ratio to 00% or more, it is necessary to mix the mercerized pulp in an amount of 35% by weight or more. In this case, the area shrinkage becomes as large as 5 to 10%. %, But the liquid retaining property is insufficient and the compactness is also lacking, and as a practical problem, it has not yet been possible to provide a satisfactory separator paper for alkaline dry batteries.
【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 case of an alkaline dry battery using zinc as a cathode active material, means for amalgamating the surface of zinc particles with mercury to obtain an active material has been used in order to smoothly perform a discharge reaction. In recent years, mercury-free mercury-free has been premised from the viewpoint of preventing environmental pollution by mercury. In this mercury-free alkaline battery, the physical contact between the 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, alkaline manganese dry batteries, for example, are becoming more diversified as portable power supplies with mercury-free cathodes, and their applications are expanding, and battery performance is improved, such as continuous discharge after storage and extension of discharge maintenance time of 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 apply a large amount of electrolyte to the separator paper to assist the diffusion of zinc ions in the cathode, thereby not impairing the conductivity and reducing the electric resistance. Part of the electrolyte injected into the separator paper in the dry battery involves migration to the anode active material wall and migration to the cathode side during discharge, and the separator layer causes an electromotive reaction due to the remaining electrolyte. The necessary and sufficient amount of electrolyte must be kept in the fibrous material of the separator paper. That is, the material (fiber) of the separator paper must be a fibrous material having wettability capable of holding an electrolytic solution that does not hinder ion diffusion. Physically, it can be said that a separator paper designed to be more porous is advantageous in temporarily retaining the electrolyte. However, on the other hand, it is required that the isolation between the two electrodes be denser in order to prevent a short circuit. Generally, as the density increases, the electric resistance increases and the discharge characteristics of the dry battery deteriorate. Therefore, there is no separator paper that satisfies various characteristics required of recent separator papers at the same time.
【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。Accordingly, the present invention provides a separator paper for an alkaline dry battery, which prevents internal short circuits and simultaneously satisfies at a high level various properties required for the separator paper, such as alkali resistance, denseness, liquid retention and electrical properties. Specifically, the area shrinkage rate is 5% or less for alkali resistance, the gas density is 3.0 seconds / 100 ml or more for denseness, and the liquid retention rate is 5 for liquid retention.
An object of the present invention is to provide an alkaline dry battery separator paper having an electrical characteristic of not less than 00% and 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配
合したものを原料として、気密度３．０秒／１００ｍｌ
以上に抄紙してなるアルカリ乾電池用セパレータ紙、及
び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配合したもの
を原料として、気密度３．０秒／１００ｍｌ以上で、か
つ、保液率５００％以上に抄紙してなるアルカリ乾電池
用セパレータ紙を基本として提供する。そして、面積収
縮率５％以下とする。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、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％〜２
０重量％配合した構成を提供する。In order 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 and is beaten. A gaseous density of 3.0 seconds / 100 ml using a raw material obtained by blending an organic solvent-spun rayon fiber of a possible purified cellulose fiber.
The separator paper for an alkaline dry battery prepared as described above, and the separator paper for separating the anode active material and the cathode active material in the alkaline dry battery, wherein the separator paper has an alkali resistance and can be beaten, and can be beaten. The present invention provides, as a base material, a separator paper for an alkaline dry battery, which is prepared by mixing a solvent-spun rayon fiber as a raw material and having a gas density of 3.0 seconds / 100 ml or more and a liquid retention rate of 500% or more. The area shrinkage is set to 5% or less. In addition, a mixture of alkali-resistant synthetic fibers, wherein the alkali-resistant synthetic fibers are vinylon fibers, and a part of the organic solvent-spun rayon fibers is selected from linter pulp or mercerized kraft pulp having an α-cellulose component of 98% or more. 30 for one or more
5 wt% to 2 wt% or less as a binder and a soluble polyvinyl alcohol fiber as a binder.
A composition containing 0% by weight is provided.
【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陰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-described structure, the obtained separator paper contains fibrillated ultrafine cellulose fibers in the separator paper, and has high density and excellent airtightness. When used as separator paper for alkaline batteries, the effect of preventing internal short circuits due to contact of bipolar active materials and internal short circuits due to mercury-free is large, and
It is possible to obtain a separator paper having a small 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 of the thickness by the electrolytic solution and is good along the anode wall. It has a remarkably strong property, and has a performance of lowering the electric resistance by holding a sufficient electrolytic solution between the electrodes, so that the electrolytic solution can be supplied to the gap between the cathode zinc particles even during the discharge. In addition, a dense paper layer is formed by the ultrafine branching fibers fibrillated by beating and has a more porous property than conventional products, so that both electrodes have more sufficient isolation and the cathode product is transferred to the anode. Penetration can be prevented, and the storage stability of the dry battery can be improved in addition to the high liquid retention. Therefore, while preventing internal short circuit, the alkali resistance and denseness required for the separator paper,
Various properties such as liquid retention and electrical properties can be simultaneously satisfied 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
用することにより、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％以上のセパレータを得るこ
とに特徴を有する。EXAMPLES Various examples of the separator paper for alkaline dry batteries according to the present invention will be described below. The present invention uses an organic solvent-spun rayon fiber of a refined cellulose fiber which has alkali resistance and can be beaten as a raw material of the separator paper, and thereby has an area shrinkage of 5% as alkali resistance.
Hereinafter, air tightness of 3.0 seconds / 100 ml or more as denseness,
It is characterized by obtaining a separator having a liquid retention of 500% or more as liquid retention.
【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。Organic solvent spun rayon fiber 40% -KO
The decomposition rate of the H aqueous solution at 70 ° C. × 100 hours is only 1.5
%, Which is much better in alkali resistance than the decomposition rate of general viscose rayon fiber under the same conditions of 12%. This indicates that shrinkage due to the electrolytic solution is extremely small as a separator paper for an alkaline dry battery using a high-concentration alkaline electrolytic solution, and is an optimal material for preventing shrinkage. In addition, organic solvent spun rayon fiber has the same wettability by electrolytic solution as viscose rayon fiber, excellent liquid retention with swelling action of fiber, and refiner like linter pulp and mercerized kraft pulp. It is possible to easily produce fibrillated microfibers by beating with such a method.
【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 fiber used in the present invention is a purified cellulose fiber. In the present invention, the term "refining" refers to a substance having a low content of metal components that adversely affect a dry battery, for example, iron and copper (several ppm order), an α-cellulose content of 99.8% or more, and an electrolytic solution. Of 40
% -KOH means that there is almost no eluting component in the aqueous solution.
This is because the organic solvent-spun rayon fiber uses only an organic solvent in the process of producing regenerated cellulose and does not use sodium hydroxide (NaOH) or carbon disulfide (CS 2 ) as in general viscose rayon. It is considered that there is almost no decrease in the amount of used chemicals or impurities remaining in the used chemicals.
【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 ultrafine fibers, and the beaten organic solvent-spun rayon fiber is used as a raw material for separator paper. To make paper. The content of organic solvent spun rayon fiber and beating degree
Although it can be set to an appropriate value in accordance with the characteristics required of the battery separator, in the case of the present invention, the content of the organic solvent-spun rayon fiber is in the range of 20% by weight to 90% by weight. And the beating degree is CS
F (Canadian Standard Freenes
In s), the range is from 500 ml to 0 ml. 90% by weight of organic solvent spun rayon fiber
Above, the liquid retention is close to the limit, the dimensional shrinkage increases, and there is no practicality. If it is less than 20% by weight, the liquid retention is not so different from the conventional product and is insufficient. Further, when the beating degree exceeds 500 ml or more of CSF, the fibrillation of the fibers by beating is insufficient and the density is inferior. And yields such as a decrease in yield.
【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 beating is mixed with alkali-resistant synthetic fiber such as vinylon fiber or alkali-resistant regenerated cellulose fiber such as polynosic rayon fiber. It is possible to obtain a separator paper having excellent denseness by increasing the denseness and reducing the pore diameter between 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ができ、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 added to one or a plurality of linter pulp or mercerized kraft pulp having an α-cellulose component of 98% or more by 30% by weight or less (preferably 15% by weight or less). 30% by weight), and a separator paper with a high content of alkali-resistant cellulose fibers having a small area shrinkage can be obtained by this substitution. The linter pulp and mercerized kraft pulp are economically cheaper than the organic solvent-spun rayon fiber, and substituting a part of the material with these materials has practical advantages. When the substitution range is 30% by weight or more, the dimensional shrinkage is too large and the desired effect cannot be obtained.
【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 blended as a binder depending on the required strength of the separator paper. The soluble polyvinyl alcohol fibers are dissolved in the drying step of the paper machine with increasing water temperature in the wet paper, and after being dried, bind the fibers to strengthen the strength. If the compounding ratio is less than 5% by weight, the required strength cannot be obtained. Conversely, if it exceeds 20% by weight, the porosity between the fibers decreases, and the electric resistance increases, 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 producing 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 of COURTAULDS in water and subjecting it to a predetermined beating with a double disc refiner to obtain another fiber material. The mixture was mixed and paper was made using a circular paper machine. The beating degree of the organic solvent spun rayon fiber was CSF5.
The blending in the region 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 are 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% by weight of an organic solvent spun rayon fiber (1.5d × 3mm) was beaten to 500ml of CSF with a double disc refiner, and then 15% by weight of vinylon fiber (1d × 3mm) and soluble polyvinyl alcohol fiber (1d × 3mm) 5 wt% was blended to obtain a raw material, and the paper was made by a circular 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 (1.5d × 3mm) was beaten to 380ml of CSF with a double disc refiner, and then 40% by weight of vinylon fiber (1d × 3mm) and soluble polyvinyl alcohol fiber (1d × 3mm) 10% by weight was blended to obtain a raw material, and papermaking was performed using a circular paper machine to obtain 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 × 3mm) 10 wt% was blended to make a raw material, and the paper was made with a circular paper machine to a thickness of 125 μm and a basis weight of 3
8.0 g / m 2 of separator paper 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 An organic solvent spun rayon fiber (1.5 d × 3 mm) was beaten to 300 ml CSF with a double disc refiner and then dissolved with 30 wt% polynosic rayon fiber (1.5 d × 3 mm). Polyvinyl alcohol fiber (1d × 3mm) 20% by weight is blended to make a raw material, and the paper is made with a circular 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 an organic solvent-spun rayon fiber (1.5d.times.3 mm) was beaten to 300 ml of CSF with a double disc refiner, and then 20% by weight of mercerized kraft pulp and vinylon fiber (1d.times.3 m
m) 20% by weight of soluble polyvinyl alcohol fiber (1
(d × 3 mm) as a raw material by blending 10% by weight, and papermaking was performed using a circular 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% by weight of an organic solvent spun rayon fiber (1.5d.times.3 mm) was beaten to 200 ml of CSF with a double disc refiner, and then 25% by weight of linter pulp and polynosic rayon fiber (1.5d)
× 3 mm) of 25% by weight and soluble polyvinyl alcohol fiber (1d × 3mm) of 15% by weight were blended to obtain a raw material, which was then paper-made with a round paper machine to have a thickness of 128 μm and a basis weight of 37.8 g /
It was obtained m 2 separator sheets.
【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 an organic solvent-spun rayon fiber (1.5d.times.3 mm) was beaten to 0 ml of CSF by a double disc refiner, and then 10% by weight of linter pulp was blended into a raw material paper machine. Papermaking was performed 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 × 3mm) 1
0 wt% was blended to obtain a raw material, and papermaking was performed with a circular 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 Mercerized Pulp 35% by Weight
Was beaten to CSF 500 ml with a double disc refiner, and then 55% by weight of vinylon fiber (0.5 d × 2 mm) and soluble polyvinyl alcohol fiber (1 d × 3 mm) were used.
10 wt% was blended to obtain a raw material, and papermaking was performed by a circular 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 mercerized pulp of Comparative Example 2 and viscose rayon fiber (0.7 d × 3 m
m) Vinylon fiber (0.5d × 2mm) 4 in 25% by weight
0% by weight and soluble polyvinyl alcohol fiber (1d × 3
mm) 10 wt% was blended as a raw material to make a paper using a circular 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, vinylon fiber (0.5d × 2mm) 40% by weight and soluble polyvinyl alcohol fiber (1d × 3mm)
10 wt% was blended and used as a raw material to make paper with a round 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。With respect to 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 / 15 mm), airtightness ( Seconds), liquid retention (%), shrinkage (%), electrical 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 five locations on the obtained separator paper with a dial thickness gauge and the average value was obtained.
【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 used was a method specified in JIS P 8124, and the tensile strength was a 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 The airtightness was measured by attaching a 6 mm-diameter cylindrical throttle to the lower test piece mounting part of a B-type measuring instrument according to JIS P 8117 (air permeability test method for paper and paperboard), and placing a separator paper on the narrowing surface. , And the cylindrical surface of the separator paper is 6 mm in diameter and 100 m in length.
Time required for 1 l of air to pass (seconds / 100 ml)
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 ratio A test piece having a size of 50 × 50 mm was immersed in a 40% -KOH aqueous solution for 10 minutes, 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 equation. 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 Rate The length of a test piece having a size of 100 × 100 mm after being immersed in a 40% -KOH aqueous solution at 70 ° C. for 24 hours was measured, and the area shrinkage rate was obtained by the following equation. 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 The electric resistance is determined by using a 40% -KOH aqueous solution as an electrolytic solution.
Insert separator paper between platinum electrodes at 3 mm intervals,
The increase in the electrical resistance between the electrodes due to the insertion was measured using an ESR meter at a frequency of 1 Kz and defined as the electrical 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 measurement of the separator papers of the above-mentioned Examples and Comparative Examples using such a 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 the organic solvent spun rayon fiber was CSF 500 to 1
It was beaten to 00 ml and fibrillated. Compared to Comparative Examples 1 to 3 having substantially the same thickness and basis weight, the airtightness indicating the denseness was 1.4 to 2.2 seconds of the conventional product. From 3.0
To 3.5 seconds, the compactness is improved, and at the same time, the retention rate of the electrolyte is also improved 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. I have.
【００４１】実施例５，６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６１０〜６３０％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 5 and 6, in order to further improve the liquid retention rate and to obtain an economic effect, a part of the organic solvent-spun rayon fiber was converted to linter pulp or mercerized with an inexpensive α-cellulose component of 98% or more. Although it is an alternative to kraft pulp, the airtightness indicating the denseness is improved to be equal to or higher than 3.5 to 4.0, and the denseness is improved as compared with Examples 1 to 3, and at the same time, the electrolytic solution And the electrical resistance is also 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, the organic solvent-spun rayon fiber 9
It is made from ultra-fine fibers obtained by beating 0% by weight to a region having a CSF value of 0 ml, and has a tensile strength of 3.0 kg, a practically acceptable strength, a gas density of 19 seconds, and a liquid retention ratio. Of 665% and an electrical resistance of 11 mΩ was 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
とを知ることができる。Comparative Example 4 confirms the characteristics of a separator paper obtained by mixing a conventional alkali-resistant cellulose fiber at a high mixing ratio. The shrinkage was 11.2% by an electrolytic solution (40% -KOH aqueous solution). And 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 can prevent an internal short circuit, and at the same time, have the alkali resistance, denseness, liquid holding property, and electric resistance required for the separator paper. Alkaline dry battery separator paper that simultaneously satisfies various characteristics such as characteristics at a high level, more specifically, 5% area shrinkage as alkali resistance
Hereinafter, air tightness of 3.0 seconds / 100 ml or more as denseness,
Liquid retention rate of 500% or more for liquid retention, ES for electrical properties
R20 mΩ or less separator paper can be obtained. Therefore, the separator paper obtained by using the conventional alkali-resistant cellulose fiber, has a high airtightness and dense, has a sufficient isolation function of the mercury-free cathodic zinc and anode active material, beaten fine and The ultrafine fibers exhibit a low electric resistance by retaining a sufficient electrolytic solution, have a high liquid retention function for improving battery performance, and can provide a surprising separator paper having a small area shrinkage.
【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 mercury-free zinc was prototyped.
Table 2 shows the results of conducting continuous discharges of 75Ω and 390Ω at 0 ° C. and testing the voltage retention time up to the end voltage (0.9V).
【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。[0047] In 75Ω continuous discharge As is evident from Table 2, whereas the batteries of Comparative Examples 1 to 3 using the conventional separator paper voltage sustaining time is 151 to 154 hours, carried according to the present invention embodiment It was confirmed that the batteries of Nos. 1 to 3 took 161 hours or more, and the batteries of Examples 4 to 6 took 166 hours or more. Comparative example 1 even in 390Ω continuous discharge
The batteries of Examples 1 to 3 according to the present invention were 905 hours or more, whereas the batteries of Examples 4 to 3 were 794 to 830 hours.
Battery No. 6 was confirmed to be 930 hours or more. Further, in the battery of Example 7, 162
The time was 965 hours in a 390Ω continuous discharge. It is considered that a short circuit inside the battery was prevented, and an electrolytic solution sufficient for battery discharge was interposed between the two electrodes until the end of discharge to allow sufficient diffusion of zinc ions as compared with a conventional product.
【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
を配合することにより、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、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得ることができる。As described in detail above, the separator paper for an alkaline dry battery according to the present invention can have a high liquid retaining property in a high-concentration alkaline electrolyte by mixing a general alkali-resistant cellulose fiber. Eliminates the drawbacks of conventional alkaline paper dry paper separator paper, which cannot design separator paper with small dimensional shrinkage and high density, and has higher alkali resistance, better wettability, and higher concentration than conventional alkali-resistant cellulose fiber. By blending organic solvent spun rayon fiber with small dimensional shrinkage even in alkaline electrolyte, alkali with low dimensional shrinkage, denseness, wettability, liquid retention and low electrical resistance compared to conventional products by blending with organic solvent spun rayon fiber. Separator paper for dry batteries, specifically, an area shrinkage of 5% or less as alkali resistance, and an air density of 3.0 seconds / 1 as denseness. 0ml above, liquid retention rate as the liquid retaining 5
It is possible to obtain an alkaline dry battery separator paper having an electric property of not less than 00% and ESR of not more than 20 mΩ.
【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 organic solvent-spun rayon fibers have a swelling property without shrinkage due to the electrolyte of the alkaline dry battery, and the holding power of the electrolyte is increased, so that a high liquid retention function as a separator is obtained. It is a separator paper having a small pore size and a high density due to having a paper layer structure of fibrillated ultrafine branched fibers. As a result, when used as separator paper for alkaline dry batteries, the effect of preventing internal short circuit due to contact between the bipolar active materials is large, the number of stacked separator papers can be reduced, the filling amount of cathode zinc particles is increased, and the electric power of dry batteries is increased. The capacity can be increased. Furthermore, since the denseness is uniformly high, an internal short circuit due to a conductive product from cathodic zinc accompanying mercury-free can be prevented, and the long-term storability of the dry battery can be improved. In addition, the paper layer structure of the ultrafine branched fibers having a good electrolyte retention property has an advantage that the electric resistance is reduced and the heavy load discharge performance of the alkaline dry battery is remarkably improved.
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
配合したものを原料として、気密度３．０秒／１００ｍ
ｌ以上に抄紙してな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 is blended with an organic solvent-spun rayon fiber of purified cellulose fiber which has alkali resistance and can be beaten. 3.0 seconds / 100m
1. A separator paper for alkaline dry batteries, characterized by being made into paper at least l.
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
配合したものを原料として、気密度３．０秒／１００ｍ
ｌ以上で、かつ、保液率５００％以上に抄紙してなるこ
とを特徴とするアルカリ乾電池用セパレータ紙。2. A separator paper for separating an anode active material and a cathode active material in an alkaline dry battery, wherein the separator paper is blended with an organic solvent-spun rayon fiber of purified cellulose fiber which has alkali resistance and can be beaten. 3.0 seconds / 100m
A separator paper for alkaline dry batteries, characterized in that the paper is made to have a liquid retention rate of 500% or more.
２記載のアルカリ乾電池用セパレータ紙。3. The alkaline dry battery separator paper according to claim 1, wherein the area shrinkage is 5% or less.
求項１，２又は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 paper is a mixture of alkali-resistant synthetic fibers.
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 according to claim 4, wherein the alkali-resistant synthetic fiber is vinylon 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又は５記載のアルカリ乾電池用セパレータ紙。6. An organic solvent-spun rayon fiber having a portion
3. The composition according to claim 1, wherein the composition is replaced by one or more selected from linter pulp or mercerized kraft pulp having a cellulose content of 98% or more in a blending range of 30% by weight or less.
6. The separator paper for alkaline dry batteries according to 3, 4 or 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又は６記載のアルカリ乾電池用セパレー
タ紙。7. The method according to claim 1, wherein 5 to 20% by weight of the soluble polyvinyl alcohol fiber is used as a binder.
7. The separator paper for an alkaline dry battery according to 2, 3, 4, 5, or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002009371A JP2002251988A (en) | 2002-01-18 | 2002-01-18 | Separator paper for alkaline dry battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002009371A JP2002251988A (en) | 2002-01-18 | 2002-01-18 | Separator paper for alkaline dry battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04184193A Division JP3290734B2 (en) | 1993-02-04 | 1993-02-04 | Separator paper for alkaline batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002251988A true JP2002251988A (en) | 2002-09-06 |
Family
ID=19191508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002009371A Pending JP2002251988A (en) | 2002-01-18 | 2002-01-18 | Separator paper for alkaline dry battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002251988A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006236808A (en) * | 2005-02-25 | 2006-09-07 | Kuraray Co Ltd | Separator for alkaline battery and alkaline primary battery |
| JP2009080998A (en) * | 2007-09-25 | 2009-04-16 | Fdk Energy Co Ltd | Separator material for alkaline cell, and alkaline cell |
| JP2014123443A (en) * | 2012-12-20 | 2014-07-03 | Lenzing Ag | Alkali battery separator, and alkali battery |
| CN115117555A (en) * | 2022-04-13 | 2022-09-27 | 中国制浆造纸研究院有限公司 | Composite diaphragm material for alkaline manganese battery and preparation method thereof |
-
2002
- 2002-01-18 JP JP2002009371A patent/JP2002251988A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006236808A (en) * | 2005-02-25 | 2006-09-07 | Kuraray Co Ltd | Separator for alkaline battery and alkaline primary battery |
| JP2009080998A (en) * | 2007-09-25 | 2009-04-16 | Fdk Energy Co Ltd | Separator material for alkaline cell, and alkaline cell |
| JP2014123443A (en) * | 2012-12-20 | 2014-07-03 | Lenzing Ag | Alkali battery separator, and alkali battery |
| CN115117555A (en) * | 2022-04-13 | 2022-09-27 | 中国制浆造纸研究院有限公司 | Composite diaphragm material for alkaline manganese battery and preparation method thereof |
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