JPS62223245A - Production of porous permeable polyolefin film - Google Patents
Production of porous permeable polyolefin filmInfo
- Publication number
- JPS62223245A JPS62223245A JP6685786A JP6685786A JPS62223245A JP S62223245 A JPS62223245 A JP S62223245A JP 6685786 A JP6685786 A JP 6685786A JP 6685786 A JP6685786 A JP 6685786A JP S62223245 A JPS62223245 A JP S62223245A
- Authority
- JP
- Japan
- Prior art keywords
- film
- plasticizer
- polyolefin
- molding
- solvent
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 34
- 238000000465 moulding Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- 230000035699 permeability Effects 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 21
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 9
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 abstract description 8
- -1 polyethylene Polymers 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000012188 paraffin wax Substances 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 235000019809 paraffin wax Nutrition 0.000 description 4
- 235000019271 petrolatum Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000041377 Hiroa Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はポリオレフィン透過性多孔膜の製造方法に関す
る。詳しくは、ポリオレフィン樹脂からなる、微細孔を
有する透過性多孔質膜の製造方法に関する。更に詳しく
は、高分子量ポリオレフィンとその可塑剤を押出機で混
合しながう、インフレーション成形を行いフィルムを得
、このフィルムから、可塑剤を抽出除去することにより
透過性多孔膜を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a porous membrane permeable to polyolefin. Specifically, the present invention relates to a method for producing a permeable porous membrane having micropores made of polyolefin resin. More specifically, it relates to a method for manufacturing a permeable porous membrane by mixing a high molecular weight polyolefin and its plasticizer in an extruder, performing inflation molding to obtain a film, and extracting and removing the plasticizer from this film. .
〈従来の技術及びその問題点〉
従来、ポリオレフィンの多孔膜は、例えば下記のような
方法で作られている。<Prior art and its problems> Conventionally, porous polyolefin membranes have been produced, for example, by the following method.
■樹脂に後で抽出除去可能な、たとえばパラフィンワッ
クス、フィラー／可塑剤、他のポリマーを混合し、シー
トを成形した後シート中の抽出可能物質を除去する方法
。（特開昭５５−６０３３７、！Ｊ−／１，０り７、ｊ
Ａ−７！９／１ｇ等）しかしながら、これらの方法は上
記抽出可能物質を加える為に、安定して高速で成形出来
ない、高透気で強度の高いフィルムを得る事が困難であ
る、強度が低くもろいためにフィルムの（あるいはシー
ト）の肉厚を薄くする事が出来ず、抽出するために長時
間かかる等の欠点を有する。又強度を上げるために抽出
除去した後のフィルムを延伸する方法も示されているが
、延伸機を用いるために工程が複雑となシ生産コストも
大巾に上がってしまうという欠点を有する。■ A method in which extractable substances in the sheet are removed after the resin is mixed with later extractable substances such as paraffin wax, fillers/plasticizers, and other polymers, and the sheet is formed. (JP-A-55-60337,!J-/1,0ri7,j
A-7!9/1g, etc.) However, these methods add the above-mentioned extractable substances, making it difficult to form films stably and at high speeds, making it difficult to obtain high-strength films with high air permeability, and reducing strength. It has drawbacks such as the fact that the film (or sheet) cannot be made thinner due to its low strength and brittleness, and it takes a long time to extract it. A method has also been proposed in which the film after extraction and removal is stretched in order to increase its strength, but this method has the drawbacks of using a stretching machine, which complicates the process and greatly increases the production cost.
他の方法としては、例えば■熱可塑性樹脂を溶融延伸し
、得られたフィルムを更に延伸して更に熱処理を加えて
、多孔膜とする方法（特開昭１４−１４０／／９等）が
あるが、この場合透気性を上げる事がむずかしい事、又
一方向に非常に裂は易い事、更には工程が複雑で生産性
が上がらない等の欠点を有する。Other methods include, for example, a method in which a thermoplastic resin is melt-stretched, the resulting film is further stretched, and further heat-treated to form a porous film (Japanese Patent Application Laid-Open No. 140-140/9, etc.). However, in this case, it has disadvantages such as it is difficult to increase air permeability, it is very easy to tear in one direction, and the process is complicated and productivity cannot be improved.
〈発明の目的〉
本発明は、上記の様表従来法の欠点をなくし簡単な工程
で高速に高性能な多孔質透過性フィルムを製造する方法
を提供することを目的としたものである。<Objective of the Invention> The object of the present invention is to provide a method for manufacturing a high-performance porous permeable film at high speed and in a simple process by eliminating the drawbacks of the above-mentioned conventional methods.
く問題点を解決するための手段〉
本発明の方法線、高分子量のポリエチレンと可塑剤を押
出機を用いて混合しながら溶融体を押し出す除インフレ
ーション成形を用いることによシ、フィルムを得、そこ
から可塑剤を抽出除去することＫより透過性フィルムを
得る方法に関するものである。Means for Solving the Problems> The method of the present invention is to obtain a film by using anti-inflation molding in which a melt is extruded while mixing high molecular weight polyethylene and a plasticizer using an extruder, It concerns a method of obtaining a more permeable film by extracting and removing the plasticizer therefrom.
本発明の要旨は／３！ｒ℃デカリン中の極限粘度〔り〕
がＪ ｄＶＩ以上の高分子量ポリオレフィン（Ａ） ｋ
〜？ Ｏｗｔ％と（Ａ）の融点以上の沸点を有し、溶媒
に可溶な可塑剤（Ｂ） ｅｔ ｓ〜Ｊ Ｏｗｔ％の混合
物を、環状ダイスを用いて筒状に押出してインフレーシ
ョン成形することによシフイルムを得、得られたフィル
ムを溶媒で処理することにより成分（Ｂ）を抽出除去す
る事を特徴とする透過性を有するポリオレフィン多孔層
の製造方法に存する。The gist of the invention is /3! Intrinsic viscosity in decalin at r℃
High molecular weight polyolefin (A) with J dVI or more k
~? A mixture of Owt% and a plasticizer (B) having a boiling point higher than the melting point of (A) and soluble in the solvent is extruded into a cylindrical shape using an annular die and subjected to inflation molding. The present invention relates to a method for producing a porous polyolefin layer having permeability, which comprises obtaining a silica film and extracting and removing component (B) by treating the obtained film with a solvent.
この発明の特長を示すと次の通りでおる０■ 透気量は
、気孔率に大きく依存するが、高分子量のポリオレフィ
ンを使用する事により、多量に可塑剤を使用しても、安
定した成形が出来る。従って高い気孔率のフィルムを得
る事が出来、高透気性を得る事が出来る０■ 高透気を
得るためにはフィルムを薄くすることが１つの手段であ
るが高分子量のポリオレフィンを使用する為に薄くして
も強度、するいはタフさを確保する事が出来る。The features of this invention are as follows: 0 ■ Air permeability largely depends on porosity, but by using high molecular weight polyolefin, stable molding is possible even when a large amount of plasticizer is used. I can do it. Therefore, it is possible to obtain a film with high porosity and high air permeability. One way to obtain high air permeability is to make the film thinner, but since high molecular weight polyolefin is used. Even if it is made thinner, it can maintain strength or toughness.
■ ■の目的の・ために薄肉（具体的には２００μ以下
）のフィルムを得る手段としては各種の手段が考えられ
るが、本発明における様にインフレーション法で成形す
るとポリオレフィンポリマーの融点以上の温度でλ軸方
向に分子配向を起こさすことが出来るので高透気で縦横
の強度バランスのとれた薄肉フィルムを簡単な装置の構
成で得る事が出来る０比較として、他の手段を用いた場
合をいくつか示すＯａ） Ｔダイ成形：薄肉のものを
得るためにダイのクリアランスをせまくすると流動ムラ
、肌荒れが発生し安定した成形が出来ない。Various means can be considered to obtain a thin film (specifically, 200μ or less) for the purpose of (■), but when molded by the inflation method as in the present invention, the temperature is higher than the melting point of the polyolefin polymer. Since molecular orientation can be caused in the λ-axis direction, a thin film with high air permeability and well-balanced strength in the longitudinal and lateral directions can be obtained with a simple equipment configuration. Oa) T-die molding: If the clearance of the die is narrowed to obtain a thin-walled product, uneven flow and rough skin will occur, making stable molding impossible.
又、Ｔダイから出た組成物の溶融体を引き伸ばして薄肉
化する場合−軸方向（引取方向）にだけしか延伸出来な
いために、最終的に得られる透過性多孔フィルムの孔が
つぶれ透気性が大巾に低下する。又強度も非常に異方性
の大きいものとなる。In addition, when the molten body of the composition coming out of the T-die is stretched to make it thinner, the pores of the finally obtained permeable porous film are collapsed and the air permeability is reduced because it can be stretched only in the axial direction (pulling direction). decreases dramatically. In addition, the strength is also highly anisotropic.
ｂ）融点以下でのコ軸延伸：上記で示し丸様なＴダイ成
形で得られたシートを融点以下の温度でコ軸延伸すれば
縦横の゛強度バランスのとれたフィルムを得る事が出来
るが、本発明の様に高分子量のポリマーを素材とする場
合は、孔のつぶれが大きくこの場合も透気性が大巾に低
下する。更に、この場合コ軸延伸機も必要となシ生産工
程が複雑となる。b) Coaxial stretching at a temperature below the melting point: If the sheet obtained by round T-die molding as shown above is coaxially stretched at a temperature below the melting point, a film with well-balanced longitudinal and lateral strength can be obtained. When the material is made of a high molecular weight polymer as in the present invention, the pores are largely collapsed and the air permeability is greatly reduced in this case as well. Furthermore, in this case, a coaxial stretching machine is also required, which complicates the production process.
次に本発明の具体的な方法について以下詳細に説明する
。Next, a specific method of the present invention will be explained in detail below.
本発明に用いるポリオレフィンとしては、工テレン、プ
ロピレン、ダーメチルー／−ペンテン、３−メチル−／
−ブテン、／−ブテン、／−ヘキセン等の七ツマ−を重
合して得られるポリマーあるいはこれらモノマーの共重
合体である。その分子量を７３５℃デカリン中の極限粘
度〔η〕であられすと、３４１１１１以上好ましくは５
ｄｌ／ｇ以上のものである。Ｊｄｌ１１未満であると下
記に示す、可塑剤と混合して成形する除に非常に成形性
が悪い。Examples of polyolefins used in the present invention include terene, propylene, dermethyl-/-pentene, and 3-methyl-/-pentene.
-butene, /-butene, /-hexene, etc., or a copolymer of these monomers. If its molecular weight is expressed as the intrinsic viscosity [η] in decalin at 735°C, it is 341111 or more, preferably 5
dl/g or more. When the Jdl is less than 11, the moldability is extremely poor even when mixed with a plasticizer as shown below.
可塑剤の役割は１つには高分子量のポリマーの押出機で
の押出性あるいはインフレーション成形での成形性を改
良する事、第一には後工程で抽出除去する事によシフィ
ルムを多孔化し透過性をもたらす事である。この役割を
考えると、可塑剤はポリオレフィンと相溶性が良く溶媒
に可溶で抽出除去され易い事が要求される。可塑剤は常
温で液状のものでも特別な装置を工夫すればポリマーと
混合出来るが、ポリマーと混合する際にすべりが発生し
易く混合が難かしいので、常温固形でポリオレフィンの
融点以上の沸点を有する可塑剤が適切である。具体的に
はパラフィンワックス類、カプリルアルコール、ラウリ
ルアルコール、パルミチルアルコール、ステアリルアル
コール等の高級脂肪族アルコールが最適である。The role of plasticizers is, firstly, to improve the extrudability of high molecular weight polymers in extruders or the formability in inflation molding, and firstly, to make the film porous by extraction and removal in the post-process. It is about bringing transparency. Considering this role, the plasticizer is required to have good compatibility with the polyolefin, be soluble in a solvent, and be easily extracted and removed. Even if a plasticizer is liquid at room temperature, it can be mixed with a polymer by devising a special device, but when mixed with the polymer, slippage tends to occur and mixing is difficult, so plasticizers are solid at room temperature and have a boiling point higher than the melting point of polyolefin. Plasticizers are suitable. Specifically, paraffin waxes, higher aliphatic alcohols such as caprylic alcohol, lauryl alcohol, palmityl alcohol, and stearyl alcohol are most suitable.
可塑剤の沸点はポリマーの融点よ）高いことが必要であ
るが、これは、成形時に可塑剤が気化してしまうと発煙
による作業環境の低丁、成形品中での気泡の発生等の不
都合が生ずるためであり、好ましくは、可塑剤の沸点は
使用するポリオレフィンの融点よＦ）１０℃以上高いの
が良い。The boiling point of the plasticizer needs to be higher (than the melting point of the polymer), but this is because if the plasticizer evaporates during molding, it will cause problems such as a poor working environment due to smoke and the formation of air bubbles in the molded product. This is because the boiling point of the plasticizer is preferably 10° C. or more higher than the melting point of the polyolefin used.
ポリオレフィンと可塑剤の混合割合は、ポリオレフィン
ｊ〜７０ ｗｔ％（重量％）に対し可塑剤？！〜Ｊ Ｏ
ｗｔ％であシ、よ）好ましくはポリオレフィン１０〜Ａ
Ｏｗｔ％、可塑剤９０〜ダＯ％である。可塑剤量が、
９５％以上になると特にインフレーション成形の際の成
形性が不良となり３０％以下であると押出性の不良が発
生、又高透気性も得られなくなる。The mixing ratio of polyolefin and plasticizer is ~70 wt% (weight%) of polyolefin and plasticizer? ! ~J.O.
wt%, preferably polyolefin 10-A
Owt%, plasticizer 90-da0%. The amount of plasticizer is
If it exceeds 95%, moldability will be poor especially during inflation molding, and if it is below 30%, poor extrudability will occur and high air permeability will not be obtained.
次にインフレーション成形は、全く通常のポリエチレン
等を成形する装置にポリオレフィンと可塑剤のトライブ
レンド物を供給する事により実施する事が出来る。但し
、本発明者らが特願昭Ａ Ｏ−２／ ＩＩ／ 弘Ａ号で
示した様に、供給部の一部を冷却して可塑剤の気化を防
止したり、押出を一段式で行う事により混練効果を上げ
たシして安定な成形を行う事が出来る。Inflation molding can then be carried out by feeding the triblend of polyolefin and plasticizer into equipment that molds completely conventional polyethylene and the like. However, as the present inventors have shown in Japanese Patent Application No. ShoA O-2/II/HiroA, it is possible to cool a part of the supply section to prevent the plasticizer from evaporating, or to carry out extrusion in one stage. By doing so, it is possible to improve the kneading effect and perform stable molding.
インフレーション成形では押出機で溶融混合した組成物
を押出機先端に取り付けた環状ダイから、筒状溶融成形
物として押出し、筒状体内部に空気を吹き込んで膨張さ
せる事によシフィルムの薄肉化を実現するわけであるが
、本発明に用いる組成物ではそのブローアンプ比（ＢＵ
Ｒ）（筒状体の径／ダイの環状スリットの極）及びドラ
フト率（ＤＲ）（引取速度／押出速度）を大きく取る事
ができ、その展開倍率（ＥＵＲＸＤＲ）は１００倍以上
にも達し、数μのフィルムも得る事が出来る。In inflation molding, a composition melt-mixed in an extruder is extruded from an annular die attached to the tip of the extruder as a cylindrical melt-molded product, and the film is made thinner by blowing air into the cylindrical body and expanding it. However, the composition used in the present invention has a blow amplifier ratio (BU
R) (diameter of the cylindrical body/pole of the annular slit of the die) and draft rate (DR) (take-up speed/extrusion speed) can be made large, and the expansion magnification (EURXDR) reaches more than 100 times, Films of several microns can also be obtained.
本発明においては、得ようとする製品にもよるが、通常
、展開倍率参倍以上で成形するのが良い。又通常のポリ
エチレン等の成形と同様にエアーリングを設置して冷却
する事により、よシ安定な成形性を得る事が出来る。In the present invention, although it depends on the product to be obtained, it is usually preferable to perform molding at a development magnification of 1:3 or higher. In addition, by installing an air ring and cooling as in the case of ordinary molding of polyethylene, etc., more stable moldability can be obtained.
このようにしてインフレーション成形により得られたフ
ィルムから可塑剤を抽出除去するが、たとえば可塑剤と
してパラフィンワックス類を用いた場合は、ヘプタン、
ヘキサン、リグロイン、トルエン、キシレン、クロロホ
ルム等の常温で液状の脂肪族、脂環族もしくは芳香族炭
化水素又はそれらのハロゲン化物等の溶媒にフィルムを
浸漬したシ、該溶媒をフィルムに噴霧したりすること等
によシ行なわれる。又ステアリルアルコール等の高級脂
肪族アルコール類はメタノール、エタノール、ブタノー
ル等の低級アルコールに浸漬すること等により除去する
事が出来る。更にこれら溶媒の温度を上げて使用する事
は抽出速度を早くする点でよシ好ましい。In this way, the plasticizer is extracted and removed from the film obtained by inflation molding. For example, when paraffin wax is used as the plasticizer, heptane,
The film is immersed in a solvent such as hexane, ligroin, toluene, xylene, chloroform, etc., such as aliphatic, alicyclic, or aromatic hydrocarbons or their halides that are liquid at room temperature, and the solvent is sprayed onto the film. This is done in various ways. Further, higher aliphatic alcohols such as stearyl alcohol can be removed by immersion in lower alcohols such as methanol, ethanol, butanol, etc. Furthermore, it is preferable to use these solvents at elevated temperatures in order to increase the extraction rate.
たとえばステアリルアルコールを可塑剤として用いた！
Ｏμのフィルムでは、５０℃エタノール中に浸漬すれば
１０秒程度で抽出除去する事が出来るが２００μシート
では、２００秒はどかかる。この事から厚肉シートを作
成し可塑剤を抽出してから延伸して薄肉フィルムを得る
よシも本発明の様に、もともと薄肉のフィルムを成形し
てから抽出した方が非常に生産効率が上ることが判る。For example, stearyl alcohol was used as a plasticizer!
An Oμ film can be extracted and removed in about 10 seconds by immersing it in ethanol at 50°C, but a 200μ sheet takes 200 seconds. Therefore, although it is possible to create a thick sheet, extract the plasticizer, and then stretch it to obtain a thin film, it is much more productive to form a thin film and then extract it, as in the present invention. I know it's going up.
以上の様にして得られた多孔質の透過性フィルムは強度
が高く、又縦横のバランスが良い事、引裂強度が高い事
そして透気性が高いことがら各徨透湿性フィルム、電池
セパレーター等に使用する事が出来る。又、粒子（開孔
）の分画性も優れておりミクロフィルターとしても使用
出来る。The porous permeable film obtained in the above manner has high strength, good horizontal and vertical balance, high tear strength, and high air permeability, so it is used for various moisture permeable films, battery separators, etc. I can do it. Furthermore, it has excellent particle (open pore) fractionation properties and can be used as a microfilter.
〈実施例〉
次に本発明を実施例をあげて更に詳細に説明するが、本
発明はその要旨を越えない限り、以下の実施例によって
限定されるものではない。<Examples> Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
本発明の明細書および実施例に示される諸物性は次の方
法に従って測定した。The various physical properties shown in the specification and examples of the present invention were measured according to the following methods.
・空孔率（％） ： （、空孔容積／多孔化フィルム容
積）×ｌＯＯ・透気度Ｃａｅｃ／１ｏｏａ−） ： ：
ｒ工５−ｐ−ｔｔ／ｑによシガーレ一式デンンーメータ
ーにより
１００Ｃｒ、の空気の透気時間（秒）を測定した。・Porosity (%): (, pore volume/porous film volume) x lOO・Air permeability Caec/1ooa-): :
The permeation time (seconds) of 100 Cr of air was measured using a 5-p-tt/q Cigarette meter.
・引裂強度（９） ： Ｊ工５−ｐ−ざ／１０に準拠し
て測定した。- Tear strength (9): Measured in accordance with J Engineering 5-p-za/10.
・引張強度（Ｋｐ／ｄ） ： ＡＥＩＴＭ Ｄ−ｔｔｒ
ａ に準拠実施例−７
極限粘度〔η） ＝＊ ／ Ｊ、ｒの高分子量ポリエチ
レンハｆ） ｐ” −，２０ｗｔ％とステアリルアルコ
ール１０ ｗｔ％をポリ袋中でトライブレンドしたブレ
ンド物をダ０ＩｌＩＩφ押出機に供給し押出機内で溶融
混合し、更にこの混合物を溶融状態のまま一〇ｆｆ１ｌ
ｌφ押出機に供給その先端に設置した。外径３０１、内
径−デ■の環状ダイスから樹脂温／９０℃で円筒状溶融
成形物として押出し、この円筒状体内部に空気を吹き込
んで、イン７レーシヨ／成形を行った。この際ダＯ■φ
押出機のホッパ下から供給部の半分の長さについて水冷
ジャケットを用いて水冷を行った。インフレーションの
成形条件は、ＤＲ（ドラフト比）。・Tensile strength (Kp/d): AEITM D-ttr
Example-7 Based on a A blend of tri-blended high molecular weight polyethylene (f) with intrinsic viscosity [η) = * / J, r, p” -, 20 wt% and stearyl alcohol 10 wt% in a plastic bag was prepared. The mixture is fed to an extruder, melted and mixed in the extruder, and the mixture is further heated to 10ff1l in the molten state.
It was supplied to an lφ extruder and installed at its tip. A cylindrical melt-molded product was extruded from an annular die having an outer diameter of 301 cm and an inner diameter of -2 at a resin temperature of 90°C, and air was blown into the cylindrical body to perform in-7 ratio molding. At this time, daO■φ
Half the length of the feed section from below the hopper of the extruder was water-cooled using a water-cooling jacket. The inflation molding conditions are DR (draft ratio).
３．０、ＢＵＲ（ブローアツプレシオ） −，３，０で
実施した。成形は安定して行なわれた。得られたフィル
ムの平均厚さは、！−μであった。このフィルムを３５
℃のエタノールに７５秒浸漬してステアリルアルコール
を抽出除去した。抽出除去後白色の透過性多孔化フィル
ムを得た。3.0, BUR (blow-up ratio) -, 3.0. Molding was performed stably. The average thickness of the obtained film is ! −μ. This film is 35
Stearyl alcohol was extracted and removed by immersion in ethanol at ℃ for 75 seconds. After extraction and removal, a white permeable porous film was obtained.
当該フィルムの物性はフィルム厚さ弘θμ、気孔率７３
チ、透気度３λｓｅｃ／＃）（７頭、引張強度縦／！０
１横／ ３０ Ｋｆ／ａｍ 、引裂強度酸５２ｇ１横１
Ｉｏｙであった。The physical properties of the film are film thickness θμ, porosity 73
Chi, air permeability 3λsec/#) (7 heads, tensile strength vertical/!0
1 side / 30 Kf/am, tear strength acid 52g 1 side 1
It was Ioy.
比較例−／
実施例−７と同様の原料及び押出機を用い一〇ｆｉφ押
出機の先端に、巾、２０ｃｔｎのＴダイを設置して、以
下のテストを行った。Comparative Example: Using the same raw materials and extruder as in Example 7, a T-die with a width of 20 ctn was installed at the tip of the 10fiφ extruder, and the following tests were conducted.
／）クリアランスｆ０．２ｍにしてテストを行ったが、
安定してシートを押出す事が出来なかった。/) I conducted a test with the clearance f0.2m,
It was not possible to extrude the sheet stably.
２）クリアランスを０．！ｒｍに設定して、ドラフト率
（ＤＲ）を上げたところＤＲ＝、？、ｊで溶融体に破れ
が発生し始めた０即ちＴダイ成形で１００μ以下に薄肉
化することは困難であった。2) Clearance 0. ! When I set it to rm and increased the draft rate (DR), DR=,? In other words, it was difficult to reduce the thickness to 100μ or less by T-die molding, in which cracks began to occur in the melt.
比較例−一
比較例−／と同様にＴダイ成形を行った。グイクリアラ
ンスは０．！にｗｉ、、ＤＲ−３である。得られたフィ
ルムの厚さは、１７０μであった。Comparative Example - T-die molding was performed in the same manner as in Comparative Example -/. Gui clearance is 0. ! It is DR-3. The thickness of the obtained film was 170μ.
当該フィルムを、エタノールで処理し、ステアリルアル
コールを除去したがダ分を要した。得られた透過性多孔
化フィルムの物性は次の通シであった。The film was treated with ethanol to remove stearyl alcohol, but required dust removal. The physical properties of the obtained permeable porous film were as follows.
フィルム厚さ９！ｒｔｔ、ｌ気孔率ｊ Ａ ％、／透気
度ｔ ｊ Ｏｓｅｃ／１００ｃｌ：。Film thickness 9! rtt, l porosity j A %, / air permeability t j Osec/100cl:.
実施例−／に比較し気孔がつぶれ透気度が大巾に低下し
ていることを示している。This shows that the pores are collapsed and the air permeability is greatly reduced compared to Example-/.
比較例−３ 比較例−一と同様にしてＴダイ成形を行った。Comparative example-3 T-die molding was performed in the same manner as in Comparative Example-1.
グイクリアランスは八ＯｔｍＳＤＲｘ／、０である。Gui clearance is 8 OtmSDRx/,0.
このシートをコ軸延伸機を用いて７１０℃の温度で縦ダ
倍、横ダ倍延伸を行い当該フィルムを実施例−７と同様
にＳＺ℃エタノールに１３分浸漬、ステアリルアルコー
ルを抽出除去した。This sheet was stretched twice in the longitudinal direction and twice in the transverse direction using a coaxial stretching machine at a temperature of 710 DEG C., and the film was immersed in SZ DEG C. ethanol for 13 minutes in the same manner as in Example 7 to extract and remove stearyl alcohol.
得られた透過性多孔化フィルムの物性は次の通りである
０フィルム厚さ３２μ、気孔率！ｆコチ、通気度！ｒ
ｇ Ｏｓｅａ／１００ｃｃ、引裂強度縦７ｇ、横り
Ｉ ０
実施例−一
表一／に示すＤＲ及びＢＵＲで成形する他は、実施例−
７と同様の方法で透過性多孔膜を得た。The physical properties of the obtained permeable porous film are as follows: 0 film thickness: 32μ, porosity! F flat, ventilation! r
g Osea/100cc, tear strength 7g vertically, horizontally
I0 Example-1 Except for molding with DR and BUR shown in Table 1/, Example-
A permeable porous membrane was obtained in the same manner as in Example 7.
その物性を表−／に示す。Its physical properties are shown in Table-/.
実施例、７−ｊ−１比較例ダ
表−一に示す材料を使用し、環状ダイスの内径をコｔｍ
とする以外は実施例−／と同様のインフレーション成形
を行いその成形性をみた。Examples, 7-j-1 Comparative Example Using the materials shown in Table 1, the inner diameter of the annular die was
Inflation molding was carried out in the same manner as in Example-/, except that the moldability was examined.
但し、実施例５のポリプロピレンの押出温度はコ１０℃
とした。結果を表−一に示す。However, the extrusion temperature of polypropylene in Example 5 was 10°C.
And so. The results are shown in Table 1.
＊ パラフィンワックスはドライアイスで冷却しながら
、微粉砕したものを用いた。* Paraffin wax was finely ground while cooling with dry ice.
実施例−６，７、ｊ
実施例３、ダ、！で示した材料を用いてそれぞれ表−３
で示した成形条件でインフレーション成形を実施した。Example-6, 7, j Example 3, da! Using the materials shown in Table 3, respectively.
Inflation molding was carried out under the molding conditions shown in .
該フィルムについて、実施例−６、ｇについてはｊｊ℃
エタノールにて、実施例−７については、５０℃、ｎ−
ヘキサンにて可塑剤の抽出除去を行なった。得られた透
過性多孔化フィルムの物性を併せて表−３に示す０表−
３
〈発明の効果〉
本発明の方法によれば、高能率に気体透過性を有する多
孔質のポリオレフィンフィルムを作ることが可能となり
、しかも得られたフィルムは強度的に大変優れたもので
ある。Regarding the film, Example-6, g was jj℃
In ethanol, for Example-7, 50°C, n-
The plasticizer was extracted and removed using hexane. The physical properties of the obtained permeable porous film are also shown in Table 3.
3 <Effects of the Invention> According to the method of the present invention, it is possible to produce a porous polyolefin film having high gas permeability with high efficiency, and the obtained film has excellent strength.
例えばフィルター、透過性を必要とするフィルム用途、
等に用いて大変好適なフィルムが得られる。For example, filters, film applications that require transparency,
A very suitable film can be obtained.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士長香川 − （ほか７名）Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Naga Kagawa - (7 others)
Claims (4)
ｇ以上の高分子量ポリオレフィン（Ａ）５〜７０ｗｔ％
と（Ａ）の融点以上の沸点を有し、溶媒に可溶な可塑剤
（Ｂ）９５〜３０ｗｔ％の混合物を、環状ダイスを用い
て筒状に押出してインフレーシヨン成形することにより
フィルムを得、得られたフィルムを溶媒で処理すること
により成分（Ｂ）を抽出除去する事を特徴とする、透過
性を有するポリオレフィン多孔膜の製造方法。(1) Intrinsic viscosity [η] in decalin at 135°C is 3 dl/
High molecular weight polyolefin (A) of 5 to 70 wt%
A mixture of 95 to 30 wt % of a plasticizer (B) having a boiling point higher than the melting point of (A) and soluble in a solvent is extruded into a cylindrical shape using an annular die and subjected to inflation molding to form a film. A method for producing a porous polyolefin membrane having permeability, which comprises extracting and removing component (B) by treating the obtained film with a solvent.
／ｇ以上である特許請求の範囲第１項に記載の製造方法
。(2) [η] of high molecular weight polyolefin (A) is 5 dl
The manufacturing method according to claim 1, wherein the amount is at least /g.
１項又は第一項に記載の製造方法。(3) The manufacturing method according to claim 1 or 1, wherein the plasticizer (B) is solid at room temperature.
と可塑剤（Ｂ）９０〜４０ｗｔ％の混合物を用いる特許
請求の範囲第１項乃至第３項のいずれかに記載の製造方
法。(4) High molecular weight polyolefin (A) 10 to 60 wt%
The manufacturing method according to any one of claims 1 to 3, using a mixture of 90 to 40 wt% of plasticizer (B) and plasticizer (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61066857A JPH0655850B2 (en) | 1986-03-25 | 1986-03-25 | Method for producing porous polyolefin membrane having permeability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61066857A JPH0655850B2 (en) | 1986-03-25 | 1986-03-25 | Method for producing porous polyolefin membrane having permeability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62223245A true JPS62223245A (en) | 1987-10-01 |
| JPH0655850B2 JPH0655850B2 (en) | 1994-07-27 |
Family
ID=13327938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61066857A Expired - Fee Related JPH0655850B2 (en) | 1986-03-25 | 1986-03-25 | Method for producing porous polyolefin membrane having permeability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655850B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012920A1 (en) * | 1991-12-27 | 1993-07-08 | Mitsui Petrochemical Industries, Ltd. | Biaxially oriented high-molecular polyethylene film and production thereof, and surface-modified, biaxially oriented high-molecular polyethylene film and production thereof |
| US6048607A (en) * | 1996-11-19 | 2000-04-11 | Mitsui Chemicals, Inc. | Porous film of high molecular weight polyolefin and process for producing same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59227420A (en) * | 1983-06-10 | 1984-12-20 | Mitsui Petrochem Ind Ltd | Biaxially stretched film made of ultra-high molecular weight polyolefine and preparation thereof |
| JPS60255107A (en) * | 1984-05-31 | 1985-12-16 | Mitsubishi Chem Ind Ltd | Porous permeable polyethylene film |
-
1986
- 1986-03-25 JP JP61066857A patent/JPH0655850B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59227420A (en) * | 1983-06-10 | 1984-12-20 | Mitsui Petrochem Ind Ltd | Biaxially stretched film made of ultra-high molecular weight polyolefine and preparation thereof |
| JPS60255107A (en) * | 1984-05-31 | 1985-12-16 | Mitsubishi Chem Ind Ltd | Porous permeable polyethylene film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012920A1 (en) * | 1991-12-27 | 1993-07-08 | Mitsui Petrochemical Industries, Ltd. | Biaxially oriented high-molecular polyethylene film and production thereof, and surface-modified, biaxially oriented high-molecular polyethylene film and production thereof |
| AU650587B2 (en) * | 1991-12-27 | 1994-06-23 | Mitsui Chemicals, Inc. | Biaxially oriented high-molecular polyethylene film and production thereof, and surface-modified, biaxially oriented high-molecular polyethylene film and production thereof |
| US6048607A (en) * | 1996-11-19 | 2000-04-11 | Mitsui Chemicals, Inc. | Porous film of high molecular weight polyolefin and process for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655850B2 (en) | 1994-07-27 |
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