JPH10298325A - Microporous polyolefin film and its production - Google Patents
Microporous polyolefin film and its productionInfo
- Publication number
- JPH10298325A JPH10298325A JP9120256A JP12025697A JPH10298325A JP H10298325 A JPH10298325 A JP H10298325A JP 9120256 A JP9120256 A JP 9120256A JP 12025697 A JP12025697 A JP 12025697A JP H10298325 A JPH10298325 A JP H10298325A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyethylene
- temperature
- molecular weight
- polyolefin
- 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
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、低温での透過性を遮断する機能と高い溶融
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, it has excellent permeation performance and mechanical strength used in battery separators and the like, and blocks permeation at low temperatures. The present invention relates to a microporous polyolefin membrane having a function to perform and an excellent function of a high melting rupture temperature.
【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、電流を遮断（シャットダウン）させる機能と、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、シャットダウン温度を低
くすると同時に、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２−７７１
０８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２−７７１０８
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, the function of melting the lithium before the ignition of the lithium, clogging the hole and shutting off the current (shut down), and when the separator itself melts and breaks (melt down) when the temperature further rises after the shutdown, the battery Because of the danger of fire and explosion, it is desired to lower the shutdown temperature and raise the meltdown temperature at the same time. 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,
JP-A-63-308866 and JP-A-2-771
No. 08,083, by laminating a single film made of low melting point polyethylene and high melting point polypropylene,
Although a method for obtaining a microporous porous film having high strength and excellent high-temperature properties is disclosed, the electrical resistance of the separator is increased due to lamination, making it unsuitable as a high-performance battery separator. Further, JP-A-2-77108
In Japanese Patent Application Laid-Open Publication No. 2002-284, the technique of lamination extrusion is employed, so that the productivity is inferior in terms of the complexity of the manufacturing process and the 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、低分子量のポリエチレンを加えると共に特定のポリ
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、かつ低シャットダウン温度で高メルトダウン
温度、さらにシャットダウン温度とメルトダウン温度幅
を大きい、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-mentioned object, the present invention provides low-molecular-weight polyethylene and specific polypropylene to ultra-high-molecular-weight polyethylene or a composition thereof, thereby improving permeation performance and mechanical properties. The present inventors have found that a microporous film having excellent strength, a high meltdown temperature at a low shutdown temperature, a large shutdown temperature and a wide range of a meltdown temperature, and a low heat shrinkage 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３５〜９０重量％、重量平均分子量が１０００〜４
０００で、融点が８０〜１３０℃の低分子量ポリエチレ
ン５〜３０重量％及び重量平均分子量が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３５
〜９０重量％、重量平均分子量が１０００〜４０００
で、融点が８０〜１３０℃の低分子量ポリエチレン５〜
３０重量％及び重量重量平均分子量が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 35 to 90% by weight, weight average molecular weight of 1000 to 4
5 to 30% by weight of low molecular weight polyethylene having a melting point of 80 to 130 ° C. and a polypropylene having a weight average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less.
An object of the present invention is to provide a microporous polyolefin membrane comprising a polyolefin composition containing about 35% by weight. This polyolefin microporous membrane has a weight average molecular weight of 5 × 10 5
Polyethylene or its polyethylene composition 35
~ 90% by weight, weight average molecular weight of 1000-4000
The low molecular weight polyethylene having a melting point of 80 to 130 ° C.
30% by weight and a polypropylene having a weight-average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less.
A solution consisting of 10 to 50% by weight of a composition containing 35% by weight and a solvent of 50 to 90% by weight is prepared, and the solution is extruded from a die and cooled to form a gel-like composition. The composition is suitably produced by stretching the composition 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】本発明で用いる低分子量ポリエチレンと
は、分子量が１０００〜４０００、融点が８０〜１３０
℃のエチレン低重合体であり、密度が０．９２〜０．９
７ｇ／ｃｃのポリエチレンワックスが好ましい。ポリエ
チレンワックスはエチレンから低圧による直接重合法に
よって製造される。この低分子量ポリエチレンをポリエ
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
昇した時、低温でシャットダウンする機能を付与すると
同時に電解液の粘性を上げる機能を付与すると考えられ
る。したがって、低分子量ポリエチレンの分子量が範囲
外であると低温でのシャットダウン効果が得られない。
低分子量ポリエチレンの量はポリオレフィンに対して５
〜３０重量％である。５重量％以下では低温シャットダ
ウン効果が得られず、３０重量％以上では得られたポリ
オレフィン微多孔膜の強度が著しく損なわれる。The low molecular weight polyethylene used in the present invention has a molecular weight of 1000 to 4000 and a melting point of 80 to 130.
C., an ethylene low polymer having a density of 0.92 to 0.9
7 g / cc polyethylene wax is preferred. Polyethylene wax is produced from ethylene by a low pressure direct polymerization process. By adding this low-molecular-weight polyethylene to polyethylene or its polyethylene composition, a polyolefin microporous membrane is used as a separator for lithium batteries and the like, and when the electrodes are short-circuited and the temperature inside the battery rises, a function to shut down at a low temperature is provided. At the same time, it is considered that a function of increasing the viscosity of the electrolytic solution is provided. Therefore, if the molecular weight of the low-molecular-weight polyethylene is out of the range, the low-temperature shutdown effect cannot be obtained.
The amount of low molecular weight polyethylene is 5 per polyolefin.
３０30% by weight. If it is less than 5% by weight, a low-temperature shutdown effect cannot be obtained, and if it is more than 30% by weight, the strength of the obtained microporous polyolefin membrane is significantly impaired.
【００１０】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.
【００１１】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。When polypropylene is added to polyethylene or its polyethylene composition, the polyolefin microporous membrane is used as a separator of 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.
【００１２】本発明のポリオレフィン微多孔膜はポリエ
チレンに、低分子量ポリエチレン及びポリプロピレンを
加えたポリオレフィン組成物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 is obtained by mixing an organic liquid or a solid with a polyolefin composition obtained by adding low molecular weight polyethylene and polypropylene to polyethylene, melt-kneading, extruding, extracting and stretching. Can be 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.
【００１３】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、ポリオレフィン組成物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、ポリオレフィン組成物が
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 composition. 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 composition 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
-50% by weight, preferably 10-40% 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 are large at the die exit, 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.
【００１４】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.
【００１５】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.
【００１６】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.
【００１７】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.
【００１８】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 is 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.
【００１９】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８００ｋｇ／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５０℃以上、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 800 kg / cm 2 or more, a meltdown temperature of 175 ° C. or more, a shutdown temperature difference of 50 ° C. or more, and a heat shrinkage (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.
【００２０】[0020]
【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）シート成形性：ネックインの有無、シート表面荒
れを目視で判断し、成形のしやすさを○△×で評価。 （５）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。 （６）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。 （７）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) Sheet formability: The presence or absence of neck-in and the roughness of the sheet surface were visually determined, and the ease of forming was evaluated as △ ××. (5) 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. (6) Meltdown temperature: Measured as a temperature at which the film melts and breaks when heated to a predetermined temperature. (7) 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.
【００２１】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．×１０5の高密
度ポリエチレン（ＨＤＰＥ）４５重量％、ポリエチレン
ワックス（三井ハイワックス−１００Ｐ、融点 １１８
℃、分子量１０００、三井石油化学製）１５重量％及び
重量平均分子量が５．３×１０5のポリプロピレンが２
０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 , 45% by weight of × 10 5 high-density polyethylene (HDPE), polyethylene wax (Mitsui High Wax-100P, melting point 118)
15% by weight and a weight average molecular weight of 5.3 × 10 5 polypropylene 2
A polyolefin composition was obtained by adding 0.375 parts by weight of an antioxidant to 100 parts by weight of a polyolefin composition consisting of 0% by weight. 30 parts by weight of this polyolefin composition is twin-screw extruder (58 mmφ, L / D = 42, strong kneading type)
It was put in. 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.
【００２２】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.
【００２３】実施例２ 実施例１において、ポリエチレンワックスとして融点１
１３℃、分子量２０００の三井ハイワックス２００Ｐ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。Example 2 The procedure of Example 1 was repeated except that the polyethylene wax had a melting point of 1
A microporous membrane was obtained in the same manner as in Example 1 except that Mitsui High Wax 200P having a molecular weight of 2,000 and a temperature of 13 ° C. was used.
The obtained microporous membrane had the physical properties shown in Table 1.
【００２４】実施例３ 実施例１において、ポリエチレンワックスとして融点１
２５℃、分子量４０００の三井ハイワックス４００Ｐ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。Example 3 In Example 1, a polyethylene wax having a melting point of 1 was used.
A microporous membrane was obtained in the same manner as in Example 1 except that Mitsui High Wax 400P having a molecular weight of 4000 and 25 ° C was used.
The obtained microporous membrane had the physical properties shown in Table 1.
【００２５】実施例４〜５ 実施例１において、高密度ポリエチレン、ポリエチレン
ワックス及びポリプロピレンの使用量を表１に示す量に
変更する以外は、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 4 and 5 A microporous membrane was obtained in the same manner as in Example 1, except that the amounts of the high-density polyethylene, polyethylene wax and polypropylene were changed to the amounts shown in Table 1. The obtained microporous membrane had the physical properties shown in Table 1.
【００２６】実施例６〜８ 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２の物性を有していた。Examples 6 to 8 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 2.
【００２７】実施例９ 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２の物性を有していた。Example 9 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 2.
【００２８】比較例１ 実施例１において、ポリエチレンワックス及びポリプロ
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３の物性を有してい
た。Comparative Example 1 A microporous membrane was obtained in the same manner as in Example 1 except that polyethylene wax and polypropylene were not used. The obtained microporous membrane had the physical properties shown in Table 3.
【００２９】比較例２〜４ 実施例１において、ポリエチレンワックスおよびポリプ
ロピレンの使用量を表３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３の物性を有していた。Comparative Examples 2 to 4 Microporous membranes were obtained in the same manner as in Example 1 except that the amounts of polyethylene wax and polypropylene used were changed as shown in Table 3. The obtained microporous membrane had the physical properties shown in Table 3.
【００３０】比較例５ 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３の物性を有していた。Comparative Example 5 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 1 were used. The obtained microporous membrane had the physical properties shown in Table 3.
【００３１】表１〜表３から明らかなように、実施例１
〜９の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、低シャットダウン温度、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 to 3, Example 1
The polyolefin microporous membrane of the present invention exemplified in (1) to (9) has a high breaking strength, a low shutdown temperature, a high meltdown temperature, a wide difference between the shutdown temperature and the meltdown temperature, and a heat shrinkage rate of Low, high safety when used as a battery separator for lithium batteries.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【表３】 [Table 3]
【００３５】[0035]
【発明の効果】本発明のポリオレフィン微多孔膜は、高
強度かつ低温シャットダウン及び高温メルトダウン特性
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。The microporous polyolefin membrane of the present invention has high strength, low-temperature shutdown and high-temperature meltdown characteristics, a wide difference between the shutdown temperature and the meltdown temperature, and a low heat shrinkage. Therefore, when used as a separator for lithium batteries, it is highly reliable in terms of safety.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野方 鉄郎 神奈川県川崎市川崎区千鳥町３番１号 東 燃化学株式会社技術開発センター内 (72)発明者 山口 総一郎 神奈川県川崎市川崎区千鳥町３番１号 東 燃化学株式会社技術開発センター内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuro Nogata 3-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Technical Development Center, East Fuel Chemical Co., Ltd. (72) Inventor Soichiro Yamaguchi Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa No.3-1 Tonen Chemical Co., Ltd. Technology Development Center
Claims (3)
エチレンまたはそのポリエチレン組成物３５〜９０重量
％、重量平均分子量が１０００〜４０００で、融点が８
０〜１３０℃の低分子量ポリエチレン５〜３０重量％及
び重量平均分子量が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 thereof in an amount of 35 to 90% by weight, a weight average molecular weight of 1000 to 4000 and a melting point of 8
A polyolefin composition comprising a polyolefin composition containing 5 to 30% by weight of low molecular weight polyethylene at 0 to 130 ° C and 5 to 35% by weight of polypropylene having a weight average molecular weight of 3 × 10 5 or more and an ethylene content of 1.0% by weight or less. Porous membrane.
エチレンまたはそのポリエチレン組成物３５〜９０重量
％と重量平均分子量が１０００〜４０００で、融点が８
０〜１３０℃の低分子量ポリエチレン５〜３０及び重量
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. A polyethylene having a weight average molecular weight of 5 × 10 5 or more or 35 to 90% by weight of a polyethylene composition thereof, a weight average molecular weight of 1,000 to 4000, and a melting point of 8
Low molecular weight polyethylene of 5 to 30 at 0 to 130 ° C. and weight / weight average molecular weight of 3 × 10 5 or more and ethylene content of 1.
10 to 50% by weight of a polyolefin composition containing 5 to 35% by weight of polypropylene of 0% by weight or less;
To 90% by weight, the solution was extruded from a die, cooled to form a gel composition, and the gel composition was stretched at a temperature not higher than the melting point of the polyolefin composition + 10 ° C, A method for producing a microporous polyolefin membrane, comprising removing the residual solvent thereafter.
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 |
|---|---|---|---|
| JP12025697A JP3699562B2 (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 |
|---|---|---|---|
| JP12025697A JP3699562B2 (en) | 1997-04-23 | 1997-04-23 | Polyolefin microporous membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10298325A true JPH10298325A (en) | 1998-11-10 |
| JP3699562B2 JP3699562B2 (en) | 2005-09-28 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12025697A Expired - Lifetime JP3699562B2 (en) | 1997-04-23 | 1997-04-23 | Polyolefin microporous membrane and method for producing the same |
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| US6559195B1 (en) | 1999-08-31 | 2003-05-06 | Nitto Denko Corporation | Microporous film |
| JP2007311367A (en) * | 2007-08-30 | 2007-11-29 | Matsushita Electric Ind Co Ltd | Battery |
| WO2011016571A1 (en) * | 2009-08-06 | 2011-02-10 | 住友化学株式会社 | Porous film, separator for batteries, and battery |
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