JPH10298324A - Microporous polyolefin film and its production - Google Patents
Microporous polyolefin film and its productionInfo
- Publication number
- JPH10298324A JPH10298324A JP9120255A JP12025597A JPH10298324A JP H10298324 A JPH10298324 A JP H10298324A JP 9120255 A JP9120255 A JP 9120255A JP 12025597 A JP12025597 A JP 12025597A JP H10298324 A JPH10298324 A JP H10298324A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyolefin
- temperature
- composition
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリオレフィン微
多孔膜に関するものであって、より詳しくは電池用セパ
レータ等に使用される、透過性能及び機械的強度に優れ
るとともに、溶融破断温度の優れた機能を有するポリオ
レフィン微多孔膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microporous polyolefin membrane, and more particularly, to a function which is excellent in permeation performance and mechanical strength and has an excellent melt rupture temperature for use in battery separators and the like. The present invention relates to a microporous polyolefin membrane having
【０００２】[0002]
【従来の技術】微多孔膜は、各種の分離膜や、電池用セ
パーレーター、電解コンデンサー用セパレーター等に使
用されている。特にリチウム電池においては、リチウム
金属、リチウムイオンが用いられているために非プロト
ン性極性有機溶媒が電解液溶媒として用いられ、また、
電解質としては、リチウム塩を用いている。したがって
正極と負極との間に設置するセパレーターには、有機溶
媒に不溶でありかつ電解質や電極活物質に対して安定な
ポリエチレン、ポリプロピレンなどのポリオレフィン系
材料を微多孔膜や不織布に加工したものをセパレーター
として用いている。2. Description of the Related Art Microporous membranes are used for various separation membranes, separators for batteries, separators for electrolytic capacitors, and the like. Particularly in lithium batteries, lithium metal, aprotic polar organic solvent is used as the electrolyte solvent because lithium ions are used,
As the electrolyte, a lithium salt is used. Therefore, the separator installed between the positive electrode and the negative electrode should be a microporous film or nonwoven fabric made of a polyolefin-based material such as polyethylene or polypropylene that is insoluble in organic solvents and stable against the electrolyte and the electrode active material. Used as a separator.
【０００３】最近、超高分子量のポリオレフィンを用い
て高強度および高弾性の微多孔膜が開発されてきてい
る。例えば、重量平均分子量が７×１０5以上の超高分
子量ポリオレフィンを溶媒中で加熱溶解した溶液からゲ
ル状シートを成形し、前記ゲル状シート中の溶媒量を脱
溶媒処理により調整し、次いで加熱延伸した後、残留溶
媒を除去することにより、微多孔膜を製造する方法が提
案されている（特開昭６０−２４２０３５号他）。ま
た、超高分子量ポリオレフィンの高濃度溶液からのポリ
オレフィン微多孔膜の製法として、超高分子量ポリオレ
フィンを含有するポリオレフィン組成物の分子量分布を
特定の値にする方法が提案されている（特開平３−６４
３３４号）。Recently, microporous membranes having high strength and high elasticity have been developed using ultrahigh molecular weight polyolefins. For example, a gel-like sheet is formed from a solution obtained by heating and dissolving an ultra-high-molecular-weight polyolefin having a weight-average molecular weight of 7 × 10 5 or more in a solvent, adjusting the amount of the solvent in the gel-like sheet by desolvation treatment, and then heating. A method of producing a microporous membrane by removing the residual solvent after stretching has been proposed (JP-A-60-242035 and others). As a method for producing a microporous polyolefin membrane from a high-concentration solution of ultrahigh molecular weight polyolefin, a method has been proposed in which the molecular weight distribution of a polyolefin composition containing ultrahigh molecular weight polyolefin is set to a specific value (Japanese Unexamined Patent Publication (Kokai) No. Heisei 3- 64
334).
【０００４】ところで、上記ポリオレフィン微多孔膜を
電池、例えばリチウム電池用セパレーター等に用いる場
合には、電極が短絡して電池内部の温度が上昇した時
に、発火等の事故が生じるのを防止する必要がある。こ
のため、リチウムの発火以前に溶融してその孔を目詰り
させ、電流をシャットダウンさせる機能の他に、シャト
ダウン後に温度がさらに上昇した時に、セパレーター自
身が溶融破断（メルトダウン）すると、電池の発火、爆
発の危険性があるため、メルトダウン温度を高くするこ
とが望まれている。また、シャットダウン温度とメルト
ダウン温度の差が大きいほど、高温特性が良好で安全性
の高い電池用セパレーターになりうると考えられる。例
えば、特開昭６３−３０８８６６号公報や、特開平２−
７７１０８号公報では、低融点のポリエチレンおよび高
融点のポリプロピレンからなる単膜を積層化することに
より、高強度かつ優れた高温特性を有する微孔性多孔膜
を得る方法が開示されているが、積層のため、セパレー
ターの電気抵抗が高くなり、高性能電池用セパレーター
としては不向きのものとなる。さらに、特開平２−７７
１０８号公報では、積層押出という手法をとるため、製
造工程の複雑化および製造コストという点で生産性に劣
るものとなる。In the case where the above-mentioned polyolefin microporous membrane is used for a battery, for example, a separator for a lithium battery, it is necessary to prevent an accident such as ignition from occurring when an electrode is short-circuited and the temperature inside the battery rises. There is. For this reason, in addition to the function of melting the lithium before the ignition of the lithium and clogging the hole and shutting down the current, when the temperature further rises after the shutdown, the separator itself melts and breaks down (melt down). Since there is a risk of ignition and explosion, it is desired to increase the meltdown temperature. Further, it is considered that the larger the difference between the shutdown temperature and the meltdown temperature, the better the high-temperature characteristics and the higher the safety of the battery separator. For example, Japanese Patent Application Laid-Open No. 63-308866 and Japanese Patent Application Laid-Open
No. 77108 discloses a method of obtaining a microporous porous film having high strength and excellent high temperature characteristics by laminating a single film made of low melting point polyethylene and high melting point polypropylene. As a result, the electrical resistance of the separator increases, making the separator unsuitable for a high-performance battery separator. Further, JP-A-2-77
In Japanese Patent Publication No. 108, since the technique of lamination extrusion is employed, productivity is inferior in terms of complexity of the manufacturing process and manufacturing cost.
【０００５】[0005]
【発明が解決しようとする課題】したがって、本発明の
目的は、透過性能及び機械的強度に優れるとともに、低
温でのシャットダウン温度と高いメルトダウン温度を有
し、メルトダウン温度とシャットダウン温度の差の幅が
広く、かつ熱収縮率の低いポリオレフィン微多孔膜を提
供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a low-temperature shutdown temperature and a high melt-down temperature while having excellent permeation performance and mechanical strength, and a difference between the melt-down temperature and the shutdown temperature. An object of the present invention is to provide a polyolefin microporous membrane having a wide width and a low heat shrinkage.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記目的を達
成するため、超高分子量ポリエチレンまたはその組成物
に特定のポリプロピレンを加えることにより、透過性能
及び機械的強度に優れるとともに、メルトダウン温度が
高くなり、さらにシャットダウン温度とメルトダウン温
度幅が大きい、かつ熱収縮率が低い微多孔膜が得られる
ことを見い出し本発明に想到した。SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides an ultrahigh molecular weight polyethylene or a composition thereof by adding a specific polypropylene to thereby provide excellent permeation performance and mechanical strength and a meltdown temperature. And the present inventors have found that a microporous film having a large shutdown temperature and meltdown temperature range and a low heat shrinkage ratio can be obtained.
【０００７】すなわち、本発明は、重量平均分子量が５
×１０5以上のポリエチレンまたはそのポリエチレン組
成物６５〜９５重量％と、重量平均分子量が３×１０5
以上でエチレン含量が１．０重量％以下のポリプロピレ
ン５〜３５重量％を含有する組成物からなるポリオレフ
ィン微多孔膜を提供するものである。このポリオレフィ
ン微多孔膜は、重量平均分子量が５×１０5以上のポリ
エチレンまたはそのポリエチレン組成物６５〜９５重量
％と、重量平均分子量が３×１０5以上でエチレン含量
が１．０重量％以下のポリプロピレン５〜３５重量％を
含有する組成物１０〜５０重量％と、溶媒５０〜９０重
量％とからなる溶液を調製し、前記溶液をダイより押出
し、冷却してゲル状組成物を形成し、前記ゲル状組成物
をポリエチレン組成物の融点＋１０℃以下の温度で延伸
し、しかる後残存溶媒を除去することによって好適に製
造される。That is, according to the present invention, the weight average molecular weight is 5
× 10 5 or more polyethylene or its polyethylene composition 65-95 wt%, a weight average molecular weight of 3 × 10 5
The present invention provides a microporous polyolefin membrane comprising a composition containing 5-35% by weight of polypropylene having an ethylene content of 1.0% by weight or less. This polyolefin microporous membrane has a polyethylene having a weight average molecular weight of 5 × 10 5 or more or a polyethylene composition of 65 to 95% by weight and a weight average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less. A solution comprising 10 to 50% by weight of a composition containing 5 to 35% by weight of polypropylene and 50 to 90% by weight of a solvent is prepared, and the solution is extruded from a die and cooled to form a gel composition, The gel composition is suitably produced by stretching at a temperature not higher than the melting point of the polyethylene composition + 10 ° C, and then removing the residual solvent.
【０００８】[0008]
【発明の実施の形態】本発明で用いるポリエチレンは、
重量平均分子量が５×１０5以上、好ましくは１×１０6
〜１５×１０6の超高分子量のポリエチレンである。重
量平均分子量が５×１０5未満では、微多孔膜の製造時
の延伸工程において最大延伸倍率が低く、目的の微多孔
膜が得られない。一方、上限は特に限定的ではないが１
５×１０6を超えるものは、微多孔膜の製造時のゲル状
成形物の形成において成形性に劣る。また、本発明にお
いては、後述のポリオレフィン溶液の高濃度化と微多孔
膜の強度の向上を図るために、重量平均分子量１×１０
6以上の超高分子量ポリエチレンと重量平均分子量１×
１０5以上５×１０5未満の高密度ポリエチレンとの組成
物を用いることができる。超高分子量ポリエチレンのポ
リエチレン組成物中の含有量は、ポリエチレン組成物全
体を１００重量％として１重量％以上が好ましく、より
好ましくは１０〜７０重量％である。さらに前記ポリエ
チレンまたはそのポリエチレン組成物の分子量分布の尺
度として用いられる重量平均分子量／数平均分子量は３
００以下、好ましくは５〜５０である。DETAILED DESCRIPTION OF THE INVENTION The polyethylene used in the present invention is:
The weight average molecular weight is 5 × 10 5 or more, preferably 1 × 10 6
Ultra high molecular weight polyethylene of up to 15 × 10 6 . If the weight average molecular weight is less than 5 × 10 5 , the maximum stretching ratio is low in the stretching step in the production of the microporous membrane, and the desired microporous membrane cannot be obtained. On the other hand, the upper limit is not particularly limited, but is 1
Those having more than 5 × 10 6 are inferior in moldability in forming a gel-like molded product at the time of producing a microporous membrane. Further, in the present invention, in order to increase the concentration of the polyolefin solution described later and to improve the strength of the microporous membrane, the weight average molecular weight is 1 × 10 5
Ultra high molecular weight polyethylene of 6 or more and weight average molecular weight 1 ×
A composition with a high-density polyethylene of 10 5 or more and less than 5 × 10 5 can be used. The content of the ultrahigh molecular weight polyethylene in the polyethylene composition is preferably 1% by weight or more, more preferably 10 to 70% by weight, based on 100% by weight of the whole polyethylene composition. Further, the weight average molecular weight / number average molecular weight used as a measure of the molecular weight distribution of the polyethylene or the polyethylene composition is 3
00 or less, preferably 5 to 50.
【０００９】本発明で用いるポリプロピレンとしては、
重量平均分子量が３．０×１０5以上、好ましくは３．
５×１０5〜７．５×１０5のホモポリプロピレン又はエ
チレン含有量が１．０重量％以下のエチレンプロピレン
ランダムコポリマー、エチレンプロピレンブロックコポ
リマー等を用いることができる。重量平均分子量が３．
０×１０5未満では、得られるポリオレフィン微多孔膜
の開孔が困難になり、エチレン含有量が１．０重量％を
超えるとポリオレフィンの結晶性が低くなり、ポリオレ
フィン微多孔膜の開孔が困難になる。The polypropylene used in the present invention includes:
The weight average molecular weight is 3.0 × 10 5 or more, preferably 3.
5 × 10 5 to 7.5 × 10 5 homopolypropylene or an ethylene propylene random copolymer or an ethylene propylene block copolymer having an ethylene content of 1.0% by weight or less can be used. 2. The weight average molecular weight is 3.
If it is less than 0 × 10 5 , it will be difficult to open the resulting microporous polyolefin membrane. If the ethylene content exceeds 1.0% by weight, the crystallinity of the polyolefin will be low, and it will be difficult to open the microporous polyolefin membrane. become.
【００１０】ポリプロピレンをポリエチレンまたはその
ポリエチレン組成物に加えることにより、ポリオレフィ
ン微多孔膜をリチウム電池等のセパレーターとして用
い、電極が短絡して電池内部の温度が上昇した場合は、
低温でのシャットダウン機能に加えてメルトダウン温度
が高くなり、安全性の高い電池が得られる。本発明で用
いるポリプロピレンの量は、ポリオレフィン全体の５〜
３５重量％、好ましくは、１５〜２０重量％である。５
重量％未満では、メルトダウン温度の上昇効果はみられ
ず、３５重量％を超えるとポリオレフィン微多孔膜の強
度が著しく低下し、さらに多くなるとシート成形時にポ
リエチレンとポリプロピレンが相分離してしまい、成形
が困難になる。また、本発明のポリオレフィン組成物に
はポリオレフィン微多孔膜をリチウム電池等のセパレー
ターとして用い、電極が短絡して電池内部の温度が上昇
した時、低温でシャットダウンする機能を増大させる低
密度ポリエチレンや低分子量ポリエチレン等を加えるこ
とができる。When the polypropylene is added to polyethylene or its polyethylene composition, the polyolefin microporous membrane is used as a separator for a lithium battery or the like, and when the electrodes are short-circuited and the temperature inside the battery rises,
In addition to the low-temperature shutdown function, the meltdown temperature increases, and a highly safe battery can be obtained. The amount of polypropylene used in the present invention is 5 to 5
It is 35% by weight, preferably 15 to 20% by weight. 5
If the amount is less than 35% by weight, the effect of increasing the meltdown temperature is not observed. If the amount is more than 35% by weight, the strength of the microporous polyolefin membrane is significantly reduced. Becomes difficult. In addition, the polyolefin composition of the present invention uses a polyolefin microporous membrane as a separator for a lithium battery or the like, and when the electrodes are short-circuited and the temperature inside the battery rises, low-density polyethylene or low-density polyethylene that increases the function of shutting down at a low temperature is used. Molecular weight polyethylene or the like can be added.
【００１１】本発明のポリオレフィン微多孔膜はポリエ
チレンにポリプロピレンを加えた樹脂成分に有機液状体
または固体を混合し、溶融混練後押出成形し、抽出、延
伸を施すことにより得られる。また、樹脂成分および有
機液状体または固体の混合物に無機微粉体を添加しても
何等差し支えない。本発明のポリオレフィン微多孔膜を
得る好ましい方法としては、ポリオレフィン組成物にポ
リオレフィンの良溶媒を供給しポリオレフィン組成物の
溶液を調製して、この溶液を押出機のダイよりシート状
に押し出した後、冷却してゲル状組成物を形成して、こ
のゲル状組成物を加熱延伸し、しかる後残存する溶媒を
除去する方法である。The microporous polyolefin membrane of the present invention can be obtained by mixing an organic liquid or a solid with a resin component obtained by adding polypropylene to polyethylene, melt-kneading, extruding, extracting and stretching. Also, there is no problem even if inorganic fine powder is added to the mixture of the resin component and the organic liquid or solid. As a preferable method for obtaining the polyolefin microporous membrane of the present invention, a solution of the polyolefin composition is prepared by supplying a good solvent for the polyolefin to the polyolefin composition, and after extruding this solution into a sheet from a die of an extruder, This is a method in which a gel composition is formed by cooling, and the gel composition is heated and stretched, and thereafter, the remaining solvent is removed.
【００１２】本発明において、原料となるポリオレフィ
ン組成物の溶液は、上述のポリオレフィン組成物を、溶
媒に加熱溶解することにより調製する。この溶媒として
は、ポリオレフィンを十分に溶解できるものであれば特
に限定されない。例えば、ノナン、デカン、ウンデカ
ン、ドデカン、流動パラフィンなどの脂肪族または環式
の炭化水素、あるいは沸点がこれらに対応する鉱油留分
などがあげられるが、溶媒含有量が安定なゲル状成形物
を得るためには流動パラフィンのような不揮発性の溶媒
が好ましい。加熱溶解は、ポリオレフィンが完全に溶解
する温度で強力に撹拌または押出機で混練しながら行
う。その温度は、例えば１４０〜２５０℃の範囲が好ま
しい。またポリオレフィン溶液の濃度は、１０〜５０重
量％好ましくは１０〜４０重量％である。濃度が１０重
量％未満では、使用する溶媒量が多く経済的でないばか
りか、シート状に成形する際に、ダイス出口でスウェル
やネックインが大きくシートの成形が困難となる。な
お、加熱溶解にあたってはポリオレフィンの酸化を防止
するために酸化防止剤を添加するのが好ましい。In the present invention, a solution of the polyolefin composition as a raw material is prepared by heating and dissolving the above-mentioned polyolefin composition in a solvent. The solvent is not particularly limited as long as it can sufficiently dissolve the polyolefin. For example, nonane, decane, undecane, dodecane, aliphatic or cyclic hydrocarbons such as liquid paraffin, or a mineral oil fraction having a boiling point corresponding thereto, and the like. To obtain, a non-volatile solvent such as liquid paraffin is preferred. Heat dissolution is carried out at a temperature at which the polyolefin is completely dissolved, while vigorously stirring or kneading with an extruder. The temperature is preferably in the range of, for example, 140 to 250 ° C. The concentration of the polyolefin solution is 10 to 50% by weight, preferably 10 to 40% by weight. If the concentration is less than 10% by weight, not only is the amount of solvent used too uneconomical, but also when forming into a sheet, the swell and neck-in at the die exit are large, making it difficult to form the sheet. In addition, at the time of heating and dissolving, it is preferable to add an antioxidant to prevent oxidation of the polyolefin.
【００１３】次にこのポリオレフィン組成物の加熱溶液
を好ましくはダイから押し出して成形する。ダイは、通
常長方形の口金形状をしたシートダイが用いられるが、
２重円筒状のインフレーションダイなども用いることが
できる。シートダイを用いた場合のダイギャップは通常
０．１〜５ｍｍであり、押し出し成形温度は１４０〜２
５０℃である。この際押し出し速度は、通常２０〜３０
ｃｍ/分ないし１０ｍ/分である。Next, the heated solution of the polyolefin composition is preferably extruded from a die and molded. The die is usually a rectangular die-shaped sheet die is used,
A double cylindrical inflation die or the like can also be used. When a sheet die is used, the die gap is usually 0.1 to 5 mm, and the extrusion temperature is 140 to 2 mm.
50 ° C. At this time, the extrusion speed is usually 20 to 30.
cm / min to 10 m / min.
【００１４】このようにしてダイから押し出された溶液
は、冷却することによりゲル状シートに成形される。冷
却は少なくともゲル化温度以下までは５０℃／分以上の
速度で行うのが好ましい。一般に冷却速度が遅いと、得
られるゲル状シートの高次構造が粗くなり、それを形成
する疑似細胞単位も大きなものとなるが、冷却速度が速
いと、密な細胞単位となる。冷却速度が５０℃／分未満
では、結晶化度が上昇し、延伸に適したゲル状シートと
なりにくい。冷却方法としては、冷風、冷却水、その他
の冷却媒体に直接接触させる方法、冷媒で冷却したロー
ルに接触させる方法などを用いることができる。なお、
ダイから押し出された溶液は、冷却前あるいは冷却中に
好ましくは１〜１０、より好ましくは１〜５の引き取り
比で引取ってもよい。引き取り比が１０以上になるとネ
ックインが大きくなり、また延伸時に破断を起こしやす
くなり好ましくない。The solution thus extruded from the die is formed into a gel-like sheet by cooling. Cooling is preferably performed at a rate of 50 ° C./min or more at least up to the gelation temperature or less. In general, when the cooling rate is low, the higher-order structure of the obtained gel-like sheet becomes coarse, and the pseudo cell unit that forms it becomes large, but when the cooling rate is high, the cell unit becomes dense. If the cooling rate is less than 50 ° C./min, the crystallinity increases, and it is difficult to form a gel sheet suitable for stretching. As a cooling method, a method of directly contacting with cold air, cooling water, or another cooling medium, a method of contacting with a roll cooled by a refrigerant, or the like can be used. In addition,
The solution extruded from the die may be taken off before or during cooling, preferably at a take-up ratio of 1 to 10, more preferably 1 to 5. When the take-up ratio is 10 or more, neck-in becomes large, and breakage tends to occur during stretching, which is not preferable.
【００１５】次に、このゲル状成形物に延伸を行う。延
伸はゲル状シートを加熱し、通常のテンター法、ロール
法、インフレーション法、圧延法もしくはこれらの方法
の組み合わせによって所定の倍率で行う。延伸は一軸延
伸でも二軸延伸でもよいが、二軸延伸が好ましい。ま
た、二軸延伸の場合は、縦横同時延伸または逐次延伸の
いずれでもよい。延伸温度はポリオレフィンの融点＋１
０℃以下、好ましくはポリオレフィンの結晶分散温度か
ら結晶融点未満の範囲である。また延伸倍率は原反の厚
さによって異なるが、一軸延伸では２倍以上が好まし
く、より好ましくは３〜３０倍である。二軸延伸では面
倍率で１０倍以上が好ましく、より好ましくは１５〜４
００倍である。面倍率が１０倍未満では延伸が不十分で
高弾性、高強度の微多孔膜が得られない。一方、面倍率
が４００倍を超えると、延伸操作などで制約が生じる。Next, this gel-like molded product is stretched. Stretching is performed by heating the gel-like sheet and at a predetermined magnification by a usual tenter method, roll method, inflation method, rolling method or a combination of these methods. The stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred. In the case of biaxial stretching, either vertical or horizontal simultaneous stretching or sequential stretching may be used. The stretching temperature is the melting point of the polyolefin + 1.
The temperature is 0 ° C. or lower, preferably in a range from the crystal dispersion temperature of the polyolefin to less than the crystal melting point. Although the stretching ratio varies depending on the thickness of the raw material, it is preferably at least 2 times, more preferably 3 to 30 times in uniaxial stretching. In biaxial stretching, the area ratio is preferably 10 times or more, more preferably 15 to 4 times.
It is 00 times. If the area ratio is less than 10 times, stretching is insufficient and a highly elastic and high-strength microporous film cannot be obtained. On the other hand, if the area magnification exceeds 400 times, restrictions are imposed on the stretching operation and the like.
【００１６】得られた延伸成形物は、溶剤で洗浄し残留
する溶媒を除去する。洗浄溶剤としては、ペンタン、ヘ
キサン、ヘプタンなどの炭化水素、塩化メチレン、四塩
炭素などの塩素化炭化水素、三フッ化エタンなどのフッ
化炭化水素、ジエチルエーテル、ジオキサンなどのエー
テル類などの易揮発性のものを用いることができる。こ
れらの溶剤はポリオレフィン組成物の溶解に用いた溶媒
に応じて適宜選択し、単独もしくは混合して用いる。洗
浄方法は、溶剤に浸漬し抽出する方法、溶剤をシャワー
する方法、またはこれらの組合せによる方法などにより
行うことができる。The obtained stretch molded product is washed with a solvent to remove the remaining solvent. Examples of the cleaning solvent include hydrocarbons such as pentane, hexane, and heptane; chlorinated hydrocarbons such as methylene chloride and tetrachlorocarbon; fluorinated hydrocarbons such as ethane trifluoride; and ethers such as diethyl ether and dioxane. Volatile ones can be used. These solvents are appropriately selected according to the solvent used for dissolving the polyolefin composition, and used alone or as a mixture. The washing method can be performed by a method of immersing in a solvent for extraction, a method of showering the solvent, a method of a combination thereof, or the like.
【００１７】上述のような洗浄は、延伸成形物中の残留
溶媒が１重量％未満になるまで行う。その後洗浄溶剤を
乾燥するが、洗浄溶剤の乾燥方法は加熱乾燥、風乾など
の方法で行うことができる。乾燥した延伸成形物は、結
晶分散温度〜融点の温度範囲で熱固定することが望まし
い。The washing as described above is performed until the residual solvent in the stretch molded product becomes less than 1% by weight. Thereafter, the washing solvent is dried, and the washing solvent can be dried by a method such as heat drying or air drying. It is desirable that the dried stretch molded product is heat-set at a temperature in the range of the crystal dispersion temperature to the melting point.
【００１８】以上のようにして製造したポリオレフィン
微多孔膜は、破断強度が１０００ｋｇ/ｃｍ2以上で、メ
ルトダウン温度は１７５℃以上、シャットダウン温度差
の幅は４０〜４５℃、熱収縮率（１００℃／８時間）が
５％以下となり、セパレーターとして用いると、その安
全性は向上する。なお、得られたポリオレフィン微多孔
膜は、必要に応じてさらに、プラズマ照射、界面活性剤
含浸、表面グラフト等の親水化処理などの表面修飾を施
すことができる。The microporous polyolefin membrane produced as described above has a breaking strength of 1000 kg / cm 2 or more, a meltdown temperature of 175 ° C. or more, a shutdown temperature difference range of 40 to 45 ° C., and a heat shrinkage rate (100%). C./8 hours) is 5% or less, and when used as a separator, its safety is improved. The obtained microporous polyolefin membrane can be further subjected to surface modification such as hydrophilic treatment such as plasma irradiation, surfactant impregnation, and surface grafting, if necessary.
【００１９】[0019]
【実施例】以下に本発明について実施例を挙げてさらに
詳細に説明するが、本発明は実施例に特に限定されるも
のではない。なお、実施例における試験方法は次の通り
である。 （１）膜厚：断面を走査型電子顕微鏡により測定。 （２）破断強度：幅１５ｍｍ短冊状試験片の破断強度を
ＡＳＴＭ Ｄ８８２に準拠して測定。 （３）透気度：ＪＩＳ Ｐ８１１７に準拠して測定。 （４）シャットダウン温度：所定温度に加熱することに
よって、透気度が１０万ｓｅｃ／１００ｃｃ以上となる
温度として測定。 （５）メルトダウン温度：所定温度に加熱することによ
って、膜が溶けて破膜する温度として測定。 （６）熱収縮率：膜を１００℃の雰囲気下に８時間放置
し、ＭＤ方向およびＴＤ方向のそれぞれの長さの変化か
ら求めた。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not particularly limited to the examples. In addition, the test method in an Example is as follows. (1) Film thickness: The cross section was measured by a scanning electron microscope. (2) Breaking strength: The breaking strength of a 15 mm wide strip test piece was measured according to ASTM D882. (3) Air permeability: measured according to JIS P8117. (4) Shutdown temperature: Measured as a temperature at which the air permeability becomes 100,000 sec / 100 cc or more by heating to a predetermined temperature. (5) Meltdown temperature: Measured as the temperature at which the film melts and breaks when heated to a predetermined temperature. (6) Thermal shrinkage: The film was left in an atmosphere of 100 ° C. for 8 hours, and was determined from changes in the lengths in the MD and TD directions.
【００２０】実施例１ 重量平均分子量が２．５×１０6の超高分子量ポリエチ
レン（ＵＨＭＷＰＥ）２０重量％、３．３×１０5の高
密度ポリエチレン（ＨＤＰＥ）６０重量％及び重量平均
分子量が５．３×１０5のポリプロピレンが２０重量％
からなるポリオレフィン組成物１００重量部に酸化防止
剤０．３７５重量部を加えたポリオレフィン組成物を得
た。このポリオレフィン組成物３０重量部を二軸押出機
（５８mmφ、Ｌ／Ｄ＝４２、強混練タイプ）に投入し
た。またこの二軸押出機のサイドフィーダーから流動パ
ラフィン７０重量部を供給し、２００ｒｐｍで溶融混練
して、押出機中にてポリオレフィン溶液を調製した。Example 1 20% by weight of ultra high molecular weight polyethylene (UHMWPE) having a weight average molecular weight of 2.5 × 10 6 , 60% by weight of high density polyethylene (HDPE) of 3.3 × 10 5 and a weight average molecular weight of 5 20% by weight of 3 × 10 5 polypropylene
Was obtained by adding 0.375 parts by weight of an antioxidant to 100 parts by weight of a polyolefin composition comprising 30 parts by weight of this polyolefin composition was charged into a twin-screw extruder (58 mmφ, L / D = 42, strong kneading type). Also, 70 parts by weight of liquid paraffin was supplied from a side feeder of the twin-screw extruder, and melt-kneaded at 200 rpm to prepare a polyolefin solution in the extruder.
【００２１】続いて、この押出機の先端に設置されたＴ
ダイから１９０℃で押し出し、冷却ロールで引取りなが
らゲル状シートを成形した。続いてこのゲル状シート
を、１１５℃で５×５に同時２軸延伸を行い、延伸膜を
得た。得られた延伸膜を塩化メチレンで洗浄して残留す
る流動パラフィンを抽出除去した後、乾燥および熱処理
を行いポリオレフィン微多孔膜を得た。このポリオレフ
ィン微多孔膜の物性評価の結果を第１表に示す。Subsequently, the T set at the tip of the extruder
The sheet was extruded from a die at 190 ° C., and was taken up by a cooling roll to form a gel-like sheet. Subsequently, the gel-like sheet was simultaneously biaxially stretched at 115 ° C. to 5 × 5 to obtain a stretched film. The obtained stretched membrane was washed with methylene chloride to extract and remove remaining liquid paraffin, and then dried and heat-treated to obtain a polyolefin microporous membrane. Table 1 shows the results of evaluating the physical properties of this microporous polyolefin membrane.
【００２２】実施例２〜３ 実施例１において、高密度ポリエチレン及びポリプロピ
レンの使用量を表１に示す値に変更した以外は、実施例
１と同様にして微多孔膜を得た。得られた微多孔膜は表
１の物性を有していた。Examples 2 to 3 A microporous membrane was obtained in the same manner as in Example 1, except that the amounts of the high-density polyethylene and polypropylene were changed to the values shown in Table 1. The obtained microporous membrane had the physical properties shown in Table 1.
【００２３】実施例４ 実施例１において、高密度ポリエチレンを用いない以外
は、実施例１と同様にして微多孔膜を得た。得られた微
多孔膜は表１の物性を有していた。Example 4 A microporous membrane was obtained in the same manner as in Example 1 except that high-density polyethylene was not used. The obtained microporous membrane had the physical properties shown in Table 1.
【００２４】実施例５〜７ 実施例１において、ポリプロピレンの重量平均分子量及
びエチレン含有量が表１に示すものを用いる以外は、実
施例１と同様にして微多孔膜を得た。得られた微多孔膜
は表１の物性を有していた。Examples 5 to 7 Microporous membranes were obtained in the same manner as in Example 1 except that the weight average molecular weight and the ethylene content of the polypropylene shown in Table 1 were used. The obtained microporous membrane had the physical properties shown in Table 1.
【００２５】比較例１ 実施例１において、ポリプロピレンを用いない以外は、
実施例１と同様にして微多孔膜を得た。得られた微多孔
膜は表２の物性を有していた。Comparative Example 1 In Example 1, except that no polypropylene was used,
A microporous membrane was obtained in the same manner as in Example 1. The obtained microporous membrane had the physical properties shown in Table 2.
【００２６】比較例２ 実施例１において、高密度ポリエチレン及びポリプロピ
レンの使用量を表２に示す様に変更した以外は、実施例
１と同様にして微多孔膜を得た。得られた微多孔膜は表
２の物性を有していた。Comparative Example 2 A microporous membrane was obtained in the same manner as in Example 1, except that the amounts of the high-density polyethylene and polypropylene were changed as shown in Table 2. The obtained microporous membrane had the physical properties shown in Table 2.
【００２７】比較例３ 実施例１において、ポリプロピレンの重量平均分子量が
表２に示すものを用いる以外は、実施例１と同様にして
微多孔膜を得た。得られた微多孔膜は表２の物性を有し
ていた。Comparative Example 3 A microporous membrane was obtained in the same manner as in Example 1 except that the polypropylene used had a weight average molecular weight shown in Table 2. The obtained microporous membrane had the physical properties shown in Table 2.
【００２８】比較例４ 実施例１において、ポリプロピレンの重量平均分子量及
びエチレン含有量が表２示すものを用いる以外は、実施
例１と同様にして微多孔膜を得た。得られた微多孔膜は
表２の物性を有していた。Comparative Example 4 A microporous membrane was obtained in the same manner as in Example 1, except that the weight average molecular weight and the ethylene content of the polypropylene shown in Table 2 were used. The obtained microporous membrane had the physical properties shown in Table 2.
【００２９】比較例５ ポリエチレンとポリプロピレンを積層した積層微多孔膜
の膜物性を表２に示す。Comparative Example 5 Table 2 shows the physical properties of a laminated microporous film obtained by laminating polyethylene and polypropylene.
【００３０】表１及び表２から明らかなように、実施例
１〜７に例示されている本発明のポリオレフィン微多孔
膜は高破断強度、高メルトダウン温度を有し、シャット
ダウン温度とメルトダウン温度差の幅が広くなり、かつ
熱収縮率は低く、リチウム電池の電池セパレーターとし
て使用される場合の安全性が高い。As is clear from Tables 1 and 2, the microporous polyolefin membranes of the present invention exemplified in Examples 1 to 7 have high breaking strength, high meltdown temperature, shutdown temperature and meltdown temperature. The width of the difference is wide, the heat shrinkage is low, and the safety when used as a battery separator of a lithium battery is high.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【発明の効果】本発明のポリオレフィン微多孔膜は、高
強度かつ高メルトダウン特性を有しており、シャットダ
ウン温度とメルトダウン温度差の幅が広くなり、さらに
低熱収縮率であることから安全性が高く、リチウム電池
用セパレーターとして用いる場合は安全性の点でおおい
に信頼できる。As described above, the microporous polyolefin membrane of the present invention has high strength and high meltdown characteristics, has a wide difference between the shutdown temperature and the meltdown temperature, and has a low heat shrinkage, so that its safety is low. When used as a separator for lithium batteries, it is highly reliable in terms of safety.
Claims (3)
エチレンまたはそのポリエチレン組成物６５〜９５重量
％と、重量平均分子量が３×１０5以上でエチレン含量
が１．０重量％以下のポリプロピレン５〜３５重量％を
含有するポリオレフィン組成物からなるポリオレフィン
微多孔膜。1. A polyethylene having a weight average molecular weight of 5 × 10 5 or more or a polyethylene composition of 65 to 95% by weight, and a polypropylene 5 having a weight average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less. A polyolefin microporous membrane comprising a polyolefin composition containing up to 35% by weight.
エチレンまたはそのポリエチレン組成物６５〜９５重量
％と、重量平均分子量が３×１０5以上でエチレン含量
が１．０重量％以下のポリプロピレン５〜３５重量％を
含有するポリオレフィン組成物１０〜５０重量％と、溶
媒５０〜９０重量％とからなる溶液を調製し、前記溶液
をダイより押出し、冷却してゲル状組成物を形成し、前
記ゲル状組成物をポリオレフィン組成物の融点＋１０℃
以下の温度で延伸し、しかる後残存溶媒を除去すること
を特徴とするポリオレフィン微多孔膜の製造方法。2. Polyethylene having a weight-average molecular weight of 5 × 10 5 or more or 65 to 95% by weight of a polyethylene composition thereof, and polypropylene 5 having a weight-average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less. Preparing a solution consisting of 10 to 50% by weight of a polyolefin composition containing 50 to 90% by weight of a polyolefin composition containing 50 to 90% by weight of a solvent, extruding the solution from a die, and cooling to form a gel-like composition; The gel composition was melted at the melting point of the polyolefin composition + 10 ° C.
A method for producing a microporous polyolefin membrane, comprising stretching at the following temperature and then removing the residual solvent.
膜からなる電池用セパレーター。3. A battery separator comprising the microporous polyolefin membrane according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025597A JP3699561B2 (en) | 1997-04-23 | 1997-04-23 | Polyolefin microporous membrane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025597A JP3699561B2 (en) | 1997-04-23 | 1997-04-23 | Polyolefin microporous membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10298324A true JPH10298324A (en) | 1998-11-10 |
| JP3699561B2 JP3699561B2 (en) | 2005-09-28 |
Family
ID=14781680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12025597A Expired - Lifetime JP3699561B2 (en) | 1997-04-23 | 1997-04-23 | Polyolefin microporous membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3699561B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093498A (en) * | 1999-09-24 | 2001-04-06 | Nippon Muki Co Ltd | Separator for nonaqueous electrolyte solution battery |
| JP2001192487A (en) * | 2000-01-13 | 2001-07-17 | Tonen Chem Corp | Microporous polyolefin film and method for producing the same |
| WO2002092677A1 (en) * | 2001-05-17 | 2002-11-21 | Asahi Kasei Kabushiki Kaisha | Microporous polyolefin film |
| JP2003053118A (en) * | 2001-08-09 | 2003-02-25 | Seiko Epson Corp | Resin filter for ink-jet recording device |
| JP2004303475A (en) * | 2003-03-28 | 2004-10-28 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| WO2009123015A1 (en) * | 2008-03-31 | 2009-10-08 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane and products of winding |
| JP2010123465A (en) * | 2008-11-21 | 2010-06-03 | Hitachi Maxell Ltd | Separator for battery and lithium secondary battery |
| US8058348B2 (en) | 2005-08-03 | 2011-11-15 | Asahi Kasei Chemicals Corporation | Polyolefin microporous film |
| US8338017B2 (en) | 2007-10-12 | 2012-12-25 | Toray Battery Separator Film Co., Ltd. | Microporous membrane and manufacturing method |
| JP2013234263A (en) * | 2012-05-09 | 2013-11-21 | Asahi Kasei E-Materials Corp | Polyolefin microporous film and method for producing the same |
| KR20180059762A (en) | 2015-09-28 | 2018-06-05 | 니폰 제온 가부시키가이샤 | Resin composition, microporous membrane, separator, and secondary battery |
| WO2021020887A1 (en) * | 2019-07-30 | 2021-02-04 | 주식회사 엘지화학 | Composite separator for electrochemical device, and electrochemical device including same |
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1997
- 1997-04-23 JP JP12025597A patent/JP3699561B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093498A (en) * | 1999-09-24 | 2001-04-06 | Nippon Muki Co Ltd | Separator for nonaqueous electrolyte solution battery |
| JP2001192487A (en) * | 2000-01-13 | 2001-07-17 | Tonen Chem Corp | Microporous polyolefin film and method for producing the same |
| WO2002092677A1 (en) * | 2001-05-17 | 2002-11-21 | Asahi Kasei Kabushiki Kaisha | Microporous polyolefin film |
| JP2003053118A (en) * | 2001-08-09 | 2003-02-25 | Seiko Epson Corp | Resin filter for ink-jet recording device |
| JP2004303475A (en) * | 2003-03-28 | 2004-10-28 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| US8058348B2 (en) | 2005-08-03 | 2011-11-15 | Asahi Kasei Chemicals Corporation | Polyolefin microporous film |
| US8338017B2 (en) | 2007-10-12 | 2012-12-25 | Toray Battery Separator Film Co., Ltd. | Microporous membrane and manufacturing method |
| JP4733232B2 (en) * | 2008-03-31 | 2011-07-27 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane and wound product |
| WO2009123015A1 (en) * | 2008-03-31 | 2009-10-08 | 旭化成イーマテリアルズ株式会社 | Polyolefin microporous membrane and products of winding |
| JP2010123465A (en) * | 2008-11-21 | 2010-06-03 | Hitachi Maxell Ltd | Separator for battery and lithium secondary battery |
| JP2013234263A (en) * | 2012-05-09 | 2013-11-21 | Asahi Kasei E-Materials Corp | Polyolefin microporous film and method for producing the same |
| KR20180059762A (en) | 2015-09-28 | 2018-06-05 | 니폰 제온 가부시키가이샤 | Resin composition, microporous membrane, separator, and secondary battery |
| US10767019B2 (en) | 2015-09-28 | 2020-09-08 | Zeon Corporation | Resin composition, microporous membrane, separator and secondary battery |
| WO2021020887A1 (en) * | 2019-07-30 | 2021-02-04 | 주식회사 엘지화학 | Composite separator for electrochemical device, and electrochemical device including same |
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| JP3699561B2 (en) | 2005-09-28 |
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