JPS5936939B2 - Method for manufacturing porous film - Google Patents

Method for manufacturing porous film

Info

Publication number
JPS5936939B2
JPS5936939B2 JP14943476A JP14943476A JPS5936939B2 JP S5936939 B2 JPS5936939 B2 JP S5936939B2 JP 14943476 A JP14943476 A JP 14943476A JP 14943476 A JP14943476 A JP 14943476A JP S5936939 B2 JPS5936939 B2 JP S5936939B2
Authority
JP
Japan
Prior art keywords
polymer
solvent
porous film
film
aromatic
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.)
Expired
Application number
JP14943476A
Other languages
Japanese (ja)
Other versions
JPS5374572A (en
Inventor
栄二 佐藤
義昭 花田
英男 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP14943476A priority Critical patent/JPS5936939B2/en
Publication of JPS5374572A publication Critical patent/JPS5374572A/en
Publication of JPS5936939B2 publication Critical patent/JPS5936939B2/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/044—Elimination of an inorganic solid phase
    • C08J2201/0444—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids

Description

【発明の詳細な説明】 本発明は、多孔性フィルムの製造方法に関する。[Detailed description of the invention] The present invention relates to a method for manufacturing a porous film.

更に詳しくは、薯に電池用セパレーター膜として有用な
、耐熱性、耐薬品性、寸法安定性にすぐれ、かつ、内部
抵抗の小さい多孔性フィルムの製造方法に関する。従来
、電池用セパレーター素材としては、水材、多孔性エボ
ナイト板等が利用されていたが、耐薬品性に劣り、、ま
たセパレーターとして目的を達成する為には数Ｉの厚み
を必要とし、電池が大型化する等の欠点を有していた。More specifically, the present invention relates to a method for producing a porous film useful as a separator film for batteries, which has excellent heat resistance, chemical resistance, dimensional stability, and low internal resistance. Conventionally, water materials, porous ebonite plates, etc. have been used as separator materials for batteries, but they have poor chemical resistance, and require a thickness of several I to achieve the purpose as a separator. It had disadvantages such as increased size.

これらの欠点を補うものとしては、セロファン、、オイ
ロン不織布、あるいは、ポリ塩化ビニル、３ボサステレ
ン系０樹脂の使用が提案されて来た。近年一気機器の革
新などに伴つて、充放電効率の鼻い高性能電池、例えば
ニツケルーカドミウ、＾系、、ス鱗−牝−７葦鋒系など
の所謂アルカリ電離の脣東力千鼻声゛、ρ９、ある。そ
れに伴つて、鉛電池等Ｑキー的、一、−０で蒙用されて
来た従来のセパレー、ター素材・咽＊、耐薬品性、耐熱
性、又は寸法安定性などが不充分であ−ー、高性能電池
本来の特性を充分に発揮できないと〜・ラ、欠点が指摘
された。一方、最近、合成重合体、特に芳香族系重合体
は、耐熱性、耐薬品坤冬は力学的性質にすぐれ、ゆゝ・
λ電課的薯性にもすぐれている為電気関係分野の材料皐
、材としての用途開発が盛んに行われ、これちＱ所謂芳
香族系重合体のシート状物をこのようなセバｙ、一ター
膜として使用する試みがなされている、０−し一ルなが
ら、かかる重合体は、一般の有機解剖に対しては難溶性
であり、また重合体自体が不融性である為、電池用セパ
レーターあるいはその他の均一な多孔性を必要とする透
析膜等々への成型が極めて困難であるという欠点を有し
ていた。To compensate for these shortcomings, it has been proposed to use cellophane, oilon nonwoven fabric, polyvinyl chloride, or 3-bosasterene type 0 resin. In recent years, with the rapid innovation of equipment, high-performance batteries with low charging and discharging efficiency, such as the Nikkei cadmium, the ^ series, and the so-called alkaline ionization battery, such as the ``Suraka-Feng-7 Rei Feng'' type, have become popular. , ρ9, exists. Along with this, conventional separators, terminating materials, chemical resistance, heat resistance, or dimensional stability, which have been used in Q-key, -0, etc., such as lead batteries, are insufficient. It was pointed out that the high-performance battery could not fully demonstrate its original characteristics. On the other hand, recently, synthetic polymers, especially aromatic polymers, have excellent heat resistance, chemical resistance, and mechanical properties.
Due to its excellent λ electrical property, it has been actively developed for use as a material in the electrical field. Attempts have been made to use these polymers as a single film, but such polymers are poorly soluble in general organic tissues, and the polymer itself is infusible, making it difficult to use in batteries. It has the disadvantage that it is extremely difficult to mold into dialysis membranes that require uniform porosity or separators for industrial use.

本発明者は、かかる欠点のない均一多孔性であり、耐熱
性、耐薬品性にすぐれ、かつ、力学的性質にすぐれた多
孔性フイルムを得る為、鋭意研究を進めた結果、耐熱性
を有する芳香族系重合体を特定の溶媒条件からなる組成
物とした場合にのみコアセルベーシヨン（析・液）を形
成し、この組成物を成膜化することによつて目的を達成
することを見出し、本発明を完成したものである。すな
わち、本発明は、耐熱性を有する芳香族重合体のコアセ
ルベーシヨン（析・液）組成物を成膜することを特徴と
する多孔性フイルムの製造方法である。コアセルペーシ
ヨン（析・液）とは、化学大辞典（共立出版ＫＫ発行）
第３巻第４７４４７５ページの「コアセルベーシヨン」
の項にも記載されているように、親液コイロド特に高分
子溶液がいろいろな条件のもとでコロイドに富む液相と
コロイドに乏しい液相との二つの相に分離する現象がみ
られ、この現象をいうものである。The present inventor has carried out extensive research in order to obtain a porous film that has uniform porosity, excellent heat resistance, chemical resistance, and excellent mechanical properties without such drawbacks, and has found that it has heat resistance. It is possible to achieve the objective by forming a coacelvation (liquid) only when the aromatic polymer is made into a composition with specific solvent conditions, and by forming a film from this composition. The heading completes the invention. That is, the present invention is a method for producing a porous film characterized by forming a coacervation composition of an aromatic polymer having heat resistance. What is co-cellupation? Chemistry Encyclopedia (published by Kyoritsu Shuppan KK)
“Coacervation” in Volume 3, page 474475
As described in the section, there is a phenomenon in which lyophilic colloids, especially polymer solutions, separate into two phases, a colloid-rich liquid phase and a colloid-poor liquid phase, under various conditions. It refers to this phenomenon.

本発明において、この組成物は、フイルム成型時以前に
コアセルペーシヨン（析・液）化されている為、ミクロ
的に重合体濃度の違う２液相を呈しており、成型、脱溶
媒工程によつてもその状態を保持したままで進行する。In the present invention, since this composition is converted into a coacelpacion (precipitate/liquid) prior to film molding, it exhibits two liquid phases with microscopically different polymer concentrations. The process continues while maintaining that state.

従がつて、従来のように成型時に発生するフィルム表面
と内部との空孔率の相違を生じることはない。また、多
量の無機塩を導入しておき、のちにその塩類を抜き出す
方法のように、電気的物性に悪影響を及ぼす塩の残存す
ることがなく、極めて均一性にすぐれた多孔性フイルム
を得ることが出来る。Therefore, there is no difference in porosity between the surface and the inside of the film, which occurs during molding as in the prior art. In addition, unlike the method of introducing a large amount of inorganic salt and later extracting the salt, there is no residual salt that adversely affects electrical properties, and a porous film with extremely high uniformity can be obtained. I can do it.

このようにして得られたフイルムは、その均一性に基づ
く極めてすぐれた力学的性質及び寸法安定性を示す。The film thus obtained exhibits excellent mechanical properties and dimensional stability due to its uniformity.

更に、本発明方法は空孔率又は孔径か、コアセルベーシ
ヨン組成物中の成分の割合又は種類を変えることによつ
て容易に変えることが出来るという大きな利点をもつて
いる。本発明において耐熱性を有する芳香族系重合体と
は、主鎖のかなりの部分が芳香環よりなり、少くとも１
５０℃以上、好ましくは２５０℃以上の軟化点を有し、
少くとも１５０℃以上、好ましくは１８０℃以上の温度
に空気中で長時間使用しても大きな物性の変化を生じな
い重合体を意味する。Furthermore, the method of the present invention has the great advantage that the porosity or pore size can be easily varied by changing the proportions or types of components in the coacervation composition. In the present invention, an aromatic polymer having heat resistance means that a considerable portion of the main chain consists of aromatic rings, and at least one
having a softening point of 50°C or higher, preferably 250°C or higher,
It means a polymer that does not cause any major change in physical properties even when used in air at a temperature of at least 150°C or higher, preferably 180°C or higher for a long time.

かかる重合体としては、例えば次のようなものがあげら
れる。１芳香族ポリアミド １芳香族環を有するジカルボン酸の好適には酸・・ラー
ド等の高活性誘導体と芳香族環を有するジアミンとから
得られる芳香族ポリアミド。Examples of such polymers include the following. 1. Aromatic polyamide 1. An aromatic polyamide obtained from a highly active derivative of a dicarboxylic acid having an aromatic ring, preferably an acid, such as lard, and a diamine having an aromatic ring.

芳香族ジアミンとしては、下式〔１〕及び〔２〕で表わ
される芳香族ジアミン、例えばメタフゴニレンジアミン
、パラフエニレンジアミン、トリレンジアミン、４，４
′−ジアミノジフエニルエーテル、４．４′−ジアミノ
ジフエニルスルフオン、４，４′−ジアミノジフエニル
メタン等があげられる。〔但し、式〔１〕，〔２〕中、
Ｒは水素、炭素数１〜５の低級アルキル基、メトキシ基
、エトキシ基あるいはハロゲン原子である。Examples of aromatic diamines include aromatic diamines represented by the following formulas [1] and [2], such as metaphgonylene diamine, paraphenylene diamine, tolylene diamine, 4,4
Examples include '-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenylmethane. [However, in formulas [1] and [2],
R is hydrogen, a lower alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom.

ＸはＣＨ２−，−０−，−ＣＯ−，−ＳＯ２−，−Ｓ−
である。X is CH2-, -0-, -CO-, -SO2-, -S-
It is.

〕また芳香族環を有するジカルボン酸としては、テレフ
タル酸、イソフタル酸又はこれらの核置換誘導体等があ
げられる。] Examples of the dicarboxylic acid having an aromatic ring include terephthalic acid, isophthalic acid, and nuclear-substituted derivatives thereof.

これらの芳香族ジアミン又は芳香族二塩基酸ジハライド
等は、夫々１種のみからなる場合は勿論、２種以上の混
合物であつても良い。２芳香族環を有するアミノカルボ
ン酸を、好適には活性化して縮合した芳香族ポリアミド
。These aromatic diamines, aromatic dibasic acid dihalides, etc. may be composed of only one type, or may be a mixture of two or more types. An aromatic polyamide obtained by condensing an aminocarboxylic acid having two aromatic rings, preferably by activation.

例えばアミノカルボン酸としては、パラあるいはメタア
ミノ女息香酸、パラアミノメチル安息香酸を使用した１
種のみからのホモポリマーであつても良く、２種以上の
アミノカルボン酸の共重合ポリマーであつても良い。３
前記１２を共重合した芳香族ポリアミド。For example, as the aminocarboxylic acid, para- or meta-aminophenolic acid, para-aminomethylbenzoic acid, etc.
It may be a homopolymer made only from seeds, or it may be a copolymer of two or more kinds of aminocarboxylic acids. 3
An aromatic polyamide obtained by copolymerizing the above 12.

代表的なものとして、例えばメタフエニレンジアミン、
イソフタル酸シクロラード、パラアミノ安息香酸クロラ
イド塩酸塩の３成分からなるポリアミド等があげられる
。２含窒素ポリ複素環状化合物 １芳香族ポリアミドイミド １−１における芳香族ジアミンと、下式〔３〕であられ
される芳香族三塩基酸の高活性誘導体との反応により得
られる式〔４〕で表わされる単位を有する芳香族ポリア
ミドイミド。Representative examples include metaphenylenediamine,
Examples include polyamides consisting of three components: isophthalic acid cyclolade and para-aminobenzoic acid chloride hydrochloride. 2 Nitrogen-containing polyheterocyclic compound 1 Aromatic polyamideimide 1 In the formula [4] obtained by the reaction of the aromatic diamine in the aromatic polyamideimide 1-1 with a highly active derivative of an aromatic tribasic acid represented by the following formula [3] Aromatic polyamideimide having the units shown.

芳香族三塩基酸としては例えばトリメリツト酸無水物が
あげられる。（但し式〔３〕中Ｘはハロゲン原子である
。Examples of aromatic tribasic acids include trimellitic anhydride. (However, in formula [3], X is a halogen atom.

）２芳香族ポリアミドヒドラジド。例えば、テレフタル
酸あるいはイソフタル酸等の芳香族二塩基酸ジヒドラジ
ドと、芳香族二塩基酸ジハライドとの縮合反応によつて
得られる式〔５〕の構造単位を有するポリアミドヒドラ
ジド。) 2 aromatic polyamide hydrazide. For example, a polyamide hydrazide having a structural unit of formula [5] obtained by a condensation reaction between an aromatic dibasic acid dihydrazide such as terephthalic acid or isophthalic acid and an aromatic dibasic acid dihalide.

これらはメチル基、アルコキシル基、ハロゲン原子等の
不活性の置換基を有しても差し支えない。３芳香族ポリ
イミド 例えばピロメリツト酸二無水物で代表される芳香族テト
ラカルボン酸二無水物と、前記１−１であげられな芳香
族ジアミンとから得られる芳香族、ポリイミド。These may have an inert substituent such as a methyl group, an alkoxyl group, or a halogen atom. 3. Aromatic polyimide An aromatic polyimide obtained from an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride and an aromatic diamine not mentioned in 1-1 above.

４４そ０他芳香族ポリベン．ツイミダゾール、ポリベン
ツオキサゾール、ポリベンツチアゾ一歩等夫々対応する
原料（−Ｅ．ノマ一）から溶液重合法によつて得られる
含窒素ポリ複素環状化合物等があげられるが、ここに記
述された以外の芳香族系重合体であつても差し支えな，
い。44 and other aromatic polybens. Examples include nitrogen-containing polyheterocyclic compounds obtained by solution polymerization from the corresponding raw materials (-E. Nomaichi) such as tuimidazole, polybenzoxazole, and polybenzthiazo steppe. There is no problem even if it is a group-based polymer.
stomach.

殊に重合体構成単位の少くとも５０モル俤以上が芳香族
ポリアミドであるものが多孔性フイルムとして良好であ
る。 ・本発明において、耐熱性を
有する芳香族重合体のコアセルベーシヨン組成物は、耐
熱性を有する芳香族重合体と、この重合体に対する良溶
媒と良溶媒に対して不活性かつ相溶性であつてこの重合
体に対する非溶媒の比が１００／０〜７０／３０（重量
比）の範囲内である溶液とからなる。In particular, a porous film in which at least 50 moles or more of the polymer constitutional units is aromatic polyamide is suitable. - In the present invention, the coacelvation composition of a heat-resistant aromatic polymer is inert and compatible with the heat-resistant aromatic polymer, a good solvent for this polymer, and a good solvent. and a solution in which the ratio of nonsolvent to polymer is within the range of 100/0 to 70/30 (weight ratio).

コアセルベーシヨンを形成する為の良溶媒と非溶媒の比
は、耐熱性を有する芳香族重合体の種類、良溶媒に対す
る濃度または溶媒の組み合せにより異なる為、夫々の場
合に応じて実験的に決める必要がある。但し、溶液中の
非溶媒が３０重量％を越えると耐熱性を有する芳香族重
合体は完全に凝集沈澱してしまい、薄膜状に成膜できな
い。The ratio of good solvent to non-solvent for forming a coacervation varies depending on the type of heat-resistant aromatic polymer, the concentration of good solvent, and the combination of solvents, so it must be determined experimentally depending on each case. I need to decide. However, if the nonsolvent in the solution exceeds 30% by weight, the heat-resistant aromatic polymer will completely coagulate and precipitate, making it impossible to form a thin film.

本発明において，これらの耐熱性を有する芳香族系重合
体を溶解すゐ溶媒（良溶媒）としては、例えばＮ，Ｎ−
ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド
．Ｎ−メチル−２−ピロリドン、Ｎ−アセチルビロリジ
ン、テトラメチル尿素、ヘキサメチルボスボルトリアミ
ド等いわゆるアミド系溶媒又はジメチ′スルフオキシド
等があげられる。In the present invention, examples of solvents (good solvents) for dissolving these heat-resistant aromatic polymers include N, N-
Dimethylacetamide, N,N-dimethylformamide. Examples include so-called amide solvents such as N-methyl-2-pyrrolidone, N-acetylpyrrolidine, tetramethylurea, hexamethylvosvortriamide, and dimethysulfoxide.

これらの工蝶単独で使用され得ることは勿論、２種以上
の混合物であつても良いし、必要に応じて溶解性を向上
させる為に例えば塩化リチウム、塩化カルシウム、嘉る
いは塩化マグネシウム等の少量の無機塩を添加しても良
い。更にこれらの有機溶媒のほかに、この重合体を溶解
しうる溶媒として濃硫竺も，李発明畔に，４みいては極
めて有効である。本発明においてこの重合体を実質的に
溶解しない非溶媒とは、室温下でこの重合体を２重量バ
ーセント以上溶解しない溶媒であつて、前記この重合体
を溶解し得る溶媒に対して相溶性かつこの溶媒と混合し
た場合に化学反応を起こさない（不活、性）ものであれ
ばよく、例えば、水、メチルアル？ニル、エテルアルコ
ール、プロピルアルコール等の１価アルコール類、エチ
レングリコール、プロピレングリコール、グリセリン等
の多価アルコ！ル類、ジエチルエーテル、ジオキサン等
のエーテル類、塩化メチレン、クロロホルム等のハロゲ
ン，化炭化水素類、酢酸エチルなどのエステル類等があ
げられるが、ここに例示したものに限られるものではな
い。It goes without saying that these plants can be used alone or as a mixture of two or more, and if necessary, lithium chloride, calcium chloride, chloride, magnesium chloride, etc. can be used to improve solubility. A small amount of inorganic salt may be added. Furthermore, in addition to these organic solvents, concentrated sulfur is also extremely effective as a solvent capable of dissolving this polymer. In the present invention, a non-solvent that does not substantially dissolve the polymer is a solvent that does not dissolve the polymer by more than 2% by weight at room temperature, and is compatible with the solvent that can dissolve the polymer. Any substance that does not cause a chemical reaction (inert, active) when mixed with this solvent is sufficient; for example, water, methylalkaline, etc. Monohydric alcohols such as alcohol, ether alcohol, and propyl alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin! Examples include ethers such as diethyl ether and dioxane, halogens such as methylene chloride and chloroform, hydrogenated hydrocarbons, and esters such as ethyl acetate, but are not limited to those exemplified here.

但しこの重合体を溶解しうる溶媒が濃硫酸である場合に
は非溶媒としては水が望ましい。本目的を達成する為に
、コアセルペーシヨン（析・液）化しうる組成物溶液を
調整するには、この重合体を溶解し得る溶媒に溶解した
のち、非溶媒を加える方法、溶媒と非溶媒との混合溶媒
に溶解する方法、又はアミド系溶媒中で溶液重合法を行
つて得られた重合体溶液そのまま若しくは希釈、濃縮、
中和などの処理をほどこして得られる溶液に、非溶媒を
加える等いずれの方法でも良い。However, when the solvent that can dissolve this polymer is concentrated sulfuric acid, water is preferable as the non-solvent. To achieve this purpose, in order to prepare a composition solution that can be converted into coacelpation, there is a method of dissolving this polymer in a solvent that can dissolve it, and then adding a non-solvent. A method of dissolving in a mixed solvent with a solvent, or a polymer solution obtained by performing a solution polymerization method in an amide solvent, or as it is, diluted, concentrated,
Any method may be used, such as adding a non-solvent to a solution obtained through a process such as neutralization.

この重合体の濃度は、重合体の構造又は溶媒の種類、組
合せ等により異なるが、溶解しうる溶媒に対して、５〜
４０重量パーセントが好ましい。また重合体の種類、溶
媒の種類又はこれらの組合せによつてある特定な場合に
は、物理的条件のみを変えることによつて、非溶媒を加
えることなしにコアセルベーシヨン（析・液）化しうる
こともあり、この場合も本発明中に含まれる。例えば、
重合体としてポリメタフエニレンイソフタルアミド、４
−４′−ジアミノジフエニルメタンとイソフタル酸シク
ロラードから得られるポリアミド若しくはこれらの芳香
族ジアミン成分、芳香族二塩基酸成分の一部を夫々他の
芳香族ジアミン他の芳香族・族二塩基酸成分に加えた共
重合体等をＮ−メチル−２−ピロリドンに５０℃以上の
温度で溶解したのち、室温付近又はそれ以下の温度に冷
却することによつてコアセルベーシヨン（析・液）化す
ることが出来る。このようにして得られた組成物はつい
で、ダイ方式など従来公知の方法により熱風雰囲気（乾
式成型）あるいは凝固浴中（湿式成型）に押し出し成膜
される。The concentration of this polymer varies depending on the structure of the polymer, the type and combination of solvents, etc., but the concentration of this polymer varies depending on the structure of the polymer and the type and combination of solvents.
40 weight percent is preferred. In certain specific cases depending on the type of polymer, type of solvent, or a combination thereof, coacervation can be achieved without adding a non-solvent by changing only the physical conditions. This may also be included in the present invention. for example,
Polymetaphenylene isophthalamide as a polymer, 4
Polyamide obtained from -4'-diaminodiphenylmethane and cyclolade isophthalate, or a part of these aromatic diamine components and aromatic dibasic acid components, respectively, into other aromatic diamines and other aromatic/group dibasic acid components After dissolving the copolymer etc. added to N-methyl-2-pyrrolidone at a temperature of 50°C or higher, it is converted into coacervation by cooling to a temperature around room temperature or lower. You can. The composition thus obtained is then extruded into a film by a conventionally known method such as a die method in a hot air atmosphere (dry molding) or in a coagulation bath (wet molding).

熱風雰囲気中に押し出す乾式成膜法においては、その温
度は実質的に溶媒が蒸発しうる温度であれば差し支えな
いが、特に８０℃〜４００℃が良い。２５０℃以上の高
温の場合には、一部溶媒の分解などにより得られるフイ
ルムが着色することがあるので、不活性ガス例えば窒素
、アルゴン等を用いることが好ましい。In the dry film forming method in which the film is extruded into a hot air atmosphere, the temperature may be any temperature as long as the solvent can substantially evaporate, but 80°C to 400°C is particularly preferable. In the case of a high temperature of 250° C. or higher, the film obtained may be colored due to partial decomposition of the solvent, so it is preferable to use an inert gas such as nitrogen or argon.

湿式成型法において使用される凝固浴は、例えば、メタ
ノール、エタノール、エチレングリコール、プロピレン
グリコール、グリセリン等の１価あるいは多価アルコー
ル及びその水溶液、アミド系溶媒の水溶液、塩化カルシ
ウム、塩化リチウム、塩化マグネシウム、硝酸カルシウ
ム等の無機塩の水溶液叉はこれらの塩とアミド系溶媒、
水との３成分からなる組成液等があげられるが、ここに
記載されたものに限られるものではない。実質的に重合
体を溶解せず、かつ、本発明の組成物を形成しているこ
の重合体の溶媒あるいは非溶媒に相溶性のものであれば
よく、特に、経済上あるいは取扱い操作上から、水又は
無機塩の水溶液又は無機塩−アミド系溶媒水溶液がよい
。このようにして成型されたフイルムは、乾式又は湿式
いずれの方法で得られたものも、溶媒又は非溶媒等を含
んでいるため、水洗工程によつて洗浄されたのち実用に
供されるが、必要な場合には力学的性質を向上する目的
で、得られたフイルムを延伸及び／又は熱処理がほどこ
される。Coagulation baths used in the wet molding method include, for example, monohydric or polyhydric alcohols such as methanol, ethanol, ethylene glycol, propylene glycol, and glycerin and their aqueous solutions, aqueous solutions of amide solvents, calcium chloride, lithium chloride, and magnesium chloride. , an aqueous solution of inorganic salts such as calcium nitrate, or these salts and an amide solvent,
Examples include composition liquids consisting of three components including water, but are not limited to those described here. Any material may be used as long as it does not substantially dissolve the polymer and is compatible with the solvent or non-solvent of the polymer forming the composition of the present invention. Water, an aqueous solution of an inorganic salt, or an aqueous solution of an inorganic salt-amide solvent is preferable. Films formed in this way, whether obtained by dry or wet methods, contain solvents or non-solvents, so they are washed in a water washing process before being used for practical use. If necessary, the obtained film is subjected to stretching and/or heat treatment for the purpose of improving mechanical properties.

熱処理の条件は重合体の種類、用途等により異なるが、
加熱によつてかかるフイルムは数パーセント収縮を起こ
すので、熱処理は、フイルムを緊張下に１５０℃以上で
行うかまたはたて方向、よこ方向、又はたて、よこ両方
向に延伸しながら行う方法が好ましい。Heat treatment conditions vary depending on the type of polymer, application, etc.
Since such a film shrinks by several percent when heated, it is preferable to heat the film under tension at 150° C. or higher, or while stretching the film in the vertical direction, horizontal direction, or both vertical and horizontal directions. .

加熱は熱板加熱、雰囲気加熱、赤外線加熱、マイクロ波
加熱などのいずれの方法でも良いが、特に２５０℃以上
の高温で処理する場合には熱劣化を防ぐ為に窒素、アル
ゴン等の不活性ガス中で行うことが望ましい。このよう
にして本発明法によつて得られた多孔性フイルムの孔径
は、走査型電子顕微鏡によつて測定されるが、数Ｘ〜１
００μであり、空孔率は次式（１）で測定算出される値
で３０パーセント以上である。Heating can be done using any method such as hot plate heating, atmospheric heating, infrared heating, or microwave heating, but especially when processing at a high temperature of 250°C or higher, use an inert gas such as nitrogen or argon to prevent thermal deterioration. It is preferable to do it inside. The pore diameter of the porous film thus obtained by the method of the present invention is measured by a scanning electron microscope, and is several times
00μ, and the porosity is 30% or more as measured and calculated using the following equation (1).

ノ またＪＩＳＣ２３ｌ３の方法により測定される電池用セ
パレーター膜としての電気抵抗は０．００４Ω−１００
ｃｄ／枚、多くの場合０．００２Ω／１００ｃｄ／枚以
下であつて、極めてすぐれたセバレータ一膜としての性
質を示す。Also, the electrical resistance as a battery separator film measured by the method of JISC23l3 is 0.004Ω-100
CD/sheet, in most cases 0.002Ω/100cd/sheet or less, and exhibits extremely excellent properties as a separator film.

本発明によつて製造された多孔性フイルムは、前述の電
池用セパレーター膜以外の用途として、力学的性質、耐
熱、耐薬品性等にすぐれていることから、逆浸透用膜、
タンパク質溶液の濃縮、電気透析用膜等として広く使用
することが出来る。The porous film produced by the present invention has excellent mechanical properties, heat resistance, chemical resistance, etc., and can be used as a reverse osmosis membrane, in addition to the above-mentioned battery separator membrane.
It can be widely used as a membrane for concentrating protein solutions, electrodialysis, etc.

次に本発明における主要な―定値について、測定方法の
説明、及び実施例によつてより詳細に説明する。固有粘
度；９５％硫酸中で濃度０，５９／１００（η１ｎｈ）
ｍｌとして３０℃で測定した。Next, the main constant values in the present invention will be explained in more detail by explaining the measurement method and examples. Intrinsic viscosity: Concentration 0.59/100 (η1nh) in 95% sulfuric acid
Measured as ml at 30°C.

引張り強；ＪＩＳＰ８ｌｌ３の方法に準じて行伸度
い匂／ｄ及びパーセントで表わした。電気抵抗；ＪＩ
ＳＣ２３ｌ３の方法に準じて行いΩ・１００Ｃ１！ｌ／
枚で表わした。Tensile strength: Line elongation according to JISP8ll3 method
Expressed as odor/d and percentage. Electrical resistance; JI
Performed according to the method of SC23l3 Ω・100C1! l/
Expressed in sheets.

空孔率；重合体の密度と得られたフイルムの見かけ密度
より本文中（１）式により算出しバーセントで表わした
。Porosity: Calculated from the density of the polymer and the apparent density of the obtained film using the formula (1) in the text and expressed in percent.

孔 径；走査型電子顕微鏡により測定しｘあるいはμ
で表ゎした。Pore diameter: x or μ measured using a scanning electron microscope
It was expressed as.

耐薬品性：４０重量パーセントＫＯＨ水溶液ω℃、７日
間浸債前後の重量減少をパーセントで表わした。Chemical resistance: The weight loss before and after soaking in a 40 weight percent KOH aqueous solution at ω°C for 7 days was expressed as a percentage.

実施例 １ 塩化リチウム３０ｆＩを溶解したＮ，Ｎ−ジメチルアセ
トアミド８２０ｆ！．に、固有粘１η１ｎｈ１．５２で
あるポリメタフエニレンイソフタルアミド１８０９を加
えて溶解した。Example 1 820f of N,N-dimethylacetamide in which 30fI of lithium chloride was dissolved! ．． Polymetaphenylene isophthalamide 1809 having an intrinsic viscosity of 1η1nh1.52 was added and dissolved.

ついてこの溶液に室温下９８．８ｇの水を添加撹拌Ｌ１
白濁した組成溶液を得た。この組成溶液をガラス板上に
梳延し、１４０℃に設立された熱風循環乾燥機に入れ２
０分間乾燥したのち、水中に取り出し水洗、乾燥した。
得られたフイルムは半透明であつた。このフイルムの物
性値は次のどうりであり電池用セパレーター膜として極
めてすぐれたものであつた。孔 径”０．１〜５．
０μ 空孔率゛４８ｑ６ 引張り強度 １１．３ＫＩ１／ｉ 引張り・伸度 １＆８ｑ６ 電気抵抗 ０．００１４Ω１００ｃｆ１１／枚耐薬品性
２．５％以下実施例 ２〜４ 実施例１と同樺の方法により、水の添加割合を変えてフ
イルムを製造した。Add 98.8 g of water to this solution at room temperature and stir L1.
A cloudy composition solution was obtained. This composition solution was combed onto a glass plate and placed in a hot air circulation dryer set at 140℃ for 2 hours.
After drying for 0 minutes, it was taken out into water, washed with water, and dried.
The resulting film was translucent. The physical properties of this film were as follows, and it was extremely excellent as a battery separator film. Hole diameter"0.1~5.
0μ Porosity゛48q6 Tensile strength 11.3KI1/i Tensile/elongation 1&8q6 Electrical resistance 0.0014Ω100cf11/sheet Chemical resistance 2.5% or less Examples 2 to 4 By the same method as in Example 1, water Films were produced by changing the addition ratio.

その結果を表１に示した。実施例 ５ 実施例１と全く同様の方法により、非溶液としてエタノ
ール９８．８９を加えた溶液を調製し、多孔性フイール
ムを得た。The results are shown in Table 1. Example 5 In exactly the same manner as in Example 1, a solution to which 98.89% of ethanol was added as a non-solution was prepared, and a porous film was obtained.

このフイルムの物性は次の通りであつた。３孔 径；
０．０５〜３．０μ ・．５空孔率：４．９％ 引張り強度；９．３！Ｔｉ 引張り伸度；１６．４％ 電気抵抗；０．００１６Ω・１００ｃｆｉ１／枚実施例
６実施例１で得られたフイルムを３００℃．２分間Ｎ
，気流中で緊張下に熱処理を行つたところ、フイルムの
引張り強度は１５．３Ｋｆ／Ｄ，伸度７．３％であつた
。The physical properties of this film were as follows. 3 holes diameter;
0.05~3.0μ・. 5 Porosity: 4.9% Tensile strength: 9.3! Ti Tensile elongation: 16.4% Electrical resistance: 0.0016Ω・100cfi1/sheet Example 6 The film obtained in Example 1 was heated at 300°C. 2 minutes N
When the film was heat treated under tension in an air stream, the tensile strength of the film was 15.3 Kf/D and the elongation was 7.3%.

実施例 ７ 固有粘度１．４８のポリメタフエニレンイソフタルア５
ミド４５．０９を、Ｎ−メチル−２−ビロリドン１９８
ｍ１Ｋ９０℃の温度を保つて熱溶解した。Example 7 Polymetaphenylene isophthalene 5 with an intrinsic viscosity of 1.48
Mido 45.09, N-methyl-2-pyrrolidone 198
The temperature of m1K was maintained at 90°C for hot melting.

得られた透明な溶液を１０℃まで冷却することによつて
失透した組成溶液を得た。溶液の粘度は２８５０ボイズ
（１０℃）であつた。この溶液を実施例１と同様にガラ
ス板上に流延し、一方は実施例１と同時に熱風乾燥機で
乾式成型し、他方は濃度３５重量パーセントの塩化カル
シウム水溶液に投じ湿式成型した。それぞれ得られたフ
イルムを水洗乾燥した。得られたフィルムの物性を表２
に示した。実施例 ８ トリメリツト酸無水物クロライドと４，４′ジアミノジ
フエニルメタンとの溶液重合によつて得られた固有粘度
η１ｎｈ１．１７のポリアミドイミドを実施例１と同様
にして溶液を調製し、乾式法により多孔性フイルムを得
た。The resulting transparent solution was cooled to 10° C. to obtain a devitrified composition solution. The viscosity of the solution was 2850 boids (10°C). This solution was cast onto a glass plate in the same manner as in Example 1, and one part was dry molded in a hot air dryer at the same time as in Example 1, and the other part was wet molded by pouring it into an aqueous calcium chloride solution having a concentration of 35% by weight. The respective films obtained were washed with water and dried. Table 2 shows the physical properties of the obtained film.
It was shown to. Example 8 A solution of polyamideimide having an intrinsic viscosity of η1nh1.17 obtained by solution polymerization of trimellitic anhydride chloride and 4,4' diaminodiphenylmethane was prepared in the same manner as in Example 1, and a solution was prepared by dry method. A porous film was obtained.

得られたフイルムは淡黄色の半透明であり、物性は次の
通りであつた。孔 径゜０．０５〜０．５μ 空孔率゜４３（ｆ） 引張り強度”９．４Ｋｆ／１１２ 引張り伸度゜７．９（Ｆ６ 電気抵抗゜０．００２５Ω・１００ｃｒ！ｉ／枚耐薬品
性゜３．４％以下実施例 ９ ５００ｍ１（７）Ｎ，Ｎ−ジメチルアセトアミド中に４
，４′ジアミノジフエニルメタン５３．５９及びパラフ
エニレンジアミン３．２９を溶解し、これに粉末状のイ
ソフタル酸シクロラード６０．９９を一時に加えて重合
反応を行つた。The obtained film was pale yellow and translucent, and its physical properties were as follows. Pore diameter゜0.05~0.5μ Porosity゜43(f) Tensile strength 9.4Kf/112 Tensile elongation゜7.9(F6 Electrical resistance゜0.0025Ω・100cr!i/sheet Chemical resistance゜3.4% or less Example 9 4 in 500ml (7) N,N-dimethylacetamide
, 4'diaminodiphenylmethane (53.59 g) and paraphenylene diamine (3.29 g.g.) were dissolved, and 60.99 g. of powdered cyclolade isophthalate was added at once to carry out a polymerization reaction.

得られた重合体溶液の１部を、ミキサー中で撹拌されて
いる水中にとり、重合体を得た。この重合体の固有粘度
ηＩｎｈは１．８７を示した。残りの重合体溶液に水酸
化カルシウムを加えて重合反応中に副生し、塩酸を中和
後、溶媒のＮ，Ｎ−ジメチルアセトアミドに対して、７
．５重量パーセントの水を添加攪拌した。この溶液を塗
付し、実施例１と同様にして多孔性フィルムを得た。こ
のフィルムの物性は次の通りであつた。孔 径；０
．００３〜０．０１μ 空孔率；４１％ 引張り強度；１２．５Ｋｆ／ｄ 引張り伸度：１７．３％ 電気抵抗；０．００１８Ω・１００ｃｄ／枚耐薬品性；
２．０％以下実施例 １０ １０００ｍ１ｆ）Ｎ−メチル−２−ピロリドンに塩化カ
ルシウム３３．３ｆ１及びパラフエニレンジアミン１６
．２９を溶解し、０．℃に冷却した。A portion of the resulting polymer solution was placed in water being stirred in a mixer to obtain a polymer. The intrinsic viscosity ηInh of this polymer was 1.87. Calcium hydroxide was added to the remaining polymer solution to form a by-product during the polymerization reaction, and after neutralizing the hydrochloric acid, 7%
．． 5 weight percent water was added and stirred. This solution was applied to obtain a porous film in the same manner as in Example 1. The physical properties of this film were as follows. Hole diameter: 0
．． 003~0.01μ Porosity: 41% Tensile strength: 12.5Kf/d Tensile elongation: 17.3% Electrical resistance: 0.0018Ω・100cd/sheet Chemical resistance;
2.0% or less Example 10 1000ml f) Calcium chloride 33.3f1 and paraphenylenediamine 16% in N-methyl-2-pyrrolidone
．． 29 and 0. Cooled to ℃.

ついで、粉末状のテレフタル酸シクロラード３１．５９
を一時に加えて重合させた。得られた重合体溶液の一部
を実施例９と同様の処理を行つて固有粘度ηＩｎｈを測
定した。ηＩｎｈは３．８１であつた。残りの重合体溶
液に非溶媒として水を、Ｎ−メチル−２一ピロリドンに
対して８．５重量パーセントとなるように加えて撹拌し
た。この溶液から実施例１と同様の方法により乾式成型
を行い、黄色半透明の多孔性フイルムを得た。このフイ
ルムの孔径は０．００５〜０．０１μであり、空孔率は
４３．５Ｃｆ１）であつた。Next, powdered cyclolade terephthalate 31.59
was added at once to polymerize. A portion of the obtained polymer solution was treated in the same manner as in Example 9, and the intrinsic viscosity ηInh was measured. ηInh was 3.81. Water was added as a nonsolvent to the remaining polymer solution in an amount of 8.5% by weight based on N-methyl-2-pyrrolidone, and the mixture was stirred. This solution was dry-molded in the same manner as in Example 1 to obtain a yellow translucent porous film. The pore diameter of this film was 0.005 to 0.01μ, and the porosity was 43.5Cf1).

実施例 １１ 固有粘度１．６３のポリメタフエニレンイソフタルアミ
ド及び実施例９で用いられたものと同一のポリアミド共
重合体（固有粘度ηＩｎｈｌ．７２）の等量混合物を、
９５パーセント硫酸に濃度が１８重量パーセントとなる
ようにとかし、ついで溶媒が８５パーセント硫酸となる
ように水を加えた。Example 11 An equal mixture of polymetaphenylene isophthalamide with an intrinsic viscosity of 1.63 and the same polyamide copolymer as used in Example 9 (intrinsic viscosity ηInhl.72) was
It was dissolved in 95% sulfuric acid to a concentration of 18% by weight, and then water was added so that the solvent was 85% sulfuric acid.

ついでこの溶液をカラス板上に流延したものを３０パー
セント濃度の希硫酸に対して１０重量パーセント濃度と
なるように硫酸ナトリウムを溶解し調製した凝固浴中に
投じて湿式成型膜を得た、このフイルムの物性は次の通
りであつた。孔 径；０．０１〜１．０μ 空孔率；４７％ 引張り強度；７．１！／Ｍｉ 引張り伸度；１５．３ｑ６ 電気抵抗：０．００１Ω・１００ｃｆｉ１／枚実施例
１２固有粘度４．３８のポリパラフエニレンテレフタル
アミドを、９９．８バーセント硫酸に濃度が１２重量パ
ーセントとなるように６０℃で溶解した。This solution was then cast onto a glass plate and poured into a coagulation bath prepared by dissolving sodium sulfate to a concentration of 10% by weight in dilute sulfuric acid of 30% concentration to obtain a wet-molded membrane. The physical properties of this film were as follows. Pore diameter: 0.01-1.0μ Porosity: 47% Tensile strength: 7.1! /Mi Tensile elongation; 15.3q6 Electrical resistance: 0.001Ω・100cfi1/sheet Example
12 Polyparaphenylene terephthalamide having an intrinsic viscosity of 4.38 was dissolved in 99.8 percent sulfuric acid at 60° C. to a concentration of 12 weight percent.

この重合体の濃硫酸溶液は光学異方性を示した。ついで
６０℃に保つたまま徐々に水を加えて、９６パーセント
濃度となるように調製した。この溶液から実施例１１と
同様の操作により多孔性フィルムを得た。このフィルム
の物性は次の通りであつた。A concentrated sulfuric acid solution of this polymer showed optical anisotropy. Then, while maintaining the temperature at 60° C., water was gradually added to adjust the concentration to 96%. A porous film was obtained from this solution in the same manner as in Example 11. The physical properties of this film were as follows.

孔 径：０．００５〜０．１μ 空孔率；４４％ 引張り強度；１８．３！／ｉ 引張り伸度；５．２％Pore diameter: 0.005~0.1μ Porosity: 44% Tensile strength: 18.3! /i Tensile elongation: 5.2%

Claims (1)

【特許請求の範囲】 １ 耐熱性を有する芳香族重合体と、この重合体に対す
る良溶媒と良溶媒に対して不活性かつ、相溶液であつて
この重合体に対する非溶媒の比が１００／０〜７０／３
０（重量比）でおる耐熱性を有する芳香族重合体のコア
セルベイション（析・液）組成物を成膜することを特徴
とする多孔性フイルムの製造方法。 ２ 特許請求の範囲第１項において、耐熱性を有する芳
香族重合体の濃度は、良溶媒に対して５〜〜４０重量％
であることを特徴とする多孔性フィルムの製造方法。 ３ 特許請求の範囲第１項において、耐熱性を有する芳
香族系重合体構成単位の少くとも５０モルパーセント以
上が芳香族ポリアミドであることを特徴とする多孔性フ
ィルムの製造方法。 ４ 特許請求の範囲第１項において、コアセルベーショ
ン（析・液）組成物の一成分として、耐熱性を有する芳
香族重合体を５重量％以上溶解するアミド系溶媒を含む
ことを特徴とする多孔性フィルムの製造方法。 ５ 特許請求の範囲第１項において、コアセルベーショ
ン（析・液）組成物の一成分として濃硫酸を含むことを
特徴とする多孔性フィルムの製造方法。[Scope of Claims] 1. A heat-resistant aromatic polymer, a good solvent for this polymer, and an inert and phase solution with respect to the good solvent, in which the ratio of the non-solvent to the polymer is 100/0. ~70/3
A method for producing a porous film, which comprises forming a coacervation composition of an aromatic polymer having a heat resistance of 0 (weight ratio). 2 In claim 1, the concentration of the heat-resistant aromatic polymer is 5 to 40% by weight based on the good solvent.
A method for producing a porous film, characterized in that: 3. The method for producing a porous film according to claim 1, characterized in that at least 50 mol percent or more of the heat-resistant aromatic polymer structural units are aromatic polyamide. 4. Claim 1 is characterized in that the coacervation (deposition/liquid) composition contains, as a component, an amide solvent that dissolves 5% by weight or more of a heat-resistant aromatic polymer. Method for producing porous film. 5. The method for producing a porous film according to claim 1, characterized in that the coacervation (deposition/liquid) composition contains concentrated sulfuric acid as one component.
JP14943476A 1976-12-14 1976-12-14 Method for manufacturing porous film Expired JPS5936939B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14943476A JPS5936939B2 (en) 1976-12-14 1976-12-14 Method for manufacturing porous film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14943476A JPS5936939B2 (en) 1976-12-14 1976-12-14 Method for manufacturing porous film

Publications (2)

Publication Number Publication Date
JPS5374572A JPS5374572A (en) 1978-07-03
JPS5936939B2 true JPS5936939B2 (en) 1984-09-06

Family

ID=15475019

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPS5936939B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0757071A3 (en) * 1995-07-18 1997-02-19 Sumitomo Chemical Company, Limited Para-aromatic polyamide porous film
WO2001019906A1 (en) * 1999-09-13 2001-03-22 Teijin Limited Polymethaphenylene isophthalamide based polymer porous film, method for producing the same and separator for cell
JP2001329104A (en) * 2000-05-23 2001-11-27 Teijin Ltd Porous film of para-type aromatic polyamide

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6081852B2 (en) * 2013-04-12 2017-02-15 株式会社Kri Method for producing polysaccharide porous body
JP2020158640A (en) * 2019-03-27 2020-10-01 帝人株式会社 Para-type total aromatic polyamide film and method for producing the same, and separator containing said film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0757071A3 (en) * 1995-07-18 1997-02-19 Sumitomo Chemical Company, Limited Para-aromatic polyamide porous film
WO2001019906A1 (en) * 1999-09-13 2001-03-22 Teijin Limited Polymethaphenylene isophthalamide based polymer porous film, method for producing the same and separator for cell
JP4794104B2 (en) * 1999-09-13 2011-10-19 帝人株式会社 POLYMETHAPHENYLENEISOPHALAMIDE POLYMER MEMBRANE, PROCESS FOR PRODUCING THE SAME, AND SEPARATOR
JP2001329104A (en) * 2000-05-23 2001-11-27 Teijin Ltd Porous film of para-type aromatic polyamide

Also Published As

Publication number Publication date
JPS5374572A (en) 1978-07-03

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