JPH10296839A - Manufacture of polyolefin porous film - Google Patents
Manufacture of polyolefin porous filmInfo
- Publication number
- JPH10296839A JPH10296839A JP9120252A JP12025297A JPH10296839A JP H10296839 A JPH10296839 A JP H10296839A JP 9120252 A JP9120252 A JP 9120252A JP 12025297 A JP12025297 A JP 12025297A JP H10296839 A JPH10296839 A JP H10296839A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- molecular weight
- weight
- solvent
- die
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cell Separators (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、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からなる微多孔膜
を製造する方法に関し、特に高透過性ポリオレフィン微
多孔膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a microporous membrane comprising a polyolefin composition containing an ultrahigh molecular weight polyolefin, and more particularly to a highly permeable microporous polyolefin microporous membrane.
【０００２】[0002]
【従来の技術】微多孔膜は、電池用セパレーター、電解
コンデンサー用隔膜、各種フィルター、透湿防水衣料、
逆浸透濾過膜、限外濾過膜、精密濾過膜等の各種用途に
用いられている。従来から、ポリオレフィンに有機媒体
及び微粉末シリカ等の無機粉体を混合し溶融成形後、有
機媒体及び無機粉体を抽出して微多孔膜を得る方法は知
られているが、無機物の抽出する工程が必要であり、得
られた膜の透過性は無機分体の粒径によるところが大き
く、その制御は難しかった。また、超高分子量ポリオレ
フィンを用いた高強度の微多孔膜の製造法が種々提案さ
れている。例えば、特開昭６０−２４２０３５号、特開
昭６１−１９５１３２号、特開昭６１−１９５１３３
号、特開昭６３−３９６０２号、特開昭６３−２７３６
５１号等には、超高分子量ポリオレフィンを含むポリオ
レフィン組成物を溶媒に加熱溶解した溶液からゲル状シ
ートを成形し、前記ゲル状シートを加熱延伸、溶媒の抽
出除去による微多孔膜を製造する方法が記載されている
が、これらの技術によるポリオレフィン微多孔膜は孔径
が小さく、孔径分布が狭いことが特徴で、電池用セパレ
ーター等には好適であったが大孔径の微多孔膜は得られ
ていなかった。2. Description of the Related Art Microporous membranes are used for battery separators, electrolytic capacitor diaphragms, various filters, moisture-permeable waterproof clothing,
It is used for various applications such as reverse osmosis filtration membrane, ultrafiltration membrane, and microfiltration membrane. Conventionally, a method of obtaining a microporous membrane by extracting an organic medium and an inorganic powder after mixing and melt-molding an organic medium and an inorganic powder such as finely divided silica with a polyolefin is known, but extracting an inorganic substance. A process was required, and the permeability of the obtained membrane largely depended on the particle size of the inorganic particles, and it was difficult to control the permeability. Also, various methods for producing a high-strength microporous membrane using an ultrahigh molecular weight polyolefin have been proposed. For example, JP-A-60-24203, JP-A-61-195132, JP-A-61-195133.
JP-A-63-39602, JP-A-63-2736
No. 51, etc., a method for producing a microporous membrane by forming a gel-like sheet from a solution obtained by heating and dissolving a polyolefin composition containing an ultra-high-molecular-weight polyolefin in a solvent, heating and stretching the gel-like sheet, and extracting and removing the solvent. However, the microporous polyolefin membranes obtained by these techniques are characterized by a small pore size and a narrow pore size distribution, which is suitable for battery separators and the like, but a large pore size microporous membrane has been obtained. Did not.
【０００３】[0003]
【発明が解決しようとする課題】最近では各用途ごとに
種々の透過性の微多孔膜がのぞまれており、それぞれの
用途にあった特性を向上させるために膜の透過性の制御
が望まれていた。しかしながら、先行発明においては、
延伸法によって微細な孔を多数形成させており、孔径が
小さく、孔径分布がせまいため、水処理、精密濾過膜等
の用途に用いられる大孔径の微多孔膜は得られておら
ず、その開発が望まれていた。Recently, various permeable microporous membranes have been desired for each application, and it is desired to control the permeability of the membrane in order to improve the characteristics suitable for each application. Was rare. However, in the prior invention,
A large number of fine pores are formed by the stretching method, the pore size is small, and the pore size distribution is narrow, so a microporous membrane with a large pore size used for water treatment, microfiltration membrane, etc. has not been obtained. Was desired.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、超高分子
量ポリオレフィンを特定量含有する組成物を用い、その
溶媒との特定濃度の溶液を押し出して、冷却することに
より微多孔膜を得る際、冷却条件をコントロールするこ
とにより、高透過性の膜を得ることが出来ることを見い
出し、本発明に想到した。すなわち、本発明は、重量平
均分子量５×１０5以上の超高分子量ポリオレフィン
（Ａ）と重量平均分子量５×１０5未満のポリオレフィ
ン（Ｂ）の混合物で、（Ｂ）／（Ａ）の重量比が０.２
〜２０であるポリオレフィン組成物５〜４０重量％と、
溶媒９５〜６０重量％からなる溶液を調製し、前記溶液
をダイより押し出し、冷却ロールにより引き取りフィル
ムを成形後、フィルム中の残存溶媒を除去し、乾燥して
ポリオレフィン微多孔膜を製造する方法において、ダイ
と冷却ロールの間隔を５〜１００ｍｍ、冷却ロールの温
度を３０℃〜１００℃樹脂の結晶化温度及び引き取り速
度を１〜２０ｍ／分とすることにより冷却条件を調整す
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
である。Means for Solving the Problems The present inventors obtain a microporous membrane by using a composition containing a specific amount of an ultrahigh molecular weight polyolefin, extruding a solution having a specific concentration with a solvent, and cooling the mixture. In this case, it has been found that a film having high permeability can be obtained by controlling the cooling conditions, and the present invention has been made. That is, the present invention relates to a mixture of an ultrahigh molecular weight polyolefin (A) having a weight average molecular weight of 5 × 10 5 or more and a polyolefin (B) having a weight average molecular weight of less than 5 × 10 5, wherein a weight ratio of (B) / (A) is obtained. Is 0.2
5 to 40% by weight of a polyolefin composition,
A method for preparing a polyolefin microporous membrane by preparing a solution comprising 95 to 60% by weight of a solvent, extruding the solution through a die, forming a take-off film by a cooling roll, removing a solvent remaining in the film, and drying the film. The cooling conditions are adjusted by setting the distance between the die and the cooling roll to 5 to 100 mm, the temperature of the cooling roll to 30 ° C. to 100 ° C., and the crystallization temperature and take-off speed of the resin to 1 to 20 m / min. This is a method for producing a microporous polyolefin membrane.
【０００５】[0005]
【発明の実施の形態】本発明を以下に詳細に説明する。
本発明において製造するポリオレフィン微多孔膜は、重
量平均分子量５×１０5以上の超高分子量ポリオレフィ
ン（Ａ）と重量平均分子量５×１０5未満のポリオレフ
ィン（Ｂ）の混合物で、（Ｂ）／（Ａ）の重量比が０.
２〜２０、好ましくは０.５〜１０であるポリオレフィ
ン組成物からなる。ポリオレフィン組成物中の（Ｂ）／
（Ａ）の重量比が０.２未満では、得られるゲル状シー
トの厚み方向の収縮が起きやすく透過性が低下し、また
溶液粘度が高くなり成形加工性が低下する。また、
（Ｂ）／（Ａ）の重量比が２０を超えると低分子量成分
が多くなり、ゲル構造が緻密化し、得られる微多孔膜の
透過性が低下する。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
The polyolefin microporous membrane produced in the present invention is heavy
Weight average molecular weight 5 × 10FiveUltra high molecular weight polyolefin
(A) and weight average molecular weight 5 × 10FiveLess than polyolefin
(B) / (A) weight ratio of 0.
2 to 20, preferably 0.5 to 10 polyolefin
Composition. (B) in the polyolefin composition /
If the weight ratio of (A) is less than 0.2, the resulting gel-like sheet
Shrinkage in the thickness direction of the glass tends to occur, permeability decreases, and
The solution viscosity increases and the moldability decreases. Also,
When the weight ratio of (B) / (A) exceeds 20, low molecular weight components
Increases, the gel structure becomes denser, and the resulting microporous membrane becomes
The permeability decreases.
【０００６】本発明で用いる超高分子量ポリオレフィン
は、重量平均分子量が５×１０5以上であり、好ましく
は１×１０6〜１５×１０6である。また、重量平均分子
量が５×１０5未満のポリオレフィンの分子量の下限と
しては、１×１０5以上のものが好ましい。重量平均分
子量が１×１０5未満のポリオレフィンを用いると、破
断が起こりやすく、目的の微多孔膜が得られないので好
ましくない。したがって重量平均分子量が１×１０5以
上５×１０5未満のポリオレフィンを超高分子量ポリオ
レフィンに配合するのが好ましい。The ultrahigh molecular weight polyolefin used in the present invention has a weight average molecular weight of 5 × 10 5 or more, preferably 1 × 10 6 to 15 × 10 6 . The lower limit of the molecular weight of the polyolefin having a weight average molecular weight of less than 5 × 10 5 is preferably 1 × 10 5 or more. Use of a polyolefin having a weight-average molecular weight of less than 1 × 10 5 is not preferred because breakage easily occurs and a desired microporous film cannot be obtained. Therefore, it is preferable to blend a polyolefin having a weight average molecular weight of 1 × 10 5 or more and less than 5 × 10 5 with the ultrahigh molecular weight polyolefin.
【０００７】上記ポリオレフィンとしては、エチレン、
プロピレン、１−ブテン、４−メチル−ペンテン−１、
１−ヘキセンなどを重合した結晶性の単独重合体、２段
重合体、又は共重合体及びこれらのブレンド物等が挙げ
られる。これらのうちではポリプロピレン、ポリエチレ
ン（特に高密度ポリエチレン）及びこれらの組成物等が
好ましい。なお、上記ポリオレフィン組成物の分子量分
布（重量平均分子量／数平均分子量）は３００以下、特
に５〜５０であるのが好ましい。分子量分布が３００を
こえると、低分子量成分による破断が起こり膜全体の強
度が低下するため好ましくない。[0007] As the polyolefin, ethylene,
Propylene, 1-butene, 4-methyl-pentene-1,
Examples include a crystalline homopolymer obtained by polymerizing 1-hexene or the like, a two-stage polymer, a copolymer, and a blend thereof. Among these, polypropylene, polyethylene (particularly high-density polyethylene), and compositions thereof are preferred. The molecular weight distribution (weight average molecular weight / number average molecular weight) of the polyolefin composition is preferably 300 or less, particularly preferably 5 to 50. If the molecular weight distribution exceeds 300, breakage due to low molecular weight components occurs and the strength of the entire film is reduced, which is not preferable.
【０００８】このポリオレフィン組成物は、上記分子量
及び分子量分布を有していれば、多段重合によるもので
あっても、２種以上のポリオレフィンによる組成物であ
っても、いずれでもよい。多段重合の場合、例えば、重
量平均分子量が５×１０5以上の超高分子量成分（Ａ）
と重量平均分子量が５×１０5未満のポリオレフィン成
分（Ｂ）を（Ｂ）／（Ａ）の重量比が０.２〜２０で、
かつ分子量分布が３００以下となるように、オレフィン
を多段重合することにより製造することができる。多段
重合法としては、二段重合により、高分子量部分と低分
子量部分とを製造する方法を採用するのが好ましい。な
お、上述したような超高分子量成分を含有するポリオレ
フィン組成物には、必要に応じて、酸化防止剤、紫外線
吸収剤、アンチブロッキング剤、顔料、染料、無機充填
材などの各種添加剤を本発明の目的を損なわない範囲で
添加することができる。[0008] The polyolefin composition may be either a multistage polymerized composition or a composition of two or more polyolefins as long as it has the above-mentioned molecular weight and molecular weight distribution. In the case of multistage polymerization, for example, an ultrahigh molecular weight component (A) having a weight average molecular weight of 5 × 10 5 or more
And a polyolefin component (B) having a weight average molecular weight of less than 5 × 10 5 , wherein the weight ratio of (B) / (A) is 0.2 to 20,
And it can be produced by multistage polymerization of olefins such that the molecular weight distribution is 300 or less. As the multistage polymerization method, it is preferable to adopt a method of producing a high molecular weight portion and a low molecular weight portion by two-stage polymerization. In addition, the polyolefin composition containing the ultrahigh molecular weight component as described above may contain various additives such as an antioxidant, an ultraviolet absorber, an antiblocking agent, a pigment, a dye, and an inorganic filler as necessary. It can be added in a range that does not impair the object of the invention.
【０００９】本発明の微多孔膜の製造方法は、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、
溶液を調製する。この溶媒としては、ノナン、デカン、
デカリン、ｐ−キシレン、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を用いることが
できる。またこの溶媒の粘度としては、２５℃における
粘度が３０〜５００ｃＳｔ、特に５０〜２００ｃＳｔで
あるのが好ましい。２５℃における粘度が３０ｃＳｔ未
満では、不均一吐出を生じ、混練が困難であり、一方５
００ｃＳｔを超えると、後工程での脱溶媒が容易でなく
なる。In the method for producing a microporous membrane of the present invention, the above polyolefin composition is heated and dissolved in a solvent,
Prepare solution. Nonane, decane,
An aliphatic or cyclic hydrocarbon such as decalin, p-xylene, undecane, dodecane, liquid paraffin, or a mineral oil fraction having a boiling point corresponding thereto can be used. The viscosity of the solvent at 25 ° C. is preferably 30 to 500 cSt, particularly preferably 50 to 200 cSt. If the viscosity at 25 ° C. is less than 30 cSt, non-uniform discharge occurs, and kneading is difficult.
If it exceeds 00 cSt, it will not be easy to remove the solvent in the subsequent step.
【００１０】加熱溶解は、ポリオレフィン組成物を溶媒
中で完全に溶解する温度で撹拌しながら行うか、又は押
出機中で均一混合して溶解する方法で行う。溶媒中で撹
拌しながら溶解する場合は、温度は使用する重合体及び
溶媒により異なるが、例えばポリエチレン組成物の場合
には１４０〜２５０℃の範囲である。ポリオレフィン組
成物の高濃度溶液から微多孔膜を製造する場合は、押出
機中で溶解するのが好ましい。The heat dissolution is carried out with stirring at a temperature at which the polyolefin composition is completely dissolved in the solvent, or by a method in which the polyolefin composition is uniformly mixed and dissolved in an extruder. In the case of dissolving with stirring in a solvent, the temperature varies depending on the polymer and the solvent to be used. For example, in the case of a polyethylene composition, the temperature is in the range of 140 to 250 ° C. When producing a microporous membrane from a high-concentration solution of the polyolefin composition, it is preferable to dissolve it in an extruder.
【００１１】押出機中で溶解する場合は、まず押出機に
上述したポリオレフィン組成物を供給し、溶融する。溶
融温度は、使用するポリオレフィンの種類によって異な
るが、ポリオレフィンの融点＋３０〜１００℃が好まし
い。例えば、ポリエチレンの場合は１６０〜２３０℃、
特に１７０〜２００℃であるのが好ましく、ポリプロピ
レンの場合は１９０〜２７０℃、特に１９０〜２５０℃
であるのが好ましい。次に、この溶融状態のポリオレフ
ィン組成物に対して、液状の溶媒を押出機の途中から供
給する。In the case of melting in an extruder, the above-mentioned polyolefin composition is first supplied to the extruder and melted. The melting temperature varies depending on the type of the polyolefin used, but is preferably the melting point of the polyolefin + 30 to 100 ° C. For example, in the case of polyethylene, 160 to 230 ° C,
It is particularly preferably 170 to 200 ° C, and in the case of polypropylene, 190 to 270 ° C, particularly 190 to 250 ° C.
It is preferred that Next, a liquid solvent is supplied to the molten polyolefin composition in the middle of the extruder.
【００１２】ポリオレフィン組成物と溶媒との配合割合
は、ポリオレフィン組成物と溶媒の合計を１００重量％
として、ポリオレフィン組成物が５〜４０重量％、好ま
しくは１０〜３０重量％であり、溶媒が９５〜６０重量
％、好ましくは９０〜７０重量％である。ポリオレフィ
ン組成物が５重量％未満では（溶媒が９５重量％を超え
ると）、シート状に成形する際に、ダイ出口で、スウエ
ルやネックインが大きくシートの成形性、自己支持性が
困難となる。一方、ポリオレフィン組成物が４０重量％
を超えると（溶媒が６０重量％未満では）、厚み方向の
収縮が大きくなり、空孔率が低下し、大孔径を有する微
多孔膜が得られず、また成形加工性も低下する。この範
囲において濃度を変えることにより、膜の透過性をコン
トロールすることができる。The mixing ratio of the polyolefin composition and the solvent is such that the total of the polyolefin composition and the solvent is 100% by weight.
The polyolefin composition is 5 to 40% by weight, preferably 10 to 30% by weight, and the solvent is 95 to 60% by weight, preferably 90 to 70% by weight. When the polyolefin composition is less than 5% by weight (when the solvent exceeds 95% by weight), when forming into a sheet, the swell and neck-in are large at the die exit, making the sheet moldability and self-supporting difficult. . On the other hand, the polyolefin composition is 40% by weight.
If it exceeds (when the solvent is less than 60% by weight), shrinkage in the thickness direction increases, the porosity decreases, a microporous film having a large pore size cannot be obtained, and the moldability decreases. By changing the concentration in this range, the permeability of the membrane can be controlled.
【００１３】次に、このようにして溶融混練したポリオ
レフィン組成物の加熱溶液を直接に、あるいはさらに別
の押出機を介して、または一旦冷却してペレット化した
後、再度押出機を介して、ダイ等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重円筒状の中空糸ダイ、インフレーシ
ョンダイ等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である。押し
出し成形時には１４０〜２５０℃に加熱して押し出す。Next, the heated solution of the polyolefin composition thus melt-kneaded is directly or through another extruder, or once cooled and pelletized, and then again through the extruder. It is extruded from a die and molded. As the die, a sheet die having a rectangular base shape is usually used, but a double cylindrical hollow fiber die, an 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. At the time of extrusion molding, it is heated to 140 to 250 ° C. and extruded.
【００１４】ダイから押し出された溶液は、冷却ロール
により引き取られることによりゲル状物に成形される
が、この冷却条件をコントロールすることにより孔径等
を制御できる。ダイから冷却ロールの間隔は、５ｍｍ〜
１００ｍｍ、好ましくは１０ｍｍ〜５０ｍｍにする必要
がある。樹脂溶液の粘度が低い場合は、ダイから冷却ロ
ールの間隔が長いと得られたシートはネックインを起こ
しやすく短いほうが好ましい。The solution extruded from the die is formed into a gel-like material by being taken up by a cooling roll. The pore size and the like can be controlled by controlling the cooling conditions. The distance between the die and the cooling roll is 5mm ~
It needs to be 100 mm, preferably 10 mm to 50 mm. In the case where the viscosity of the resin solution is low, if the distance between the die and the cooling roll is long, the obtained sheet is liable to cause neck-in, and is preferably short.
【００１５】冷却ロールの温度は、３０℃〜ポリオレフ
ィン結晶化温度、好ましくは４０〜９０℃にする必要が
ある。冷却ロール温度が高すぎると、ゲル状シートは徐
冷されてゲル構造を形成するポリオレフィンのラメラ構
造を構成する壁が厚くなり、微多孔は独立泡になり易い
ため、脱溶媒性が低下し透過性が低下する。冷却ロール
温度が低すぎると、ゲル状シートは急冷されてゲル構造
が緻密になり過ぎるため、孔径が小さくなり、透過性が
低下する。引き取り速度は、１〜２０ｍ/分、好ましく
は３〜１０ｍ/分である。引き取り速度が速過ぎるとシ
ートがネックインを起こし、延伸されやすいため、遅い
ほうが好ましい。[0015] The temperature of the cooling roll must be 30 ° C to the polyolefin crystallization temperature, preferably 40 to 90 ° C. If the cooling roll temperature is too high, the gel-like sheet is gradually cooled, the wall constituting the lamellar structure of the polyolefin forming the gel structure becomes thick, and the microporous tends to become a closed cell, so that the solvent is reduced and the permeation is reduced. Is reduced. If the cooling roll temperature is too low, the gel-like sheet is rapidly cooled and the gel structure becomes too dense, so that the pore size becomes small and the permeability decreases. The take-off speed is 1 to 20 m / min, preferably 3 to 10 m / min. If the take-up speed is too fast, the sheet will neck-in and be easily stretched.
【００１６】ダイから押し出された溶液は、冷却ロール
を通すことにより得られたゲル状成形物は、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。上述のような洗浄は、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 solution extruded from the die is passed through a cooling roll, and the gel-like molded product obtained is washed with a solvent to remove the residual 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. The washing as described above is performed until the residual solvent in the 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. The dried molded product is desirably heat-set at a temperature in the range from the crystal dispersion temperature to the melting point.
【００１７】以上のようにして製造したポリエチレン微
多孔膜は、透気度が５〜１００秒／１００ｃｃ、空孔率
が３５〜９５％、平均貫通孔径が０.０５〜１．０μｍ
の高透過性膜である。なお、得られたポリエチレン微多
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 polyethylene membrane produced as described above has an air permeability of 5 to 100 seconds / 100 cc, a porosity of 35 to 95%, and an average through-pore diameter of 0.05 to 1.0 μm.
Is a highly permeable membrane. The obtained microporous polyethylene membrane may be further subjected to surface modification such as hydrophilic treatment such as plasma irradiation, surfactant impregnation, and surface grafting, if necessary.
【００１８】[0018]
【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）透気度：ＪＩＳ Ｐ８１１７に準拠して測定。 （３）平均孔径：コールターポロメーターＩＩ（コール
ター社製）にて測定。 （４）シートの成形性：メルトフラクチャー、ネックイ
ン、シート表面性及び厚薄ムラを目視でチェックし、成
形のしやすさを○△×で評価。 （５）シートの脱溶媒性：膜を四角の枠に固定し、室温
において塩化メチレン中に５分間含浸させた時の膜の白
色度により判定。溶媒が除去されているほど膜は白く、
残っている場合は透明となる。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) Air permeability: measured according to JIS P8117. (3) Average pore size: measured with a Coulter porometer II (manufactured by Coulter). (4) Sheet formability: Melt fracture, neck-in, sheet surface properties and thickness unevenness were visually checked, and the ease of forming was evaluated as ○ △ ×. (5) Desolvation property of sheet: Determined by whiteness of the film when the film was fixed in a square frame and immersed in methylene chloride for 5 minutes at room temperature. The more the solvent is removed, the whiter the membrane,
If it remains, it becomes transparent.
【００１９】実施例１ 重量平均分子量が３．０×１０5の高密度ポリエチレン
（ＨＤＰＥ）８０重量％と重量平均分子量が２．５×１
０6の超高分子量ポリエチレン（ＵＨＭＷＰＥ）２０重
量％からなるポリエチレン組成物に、酸化防止剤をポリ
エチレン組成物１００重量部当たり０．３７５重量部を
加えたポリエチレン組成物を得た。このポリエチレン組
成物２０重量部を二軸押出機（５８ｍｍφ、Ｌ／Ｄ＝４
２、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８０重量部を供
給し、２００℃、２００ｒｐｍで溶融混練して、押出機
にてポリエチレン溶液を調製し、押出機の先端に設置さ
れたＴダイから押し出し、ダイとロールの間隔を２０ｍ
ｍ、冷却ロール温度を６０℃、引き取り速度を５ｍ／分
の条件でゲル状シートを押し出した。得られたシートを
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１１５℃で熱処理を行いポリエ
チレン微多孔膜を得た。このポリエチレン微多孔膜の物
性評価の結果を第１表に示す。Example 1 80% by weight of high density polyethylene (HDPE) having a weight average molecular weight of 3.0 × 10 5 and a weight average molecular weight of 2.5 × 1
0 to 6 ultra high molecular weight polyethylene (UHMWPE) polyethylene composition consisting of 20 wt% of, to obtain a polyethylene composition for the antioxidant was added 0.375 parts by weight per 100 parts by weight of polyethylene composition. Twenty parts by weight of this polyethylene composition was mixed with a twin screw extruder (58 mmφ, L / D = 4).
2, strong kneading type). Further, 80 parts by weight of liquid paraffin is supplied from a side feeder of this twin-screw extruder, melt-kneaded at 200 ° C. and 200 rpm, a polyethylene solution is prepared by an extruder, and a T-die set at the tip of the extruder is prepared. Extruded from the die, the distance between the die and the roll is 20m
m, the temperature of the cooling roll was 60 ° C., and the take-up speed was 5 m / min. The obtained sheet was washed with methylene chloride to extract and remove the remaining liquid paraffin, and then dried and heat-treated at 115 ° C to obtain a microporous polyethylene membrane. Table 1 shows the results of evaluating the physical properties of this polyethylene microporous membrane.
【００２０】実施例２〜４ 実施例１において、成形条件を表１に示すように変更し
た以外は、実施例１と同様の方法で、ポリエチレン微多
孔膜を得た。このポリエチレン微多孔膜の物性評価の結
果を第１表に示す。Examples 2 to 4 A microporous polyethylene membrane was obtained in the same manner as in Example 1 except that the molding conditions were changed as shown in Table 1. Table 1 shows the results of evaluating the physical properties of this polyethylene microporous membrane.
【００２１】実施例５〜６ 実施例１において、ポリエチレン組成物の割合を表１に
示すように変更した以外は、実施例１と同様の方法で、
ポリエチレン微多孔膜を得た。このポリエチレン微多孔
膜の物性評価の結果を第１表に示す。Examples 5 to 6 In the same manner as in Example 1, except that the proportion of the polyethylene composition was changed as shown in Table 1,
A polyethylene microporous membrane was obtained. Table 1 shows the results of evaluating the physical properties of this polyethylene microporous membrane.
【００２２】実施例８〜９ 実施例１において、ポリエチレン組成物と溶媒の割合を
表１に示すように変更した以外は、実施例１と同様の方
法で、ポリエチレン微多孔膜を得た。このポリエチレン
微多孔膜の物性評価の結果を第１表に示す。Examples 8 to 9 Microporous polyethylene membranes were obtained in the same manner as in Example 1, except that the proportions of the polyethylene composition and the solvent were changed as shown in Table 1. Table 1 shows the results of evaluating the physical properties of this polyethylene microporous membrane.
【００２３】比較例１〜４ 実施例１において、成形条件を表２に示すように変更し
た以外は、実施例１と同様の方法で、ポリエチレン微多
孔膜を得た。このポリエチレン微多孔膜の物性評価の結
果を第２表に示す。Comparative Examples 1 to 4 Microporous polyethylene membranes were obtained in the same manner as in Example 1, except that the molding conditions were changed as shown in Table 2. Table 2 shows the results of evaluation of the physical properties of this polyethylene microporous membrane.
【００２４】比較例５ 実施例１において、超高分子量ポリエチレンのみを使用
する以外は、実施例１と同様の方法で、ポリエチレン微
多孔膜を得た。このポリエチレン微多孔膜の物性評価の
結果を第２表に示す。Comparative Example 5 A microporous polyethylene membrane was obtained in the same manner as in Example 1 except that only the ultrahigh molecular weight polyethylene was used. Table 2 shows the results of evaluation of the physical properties of this polyethylene microporous membrane.
【００２５】比較例６ 実施例１において、ポリエチレン組成物の割合を表１に
示すように変更した以外は、実施例１と同様の方法で、
ポリエチレン微多孔膜を得た。このポリエチレン微多孔
膜の物性評価の結果を第２表に示す。Comparative Example 6 The procedure of Example 1 was repeated, except that the proportion of the polyethylene composition was changed as shown in Table 1.
A polyethylene microporous membrane was obtained. Table 2 shows the results of evaluation of the physical properties of this polyethylene microporous membrane.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】表１及び表２から明らかなように、冷却時
の成形条件を本発明の範囲内で行うと、得られる微多孔
膜は、平均孔径が大きく高透過性の膜であることが解
る。また、超高分子量ポリエチレンのみを用いて製造し
た微多孔膜はシート成形性が悪く、樹脂溶液濃度を高く
して製造した微多孔膜は透気性が悪いことが解る。As is clear from Tables 1 and 2, when the molding conditions at the time of cooling are set within the range of the present invention, the obtained microporous membrane has a large average pore diameter and a high permeability. . Also, it can be seen that the microporous membrane produced using only ultra-high molecular weight polyethylene has poor sheet moldability, and the microporous membrane produced with a high resin solution concentration has poor air permeability.
【００２９】[0029]
【発明の効果】以上詳述したように本発明の方法により
得られるポリオレフィン微多孔膜は、孔径が大きく、高
透過性であり、液体フィルター等として好適に用いるこ
とができる。As described in detail above, the microporous polyolefin membrane obtained by the method of the present invention has a large pore size and high permeability, and can be suitably used as a liquid filter or the like.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｈ０１Ｍ 2/16 Ｈ０１Ｍ 2/16 Ｐ Ｂ２９Ｋ 23:00 Ｂ２９Ｌ 7:00 (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Continued on the front page (51) Int.Cl. 6 Identification symbol FI // H01M 2/16 H01M 2/16 P B29K 23:00 B29L 7:00 (72) Inventor Tetsuro Nogata 3 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kawasaki-ku, Kanagawa-ken No. 1 Tonen Chemical Co., Ltd. Technology Development Center (72) Inventor Soichiro Yamaguchi 3-1, Chidori-cho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture
Claims (1)
子量ポリオレフィン（Ａ）と重量平均分子量５×１０5
未満のポリオレフィン（Ｂ）の混合物で、（Ｂ）／
（Ａ）の重量比が０.２〜２０であるポリオレフィン組
成物５〜４０重量％と、溶媒９５〜６０重量％からなる
溶液を調製し、前記溶液をダイより押し出し、冷却ロー
ルにより引き取りフィルムを成形後、フィルム中の残存
溶媒を除去し、乾燥してポリオレフィン微多孔膜を製造
する方法において、ダイと冷却ロールの間隔を５〜１０
０ｍｍ、冷却ロールの温度を３０℃〜１００℃及び引き
取り速度を１〜２０ｍ／分とすることにより冷却条件を
調整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。An ultrahigh molecular weight polyolefin (A) having a weight average molecular weight of 5 × 10 5 or more and a weight average molecular weight of 5 × 10 5.
Less than a mixture of polyolefins (B), (B) /
A solution consisting of 5 to 40% by weight of a polyolefin composition having a weight ratio of (A) of 0.2 to 20 and 95 to 60% by weight of a solvent is prepared, the solution is extruded from a die, and the film is taken out by a cooling roll. After the molding, the solvent remaining in the film is removed and dried to produce a polyolefin microporous membrane.
A method for producing a microporous polyolefin membrane, wherein the cooling conditions are adjusted by adjusting the cooling roll temperature to 30 ° C. to 100 ° C. and the take-off speed to 1 to 20 m / min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025297A JP3638401B2 (en) | 1997-04-23 | 1997-04-23 | Method for producing polyolefin microporous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12025297A JP3638401B2 (en) | 1997-04-23 | 1997-04-23 | Method for producing polyolefin microporous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10296839A true JPH10296839A (en) | 1998-11-10 |
| JP3638401B2 JP3638401B2 (en) | 2005-04-13 |
Family
ID=14781603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12025297A Expired - Lifetime JP3638401B2 (en) | 1997-04-23 | 1997-04-23 | Method for producing polyolefin microporous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3638401B2 (en) |
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| JP2002050336A (en) * | 2000-08-07 | 2002-02-15 | Asahi Kasei Corp | Separator for zinc halogen battery |
| JP2005193200A (en) * | 2004-01-09 | 2005-07-21 | Kuraray Co Ltd | Hollow fiber membrane having excellent mechanical strength and its production method |
| WO2007037289A1 (en) * | 2005-09-28 | 2007-04-05 | Tonen Chemical Corporation | Process for producing microporous polyethylene film and separator for cell |
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| JP4979824B1 (en) * | 2011-03-29 | 2012-07-18 | 株式会社アストム | Ion exchange membrane |
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| KR101243070B1 (en) | 2005-09-28 | 2013-03-13 | 도레이 배터리 세퍼레이터 필름 주식회사 | Process for producing microporous polyethylene film and separator for cell |
| JP5145712B2 (en) * | 2005-10-18 | 2013-02-20 | 東レ株式会社 | Microporous film for power storage device separator and power storage device separator using the same |
| WO2007046226A1 (en) * | 2005-10-18 | 2007-04-26 | Toray Industries, Inc. | Microporous film for power storage device separator and power storage device separator making use of the same |
| US8089746B2 (en) | 2005-10-18 | 2012-01-03 | Toray Industries, Inc. | Microporous film for electric storage device separator and electric storage device separator using the same |
| WO2007117006A1 (en) * | 2006-04-07 | 2007-10-18 | Tonen Chemical Corporation | Polyolefin multilayer microporous membrane, method for producing the same, battery separator and battery |
| WO2012133538A1 (en) * | 2011-03-29 | 2012-10-04 | 株式会社アストム | Ion-exchange membrane |
| JP4979824B1 (en) * | 2011-03-29 | 2012-07-18 | 株式会社アストム | Ion exchange membrane |
| CN103443172A (en) * | 2011-03-29 | 2013-12-11 | 株式会社亚斯通 | Ion-exchange membrane |
| US20140014519A1 (en) * | 2011-03-29 | 2014-01-16 | Astom Corporation | Ion-exchange membrane |
| US9162185B2 (en) | 2011-03-29 | 2015-10-20 | Astom Corporation | Ion-exchange membrane |
| WO2018078698A1 (en) * | 2016-10-24 | 2018-05-03 | 住友化学株式会社 | Separator, and secondary battery containing separator |
| CN109891629A (en) * | 2016-10-24 | 2019-06-14 | 住友化学株式会社 | Spacer and secondary cell comprising spacer |
| US10573866B2 (en) | 2016-10-24 | 2020-02-25 | Sumitomo Chemical Company, Limited | Separator and secondary battery including the separator |
| CN106393646A (en) * | 2016-11-28 | 2017-02-15 | 中国科学院宁波材料技术与工程研究所 | High-temperature consumable wire drawing equipment for 3D printing |
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