JPS63251436A - Production of porous sheet - Google Patents
Production of porous sheetInfo
- Publication number
- JPS63251436A JPS63251436A JP8521987A JP8521987A JPS63251436A JP S63251436 A JPS63251436 A JP S63251436A JP 8521987 A JP8521987 A JP 8521987A JP 8521987 A JP8521987 A JP 8521987A JP S63251436 A JPS63251436 A JP S63251436A
- Authority
- JP
- Japan
- Prior art keywords
- stretching
- sheet
- porous sheet
- filler
- olefin
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 14
- 239000004711 α-olefin Substances 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 7
- -1 polyethylene Polymers 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 13
- 150000001991 dicarboxylic acids Chemical class 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、多孔性シートの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a porous sheet.
詳しくは、ポリオレフィン系樹脂、充填剤および可塑剤
からなる組成物をシート状に成形し、該シート状物を延
伸することにより、良好な外観と風合を有し、強度に優
れ適度の透湿性を有する多孔性シートを製造する方法を
提供するものであり、このような多孔性シートは衣料、
包装材、電池セパレータ、濾過材、衛生・医療用材等種
々の用途に応用することができる。Specifically, by molding a composition consisting of a polyolefin resin, a filler, and a plasticizer into a sheet, and stretching the sheet, a material with good appearance and texture, excellent strength, and moderate moisture permeability can be obtained. The present invention provides a method for manufacturing a porous sheet having a
It can be applied to various uses such as packaging materials, battery separators, filtration materials, sanitary and medical materials, etc.
従来より、ポリオレフィン樹脂に充填剤を配合し、溶融
成形して得られたシートを一軸ないしは二軸に延伸する
試みは、多孔性シートを製造する手段として数多〈実施
されてきた。しかるに、これらのシートに於いては、−
軸延伸物ではシート物性の異方性、特に縦方向（延伸方
向）の引裂強度、更には表面強度に問題が残り、又二軸
延伸物ではシート物性の異方性には問題ないものの、延
伸性及び表面強度に問題があり、更に両者共に全般的に
剛性が高い傾向があり、用途によっては欠点ともなって
いる。In the past, many attempts have been made to uniaxially or biaxially stretch a sheet obtained by blending a filler into a polyolefin resin and melt-molding it as a means of manufacturing a porous sheet. However, in these sheets, −
For axially oriented products, there remain problems with the anisotropy of sheet physical properties, especially tear strength in the longitudinal direction (stretching direction), and furthermore, surface strength.For biaxially oriented products, although there is no problem with anisotropy of sheet physical properties, stretching They have problems in terms of hardness and surface strength, and both tend to have high overall rigidity, which can be a drawback in some applications.
シート物性の異方性や表面強度を改良する一つの方法と
しては、可能な限り低倍率延伸を行い、多孔化を実現さ
せることであり、またシートに柔軟性を付与する方法と
しては、低融点ポリマー、ゴム状物質、可塑剤あるいは
界面活性剤を添加する方法が考えられるが、成形安定性
及び多孔化、延伸性、引裂強度や引張強度等の機械的性
質、更には表面強度等の物性バランスを満足したものは
未だ見い出されていない。One way to improve the anisotropy and surface strength of the sheet properties is to achieve porosity by stretching as low as possible. Possible methods include adding polymers, rubber-like substances, plasticizers, or surfactants, but the balance of physical properties such as molding stability, porosity, stretchability, mechanical properties such as tear strength and tensile strength, and even surface strength is considered. Nothing that satisfies this has yet been found.
こうした従来の多孔性シートの欠点を改良する方法とし
て、本出願人は特開昭５７−４７３３４にてポリオレフ
ィン樹脂に充填剤と液状ポリブタジェンあるいは液状ポ
リブテンを混合してなる組成物を、また特開昭５８−１
５５３８にて線状低密度ポリエチレン樹脂と充填剤とポ
リヒドロキシ飽和炭化水素とを配合してなる組成物を用
いることを提案した。As a method to improve these drawbacks of conventional porous sheets, the applicant of the present invention proposed a composition obtained by mixing a filler and liquid polybutadiene or liquid polybutene with a polyolefin resin in JP-A-57-47334. 58-1
No. 5538 proposed the use of a composition comprising a linear low-density polyethylene resin, a filler, and a polyhydroxy saturated hydrocarbon.
更に、特開昭６１−１４４３３１ではアジピン酸エステ
ル等のポリエステル系あるいはエポキシ化大豆油等のエ
ポキシ系可塑剤を使用する方法、特開昭６２−１０１４
１ではトリグリセライドを用いる方法も提案されている
。Furthermore, JP-A No. 61-144331 discloses a method using a polyester plasticizer such as adipic acid ester or an epoxy-based plasticizer such as epoxidized soybean oil;
1 also proposes a method using triglyceride.
しかしながら、これらの方法においてもフィルム強度、
透湿性、外観・風合等の諸性質を全て満足するような多
孔性シートを得るには至っていない。However, even with these methods, film strength,
It has not yet been possible to obtain a porous sheet that satisfies all properties such as moisture permeability, appearance and texture.
〔発明の目的］
本発明は溶融成形では良好なる押出性を有する他、特に
優れた成形の安定性を示し、溶融成形して得られたシー
トの一軸延伸物では引裂強度や引張強度等の機械的性質
と透湿性のバランスが良好で、−軸延伸物、二軸延伸物
共に表面強度が強く、延伸性に優れ、特に低倍率延伸に
於いては不均一延伸により生ずる延伸斑が非常に少なく
、且つ柔軟性に富んだ多孔性シートを提供することを目
的とする。[Objective of the Invention] The present invention has good extrudability in melt molding, and also shows particularly excellent molding stability, and the uniaxially stretched sheet obtained by melt molding has mechanical properties such as tear strength and tensile strength. It has a good balance between physical properties and moisture permeability, and both axially oriented and biaxially oriented products have strong surface strength and excellent stretchability, with very little stretching unevenness caused by non-uniform stretching, especially in low-magnification stretching. The object of the present invention is to provide a porous sheet that is highly flexible.
本発明の要旨は、ポリオレフィン系樹脂、充填剤および
可塑剤を含有する組成物を溶融成形して得られるシート
を延伸して多孔性シートを製造するに際し、可塑剤とし
て、α−オレフィンとα、β−不飽和ジカルボン酸ジア
ルキルエステルとの共重合体を用いることを特徴とする
多孔性シートの製造方法に存する。The gist of the present invention is that when manufacturing a porous sheet by stretching a sheet obtained by melt-molding a composition containing a polyolefin resin, a filler, and a plasticizer, α-olefin and α, A method for producing a porous sheet characterized by using a copolymer with a β-unsaturated dicarboxylic acid dialkyl ester.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明に用いられるポリオレフィン系樹脂としては高密
度ポリエチレン、中密度ポリエチレン、線状低密度ポリ
エチレンが単独であるいは２種以上の混合物として用い
られ、該ポリエチレンのメルトインデックスとしては０
．０１〜１０ ｇ／ｌ ０分（ＡＳＴＭ Ｄ−１２３８
−７０により１９０°Ｃ，２，１６ｋｇで測定）の範囲
が好ましい。更には該ポリエチレンには高圧法により得
られる分岐状低密度ポリエチレンが一部混合されてもよ
い。As the polyolefin resin used in the present invention, high-density polyethylene, medium-density polyethylene, and linear low-density polyethylene are used alone or as a mixture of two or more, and the melt index of the polyethylene is 0.
．． 01-10 g/l 0 min (ASTM D-1238
-70 measured at 190°C and 2.16 kg) is preferred. Furthermore, branched low-density polyethylene obtained by a high-pressure method may be partially mixed with the polyethylene.
また、結晶性ポリプロピレンも用いられる。結晶性ポリ
プロピレンとしてはプロピレンの単独重合体あるいはプ
ロピレンと他のα−オレフィンとの共重合体が単独でま
たは２種以上の混合物として利用される。これらのポリ
オレフィン樹脂には、常法に従って熱安定剤、紫外線吸
収剤、帯電防止剤、顔料、螢光剤等の添加剤を配合する
ことができる。Crystalline polypropylene is also used. As the crystalline polypropylene, a propylene homopolymer or a copolymer of propylene and other α-olefins may be used alone or in a mixture of two or more. Additives such as heat stabilizers, ultraviolet absorbers, antistatic agents, pigments, and fluorescent agents can be added to these polyolefin resins according to conventional methods.
充填剤としては、無機充填剤及び有機充填剤が使用され
、無機充填剤としては炭酸カルシウム、タルク、クレー
、カオリン、シリカ、珪藻土、炭酸マグネシウム、硫酸
カルシウム、水酸化アルミニウム、酸化亜鉛、水酸化マ
グネシウム、酸化カルシウム、酸化マグネシウム、酸化
チタン、アルミナ、マイカ、アスベスト粉、ガラス粉、
シラスバルーン、ゼオライト、珪酸白土等が使用され、
特に炭酸カルシウム、タルク、クレー、シリカ、珪藻土
、硫酸バリウム等が好適である。Inorganic fillers and organic fillers are used as fillers, and inorganic fillers include calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium sulfate, aluminum hydroxide, zinc oxide, and magnesium hydroxide. , calcium oxide, magnesium oxide, titanium oxide, alumina, mica, asbestos powder, glass powder,
Shirasu balloons, zeolite, silicate clay, etc. are used.
Particularly suitable are calcium carbonate, talc, clay, silica, diatomaceous earth, barium sulfate, and the like.
有機充填剤としては、木粉、パルプ等のセルロース系粉
末等が使用される。これらは単独又は混合して用いられ
る。As the organic filler, cellulose powder such as wood flour and pulp is used. These may be used alone or in combination.
充填剤の平均粒径としては、３０μ以下のものが好まし
く、１０μ以下のものが更に好ましく、５μ以下のもの
が最も好ましい。粒径が大きすぎると延伸物の気孔の緻
密性が悪くなる。充填剤の表面処理は、樹脂への分散性
、更には延伸性の点で、実施されていることが好ましく
、脂肪酸又はその金属塩での処理が好ましい結果を与え
る。脂肪酸又はその金属塩による表面処理量は、充填剤
１００重量部に対し、１０重量部以下が好ましい。The average particle size of the filler is preferably 30μ or less, more preferably 10μ or less, and most preferably 5μ or less. If the particle size is too large, the density of the pores in the stretched product will deteriorate. Surface treatment of the filler is preferably carried out in terms of dispersibility in the resin and further stretchability, and treatment with a fatty acid or a metal salt thereof gives preferable results. The amount of surface treatment with the fatty acid or its metal salt is preferably 10 parts by weight or less per 100 parts by weight of the filler.
表面処理量が多いと、混練・造粒更には成形に於いて白
煙が生じたり発泡することがあるので好ましくない。If the amount of surface treatment is too large, white smoke or foaming may occur during kneading, granulation, and molding, which is not preferable.
本発明において可塑剤として使用するα−オレフィン−
α、β−不飽和ジカルボン酸ジアルキルエステル共重合
体は、α−オレフィンとα、β−不飽和ジカルボン酸の
ジアルキルエステルとを、常法に従いラジカル重合開始
剤の存在下に溶液重合または無溶媒重合法にて、共重合
させることによって得られ、その重量平均分子量は１
、０００〜２０ 、０００の範囲のものが好ましい。α-Olefin used as a plasticizer in the present invention
The α,β-unsaturated dicarboxylic acid dialkyl ester copolymer is produced by solution polymerization or solvent-free polymerization of α-olefin and α,β-unsaturated dicarboxylic acid dialkyl ester in the presence of a radical polymerization initiator according to a conventional method. It is obtained by legal copolymerization, and its weight average molecular weight is 1.
,000 to 20,000 is preferred.
α−オレフィンの炭素数は、２〜４０の範囲のものが好
ましく、特に２〜２０の範囲のものは、液状の共重合体
を与え易く特に本発明における可塑剤としての効果が大
である。The α-olefin preferably has carbon atoms in the range of 2 to 40, and in particular, those in the range of 2 to 20 tend to provide a liquid copolymer and are particularly effective as a plasticizer in the present invention.
一方、α、β−不飽和ジカルボン酸ジアルキルエステル
の原料となるアルコールとしては炭素数１〜４０のアル
コールが使用できるが、炭素数１〜３０のアルコール、
例えばメタノール、エタノール、ブタノール等が実用的
であり好ましい。On the other hand, alcohols having 1 to 40 carbon atoms can be used as raw materials for α,β-unsaturated dicarboxylic acid dialkyl esters, but alcohols having 1 to 30 carbon atoms,
For example, methanol, ethanol, butanol, etc. are practical and preferred.
α、β−不飽和ジカルボン酸としては、マレイン酸また
はフマル酸及びイクコン酸が好ましく挙げられる。As the α,β-unsaturated dicarboxylic acid, maleic acid or fumaric acid and ichonic acid are preferably mentioned.
共重合体におけるα、β−不飽和ジカルボン酸ジアルキ
ルエステルとα−オレフィンとのモル比は、共重合反応
時の両者の濃度比を変えることにより適当に変化させる
ことができるが、通常はジアルキルエステル／α−オレ
フィンのモル比で０．５〜２、好ましくは１．０〜１．
５の範囲である。The molar ratio of α, β-unsaturated dicarboxylic acid dialkyl ester and α-olefin in the copolymer can be changed appropriately by changing the concentration ratio of the two during the copolymerization reaction, but usually the dialkyl ester /α-olefin molar ratio of 0.5 to 2, preferably 1.0 to 1.
The range is 5.
α−オレフィンとα、β−不飽和ジカルボン酸ジアルキ
ルエステルとの共重合体の具体例としては例えば次のよ
うなものが挙げられる。Specific examples of the copolymer of α-olefin and α,β-unsaturated dicarboxylic acid dialkyl ester include the following.
α−オレフィン／マレイン酸ジメチルエステル共重合体
（下記構造式Ｉ）、α−オレフィン／マレイン酸ジエチ
ルエステル共重合体（下記構造式構造式Ｉ
Ｒ： Ｃ１ｏ−Ｃ＋ｚのαオレフィン
構造式■
Ｒ： ＣＩ４〜ＣＩ６のαオレフイン
ポリオレフィン系樹脂、充填剤およびα−オレフィン−
α、β−不飽和ジカルボン酸ジアルキルエステル共重合
体の配合割合は、ポリオレフィン系樹脂１００重量部に
対し、充填剤２５〜４００重量部が好ましく、６０〜３
００重量部が更に好ましい範囲であり、また共重合体は
同じく１〜１００重量部が好ましく、１〜５０重量部が
更に好ましい。α-olefin/maleic acid dimethyl ester copolymer (the following structural formula I), α-olefin/maleic acid diethyl ester copolymer (the following structural formula Structural formula I R: α-olefin structural formula of C1o-C+z ■ R: CI4 ~CI6 α-olefin polyolefin resin, filler and α-olefin-
The blending ratio of the α,β-unsaturated dicarboxylic acid dialkyl ester copolymer is preferably 25 to 400 parts by weight, and 60 to 3 parts by weight of the filler per 100 parts by weight of the polyolefin resin.
00 parts by weight is a more preferable range, and the copolymer is also preferably 1 to 100 parts by weight, and even more preferably 1 to 50 parts by weight.
充填剤の配合量が少なすぎると延伸されたシートの気孔
形成が充分に行なわれず多孔化の程度が低下し、一方配
合量が多すぎると混練性、分散性が悪化し、シートの成
形性の低下、表面強度の低下を招く。また、可塑剤の共
重合体の配合量が多すぎると満足すべき混練性が得られ
ず、シートの成形性、延伸性を確保できない。If the amount of filler blended is too small, the pores in the stretched sheet will not be formed sufficiently and the degree of porosity will be reduced.On the other hand, if the amount blended is too large, kneadability and dispersibility will deteriorate, and the formability of the sheet will be affected. This results in a decrease in surface strength. Furthermore, if the amount of the plasticizer copolymer blended is too large, satisfactory kneading properties cannot be obtained, and sheet formability and stretchability cannot be ensured.
ポリオレフィン系樹脂、充填剤および前記共重合体の混
合においては通常のブレンダー又は混合機が用いられる
。A conventional blender or mixer is used to mix the polyolefin resin, filler, and the copolymer.
混合機は、ドラム、タンブラ−型混合機、リボンブレン
ダー、ヘンシェルミキサー、スーパーミキサー等が使用
されるが、ヘンシェルミキサー等の高速撹拌型の混合機
が望ましい。As the mixer, a drum, a tumbler type mixer, a ribbon blender, a Henschel mixer, a super mixer, etc. are used, and a high-speed stirring type mixer such as a Henschel mixer is preferable.
次に、混合物の混純には従来公知の装置、例えば通常の
スクリュー押出機、二軸スクリュー押出機、ミキシング
ロール、ハンバリーミキザー、二軸型混練機等により適
宜実施される。Next, the mixture is mixed and purified using a conventionally known device such as a conventional screw extruder, twin screw extruder, mixing roll, Hanbury mixer, twin screw kneader, etc.
シートの成形については、通常のシートの成形装置及び
成形方法に準じて実施すれば良く、円形ダイによるイン
フレーション成形、ＴダイによるＴダイ押出成形等を適
宜採用すれば良い。Forming of the sheet may be carried out according to a normal sheet forming apparatus and forming method, and inflation forming using a circular die, T-die extrusion forming using a T-die, etc. may be appropriately employed.
次いで成形されたシートを延伸するに際しては、−軸延
伸の場合は通常ロール延伸が採用されるが、チューブラ
−延伸で、−軸方向（引取方向）を相対的に強調させた
形であっても良い。又、延伸は一段でも二段以上の多段
でも差支えない。Next, when stretching the formed sheet, roll stretching is usually used in the case of -axial stretching, but even if it is tubular stretching, where the -axial direction (pulling direction) is relatively emphasized. good. Further, the stretching may be carried out in one stage or in multiple stages of two or more stages.
二軸延伸に於いては、同時及び逐次延伸でも一軸延伸同
様に低倍率延伸が可能であり、少なくとも一方向が１．
１倍で均一延伸と多孔化が出来る。In biaxial stretching, low-stretching is possible in simultaneous and sequential stretching as well as uniaxial stretching, and at least one direction is 1.
Uniform stretching and porosity can be achieved at 1x.
多孔化が達成され、且つ均一延伸の可能な延伸倍率は、
少なくとも一方向が１．１〜３．０倍である。The stretching ratio at which porosity is achieved and uniform stretching is possible is as follows:
At least one direction is 1.1 to 3.0 times.
更には、−軸延伸、二軸延伸ともに延伸後に熱処理を実
施し、フィルムの寸法精度を安定化することが出来る。Furthermore, the dimensional accuracy of the film can be stabilized by carrying out heat treatment after stretching in both -axial stretching and biaxial stretching.
又、公知のコロナ処理、フレーム処理等の表面処理を行
なうこともできる。Further, known surface treatments such as corona treatment and flame treatment can also be performed.
本発明においては多孔性シートは０．０１〜０．５ｍｍ
、好ましくは０．０２〜０．３肝の厚さに成形され、一
般的にフィルムと呼ばれるものも本発明のシートに包含
される。In the present invention, the porous sheet has a thickness of 0.01 to 0.5 mm.
The sheet of the present invention also includes a sheet formed to a thickness of preferably 0.02 to 0.3 mm and generally referred to as a film.
次に本発明を実施例により更に具体的に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
尚、以下の実施例及び比較例において使用した原料の一
覧を表−１乃至表−３に示す。Incidentally, a list of raw materials used in the following Examples and Comparative Examples is shown in Tables 1 to 3.
実施例１〜１６、比較例１〜１７
後記表−１のポリオレフィン系樹脂と後記表−２の充填
剤をヘンシェルミキサー中で撹拌混合し、これに後記表
−３の可塑剤を添加して更に撹拌混合し、１０ｋｇの混
合物を得た。尚、使用した原料各成分の種類および組成
は表−４，５に記載した。Examples 1 to 16, Comparative Examples 1 to 17 The polyolefin resin shown in Table 1 below and the filler shown in Table 2 below were stirred and mixed in a Henschel mixer, and the plasticizer shown in Table 3 below was added thereto. The mixture was stirred and mixed to obtain 10 kg of a mixture. The types and compositions of each raw material component used are listed in Tables 4 and 5.
上記操作を４回繰り返して得られた混合物４０ｋｇを二
軸混練機（ＤＳＭ −６５、日本製鋼所■製）により混
練し造粒したのち、５０ｍｍφ押出機により下記条件で
インフレーション成形し、厚さ６５μの原反フィルムを
得た。After repeating the above operation four times, 40 kg of the resulting mixture was kneaded and granulated using a twin-screw kneader (DSM-65, manufactured by Japan Steel Works, Ltd.), and then inflation molded using a 50 mmφ extruder under the following conditions to obtain a thickness of 65 μm. A raw film was obtained.
シリンダ一温度：１７０〜１９０〜２１０ ’Ｃヘッド
、ダイス温度：２１ｏ〜２１０°Ｃ引取速度：ＩＯｍ／
分
ブロー比＝２．５
折り径：５５０＋ｎｍ
表−１
（注） Ｍｌ（メルトインデックス） ； ＡＳＴＭ
Ｄ １２３８−７０に準拠して１９０℃で測定
密度； ＡＳＴＭ Ｄ １５０５に準拠し、密度勾配管
法により２０°Ｃで測定
表−２
表 −３
ＰＡＲ−１２１１，１６８，Ｐ−渡、 Ｆ７−６７、共
有プロセスη（ト）、ブラクセＪ凶Ｌ−０１゜ニラポラ
ン４０３２．プラクセルλ損はいずれも５６名表 −
４
表 −５
得られたフィルムをロール延伸機により下記条件で一軸
延伸した。Cylinder temperature: 170~190~210'C Head, die temperature: 21o~210°C Take-up speed: IOm/
Blow ratio = 2.5 Fold diameter: 550+nm Table 1 (Note) Ml (melt index); ASTM
Density measured at 190°C according to ASTM D 1238-70; measured at 20°C by density gradient tube method according to ASTM D 1505 , shared process η(g), Buraxe JKL-01゜Niraporan 4032. Both Praxel λ losses are 56 names −
4 Table-5 The obtained film was uniaxially stretched using a roll stretching machine under the following conditions.
延伸温度ニア０°Ｃ
但し、実施例１１及び１４では６０゛Ｃ１実施例１２及
び１６では８０°Ｃで行なった。Stretching temperature was near 0°C. However, in Examples 11 and 14, it was 60°C, and in Examples 12 and 16, it was 80°C.
延伸倍率：１．５〜２．５
延伸密度：２０ｍ／分
原反フィルム成形時の均−流動性及びバブル安定性、延
伸条件および得られた延伸フィルムの物性を表−５〜７
に示す。Stretching ratio: 1.5 to 2.5 Stretching density: 20 m/min Tables 5 to 7 show the uniform fluidity and bubble stability during raw film forming, stretching conditions, and physical properties of the obtained stretched film.
Shown below.
また、成形性及び物性評価項目の測定方法は下記のとお
りである。The methods for measuring moldability and physical property evaluation items are as follows.
■）二軸混練性
原料ペレットをＤＳＭで造粒するに際して、○：ベント
アップ（ベント孔からの）やサージングが少なく安定造
粒筒
×：ベントアンプ又はサージングがあり安定造粒不可
２）均一流動性
インフレーション成形に於いて、
○：溶融樹脂がダイスの全周から均一に出てインフレー
ション成形可能
×：溶融樹脂がダイスの全周から均一に出すインフレー
ション成形不可
３）バブル安定性
インフレーション成形に於いて、
◎：ハブルのゆれなし
○：ハブルのゆれ殆どなし
△：バブルのゆれあり
×：成形困難
４）延伸性
◎・切断なし、均一延伸、延伸斑見られず○：切断なし
、延伸斑殆ど見られず
△：切断なし、延伸斑見られる
×：切断又は延伸斑顕著に見られる
５）空隙率
次の式よりフィルムの密度から計算
り、 −Ｄ
空隙率（％） −−□ Ｘ １００ （％）Ｄ。■) When granulating biaxially kneaded raw material pellets with DSM, ○: Stable granulation tube with little vent up (from vent holes) and surging ×: Stable granulation impossible due to vent amplifier or surging 2) Uniform flow In inflation molding, ○: Molten resin comes out uniformly from the entire circumference of the die, making inflation molding possible. ×: Molten resin comes out uniformly from the entire circumference of the die, making inflation molding impossible. 3) Bubble stability In inflation molding: , ◎: No bubble wobbling ○: Hardly any hubble wobbling △: Bubble wobbling ×: Difficult to form 4) Stretchability ◎ - No cutting, uniform stretching, no stretching irregularities observed ○: No cutting, almost no stretching irregularities observed △: No cutting, stretching spots are observed ×: Cutting or stretching spots are noticeable )D.
Ｄｏ ：原反フィルムの密度（ｇ／ａｆｌ）Ｄ ：延伸
フィルムの密度（ｇ ／ ｃｒＲ）６）引張強度
八ＳＴＭ ０８８２−６４Ｔに準する。Do: Density of original film (g/afl) D: Density of stretched film (g/crR) 6) Tensile strength 8 Based on STM 0882-64T.
１０ｍｍ幅Ｘ５０ｍ＋ｎ長さ、引張速度５００＋＋ｕｎ
／分７）引裂強度
ＪＩＳ Ｐ−８１１６に準する。10mm width x 50m+n length, tensile speed 500++un
/min 7) Tear strength According to JIS P-8116.
ノツチ有り。１４岨幅Ｘ１１０ｍｍ長さ。Has a notch. 14mm width x 110mm length.
８）透湿度 ＡＳＴＭ Ｅ９６−８０（Ｃ）に準する。8) Moisture permeability Conforms to ASTM E96-80(C).
９）柔軟性 手の感触で、次の基準により判定した。9) Flexibility Judgment was made by feeling with the hand according to the following criteria.
◎：極めて柔らかい
○：柔らかい
△：少し硬い
×：硬い
１０）表面強度
フィルム表面にセロテープを貼り、すばやく引剥がした
時の表面の剥れ状態を見て、次の基準で判定した。◎: Extremely soft ○: Soft △: Slightly hard ×: Hard 10) Surface strength Sellotape was applied to the surface of the film, and when it was quickly peeled off, the peeling state of the surface was observed and judged according to the following criteria.
◎二表面剥離せず
○：表面剥離殆どなし
△：表面剥離少しあり
×：表面剥離大
表 −７
実施例１７〜３２、比較例１８〜２６
実施例１〜１６と同様にして表−８，９に示したポリオ
レフィン系樹脂、充填剤及び可塑剤を含有する組成物か
ら成るペレットを作り、これを６５ｍｍφ押出機にかけ
下記の条件でＴダイ成形し、厚さ９０μの原反フィルム
を得た。◎No peeling on two surfaces ○: Almost no surface peeling △: Slight surface peeling ×: Large surface peeling Table-7 Examples 17-32, Comparative Examples 18-26 Table-8, Pellets made of the composition containing the polyolefin resin, filler, and plasticizer shown in 9 were made, and the pellets were subjected to T-die molding using a 65 mmφ extruder under the following conditions to obtain a raw film with a thickness of 90 μm.
シリンダ一温度：１７０−２００−２３０°Ｃヘッド、
ダイス温度：２３０−２３０°Ｃダイス幅：４５０ｍｍ
取引速度：１０ｍ／分
原反幅：３３０ｍｍ
得られたフィルムをロール延伸機により下記条件で一軸
延伸した。Cylinder temperature: 170-200-230°C head,
Dice temperature: 230-230°C Dice width: 450 mm Transaction speed: 10 m/min Original fabric width: 330 mm The obtained film was uniaxially stretched using a roll stretching machine under the following conditions.
延伸温度二６０〜８０°Ｃ
延伸倍率＝１．２〜２．５
延伸速度＝２０ｍ／分
更に得られた縦延伸フィルムをテンターにより下記条件
で横延伸した。Stretching temperature: 260-80°C Stretching ratio: 1.2-2.5 Stretching speed: 20 m/min Further, the obtained longitudinally stretched film was laterally stretched using a tenter under the following conditions.
延伸温度：８０〜１１０°Ｃ
延伸倍率：２．０〜３．０
延伸速度７２０ ｍ ／ｍｉｎ
原料組成を表−８，９に、又横延伸時の延伸安定性及び
得られたフィルムの延伸性及び物性を表−１０，１１に
示す。Stretching temperature: 80-110°C Stretching ratio: 2.0-3.0 Stretching speed 720 m/min The raw material composition is shown in Tables 8 and 9, and the stretching stability during transverse stretching and the stretchability of the obtained film are shown in Tables 8 and 9. and physical properties are shown in Tables 10 and 11.
ここでテンター横延伸に於ける延伸安定性は以下の如く
評価した。Here, the stretching stability in tenter lateral stretching was evaluated as follows.
○：延伸切れなく安定延伸可能 △：時々延伸切れ発生 ×：延伸切れ多くフィルムがつながらない表−８ Ｚ 表−９ 〔発明の効果〕 本発明方法は、 （１）低延伸倍率で多孔化が達成される。○: Stable stretching possible without stretching breakage △: Stretching breaks sometimes occur ×: Too many stretching breaks and the film is not connected Table 8 Z Table-9 〔Effect of the invention〕 The method of the present invention includes (1) Porous formation is achieved at a low stretching ratio.
（２）延伸応力が低く、低温延伸が可能である。(2) Low stretching stress and low temperature stretching possible.
（３）低延伸倍率で均一延伸が可能である。(3) Uniform stretching is possible at a low stretching ratio.
などの特徴を有し、得られる多孔性シートは、（１）延
伸斑が殆ど認められない。The resulting porous sheet has the following characteristics: (1) Almost no stretching unevenness is observed.
（２）透湿性、ガス透過性にすくれ、耐水圧が高い。(2) High moisture permeability, gas permeability, and water pressure resistance.
（３）柔軟性にすぐれている。(3) Excellent flexibility.
（４）物性の異方性が少ない。(4) Less anisotropy in physical properties.
（５）引裂強度、引張強度が高い。(5) High tear strength and tensile strength.
（６） ヒートシール性が良好で収縮包装が可能であ
る。(6) Good heat sealability and shrink packaging is possible.
（７）易焼却性であり、有害ガスを発生しない。(7) It is easily incinerated and does not generate harmful gases.
などの特性を示し、衣料用、包装用、電池セパレータ用
、が過材用、医療用等種々の用途に応用することができ
る。It exhibits the following characteristics and can be applied to various uses such as clothing, packaging, battery separators, filter materials, and medical applications.
Claims (1)
有する組成物を溶融成形して得られるシートを延伸して
多孔性シートを製造するに際し、可塑剤として、α−オ
レフィンとα、β−不飽和ジカルボン酸ジアルキルエス
テルとの共重合体を用いることを特徴とする多孔性シー
トの製造方法。(1) When manufacturing a porous sheet by stretching a sheet obtained by melt-molding a composition containing a polyolefin resin, a filler, and a plasticizer, α-olefin and α,β-immobilizer are used as plasticizers. A method for producing a porous sheet, characterized by using a copolymer with a saturated dicarboxylic acid dialkyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8521987A JPH0764942B2 (en) | 1987-04-07 | 1987-04-07 | Method for producing porous sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8521987A JPH0764942B2 (en) | 1987-04-07 | 1987-04-07 | Method for producing porous sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63251436A true JPS63251436A (en) | 1988-10-18 |
| JPH0764942B2 JPH0764942B2 (en) | 1995-07-12 |
Family
ID=13852459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8521987A Expired - Fee Related JPH0764942B2 (en) | 1987-04-07 | 1987-04-07 | Method for producing porous sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764942B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073316A (en) * | 1987-08-27 | 1991-12-17 | Mitsubishi Kasei Vinyl Company | Process for producing a porous film |
| EP1698656A1 (en) * | 2003-12-24 | 2006-09-06 | Asahi Kasei Chemicals, Inc. | Microporous membrane made from polyolefin |
| WO2013168663A1 (en) * | 2012-05-11 | 2013-11-14 | 住友化学株式会社 | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
| WO2013168662A1 (en) * | 2012-05-11 | 2013-11-14 | 住友化学株式会社 | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
-
1987
- 1987-04-07 JP JP8521987A patent/JPH0764942B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073316A (en) * | 1987-08-27 | 1991-12-17 | Mitsubishi Kasei Vinyl Company | Process for producing a porous film |
| EP1698656A1 (en) * | 2003-12-24 | 2006-09-06 | Asahi Kasei Chemicals, Inc. | Microporous membrane made from polyolefin |
| EP1698656A4 (en) * | 2003-12-24 | 2007-10-17 | Asahi Kasei Chemicals Inc | Microporous membrane made from polyolefin |
| WO2013168663A1 (en) * | 2012-05-11 | 2013-11-14 | 住友化学株式会社 | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
| WO2013168662A1 (en) * | 2012-05-11 | 2013-11-14 | 住友化学株式会社 | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
| US9608246B2 (en) | 2012-05-11 | 2017-03-28 | Sumitomo Chemical Company, Limited | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
| US9783641B2 (en) | 2012-05-11 | 2017-10-10 | Sumitomo Chemical Company, Limited | Resin composition, separator for non-aqueous electrolyte secondary battery and production method therefor, and non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764942B2 (en) | 1995-07-12 |
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| LAPS | Cancellation because of no payment of annual fees |