JPH0249350A - Separator for alkaline battery - Google Patents
Separator for alkaline batteryInfo
- Publication number
- JPH0249350A JPH0249350A JP63200616A JP20061688A JPH0249350A JP H0249350 A JPH0249350 A JP H0249350A JP 63200616 A JP63200616 A JP 63200616A JP 20061688 A JP20061688 A JP 20061688A JP H0249350 A JPH0249350 A JP H0249350A
- Authority
- JP
- Japan
- Prior art keywords
- nonwoven fabric
- separator
- melt
- fiber
- alkali
- 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
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 59
- 239000003513 alkali Substances 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 5
- 229920001410 Microfiber Polymers 0.000 claims description 21
- 229920002994 synthetic fiber Polymers 0.000 claims description 17
- 239000012209 synthetic fiber Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000835 fiber Substances 0.000 abstract description 43
- 125000005456 glyceride group Chemical group 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000080 wetting agent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 1
- 150000002194 fatty esters Chemical class 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract 1
- 238000007127 saponification reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000010030 laminating Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003658 microfiber Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000004627 regenerated cellulose Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 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
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は保液性、吸液性にすぐれ、放電特性の良好なア
ルカリ電池用セパレータに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a separator for alkaline batteries that has excellent liquid retention and liquid absorption properties and good discharge characteristics.
従来、アルカリ電池用セパレータとして様ざまな素材が
提案されている。例えば、平均礒度０１０１〜０、５
ｆニールのポリプロピレン極細繊維の不織布と耐アルカ
リ性合成繊維の不織布をラミネートしたものをセパレー
タにすることが特開昭６０−９０５６号公報に、０．３
〜１．０デニールのポリプロピレン繊維からなる不織布
と、２〜３デニールのポリプロピレン繊維からなる不織
布とを圧着し九セパレータが特開昭６０−１７０１５９
号公報に、ビスコースレーヨンａｓとｓ溶解性ポリビニ
ルアルコール系繊維と易溶解性ポリビニルアルコール系
繊維とを混抄して得た紙あるいは不織布をセパレータに
用いた電池が特開昭４８−８３３３４号公報に提案され
ている。また、本願出願人は高純度天然セルロース繊維
と直径が３〜１５μｍの化合繊維との混合物をシート状
物にしたセパレータを特開昭６１−３９４５１号公報に
、繊度が２デニール以下の合成線維または化学繊維と熱
融着性繊維状バインダーから作られた紙筒のセパレータ
であって、アルカリ吸液量が４り／ｆ以上、２５ｗ当り
のアルカリ吸液時間が１２０秒以下であるセパレータを
特開昭６１−１２８４６０号公報に、そしてセパレータ
紙の構成線維として、繊度０．８デニール以下の合成繊
維を使用することを特開昭６２−１５４５５９号公報に
既に提案している。Conventionally, various materials have been proposed as separators for alkaline batteries. For example, average hardness 0101~0,5
JP-A No. 60-9056 discloses that a separator made by laminating a non-woven fabric made of ultrafine polypropylene fibers and a non-woven fabric made of alkali-resistant synthetic fibers is used as a separator.
A non-woven fabric made of ~1.0 denier polypropylene fiber and a non-woven fabric made of 2-3 denier polypropylene fiber are bonded together to produce a nine separator made in JP-A-60-170159.
JP-A No. 48-83334 discloses a battery using paper or nonwoven fabric obtained by mixing viscose rayon AS, S-soluble polyvinyl alcohol fiber, and easily soluble polyvinyl alcohol fiber as a separator. Proposed. In addition, the applicant of the present application has published a separator made of a sheet-like mixture of high-purity natural cellulose fibers and synthetic fibers with a diameter of 3 to 15 μm in Japanese Patent Application Laid-Open No. 61-39451. A separator in the form of a paper tube made from chemical fibers and a heat-fusible fibrous binder, which has an alkali absorption amount of 4 l/f or more and an alkali absorption time of 120 seconds or less per 25 W, is disclosed in Japanese Patent Publication No. The use of synthetic fibers having a fineness of 0.8 denier or less as the constituent fibers of separator paper has already been proposed in Japanese Patent Application Laid-open No. 62-154559.
従来のアルカリ電池用セパレータは耐アルカリ性を主体
とした性能の改善を計るために１疎水性繊維、とシわけ
ポリプロピレン繊維を主体とした繊維構造物を用いてい
る。このセパレータでは耐アルカリ性が増大し、耐用時
間は長くなったが、保液性、吸液性において劣るため電
解液の偏在化をまねき、内部放電を生じて電池の寿命を
短かくする。そうした欠点を解決する１つの手段として
ポリプロピレン極細繊維からなる不織布、例えばメルト
プローン法で作られたポリプロピレン極細繊維の不織布
にポリオキシエチレンアルキルエーテル型活性剤などの
親水化剤を付与する方法も提案されている（％開昭６０
−９０５６号公報）が、後処理による親水化処理では、
初期には活性剤が有効に作用し、電池の寿命は多少は改
善されるが、放電回数の増加に伴なって電解液の偏在化
現象が見られるようになる。更に、均一な濡れ状態を作
ることが難かしいなどの問題がある。Conventional separators for alkaline batteries use a fibrous structure mainly composed of hydrophobic fibers and partially separated polypropylene fibers in order to improve performance mainly in terms of alkali resistance. Although this separator has increased alkali resistance and has a longer service life, it has poor liquid retention and liquid absorption properties, leading to uneven distribution of the electrolyte, causing internal discharge and shortening the life of the battery. As one means of solving these drawbacks, a method has also been proposed in which a hydrophilic agent such as a polyoxyethylene alkyl ether type activator is added to a nonwoven fabric made of ultrafine polypropylene fibers, such as a nonwoven fabric made of ultrafine polypropylene fibers made by a melt-prone method. (% 1986)
-9056), but in the hydrophilic treatment by post-treatment,
Initially, the activator acts effectively and the battery life is improved to some extent, but as the number of discharges increases, the electrolyte becomes unevenly distributed. Furthermore, there are other problems such as difficulty in creating a uniform wet state.
本発明は、耐アルカリ性で保液性、吸液性、目止め性に
優れ、かつ吸水速度の速いアルカリ電池用セパレータを
提供するにある。The present invention provides a separator for alkaline batteries that is resistant to alkali, has excellent liquid retention, liquid absorption, and sealing properties, and has a high water absorption rate.
本発明はエチレン含有量３５〜６０モルチのエチレン・
酢酸ビニル共重合体ケン化物、親水性化ポリエチレンあ
るいは親水性化エチレン共重合体の群から選ばれた少な
くともＩＰ／１のポリマーを主体とするポリ！−のメル
トプローン極細繊維不織布と耐アルカリ性合成轍維不織
布との積層不織布で構成したことを特徴とするアルカリ
電池用セパレータである。The present invention uses ethylene with an ethylene content of 35 to 60 molt.
Poly!, which is mainly composed of a polymer with an IP/1 of at least selected from the group of saponified vinyl acetate copolymer, hydrophilized polyethylene, or hydrophilized ethylene copolymer. - A separator for alkaline batteries characterized by being constructed of a laminated nonwoven fabric of a melt-prone microfiber nonwoven fabric and an alkali-resistant synthetic rutted fiber nonwoven fabric.
すなわち、本発明のアルカリ電池用セパレータは、■エ
チレン含有量３５〜６０モルチのエチレン・酢酸ビニル
共重合体ケン化物、■親水性化ポリエチレンあるいは親
水性化エチレン共重合体の群から選ばれた少なくとも１
種のポリマーの溶融物を流体流によって極細愼維流とし
て紡出し、捕集体に集積して得たメルトプローン極細繊
維不織布と、耐アルカリ性合成繊維あるいは該合成繊維
とセルロース繊維、再生セルロース繊維との混合繊維で
作られ九不織布とを積層し、積層不織布は必要に応じて
一体化処理するととＫよって製造することができる。That is, the separator for alkaline batteries of the present invention comprises at least one selected from the group of: (1) a saponified ethylene/vinyl acetate copolymer having an ethylene content of 35 to 60 moles, and (2) hydrophilized polyethylene or hydrophilized ethylene copolymer. 1
A melt-prone ultrafine fiber nonwoven fabric obtained by spinning a melt of a seed polymer into an ultrafine fiber stream using a fluid stream and accumulating it in a collection body, and alkali-resistant synthetic fibers or a mixture of the synthetic fibers and cellulose fibers or regenerated cellulose fibers. The laminated nonwoven fabric can be manufactured by laminating nonwoven fabrics made of fibers, and performing an integration process if necessary.
本発明のアルカリ電池用セパレータは、特定のポリマー
のメルトプローン極細繊維不織布を使用することによっ
て、吸液性、保液性および吸液速度を高めることができ
るとともに、活物質のセパレータ通過を抑制することが
できる。The alkaline battery separator of the present invention uses a melt-prone microfiber nonwoven fabric made of a specific polymer to improve liquid absorption, liquid retention, and liquid absorption speed, and to suppress the active material from passing through the separator. be able to.
すなわち、メルトプローン極細繊維不織布を構成するポ
リマーは、親水性、耐アルカリ性であって、かつメルト
プローン法で紡出して極細礒維流を形成するポリマーで
ある。好ましくは平均繊維直径が約５μｍ以下の極細繊
維流となるポリマーである。そのようなポリマーとして
は、■エチレン含有量が３５〜６０モルチ、モル化度８
０チ以上のエチレン・酢酸ビニル共重合体のケン化物〔
例えば、商品名「エバール」（株式会社クラレ製品）〕
であシ、この範囲外のポリマーではアルカリ膨潤度が大
きくなつ九り、紡出繊維の太さが不均一になつ九り、電
解液の親和性が低下したりして好ましくない。■混合グ
リセライド、アルコキシ化アルキルフェノール、ポリオ
キシアルキレン脂肪酸エステルなどの湿潤剤を配合して
得た親水性化ポリエチレンあるいは親水性化エチレン共
重合体〔例えば、商品名’ ＡＳＰＵＮ ” （アスパ
ン：ザ・ダウ・ケミカル社製品）〕である。これらのポ
リマー群から選ばれた少なくとも１種のポリマーを主体
としたポリマーを溶融し、メルトプローン用ダイを用い
て流体流によって極ａｔ繊維流として紡出させて不織布
とする。この場合、不織布の親水性を高め九ものにしよ
うとするなら、ポリマーの溶融系あるいはメルトプロー
ン紡出系までの過程で親水性化剤、例えば混合グリセラ
イド、アルコキシ化アルキルフェノール、ポリオキシア
ルキレン脂肪酸エステル、などの湿潤剤あるいはノニオ
ン活性剤を添加することも電解液の移動、保液性などか
ら好ましい。添加量はポリマー重量に対して０．１〜５
重量％である。また、上記ポリマー■あるいはポリマー
■には熱可塑性で耐アルカリ性ポリマー例えばポリプロ
ピレン、ポリエチレン、エチレン共重合体、ポリビニル
アルコールなどから選ばれたポリマーを混合して溶融紡
出を行って不織布とすることも、不織布の成形性に有効
である。That is, the polymer constituting the melt-prown ultrafine fiber nonwoven fabric is a polymer that is hydrophilic, alkali-resistant, and can be spun by the melt-prone method to form an ultrafine fiber stream. Preferably, it is a polymer that results in ultrafine fiber flow with an average fiber diameter of about 5 μm or less. Such polymers include: (1) an ethylene content of 35 to 60 mol/mole, and a molarization degree of 8;
Saponified product of 0% or more ethylene/vinyl acetate copolymer [
For example, the product name “EVAL” (Kuraray Co., Ltd. product)
However, polymers outside this range are undesirable because the degree of alkali swelling increases, the thickness of the spun fibers becomes non-uniform, and the affinity for the electrolyte decreases. ■Hydrophilized polyethylene or hydrophilized ethylene copolymer obtained by blending a wetting agent such as mixed glyceride, alkoxylated alkylphenol, or polyoxyalkylene fatty acid ester [for example, the product name 'ASPUN' (The Dow) A non-woven fabric is produced by melting a polymer mainly composed of at least one polymer selected from these polymer groups and spinning it as a super at fiber stream using a melt-prone die using a fluid stream. In this case, if you want to increase the hydrophilicity of the nonwoven fabric, you can add a hydrophilic agent such as mixed glyceride, alkoxylated alkylphenol, or polyoxyalkylene in the process up to the polymer melt system or melt-prone spinning system. It is also preferable to add a wetting agent such as a fatty acid ester or a nonionic activator from the viewpoint of electrolyte movement, liquid retention, etc. The amount added is 0.1 to 5% based on the weight of the polymer.
Weight%. Alternatively, a thermoplastic and alkali-resistant polymer selected from polypropylene, polyethylene, ethylene copolymer, polyvinyl alcohol, etc. may be mixed with the above polymer (1) or polymer (2) and melt-spun to obtain a nonwoven fabric. Effective for moldability of nonwoven fabrics.
メルトブローン法で紡出した極細繊維流は捕集体に集積
して極細繊維不織布とする。不織布の平均目付は１０〜
４０ ｆ／ｒｌの範囲であり、この範囲外の目付では繊
維密度や厚みの均質が悪くなる、セパレータとしての隔
膜が厚くなるなどのために保液性、通液性あるいは目止
め性が悪くなる。The ultrafine fiber stream spun by the melt-blown method is collected in a collecting body to form an ultrafine fiber nonwoven fabric. The average basis weight of nonwoven fabric is 10~
40 f/rl, and if the basis weight is outside this range, the fiber density and thickness will become less uniform, and the diaphragm serving as a separator will become thicker, resulting in poor liquid retention, liquid permeability, or sealing properties. .
また、極細繊維不織布罠積層する耐アルカリ性合成線維
およびその不織布は、ポリエチレン繊維、ポリプロピレ
ン線維、ポリエチレン・ポリプロピレン線維、エチレン
・酢酸ビニル共重合体ケン化物系繊維、ポリビニルアル
コール系繊維から選ばれた少なくとも１種の合成繊維あ
るいは該合成繊維とセルロース繊維、再生セルロース繊
維との混合繊維を用い、湿式法あるいは乾式法で作られ
た不織布である。この不織布を構成する繊維の繊度は５
デニール以下、好ましくは３〜０．３デニールの範囲で
ある。また、不織布の平均目付は５〜４０ｆ／ｒｌの範
囲である。In addition, the alkali-resistant synthetic fibers and nonwoven fabrics to be laminated in the microfiber nonwoven fabric trap are at least one selected from polyethylene fibers, polypropylene fibers, polyethylene/polypropylene fibers, saponified ethylene/vinyl acetate copolymer fibers, and polyvinyl alcohol fibers. It is a nonwoven fabric made by a wet method or a dry method using synthetic fibers or mixed fibers of synthetic fibers and cellulose fibers or regenerated cellulose fibers. The fineness of the fibers that make up this nonwoven fabric is 5
Denier or less, preferably in the range of 3 to 0.3 denier. Moreover, the average basis weight of the nonwoven fabric is in the range of 5 to 40 f/rl.
次に、メルトプローン極細繊維不織布と耐アルカリ性合
成砿維不織布の積層は、それぞれの不織布を通常の接着
剤、熱溶融接着剤などで積層接着する方法、耐アルカリ
性合成繊維不織布を捕集体としてメルトブローン法で紡
出し九極細繊維流を捕集・集積して積層不織布とし、熱
プレスまたはプレスして積層接着する方法あるいは耐ア
ルカリ性合成繊維不織布とメルトブロン極細繊維不織布
とを積層し、熱プレスまたはプレスして積層接着する方
法などで積層不織布を得る。積層不織布の目付は１５〜
８０９／ｒｌの範囲で、メルトプローン極細繊維不織布
と耐アルカリ性合成繊維不織布との積層比は目付でｌ：
１〜３：１の範囲である。Next, the melt-blown microfiber non-woven fabric and the alkali-resistant synthetic fiber non-woven fabric are laminated by laminating and bonding the respective non-woven fabrics using a conventional adhesive, hot-melt adhesive, etc., or by the melt-blown method using the alkali-resistant synthetic fiber non-woven fabric as a collector. A method of collecting and accumulating nine ultra-fine fiber streams spun in a method to make a laminated non-woven fabric, and then laminating and bonding by heat pressing or pressing, or laminating an alkali-resistant synthetic fiber non-woven fabric and a melt-blown ultra-fine fiber non-woven fabric, and then hot pressing or pressing. A laminated nonwoven fabric is obtained by a method such as lamination and adhesion. The basis weight of laminated nonwoven fabric is 15~
In the range of 809/rl, the lamination ratio of the melt-prone ultrafine fiber nonwoven fabric and the alkali-resistant synthetic fiber nonwoven fabric is l:
It is in the range of 1 to 3:1.
それＫよって保液性、通液性および目止め性の均衡のと
れたセパレータが得られる。As a result, a separator with well-balanced liquid retention, liquid permeability and sealing properties can be obtained.
また、積層不織布には通常界面活性剤処理が行われるが
、本発明ではメルトブローン法で紡出するまでの過程で
活性剤の付与が行われ、積層不織布での処理は補助的に
行われるものである。従って、界面活性剤の付与Ｌ′ｃ
は通常のものよシ少ない量の、積層不織布に対して０．
２〜３重量−の範囲である。In addition, laminated nonwoven fabrics are usually treated with a surfactant, but in the present invention, the surfactant is applied during the process up to spinning by the melt-blown method, and the treatment on the laminated nonwoven fabric is performed as an auxiliary treatment. be. Therefore, the application of surfactant L'c
is 0.0 for the laminated nonwoven fabric, which is a smaller amount than the normal one.
It is in the range of 2 to 3 weight.
本発明のアルカリ電池用セパレータは耐アルカリ性に優
れ、目止め効果が高いために活物質（例えばＺ ｎ ｅ
）のセパレータ貫通を防止し、吸液性、保液性に優れた
ものが得られる。特に低水銀化の電池用に好適である。The separator for alkaline batteries of the present invention has excellent alkali resistance and has a high sealing effect, so it can be used as an active material (for example, Z
) can be prevented from penetrating the separator, resulting in a product with excellent liquid absorption and liquid retention properties. It is particularly suitable for low mercury batteries.
次Ｋ、本発明の実施態様を具体的な実施例で説明するが
、これら実施例に限定されるものではない。なお、実施
例中の部および％はことわりのない限り重量に関するも
のである。Next, embodiments of the present invention will be explained with specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified.
また、実施例中の測定値については、次の試験法による
。In addition, the measured values in the examples are based on the following test method.
（１）吸液量；大きさが５ｃｒＩｔ×５ＣＩＩＮの試料
をとって重量を測定（Ｗ ｏ ）、次いでＫＯＨ濃度４
０ｑ６水溶液に試料を３０分間浸漬した後、取〕出して
３０秒間吊し、試料に含浸した液を自然落下で除去し、
再度試料の重量を測定（Ｗｌ）して、保液量（Ｗ）を算
出する。（Ｗｌ−Ｗｏ） ／Ｗｏ＝Ｗ （ｆ／Ｑ（２）
吸液速度：大きさが５ｃｂ
ＫＯＨ９度４０％水溶液を０．０５ｃｃ（１滴）を滴下
し、その液滴が試料内に浸透するまでの時間を測定する
。(1) Amount of liquid absorbed: Take a sample with a size of 5 crIt x 5 CIIN, measure its weight (W o ), and then absorb a sample with a KOH concentration of 4
After immersing the sample in the 0q6 aqueous solution for 30 minutes, take it out and hang it for 30 seconds to remove the liquid impregnated with the sample by gravity.
The weight of the sample is measured again (Wl) and the amount of liquid retained (W) is calculated. (Wl-Wo) /Wo=W (f/Q(2)
Liquid absorption rate: Drop 0.05 cc (1 drop) of a 5 cb KOH 9°C 40% aqueous solution and measure the time it takes for the droplet to penetrate into the sample.
実施例１
〔極細繊維不織布の製造〕
エチレン含有量の異なるエチレン・ビニルアルコール共
重合体（メルトインデックス４０〜４１の範囲）を溶融
温度２５０℃、メルトブローン用ダイに直径０．３ ｍ
ｓの孔を１ｊＩＪ間隔で一列に配列したノズル部と、そ
の両側にＩｔＧｌ ０．２５ ａｍの気体吐出用スリッ
トを設けたダイを用い、孔当シの吐出１０．２Ｆ／分、
気体温度２６０°Ｃ１気体圧力１．５に９．／ｙｌの条
件で紡出し、紡出極細゛繊維流はダイより約２５鼾の位
置に設置した一定速度で移動するベルトコンベアネット
捕集様に捕集して目標平均目付３゜ｆ／−の繊維ウェブ
を得た。Example 1 [Manufacture of ultrafine fiber nonwoven fabric] Ethylene-vinyl alcohol copolymers with different ethylene contents (melt index in the range of 40 to 41) were melted at a melting temperature of 250°C and placed in a melt-blown die with a diameter of 0.3 m.
Using a die with a nozzle part in which s holes were arranged in a row at 1jIJ intervals and slits for discharging ItGl 0.25 am gas on both sides, the discharge rate of the hole per hole was 10.2F/min,
Gas temperature 260°C1 Gas pressure 1.59. /yl, and the spun ultra-fine fiber stream is collected by a belt conveyor net that moves at a constant speed and is installed at a position of about 25 mm from the die to achieve a target average basis weight of 3°f/-. A fibrous web was obtained.
この繊維ウェブのアルカリ膨潤度を調べた結果を表１に
示した。すなわち、繊維ウェブを１２０℃に加温したカ
レンダーで処理し、平均厚さ０．２藺の不織布としたも
のを試料とし、２０℃のＮａＯＨ１０ｑ６水溶液に７日
間浸漬したときの膨潤度を測定した。更に、メルトプロ
ーンによる紡糸性を併せて表１に示した。Table 1 shows the results of examining the degree of alkali swelling of this fibrous web. That is, a fibrous web was treated with a calender heated to 120°C to obtain a nonwoven fabric with an average thickness of 0.2 cm, and the degree of swelling was measured when the sample was immersed in a 20°C NaOH10q6 aqueous solution for 7 days. Furthermore, the spinnability by melt prone is also shown in Table 1.
表 １ 紡糸性評価；×は悪い、○は良い。Table 1 Spinnability evaluation: × is bad, ○ is good.
＊液の濡れ性が低下
すなわち、実施例の不織布はアルカリ膨潤度が小さく、
紡糸性、繊維の均質性の良好なものが得られた。*The wettability of the liquid is decreased, that is, the nonwoven fabric of the example has a small degree of alkali swelling.
A product with good spinnability and fiber homogeneity was obtained.
〔耐アルカリ性合成繊維不織布の製造〕繊度０．８デニ
ール、繊維長５１１Ｊのポリビニルアルコール繊維７０
部、繊度１デニール、繊維長５Ｕの水溶性ポリビニルア
ルコール繊維（バインダー繊維）１５部、繊度３デニー
ル、繊維長５ｍｊの熱融着繊維（ポリプロピレン・ポリ
エチレン複合繊維；バインダー繊維）１５部を混繊し、
湿式法（抄紙法）により平均目付２５ ｔ／ｄの繊維ウ
ェブを作、９，１２０℃に加温したカレンダーで処理し
て不織布を得た。[Manufacture of alkali-resistant synthetic fiber nonwoven fabric] Polyvinyl alcohol fiber 70 with a fineness of 0.8 denier and a fiber length of 511 J
15 parts of water-soluble polyvinyl alcohol fiber (binder fiber) with a fineness of 1 denier and a fiber length of 5 U, and 15 parts of heat-sealable fiber (polypropylene/polyethylene composite fiber; binder fiber) with a fineness of 3 denier and a fiber length of 5 mJ are mixed. ,
A fibrous web with an average basis weight of 25 t/d was produced by a wet method (paper making method) and treated in a calender heated to 9,120°C to obtain a nonwoven fabric.
試料４で得たメルトプローン極細繊維不織布と合成繊維
不織布を積層し、温度１３５℃のカレンダーロールで熱
処理−プレスして積層一体化不織布を得た。この積層不
織布は平均目付５５ ｆ／ｎ？、厚み０．１５ｍのシー
ト状物であった。このシート状物にはノニオン系活性剤
水溶液で処理して０．５チ付着させた。このシート状物
の吸液速度８．７秒、吸液量９．９’ｌ／ｆであり、し
かもシート状物のアルカリ液の濡れ状態を観察すると、
内部まで均一に濡れていた。The melt-prone ultrafine fiber nonwoven fabric obtained in Sample 4 and the synthetic fiber nonwoven fabric were laminated and heat treated and pressed using a calendar roll at a temperature of 135°C to obtain a laminated integrated nonwoven fabric. This laminated nonwoven fabric has an average basis weight of 55 f/n? It was a sheet-like material with a thickness of 0.15 m. This sheet-like material was treated with an aqueous solution of a nonionic activator to adhere 0.5 inch. The liquid absorption rate of this sheet-like material was 8.7 seconds, and the liquid absorption amount was 9.9'l/f, and when observing the wet state of the alkaline liquid on the sheet-like material,
It was evenly wet inside.
また、極細繊維不織布側の面は緻密化しているが、液の
透過性は良く、液体以外の物質の通過は見られないもの
であシ、アルカリ電池のセパレータとして適し念もので
あった。Furthermore, although the surface on the side of the ultrafine fiber nonwoven fabric is dense, it has good liquid permeability and no substances other than liquid can pass through it, making it suitable as a separator for alkaline batteries.
実施例２
線状低密度ポリエチレン〔商品名’ＡＳＰＵＮ６８０６
” ダウケミカル社製品、メルトインデックス１０
５］５０部、親水化ノニオン系界面活性剤５Ｌｓ、線状
低密度ポリエチレン９５％からなる親水性化ポリエチレ
ン〔商品名’ＡＳＰＵＮ ６１５１８−１５”、ダウケ
ミカル社製品）１０部をベレットで混合し、ポリマー溶
融温度２８０℃、実施例１で用いたメルトプローン用ダ
イを用いて気体温度３００℃、気体圧力１．２ Ｋｐ
／−の条件で紡出し、紡出極細繊維流は実施例１と同様
にして平均目付３１ｆ／♂の繊維ウェブを得た。Example 2 Linear low density polyethylene [Product name 'ASPUN6806
” Dow Chemical Company product, melt index 10
5] Mix 50 parts of hydrophilized nonionic surfactant, 5Ls of hydrophilized nonionic surfactant, and 10 parts of hydrophilized polyethylene made of 95% linear low-density polyethylene [trade name 'ASPUN 61518-15'', product of Dow Chemical Company] using a pellet, The polymer melting temperature was 280°C, the gas temperature was 300°C, and the gas pressure was 1.2 Kp using the melt-prone die used in Example 1.
/- conditions, and the spun ultrafine fiber flow was the same as in Example 1 to obtain a fiber web with an average basis weight of 31 f/♂.
一方、繊度１デニール、繊維長３８０のポリプロピレン
繊維４０部、礒度０．６デニール、繊維長３８ｗａのポ
リプロピレン繊維３０部、ポリプロピレン−ポリエチレ
ン複合繊維（熱バインダー繊維）１５部、ｆｆ１ｉｔ、
ｓデニールの再生セルロース繊維１５部を混繊し、カー
ド機を通して乾式法の平均目付２５１／ｒｒｌの合成繊
維ウェブを得た。On the other hand, 40 parts of polypropylene fibers with a fineness of 1 denier and a fiber length of 380, 30 parts of polypropylene fibers with a tenacity of 0.6 denier and a fiber length of 38 wa, 15 parts of polypropylene-polyethylene composite fibers (thermal binder fibers), ff1it,
15 parts of regenerated cellulose fibers of S denier were mixed and passed through a carding machine to obtain a synthetic fiber web having an average basis weight of 251/rrl by dry process.
次いで、メルトプローン極細繊維ウェブと合成繊維ウェ
ブを積層し、温度１３０℃のカレンダーロールで熱処理
−プレスして積層一体化不織布を得た。この積層不織布
は平均口１寸５６ ｆ ／ｌｏ’、厚み０．１３ｍのシ
ート状物であった。このシート状物の吸液量９．６５ｆ
／ｆ、吸液速度１２．６秒であり、アルカリ電池のセパ
レータとして適したものであった。Next, the melt-prone ultrafine fiber web and the synthetic fiber web were laminated and heat-treated and pressed using a calendar roll at a temperature of 130°C to obtain a laminated integrated nonwoven fabric. This laminated nonwoven fabric was a sheet-like material with an average width of 56 f/lo' and a thickness of 0.13 m. Liquid absorption amount of this sheet-like material: 9.65f
/f, the liquid absorption rate was 12.6 seconds, and it was suitable as a separator for alkaline batteries.
本発明のアルカリ電池用セパレータは耐アルカリ性に優
れ、目止め効果が高いため活物質の貫通を防止でき、吸
液性、保液性に優れたものである。The separator for alkaline batteries of the present invention has excellent alkali resistance, has a high sealing effect, can prevent penetration of the active material, and has excellent liquid absorption and liquid retention properties.
特に低水銀化に伴なう活物質のセパレータ貫通の問題に
も対処可能である・
しかも、
薄いセパレー
タを作ることができる。In particular, it is possible to deal with the problem of active materials penetrating the separator due to the reduction in mercury. Moreover, thin separators can be made.
Claims (1)
酸ビニル共重合体ケン化物、親水性化ポリエチレンある
いは親水性化エチレン共重合体の群から選ばれた少なく
とも１種のポリマーを主体とするポリマーのメルトブロ
ーン極細繊維不織布と耐アルカリ性合成繊維不織布との
積層不織布で構成したことを特徴とするアルカリ電池用
セパレータ。(1) A polymer mainly composed of at least one polymer selected from the group of saponified ethylene/vinyl acetate copolymer with an ethylene content of 35 to 60 mol%, hydrophilized polyethylene, or hydrophilized ethylene copolymer. 1. A separator for alkaline batteries comprising a laminated nonwoven fabric of a melt-blown ultrafine fiber nonwoven fabric and an alkali-resistant synthetic fiber nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63200616A JPH0249350A (en) | 1988-08-10 | 1988-08-10 | Separator for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63200616A JPH0249350A (en) | 1988-08-10 | 1988-08-10 | Separator for alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0249350A true JPH0249350A (en) | 1990-02-19 |
Family
ID=16427336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63200616A Pending JPH0249350A (en) | 1988-08-10 | 1988-08-10 | Separator for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0249350A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS609056A (en) * | 1983-06-27 | 1985-01-18 | Dynic Corp | Separator for alkaline battery |
| JPS6334849A (en) * | 1986-07-29 | 1988-02-15 | Japan Vilene Co Ltd | Separator for alkaline cell |
-
1988
- 1988-08-10 JP JP63200616A patent/JPH0249350A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS609056A (en) * | 1983-06-27 | 1985-01-18 | Dynic Corp | Separator for alkaline battery |
| JPS6334849A (en) * | 1986-07-29 | 1988-02-15 | Japan Vilene Co Ltd | Separator for alkaline cell |
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