JPH06345893A - Porous film or sheet - Google Patents
Porous film or sheetInfo
- Publication number
- JPH06345893A JPH06345893A JP13754593A JP13754593A JPH06345893A JP H06345893 A JPH06345893 A JP H06345893A JP 13754593 A JP13754593 A JP 13754593A JP 13754593 A JP13754593 A JP 13754593A JP H06345893 A JPH06345893 A JP H06345893A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- molecular weight
- weight
- plasticizer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004014 plasticizer Substances 0.000 claims abstract description 41
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 21
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
(57)【要約】
【目的】 機械的強度に優れたポリエチレン製多孔質フ
ィルム又はシートを提供する。
【構成】 粘度平均分子量８０万以上の超高分子量ポリ
エチレンと、粘度平均分子量６０万以下のポリオレフィ
ンと、可塑剤とを含有する組成物からフィルム又はシー
トを成形し、次いで可塑剤を抽出除去して得られるも
の。(57) [Abstract] [Purpose] To provide a polyethylene porous film or sheet excellent in mechanical strength. [Structure] A film or sheet is molded from a composition containing an ultrahigh molecular weight polyethylene having a viscosity average molecular weight of 800,000 or more, a polyolefin having a viscosity average molecular weight of 600,000 or less, and a plasticizer, and then the plasticizer is extracted and removed. What you get.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、バッテリー・セパレー
ター、精密濾過膜などの分離膜、透気性ジャンパーなど
の衣料品、オムツ、生理用品などの衛生用品等として有
用な多孔性フィルムまたはシートに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous film or sheet useful as a battery separator, a separation membrane such as a microfiltration membrane, clothing such as air-permeable jumpers, sanitary articles such as diapers and sanitary articles. Is.
【０００２】[0002]
【従来の技術】多孔性フィルム或いはシートは、従来よ
り各種用途に広く使用されている。例えば、バッテリー
・セパレーターとして使用するための多孔性フィルムま
たはシートは、一般に、超高分子量ポリエチレンおよび
可塑剤を含有する樹脂組成物から、一旦、フィルムまた
はシートを溶融押出成形して製造し、次いで、フィルム
またはシートに含まれる可塑剤をイソプロパノール、エ
タノール、ヘキサンなどの有機溶媒で溶解除去した後、
ロール延伸機、テンター横延伸機などの延伸機で延伸す
ることによって機械的強度を向上させたフィルムを製造
していた。2. Description of the Related Art Porous films or sheets have been widely used for various purposes. For example, porous films or sheets for use as battery separators are generally made from a resin composition containing ultra-high molecular weight polyethylene and a plasticizer by once melt-extruding the film or sheet, then After removing the plasticizer contained in the film or sheet with an organic solvent such as isopropanol, ethanol or hexane,
A film having improved mechanical strength was produced by stretching with a stretching machine such as a roll stretching machine or a tenter transverse stretching machine.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
ように超高分子量ポリエチレンのみから形成された多孔
性フィルムまたはシートは、その機械的強度に限界があ
り、例えば、セパレーターとしてバッテリーに組み込む
作業の際や、包装材として用いる場合に機械で取扱う場
合等においてフィルムまたはシートが破膜するという問
題があり、フィルムまたはシートの機械的強度の向上が
望まれていた。However, the conventional porous film or sheet formed of only ultra-high molecular weight polyethylene has a limit in mechanical strength, and for example, when it is incorporated into a battery as a separator, In addition, there is a problem that the film or sheet is broken when it is used as a packaging material and handled by a machine, and it has been desired to improve the mechanical strength of the film or sheet.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、機械的強
度のより向上したフィルムまたはシートを得るために、
超高分子量ポリエチレンと特定分子量以下のポリオレフ
ィンに対する可塑剤の浸透量の差に着目し、鋭意検討し
た結果、超高分子量ポリエチレンと特定分子量以下のポ
リオレフィンとを併用して得られる多孔性フィルムまた
はシートは、特に、面強度に優れていることを知得し、
本発明を完成するに至った。In order to obtain a film or sheet with improved mechanical strength, the present inventors have
Focusing on the difference in the penetration amount of the plasticizer to the ultra-high molecular weight polyethylene and the polyolefin having a specific molecular weight or less, as a result of diligent study, a porous film or sheet obtained by using the ultra-high molecular weight polyethylene and the polyolefin having a specific molecular weight or less in combination is , Especially knowing that the surface strength is excellent,
The present invention has been completed.
【０００５】即ち、本発明の要旨は、粘度平均分子量８
０万以上の超高分子量ポリエチレンと、粘度平均分子量
６０万以下のポリオレフィンと、可塑剤とを含有する樹
脂組成物からフィルムまたはシートを形成した後、該フ
ィルムまたはシートから可塑剤を除去して得られる多孔
性フィルムまたはシートに存する。以下本発明を説明す
る。That is, the gist of the present invention is that the viscosity average molecular weight is 8
Obtained by forming a film or sheet from a resin composition containing a high-molecular-weight polyethylene of 0,000 or more, a polyolefin having a viscosity average molecular weight of 600,000 or less, and a plasticizer, and then removing the plasticizer from the film or sheet. Porous film or sheet. The present invention will be described below.
【０００６】本発明の多孔性フィルムまたはシートを形
成するための樹脂組成物は、少なくとも粘度平均分子量
８０万以上の超高分子量ポリエチレン（Ａ樹脂）と粘度
平均分子量６０万以下のポリオレフィン（Ｂ樹脂）およ
び可塑剤を含有する。本発明で使用する超高分子量ポリ
エチレンとしては、粘度平均分子量（以下単に「分子
量」という。）が８０万以上、特に、分子量が１５０万
〜３５０万の直鎖状のポリエチレンが好適である。分子
量が８０万より小さいと得られるフィルムまたはシート
の機械的強度が不十分となる。The resin composition for forming the porous film or sheet of the present invention comprises an ultra high molecular weight polyethylene (A resin) having a viscosity average molecular weight of 800,000 or more and a polyolefin (B resin) having a viscosity average molecular weight of 600,000 or less. And a plasticizer. As the ultrahigh molecular weight polyethylene used in the present invention, linear polyethylene having a viscosity average molecular weight (hereinafter simply referred to as “molecular weight”) of 800,000 or more, and particularly a molecular weight of 1,500,000 to 3,500,000 is suitable. If the molecular weight is less than 800,000, the mechanical strength of the obtained film or sheet will be insufficient.
【０００７】分子量６０万以下のポリオレフィン（以
下、「低分子量ポリオレフィン」という。）としては、
超高分子量ポリエチレンと比較して後述の可塑剤の浸透
量の少ないポリオレフィンの単独重合体、ブロック共重
合体、ランダム共重合体などが挙げられる。As a polyolefin having a molecular weight of 600,000 or less (hereinafter referred to as "low molecular weight polyolefin"),
Examples include polyolefin homopolymers, block copolymers, random copolymers, and the like, which have a smaller penetration amount of a plasticizer described below as compared with ultrahigh molecular weight polyethylene.
【０００８】具体的には、例えば、分子量が６０万以
下、好ましくは、２万〜５５万のポリエチレンやポリプ
ロピレン、エチレンと他のオレフィン（炭素数２〜６）
との共重合体、エチレン−酢酸ビニル共重合体、エチレ
ン−エチルアクリレート共重合体、アイオノマー、エチ
レンープロピレンージエン類（ジエン類としては、例え
ば、ジビニルベンゼン、１，４−シクロヘキサジエン、
ジシクロペンタジエン、シクロオクタジエン）のターポ
リマーなどが挙げられる。好ましくは、結晶性のポリオ
レフィン、特に、直鎖状のポリエチレン、ポリプロピレ
ンが好適である。これら低分子量ポリオレフィンは１種
類以上使用することができる。分子量が６０万以上のポ
リオレフィンを用いると、可塑剤が吸収されてしまい強
度の向上が望めず、分子量が２万未満のものでは脆くな
りすぎ、強度の向上が望めない。Specifically, for example, polyethylene or polypropylene having a molecular weight of 600,000 or less, preferably 20,000 to 550,000, ethylene and other olefins (having 2 to 6 carbon atoms).
Copolymer with ethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ionomer, ethylene-propylene-diene (as the diene, for example, divinylbenzene, 1,4-cyclohexadiene,
Examples thereof include terpolymers of dicyclopentadiene and cyclooctadiene). Crystalline polyolefins, particularly linear polyethylene and polypropylene, are preferable. One or more kinds of these low molecular weight polyolefins can be used. If a polyolefin having a molecular weight of 600,000 or more is used, the plasticizer is absorbed and the strength cannot be improved. If the molecular weight is less than 20,000, the strength becomes too brittle and the strength cannot be improved.
【０００９】超高分子量ポリエチレンと低分子量ポリオ
レフィンとの使用割合は、通常、超高分子量ポリエチレ
ンが６０〜９９重量％、好ましくは、７０〜９８重量％
で、低分子量ポリオレフィンが１〜４０重量％、好まし
くは、２〜３０重量％の範囲から選択される。低分子量
ポリオレフィンの使用割合があまり多過ぎると分散不良
を起し、少な過ぎると強度の向上は望めない機械的強度
の向上したフィルムまたはシートを得ることができな
い。The proportion of ultrahigh molecular weight polyethylene and low molecular weight polyolefin used is usually 60 to 99% by weight, preferably 70 to 98% by weight, of ultrahigh molecular weight polyethylene.
The low molecular weight polyolefin is selected from the range of 1 to 40% by weight, preferably 2 to 30% by weight. If the proportion of the low molecular weight polyolefin used is too large, poor dispersion will occur, and if it is too small, it is not possible to obtain a film or sheet with improved mechanical strength, which cannot be expected to improve strength.
【００１０】可塑剤としては、超高分子量ポリエチレン
との相溶性がよく、溶融混練や成形時に蒸発しないよう
な、例えば、超高分子量ポリエチレンの溶融温度より高
い沸点を有するものであって抽出時の温度（４０〜１０
０℃程度）以下の融点を有するものが好ましい。具体的
には、例えば、常温で固体であるパラフィンワックス、
或いは、ステアリルアルコール、セリルアルコールなど
の高級脂肪族アルコール、常温で液体のｎ−デカン、ｎ
−ドデカン等のｎ−アルカン、流動パラフィン、灯油な
どを挙げることができる。The plasticizer has a good compatibility with the ultra-high molecular weight polyethylene and does not evaporate during melt-kneading or molding, for example, a plasticizer having a boiling point higher than the melting temperature of the ultra-high-molecular-weight polyethylene and used during extraction. Temperature (40-10
Those having a melting point of about 0 ° C.) or less are preferable. Specifically, for example, paraffin wax that is solid at room temperature,
Alternatively, higher aliphatic alcohols such as stearyl alcohol and ceryl alcohol, n-decane that is liquid at room temperature, n
Examples include n-alkanes such as dodecane, liquid paraffin, and kerosene.
【００１１】可塑剤のマトリックス樹脂への相溶性の
良、不良は１６０〜２００℃における、この２つの成分
の溶融混練体が安定的に溶融押出できる程度の均一分散
系であるか否かで分かれる。具体的にはフローテスター
で該溶融混練体の見掛け粘度を多数測定した場合、その
振れ幅が３０％以下、好ましくは１０％以下に収まる程
度の安定した流動性を有するものを相溶性が良いとす
る。The compatibility of the plasticizer with the matrix resin is good or poor depending on whether or not the melt-kneaded product of these two components at 160 to 200 ° C. is a uniform dispersion system capable of stable melt extrusion. . Specifically, when a large number of apparent viscosities of the melt-kneaded product are measured with a flow tester, those having stable fluidity with a swing range of 30% or less, preferably 10% or less are considered to have good compatibility. To do.
【００１２】超高分子量ポリエチレンと低分子量ポリオ
レフィンから成る樹脂成分に対して可塑剤の使用割合
は、通常、樹脂成分が５〜６０重量％、好ましくは、１
０〜５０重量％で、可塑剤が４０〜９５重量％、好まし
くは、９０〜５０重量％の範囲から選ばれる。可塑剤４
０重量％未満では押出成形性が悪く、９５重量％以上で
は生産効率が悪くなる。The ratio of the plasticizer used to the resin component consisting of ultrahigh molecular weight polyethylene and low molecular weight polyolefin is usually 5 to 60% by weight of the resin component, preferably 1
The plasticizer is selected from the range of 0 to 50% by weight and the plasticizer of 40 to 95% by weight, preferably 90 to 50% by weight. Plasticizer 4
When it is less than 0% by weight, extrusion moldability is poor, and when it is 95% by weight or more, production efficiency is poor.
【００１３】また、本発明の樹脂組成物には、公知の各
種添加剤、例えば、酸化防止剤などを樹脂組成物中、
０．０１〜５重量％程度併用してもよい。上記樹脂組成
物の各成分は、公知の一軸または二軸の押出機で均一に
混練し、溶融押出成形する。押出量、押出安定性の点か
ら二軸の押出機が好適に使用される。溶融押出成形は、
通常、１４０〜２４０℃の温度で行い、５〜５０μ或い
は５０〜３００μの厚さでフィルム状或いはシート状に
押し出す。冷却後、可塑剤を除去することによりフィル
ムまたはシートを多孔化する。Further, in the resin composition of the present invention, various well-known additives such as antioxidants may be added to the resin composition,
You may use together about 0.01-5 weight%. Each component of the above resin composition is uniformly kneaded by a known uniaxial or biaxial extruder and melt-extruded. A twin-screw extruder is preferably used in terms of extrusion amount and extrusion stability. Melt extrusion
Usually, it is carried out at a temperature of 140 to 240 ° C. and extruded into a film or sheet with a thickness of 5 to 50 μ or 50 to 300 μ. After cooling, the film or sheet is made porous by removing the plasticizer.
【００１４】可塑剤の除去方法としては、フィルムまた
はシート中の可塑剤をイソプロパノール、エタノール、
ヘキサンなどの有機溶媒で溶解し、溶媒置換により抽出
除去する、所謂、公知の有機溶媒法によって行うことが
できる。可塑剤の除去は、成形体を、水と有機溶媒との
混合溶液で処理することによって行なっても良い。この
ような混合溶液は、可塑剤を多量に溶解することはない
が、樹脂中に分散された可塑剤とマトリックス樹脂との
界面に浸透し、可塑剤を剥離するように成形体から抽出
することとなる。このような現象は思いもかけなかった
ものである。水と有機溶媒との混合物としては、その割
合を適宜決めることができるが、この混合液の引火点を
水の沸点以上となるように混合割合を決めれば作業の安
全性は増す。また、この混合液の１００℃以下での可塑
剤の溶解量が５重量％以下となるように混合割合を決め
れば後で可塑剤の回収が容易となる。As a method for removing the plasticizer, the plasticizer in the film or sheet is treated with isopropanol, ethanol,
It can be carried out by a so-called known organic solvent method in which the compound is dissolved in an organic solvent such as hexane and extracted and removed by solvent substitution. The plasticizer may be removed by treating the molded body with a mixed solution of water and an organic solvent. Such a mixed solution does not dissolve a large amount of the plasticizer, but it must be extracted from the molded article so that it penetrates into the interface between the plasticizer dispersed in the resin and the matrix resin and peels the plasticizer. Becomes This kind of phenomenon was unexpected. The ratio of the mixture of water and the organic solvent can be appropriately determined, but if the mixing ratio is determined so that the flash point of this mixed liquid is equal to or higher than the boiling point of water, the safety of work is improved. Further, if the mixing ratio is determined so that the dissolved amount of the plasticizer in this mixed liquid at 100 ° C. or lower is 5% by weight or less, the recovery of the plasticizer becomes easy later.
【００１５】このような混合液を用いる場合、多孔化さ
れた成形体を、１００℃以下で可塑剤の融点以上、好ま
しくは、４０〜１００℃、特に、６０〜８０℃に保持さ
れた上記混合溶液に浸漬することにより可塑剤を抽出す
れば良い。温度が低すぎると抽出効率が悪く、高すぎる
と発火等の危険が増す。水と有機溶媒とからなり１００
℃以下での可塑剤の溶解量が５重量％以下であるような
混合溶液としては、例えば、Ｎ−２−メチルピロリド
ン、２−ピロリドンなどのピロリドン類、γ−ブチロラ
クトンなどのラクトン類、ジメチルホルムアミドなどの
アミド類等と水とを混合して得られる混合溶液が挙げら
れる。特に、Ｎ−２−メチルピロリドン、２−ピロリド
ンなどのピロリドン類と水との混合溶液を好適に使用す
ることができる。When such a mixed solution is used, the porous body is kept at 100 ° C. or lower and the melting point of the plasticizer or higher, preferably 40 to 100 ° C., especially 60 to 80 ° C. The plasticizer may be extracted by immersing it in the solution. If the temperature is too low, the extraction efficiency will be poor, and if it is too high, the risk of ignition will increase. 100 consisting of water and organic solvent
Examples of the mixed solution in which the amount of the plasticizer dissolved at 5 ° C or lower is 5% by weight or less include, for example, pyrrolidones such as N-2-methylpyrrolidone and 2-pyrrolidone, lactones such as γ-butyrolactone, and dimethylformamide. A mixed solution obtained by mixing amides such as and the like with water. Particularly, a mixed solution of water and pyrrolidones such as N-2-methylpyrrolidone and 2-pyrrolidone can be preferably used.
【００１６】１００℃以下での可塑剤の溶解量が５重量
％以下であるような混合溶液を得るための有機溶媒と水
との混合割合は、使用する有機溶媒および可塑剤の種
類、処理温度によって異なるので、予め使用する溶媒お
よび化合物毎に水との各種混合溶液を作成して処理温度
における可塑剤の溶解量が５重量％以下、好ましくは、
１重量％以下となるような混合割合を求めておく。The mixing ratio of the organic solvent and water for obtaining a mixed solution in which the amount of the plasticizer dissolved at 100 ° C. or less is 5% by weight or less is determined by the kind of the organic solvent and the plasticizer used, the treatment temperature. The amount of plasticizer dissolved at the treatment temperature is 5% by weight or less, preferably, by preparing various mixed solutions with water for each solvent and compound used in advance.
The mixing ratio is determined so as to be 1% by weight or less.
【００１７】例えば、有機溶媒としてＮ−２−メチルピ
ロリドンを使用し、可塑剤としてステアリルアルコール
を使用する場合、処理温度が７０℃においては、Ｎ−２
−メチルピロリドン８２重量％以下と水１８重量％以上
とを混合することによって、ステアリルアルコールの溶
解量が０．５重量％の混合溶液を得ることができる。混
合物の引火点を水の沸点以上とする場合の割合は、例え
ばＮ−２−メチルピロリドンと水の場合、水を１３重量
％以上用いれば良い。For example, when N-2-methylpyrrolidone is used as the organic solvent and stearyl alcohol is used as the plasticizer, N-2 at the treatment temperature of 70 ° C.
-By mixing 82% by weight or less of methylpyrrolidone and 18% by weight or more of water, a mixed solution having a dissolved amount of stearyl alcohol of 0.5% by weight can be obtained. When the flash point of the mixture is equal to or higher than the boiling point of water, for example, in the case of N-2-methylpyrrolidone and water, 13% by weight or more of water may be used.
【００１８】Ｎ−２−メチルピロリドンの割合が８０重
量％以下になると可塑剤の溶解量はほとんど０に近づく
が、上述した剥離による成形体からの抽出は充分効果的
に行なわれる。本発明においては、Ｎ−２−メチルピロ
リドン５〜８７重量％、好ましくは、６０〜８２重量％
と水９５〜１３重量％、好ましくは、４０〜１８重量％
の割合で混合した混合溶液が好適に使用できる。When the proportion of N-2-methylpyrrolidone is 80% by weight or less, the dissolved amount of the plasticizer approaches almost 0, but the extraction from the molded body by the above-mentioned peeling is sufficiently effective. In the present invention, N-2-methylpyrrolidone 5 to 87% by weight, preferably 60 to 82% by weight
And water 95 to 13% by weight, preferably 40 to 18% by weight
A mixed solution mixed in the ratio of is preferably used.
【００１９】浸漬処理は、上記混合溶液中で、通常、１
０秒以上、好ましくは、３０秒〜３０分程度行えばよ
い。超音波或いは撹拌などの機械的な振動を加えること
により除去効率を向上させることができる。超音波処理
を行う場合は、通常、周波数が１０ｋＨｚ以上、好まし
くは、２０〜６０ｋＨｚ、単位水量当たりの超音波出力
が２Ｗ／リットル以上、好ましくは、１０Ｗ／リットル
以上、特に、１５〜５０Ｗ／リットルで、５秒以上、好
ましくは、２０秒〜３０分の条件で行うことができる。The dipping treatment is usually carried out in the above mixed solution by 1
It may be performed for 0 seconds or more, preferably about 30 seconds to 30 minutes. Removal efficiency can be improved by applying mechanical vibration such as ultrasonic waves or stirring. When performing ultrasonic treatment, the frequency is usually 10 kHz or higher, preferably 20 to 60 kHz, and the ultrasonic output per unit amount of water is 2 W / liter or higher, preferably 10 W / liter or higher, particularly 15 to 50 W / liter. Then, it can be performed under conditions of 5 seconds or more, preferably 20 seconds to 30 minutes.
【００２０】また、撹拌処理を行う場合は、通常、単位
体積当たりの撹拌所要動力が５Ｗ／ｍ3 以上、好ましく
は、４０〜２，２００Ｗ／ｍ3 で、５秒以上、好ましく
は、２０秒〜３０分の条件で行うことができる。処理液
として上記のような可塑剤に対して貧溶媒である混合溶
液を使用した場合、成形体から剥離除去されて処理液中
に存在する可塑剤を静置分離、濾過、遠心分離などによ
って容易に処理液から分離することができ、可塑剤や処
理液の循環使用が可能となるので有利である。When the stirring treatment is carried out, the power required for stirring per unit volume is usually 5 W / m 3 or more, preferably 40 to 2,200 W / m 3 , and 5 seconds or more, preferably 20 seconds. It can be performed under the condition of -30 minutes. When a mixed solution that is a poor solvent for the plasticizer as described above is used as the treatment liquid, the plasticizer present in the treatment liquid peeled off from the molded body can be easily removed by static separation, filtration, centrifugation or the like. This is advantageous because it can be separated from the processing liquid and the plasticizer and the processing liquid can be circulated.
【００２１】例えば、底面積５０ｃｍ2 の円筒型ビーカ
ーに、８０重量％Ｎ−２−メチルピロリドン−２０重量
％水混合溶液を２００ｃｃ導入し、液温を７０℃に保持
して、この溶液にステアリルを５重量％となるように添
加し充分撹拌した後、３０〜５０秒間静置するとステア
リルアルコールと溶液とは完全に分離する。次いで、液
温を２０℃まで冷却してステアリルアルコールを分離し
て、回収して得られるステアリルアルコール中のＮ−２
−メチルピロリドン含有量および処理液中のステアリル
アルコールの濃度を測定したところ、それぞれ１重量％
以下および０．５重量％以下であり、十分循環再使用で
きることが分かる。For example, 200 cc of 80 wt% N-2-methylpyrrolidone-20 wt% water mixed solution was introduced into a cylindrical beaker having a bottom area of 50 cm 2 , the liquid temperature was kept at 70 ° C., and stearyl was added to this solution. Is added so as to be 5% by weight and sufficiently stirred, and then allowed to stand for 30 to 50 seconds, the stearyl alcohol and the solution are completely separated. Then, the liquid temperature is cooled to 20 ° C. to separate stearyl alcohol, and N-2 in stearyl alcohol obtained by recovery is collected.
-Methylpyrrolidone content and concentration of stearyl alcohol in the treatment liquid were measured to be 1% by weight each
It is below and 0.5% by weight or less, and it can be seen that it can be sufficiently recycled and recycled.
【００２２】上記のようにして多孔化したフィルムまた
はシートは、その用途により、機械的強度や通気性の向
上のため、或いは、孔の微多孔化のために、常法に従
い、一軸または二軸延伸或いは１００〜１８０℃程度で
熱処理を行ってもよい。本発明によれば、通常、１０μ
以上の多孔性フィルムまたはシートを得ることができ
る。多孔性フィルムまたはシートの物性は使用する用途
によって異なるが、例えば、バッテリー・セパレーター
として使用する場合は、平均孔径が１μ以下、好ましく
は、０．０１〜１μで、空孔率が２５〜８０％、好まし
くは、３０〜６０％の範囲のものが好ましい。The film or sheet made porous as described above may be uniaxially or biaxially made in accordance with a conventional method in order to improve mechanical strength and air permeability, or to make the pores microporous depending on its use. Stretching or heat treatment may be performed at about 100 to 180 ° C. According to the invention, typically 10 μ
The above porous film or sheet can be obtained. The physical properties of the porous film or sheet vary depending on the intended use, but when used as a battery separator, for example, the average pore size is 1 μm or less, preferably 0.01 to 1 μm, and the porosity is 25 to 80%. , Preferably in the range of 30 to 60%.
【００２３】また、本発明によれば、得られる多孔性フ
ィルムまたはシートは機械的強度、特に、面強度、具体
的には、ピン刺強度が良好である。ピン刺強度は日本農
林規格告示１０１９号に準じて測定（使用機器：不動工
業社製、レオメーターＮＲＭ−２００２Ｊ、ピン径１ｍ
ｍ、ピン先０．５Ｒ、ピン刺速度３００ｍｍ／ｍｉｎ）
した値で膜厚２５μ当り１５０ｇ以上（ｇ／２５μと表
わす）、好ましくは、１６０〜４００ｇ／２５μのもの
が得られる。Further, according to the present invention, the obtained porous film or sheet has good mechanical strength, particularly surface strength, specifically pin puncture strength. The pin puncture strength is measured according to Japanese Agriculture and Forestry Standards Notification No. 1019 (used equipment: Fudo Kogyo Co., Ltd., Rheometer NRM-2002J, pin diameter 1 m
m, pin tip 0.5R, pin sticking speed 300 mm / min)
With the above value, a film having a thickness of 150 g or more per 25 μm (expressed as g / 25 μ), preferably 160 to 400 g / 25 μm is obtained.
【００２４】[0024]
【実施例】以下に実施例を示すが、本発明はその要旨を
越えない限り以下の実施例に限定されるものではない。EXAMPLES Examples will be shown below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
【００２５】実施例１ 分子量２×１０6 密度０．９３５ｇ／ｃｃの直鎖状超高
分子量ポリエチレン（ＵＨＭＷＰＥ）パウダー１９重量
％と分子量６×１０4 、密度０．９０ｇ／ｃｃのポリプ
ロピレン１重量％と粒状のステアリルアルコール（Ｓｔ
ＯＨ）８０重量％のドライブレンド物を押出機に供給し
て２００℃で混練しながら、連続的に巾５５０ｍｍ、ダ
イクリアランス０．１５ｍｍのＴダイより押し出し、厚
さ５０μのシートを得た。このシートを６０℃のイソプ
ロピルアルコール浴に浸漬し、ＳｔＯＨを抽出した。次
いで表１に示した熱処理（１１０℃）を行い、多孔性シ
ートを得た。この多孔性シートの物性を表１に示した。Example 1 19% by weight of linear ultra high molecular weight polyethylene (UHMWPE) powder having a molecular weight of 2 × 10 6 and a density of 0.935 g / cc and 1% by weight of polypropylene having a molecular weight of 6 × 10 4 and a density of 0.90 g / cc. And granular stearyl alcohol (St
A dry blend of 80% by weight of OH) was supplied to an extruder and kneaded at 200 ° C., and continuously extruded through a T die having a width of 550 mm and a die clearance of 0.15 mm to obtain a sheet having a thickness of 50 μm. This sheet was immersed in a 60 ° C. isopropyl alcohol bath to extract StOH. Then, the heat treatment (110 ° C.) shown in Table 1 was performed to obtain a porous sheet. The physical properties of this porous sheet are shown in Table 1.
【００２６】実施例２ 分子量３×１０6 のＵＨＭＷＰＥパウダー１９重量％と
分子量５×１０5 、密度０．９４ｇ／ｃｃのポリエチレ
ン１重量％と粒状のＳｔＯＨ８０重量％のドライブレン
ド物を押出機に供給して１８０℃で混練しながら、ダイ
クリアランス１ｍｍのインフレダイを用いブローアップ
比３．０で成形し４５μのシートを得た。このシートを
６０℃のイソプロピルアルコール浴でＳｔＯＨを抽出
し、次いで表１に示した熱処理（１２０℃）を行い多孔
性シートを得た。この多孔性シートの物性を表１に示し
た。Example 2 A dry blend of 19% by weight of UHMWPE powder having a molecular weight of 3 × 10 6 , 1% by weight of polyethylene having a molecular weight of 5 × 10 5 , a density of 0.94 g / cc and 80% by weight of granular StOH was fed to an extruder. Then, while kneading at 180 ° C., an inflation die having a die clearance of 1 mm was used to perform molding at a blow-up ratio of 3.0 to obtain a 45 μ-sheet. StOH was extracted from this sheet in an isopropyl alcohol bath at 60 ° C, and then the heat treatment (120 ° C) shown in Table 1 was performed to obtain a porous sheet. The physical properties of this porous sheet are shown in Table 1.
【００２７】実施例３ 分子量２×１０6 のＵＨＭＷＰＥパウダー１９重量％と
分子量３×１０4 、密度０．９２ｇ／ｃｃの直鎖状低密
度ポリエチレン１重量％と粒状のＳｔＯＨ８０重量％の
ドライブレンド物を実施例１と同様の方法で、シート
化、抽出し、多孔性シートを得た。この多孔性シートの
物性を表１に示した。Example 3 Dry blend of 19% by weight of UHMWPE powder having a molecular weight of 2 × 10 6 and 1% by weight of linear low-density polyethylene having a molecular weight of 3 × 10 4 and a density of 0.92 g / cc and 80% by weight of granular StOH. Was formed into a sheet and extracted in the same manner as in Example 1 to obtain a porous sheet. The physical properties of this porous sheet are shown in Table 1.
【００２８】実施例４ 実施例３と同様にしてＳｔＯＨを抽出したシートを１２
７℃で熱処理後、縦方向（押出方向）に１２７℃で１．
４倍に延伸した後１２７℃で熱処理し、多孔性シートを
得た。この多孔性シートの物性を表１に示した。Example 4 In the same manner as in Example 3, 12 sheets of StOH-extracted sheets were used.
After heat treatment at 7 ° C., the longitudinal direction (extrusion direction) was 127 ° C. at 1.
After being stretched 4 times, it was heat-treated at 127 ° C. to obtain a porous sheet. The physical properties of this porous sheet are shown in Table 1.
【００２９】実施例５ 分子量２×１０6 のＵＨＭＷＰＥパウダー１８重量％と
分子量４×１０4 、密度０．８９ｇ／ｃｃのエチレン−
ブチレンコポリマー２重量％と粒状のＳｔＯＨ８０重量
％のドライブレンド物を実施例２と同様の方法で、シー
ト化し７５μのシートを得た。このシートを実施例２と
同様に抽出処理した後１２４℃で熱処理を行ない縦方向
に２．５倍に延伸し多孔性シートを得た。この多孔性シ
ートの物性を表１に示した。Example 5 18% by weight of UHMWPE powder having a molecular weight of 2 × 10 6 and ethylene having a molecular weight of 4 × 10 4 and a density of 0.89 g / cc
A dry blend of 2% by weight of butylene copolymer and 80% by weight of granular StOH was formed into a sheet in the same manner as in Example 2 to obtain a sheet of 75μ. This sheet was subjected to extraction treatment in the same manner as in Example 2 and then heat-treated at 124 ° C. and stretched 2.5 times in the machine direction to obtain a porous sheet. The physical properties of this porous sheet are shown in Table 1.
【００３０】実施例６ 分子量１×１０6 のＵＨＭＷＰＥパウダー１８重量％、
分子量６×１０4 で密度が０．９０ｇ／ｃｃのポリプロ
ピレンホモポリマー１重量％、分子量４×１０ 4 で密度
０．９０ｇ／ｃｃのエチレン−ブチレンコポリマー１重
量％とＳｔＯＨ８０重量％のドライブレンド物を実施例
２と同様の方法でシート化、抽出した後１１０℃で熱処
理を行ない多孔性シートを得た。この多孔性シートの物
性を表１に示した。Example 6 Molecular weight 1 × 10618% by weight of UHMWPE powder,
Molecular weight 6 × 10FourWith a density of 0.90 g / cc
Pyrene homopolymer 1% by weight, molecular weight 4 × 10 FourAt density
0.90 g / cc ethylene-butylene copolymer single layer
% Dry blend with 80 wt% StOH
Sheeted and extracted in the same manner as in 2 and then heat treated at 110 ° C.
After that, a porous sheet was obtained. This porous sheet
The sex is shown in Table 1.
【００３１】比較例１ 分子量２×１０6 のＵＨＭＷＰＥパウダー２０重量％と
粒状のＳｔＯＨ８０重量％のドライブレンド物を実施例
１と同様の方法で、シート化、抽出した後１２７℃で熱
処理を行ない、多孔性シートを得た。この多孔性シート
の物性を表１に示した。Comparative Example 1 A dry blend of 20% by weight of UHMWPE powder having a molecular weight of 2 × 10 6 and 80% by weight of granular StOH was formed into a sheet in the same manner as in Example 1, extracted, and then heat treated at 127 ° C. A porous sheet was obtained. The physical properties of this porous sheet are shown in Table 1.
【００３２】比較例２ 分子量２×１０6 のＵＨＭＷＰＥパウダー２０ｗｔ％と
粒状のＳｔＯＨ８０ｗｔ％のドライブレンド物を実施例
６と同様の方法でシート化、抽出した後、１１０℃で熱
処理し、多孔性シートを得た。得られた多孔性シートの
物性を表１に示した。Comparative Example 2 A dry blend of 20 wt% UHMWPE powder having a molecular weight of 2 × 10 6 and 80 wt% granular StOH was formed into a sheet by the same method as in Example 6, extracted, and then heat treated at 110 ° C. to obtain a porous sheet. Got Table 1 shows the physical properties of the obtained porous sheet.
【００３３】実施例７ 実施例１で得られた可塑剤を抽出する前のシートを７０
℃に保持された２０重量％、水−８０重量％、Ｎ−メチ
ルピロリドン混合溶液に浸漬し、プロペラ翼の付いた撹
拌機で単位体積当たりの撹拌所要動力が５０Ｗ／ｍ3 に
相当する撹拌を加えながら、１２００秒間処理してシー
ト中のステアリルアルコールをシート中の濃度が０．５
重量％となるまで除去した。次いで、表面温度１１０℃
の加熱ピンチロールにて１秒間熱処理して膜厚２８μｍ
の多孔性シートを得た。この多孔性シートの物性を表１
に示した。また処理液中のシートから除去したＳｔＯＨ
は処理液を１分間静置する事により静置分離し、冷却
後、ＳｔＯＨ、処理液を各々回収した。Example 7 The sheet obtained by extracting the plasticizer obtained in Example 1 was mixed with 70
It was immersed in a mixed solution of 20% by weight, 80% by weight of water, and N-methylpyrrolidone maintained at 0 ° C., and agitated with a propeller blade so that the power required for agitating per unit volume was 50 W / m 3. While adding, stearyl alcohol in the sheet is treated for 1200 seconds so that the concentration in the sheet is 0.5.
It was removed until it reached a weight percentage. Then, the surface temperature 110 ℃
Heat treatment for 1 second with the heated pinch roll of 28 μm
A porous sheet of The physical properties of this porous sheet are shown in Table 1.
It was shown to. In addition, StOH removed from the sheet in the treatment liquid
The treatment liquid was allowed to stand for 1 minute for stationary separation, and after cooling, StOH and the treatment liquid were respectively collected.
【００３４】実施例８ 実施例２で得られた可塑剤を抽出する前のシートを７０
℃に保持された３０％水−７０％ジエチレングリコール
混合溶液に１５分間浸漬してシート中のステアリルアル
コールをシート中の濃度が０．５重量％となるまで除去
した。次いで、表面温度１２０℃の加熱ピンチロールに
て１秒間熱処理して膜厚３０μｍの多孔性樹脂成形体を
得た。この成形体の特性を表１に示した。Example 8 The sheet obtained before extracting the plasticizer obtained in Example 2 was 70
The stearyl alcohol in the sheet was removed by immersing in a 30% water-70% diethylene glycol mixed solution kept at 0 ° C for 15 minutes until the concentration in the sheet became 0.5% by weight. Then, it was heat-treated for 1 second by a heating pinch roll having a surface temperature of 120 ° C. to obtain a porous resin molded product having a film thickness of 30 μm. The characteristics of this molded product are shown in Table 1.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【発明の効果】本発明によれば各種の用途に用いられる
強度的に向上した多孔性フィルム又はシートが得られ
る。INDUSTRIAL APPLICABILITY According to the present invention, a porous film or sheet having improved strength, which is used for various purposes, can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 恭資 岡山県倉敷市潮通三丁目10番地 三菱化成 株式会社水島工場内 (72)発明者 宇佐見 康 岡山県倉敷市潮通三丁目10番地 三菱化成 株式会社水島工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kyosuke Watanabe 3-10, Shiodo, Kurashiki City, Okayama Prefecture Mitsubishi Kasei Co., Ltd. Mizushima Plant (72) Inventor, Yasushi Usami 3-10, Shiodo, Kurashiki, Okayama Prefecture Mizushima Plant, Mitsubishi Kasei Co., Ltd.
Claims (2)
ポリエチレンと、粘度平均分子量６０万以下のポリオレ
フィンと、可塑剤とを含有する樹脂組成物からフィルム
またはシートを形成した後、該フィルムまたはシートか
ら可塑剤を除去して得られる多孔性フィルムまたはシー
ト。1. A film or sheet is formed from a resin composition containing an ultra high molecular weight polyethylene having a viscosity average molecular weight of 800,000 or more, a polyolefin having a viscosity average molecular weight of 600,000 or less, and a plasticizer, and then the film or sheet. A porous film or sheet obtained by removing a plasticizer from the film.
ポリエチレン（Ａ樹脂）と粘度平均分子量６０万以下の
ポリオレフィン（Ｂ樹脂）との使用割合が、Ａ樹脂６０
〜９９重量％およびＢ樹脂１〜４０重量％である請求項
１に記載の多孔性フィルムまたはシート。2. The ratio of the ultrahigh molecular weight polyethylene (A resin) having a viscosity average molecular weight of 800,000 or more and the polyolefin (B resin) having a viscosity average molecular weight of 600,000 or less is A resin 60.
~ 99 wt% and B resin 1 to 40 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13754593A JPH06345893A (en) | 1993-06-08 | 1993-06-08 | Porous film or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13754593A JPH06345893A (en) | 1993-06-08 | 1993-06-08 | Porous film or sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06345893A true JPH06345893A (en) | 1994-12-20 |
Family
ID=15201200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13754593A Pending JPH06345893A (en) | 1993-06-08 | 1993-06-08 | Porous film or sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06345893A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020883A1 (en) * | 1995-12-05 | 1997-06-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Microporous polyethylene membranes having low fusing temperatures |
| JP2001122998A (en) * | 1999-08-30 | 2001-05-08 | Celgard Inc | Microporous membrane, battery separator and method for producing the same |
| JP2002502446A (en) * | 1996-10-18 | 2002-01-22 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Ultra-thin microporous material |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US7619026B2 (en) | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7622523B2 (en) | 2002-08-12 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| EP4362201A1 (en) * | 2022-10-28 | 2024-05-01 | SK On Co., Ltd. | Separator for secondary battery, manufacturing method thereof, and lithium secondary battery |
-
1993
- 1993-06-08 JP JP13754593A patent/JPH06345893A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020883A1 (en) * | 1995-12-05 | 1997-06-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Microporous polyethylene membranes having low fusing temperatures |
| US6168858B1 (en) | 1995-12-05 | 2001-01-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Microporous polyethylene membranes having low fusing temperatures |
| JP2002502446A (en) * | 1996-10-18 | 2002-01-22 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Ultra-thin microporous material |
| JP2001122998A (en) * | 1999-08-30 | 2001-05-08 | Celgard Inc | Microporous membrane, battery separator and method for producing the same |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US7619026B2 (en) | 2002-08-12 | 2009-11-17 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7622523B2 (en) | 2002-08-12 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7632887B2 (en) | 2002-08-12 | 2009-12-15 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| EP4362201A1 (en) * | 2022-10-28 | 2024-05-01 | SK On Co., Ltd. | Separator for secondary battery, manufacturing method thereof, and lithium secondary battery |
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