JPH02222430A - Microcellular aromatic polyamide film - Google Patents
Microcellular aromatic polyamide filmInfo
- Publication number
- JPH02222430A JPH02222430A JP4342789A JP4342789A JPH02222430A JP H02222430 A JPH02222430 A JP H02222430A JP 4342789 A JP4342789 A JP 4342789A JP 4342789 A JP4342789 A JP 4342789A JP H02222430 A JPH02222430 A JP H02222430A
- Authority
- JP
- Japan
- Prior art keywords
- film
- aromatic polyamide
- expansion coefficient
- stock solution
- water
- 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
- 239000004760 aramid Substances 0.000 title claims abstract description 14
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000011550 stock solution Substances 0.000 abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 9
- 239000002798 polar solvent Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000005266 casting Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 64
- 239000011148 porous material Substances 0.000 description 16
- 229940057995 liquid paraffin Drugs 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000037303 wrinkles Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007791 dehumidification Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、耐熱性、湿度安定性、耐薬品性に優れた微孔
性芳香族ポリアミドフィルムに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a microporous aromatic polyamide film having excellent heat resistance, humidity stability, and chemical resistance.
[従来の技術]
微孔性フィルムとしては、ポリプロピレンを始めとした
ポリオレフィン系のものが知られているが耐熱性、耐薬
品性に乏しく、例えば電解コンデンサのセパレータ用途
などでは年々より高温での寸法安定性を必要とされてき
ており、これらのフィルムでは経時変化によるフィルム
劣化のため長期信頼性に欠けるなどの問題がでてきた。[Conventional technology] Polyolefin-based films such as polypropylene are known as microporous films, but they have poor heat resistance and chemical resistance, and their dimensions at higher temperatures are increasing year by year when used as separators in electrolytic capacitors, for example. Stability has been required, and problems have arisen with these films, such as a lack of long-term reliability due to film deterioration due to changes over time.
耐熱性、耐薬品性ともに優れているフィルムとしては芳
香族ポリアミドフィルムが知られており、多孔性芳香族
ポリアミドフィルムの製造方法についても特公昭59−
14494や59−36939に記載されている。Aromatic polyamide film is known as a film that is excellent in both heat resistance and chemical resistance, and a method for producing porous aromatic polyamide film was also published in Japanese Patent Publication No. 1983-
14494 and 59-36939.
[発明が解決しようとする課題]
しかしながら、電解コンデンサなどはさらに使用温度が
高くなっていく傾向が見られ、該方法で製造されたフィ
ルムでも耐熱性が不十分になってきており、たとえば、
電解コンデンサのセパレーターとして用いた場合、巻き
じまりや巻きだるみが発生し導通するなど長期安定性に
欠ける。また、湿度膨張係数や吸湿率が大きく、寸法安
定性に欠けており、水系の電解液を使用する用途には使
用できないことが明らかになってきた。[Problems to be Solved by the Invention] However, there is a tendency for electrolytic capacitors to be used at higher temperatures, and even films produced by this method have insufficient heat resistance.
When used as a separator for electrolytic capacitors, it lacks long-term stability as it tends to curl or sag, resulting in conductivity. Furthermore, it has become clear that they have large humidity expansion coefficients and moisture absorption rates, lack dimensional stability, and cannot be used in applications that use aqueous electrolytes.
本発明は、耐熱性、耐薬品性、湿度寸法安定性に優れて
いる微孔性芳香族ポリアミドフィルムを提供することを
目的とするものである。An object of the present invention is to provide a microporous aromatic polyamide film that has excellent heat resistance, chemical resistance, and humidity dimensional stability.
[課題を解決するための手段]
本発明は、連続する微孔を有する芳香族ポリアミドフィ
ルムであって、少なくとも縦方向の湿度膨張係数が50
X 10−6cm/am/RH%以下、少なくとも縦
方向の100〜300℃の温度範囲における収縮応力が
2 kg/mm2以下であることを特徴とする微孔性芳
香族ポリアミドフィルムに関するものである。[Means for Solving the Problems] The present invention provides an aromatic polyamide film having continuous micropores, the film having a humidity expansion coefficient of at least 50 in the longitudinal direction.
The present invention relates to a microporous aromatic polyamide film having a shrinkage stress of 2 kg/mm2 or less in a temperature range of 100 to 300° C. in at least the longitudinal direction.
本発明の芳香族ポリアミドとは一般式
%式%
で示される繰り返し単位を50モル%以上含む重合体か
ら成るものが好ましい。The aromatic polyamide of the present invention is preferably a polymer containing 50 mol% or more of repeating units represented by the general formula %.
ここでArl 、Ar2は少なくとも一個の芳香環を含
み、同一でも異なっていてもよく、これらの代表例とし
ては次のものが挙げられる。Here, Arl and Ar2 contain at least one aromatic ring and may be the same or different, and representative examples thereof include the following.
ハロゲン基(特に塩素)、ニトロ基、01〜C1のアル
キル基(特にメチル基)、C□〜C5のアルコキシ基な
どの置換基で置換されているものも含む。また、Xは、
−0−−CH2−
−5o2−、−s−、−co−などである。これらは単
独または共重合の形で含まれる。It also includes those substituted with substituents such as a halogen group (especially chlorine), a nitro group, an 01-C1 alkyl group (especially a methyl group), and a C□-C5 alkoxy group. Also, X is
-0--CH2- -5o2-, -s-, -co-, etc. These may be included alone or in copolymerized form.
アルキル基や−CH2−を有するポリマは、ポリマ溶液
中での溶解性が置換基のないものより向上し、無機塩と
の相性がよくなり非常に細かい細孔を得られるので、好
ましい。また、ハロゲン基を有するものは、特に吸湿率
が低くなりより好ましい。Polymers having an alkyl group or -CH2- are preferred because their solubility in a polymer solution is improved over those without substituents, their compatibility with inorganic salts is good, and very fine pores can be obtained. Moreover, those having a halogen group are particularly preferable because they have a low moisture absorption rate.
例えば、
(ここでI)+Q≧1)
また、これらの芳香環の環上の水素の一部が、(ここで
Q=O〜4)
(ここでq=−Q〜4)
などを50モル%以上含むポリマが挙げられる。For example, (here I)+Q≧1) Also, if some of the hydrogens on the aromatic rings are (here Q=O~4) (here q=-Q~4), etc., 50 mol % or more.
本発明は、上記の一般式で示される基本構成単位を50
モル%以上、好ましくは70モル%以上含むことが必要
である。上記範囲より少ないと、耐熱性が低下して、本
発明の目的を達成することができない。50モル%未満
の共重合成分は、特に限定されるものではなく、エステ
ル結合、ウレタン結合、イミド結合、複素環結合などを
含有していてもよい。なお、機械特性、耐熱性の優れた
フィルムを得るには、ポリマとしては、固有粘度(ポリ
マ0.5gを臭化リチウム2.5重量%を含むN−メチ
ルピロリドンで100m1の溶液として、30℃で測定
した値)は0.5〜6.0が好ましい。The present invention comprises 50 basic structural units represented by the above general formula.
It is necessary to contain at least 70 mol%, preferably at least 70 mol%. If it is less than the above range, the heat resistance will deteriorate and the object of the present invention cannot be achieved. The copolymerization component of less than 50 mol% is not particularly limited, and may contain ester bonds, urethane bonds, imide bonds, heterocyclic bonds, and the like. In order to obtain a film with excellent mechanical properties and heat resistance, the intrinsic viscosity of the polymer (0.5 g of the polymer is dissolved in 100 ml of N-methylpyrrolidone containing 2.5% by weight of lithium bromide at 30° C. The value measured in ) is preferably 0.5 to 6.0.
また、本発明の芳香族ポリアミドにはフィルムの物性を
損わない程度に、滑剤、酸化防止剤、その他の添加剤等
や、また他のポリマがブレンドされていてもよい。Further, the aromatic polyamide of the present invention may be blended with lubricants, antioxidants, other additives, and other polymers to the extent that the physical properties of the film are not impaired.
本発明の微孔性フィルムとは、空孔径が0.1nm以上
100μm以下、好ましくはlnm以上10μm以下、
空孔率が20%以上90%以下のものをいう。連続する
微孔とはフィルムの表裏に微孔が連続していることを意
味し、流動パラフィン透過時間が0.5秒以上5秒以下
のものをいう。The microporous film of the present invention has a pore diameter of 0.1 nm or more and 100 μm or less, preferably 1 nm or more and 10 μm or less,
The porosity is 20% or more and 90% or less. Continuous pores mean that pores are continuous on the front and back sides of the film, and mean that the liquid paraffin permeation time is 0.5 seconds or more and 5 seconds or less.
また、本発明の微孔性フィルムの少な(とも縦方向の湿
度膨張係数は50 X 10−6cm/cm/%RH以
下が必要であり、20 X 10−6cm/cm/%R
H以下が好ましい。これより大きいと例えばフィルムを
巻回して用いた場合、湿度変化によってフィルムにしわ
などが入り電気特性を悪化させる原因となる。In addition, the microporous film of the present invention must have a humidity expansion coefficient of 50 X 10-6 cm/cm/%RH or less in the vertical direction, and a humidity expansion coefficient of 20 X 10-6 cm/cm/%R.
H or less is preferable. If it is larger than this, for example, when the film is used in a wound manner, the film may be wrinkled due to changes in humidity, causing deterioration of electrical characteristics.
さらにフィルムの吸湿率は、好ましくは5%以下、より
好ましくは4%以下である。これより大きいと、水分の
影響で電気特性が悪化してしまう。Further, the moisture absorption rate of the film is preferably 5% or less, more preferably 4% or less. If it is larger than this, the electrical characteristics will deteriorate due to the influence of moisture.
また、少なくとも縦方向の100〜300℃の温度範囲
における収縮応力は2 kg/mm’以下が必要である
。これより大きいと高温で使用した際フィルムにしわな
どが入り電気特性などを悪化させる。好ましくはl k
g/mm2以下である。また、熱膨張係数は、5 x
l Q−6cm/cm/℃以上50X10−6cm/c
o+/℃以下が好ましい。この範囲外では、温度変化に
よってフィルムにしわなどが入り電気特性を悪化させた
り、アルミ箔などの金属箔と巻回して用いた場合熱膨張
係数の差が大きすぎてしわが入ってしまう。また、少な
くとも一方向の250℃の熱収縮率は、好ましくは5%
以下、より好ましくは2%以下である。これより大きい
と、高温で使用した際寸法変化が大きべ電気特性を悪化
させる。Further, the shrinkage stress in the temperature range of 100 to 300°C in the longitudinal direction at least needs to be 2 kg/mm' or less. If it is larger than this, the film will wrinkle when used at high temperatures, deteriorating its electrical properties. Preferably l k
g/mm2 or less. Also, the coefficient of thermal expansion is 5 x
l Q-6cm/cm/℃ or more 50X10-6cm/c
The temperature is preferably 0+/°C or lower. Outside this range, the film will wrinkle due to temperature changes, deteriorating its electrical properties, and if it is wound with metal foil such as aluminum foil, the difference in thermal expansion coefficient will be too large, causing wrinkles. Further, the heat shrinkage rate at 250°C in at least one direction is preferably 5%.
It is preferably 2% or less. If it is larger than this, the dimensional change will be large when used at high temperatures and the electrical characteristics will deteriorate.
さらにフィルムの強度は少なくとも一方向が好ましくは
3 kg/mm2以上、より好ましくは5 kg/mm
2以上である。伸度は、少なくとも一方向が5%以上が
好ましく、より好ましくは10%以上である。Furthermore, the strength of the film is preferably 3 kg/mm2 or more in at least one direction, more preferably 5 kg/mm2.
It is 2 or more. The elongation is preferably 5% or more in at least one direction, more preferably 10% or more.
また、本発明のフィルムは強度が大きいため薄膜化が容
易で、フィルム厚みは3μm以上が可能であり好ましく
は5μm以上500μm以下である。Further, since the film of the present invention has high strength, it can be easily made into a thin film, and the film thickness can be 3 μm or more, and preferably 5 μm or more and 500 μm or less.
本発明によって得られるフィルムは、25℃の10重量
%NaOH水溶液中に5日間浸した場合の強度保持率は
80%以上が好ましい。The film obtained by the present invention preferably has a strength retention rate of 80% or more when immersed in a 10% by weight NaOH aqueous solution at 25° C. for 5 days.
次に、製法について説明する。本発明のフィルムは、芳
香族ポリアミドの溶液中に、無機塩をポリマに対して0
〜100重量%存在させ、この溶液(製膜原液)を湿式
製膜することにより形成される。まず、製膜原液である
が、溶媒としては非プロトン性の極性溶媒が好ましくジ
メチルホルムアミド、ジメチルアセトアミド、N−メチ
ルピロリドン、ジメチルスルフオキシド、ヘキサメチル
フォスホルアミドなどが挙げられる。無機塩としては塩
化カルシウム、塩化リチウム、塩化マグネシウムなどが
好ましい。製膜原液としては、上記芳香族ポリアミドを
上記非プロトン性極性溶媒に2重量%以上40重量%以
下の濃度で溶解したものを用いることができる。これは
有機極性溶媒中で合成したままの溶液を用いてもよいし
、−旦単離して再溶解したものでもよい。たとえば、酸
クロリドとジアミンとの反応から得る場合は、N−メチ
ルピロリドン、ジメチルアセトアミド、ジメチルホルム
アミドなどの非プロトン性有機極性溶媒中で、溶液重合
したり、水系媒体を使用する界面重合などで合成される
。ポリマ溶液は、単量体として酸クロリドとジアミンを
使用すると塩化水素が副生ずるため、これを中和するた
めに水酸化カルシウムなどの無機の中和剤、又はエチレ
ンオキサイドなどの有機の中和剤を添加する。また、イ
ソシアネートとカルボン酸との反応は、非プロトン性有
機極性溶媒中、触媒の存在下で行なわれる。製膜原液に
はポリマが析出しない範囲で貧溶媒を添加してもよい。Next, the manufacturing method will be explained. The film of the present invention is produced by adding an inorganic salt to the polymer in a solution of an aromatic polyamide.
~100% by weight is present, and this solution (film forming stock solution) is formed by wet film forming. First, regarding the membrane forming stock solution, the solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, and the like. Preferred inorganic salts include calcium chloride, lithium chloride, and magnesium chloride. As the film-forming stock solution, a solution obtained by dissolving the above-mentioned aromatic polyamide in the above-mentioned aprotic polar solvent at a concentration of 2% by weight or more and 40% by weight or less can be used. The solution may be used as it is synthesized in an organic polar solvent, or it may be isolated and redissolved. For example, when it is obtained from the reaction of acid chloride and diamine, it can be synthesized by solution polymerization in an aprotic organic polar solvent such as N-methylpyrrolidone, dimethylacetamide, or dimethylformamide, or by interfacial polymerization using an aqueous medium. be done. Hydrogen chloride is produced as a by-product when acid chloride and diamine are used as monomers in the polymer solution. To neutralize this, an inorganic neutralizing agent such as calcium hydroxide or an organic neutralizing agent such as ethylene oxide is used to neutralize the hydrogen chloride. Add. Further, the reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst. A poor solvent may be added to the film-forming stock solution to the extent that the polymer does not precipitate.
これにより空孔径を制御できることもある。この場合の
貧溶媒とは、特に限定はされないが水、メタノール、エ
タノール、クロロホルムなどが挙げられる。This may allow the pore diameter to be controlled. Examples of the poor solvent in this case include, but are not limited to, water, methanol, ethanol, chloroform, and the like.
次に微孔性フィルムの作製であるが、いわゆる湿式製膜
法で行なわれる。湿式浴としては、ポリマが不溶でかつ
溶媒が溶解するものであればよいが、取ゆ扱い易さなど
から通常は水が好ましい。Next, a microporous film is produced by a so-called wet film forming method. The wet bath may be one in which the polymer is insoluble and the solvent is soluble, but water is usually preferred from the viewpoint of ease of handling.
また、この水浴には塩化リチφムなどの無機塩や水に可
溶性の他の溶媒を含んでいてもよい。これにより、孔径
や空孔率をコントロールすることができる。この製膜原
液を金属ドラムやエンドレスの金属ベルトなどの支持体
上にキャストし支持体とともに水中に導入されるか、あ
るいは、水中や水面上の口金からそのままで水中に浸さ
れた後すみやかに縦方向に1.01〜185倍延伸する
。The water bath may also contain an inorganic salt such as lithium chloride or other water-soluble solvent. Thereby, the pore diameter and porosity can be controlled. This film-forming stock solution is cast onto a support such as a metal drum or an endless metal belt and introduced into the water together with the support, or it is immediately immersed vertically into the water from a nozzle above the water or the water surface. Stretch 1.01 to 185 times in the direction.
これにより、収縮応力や湿度膨張係数を目的の範囲とす
ることができる。その後、無機塩を添加した場合は無機
塩が完全にフィルム中からなくなるまで、また、非プロ
トン性極性溶媒の残存率が5%以下になるまで水中を通
す。水温は、0℃以上90℃以下が好ましく20℃以上
80℃以下がより好ましい。水温を変えることでも、孔
径や空孔率をコントロールすることができる。その後、
通常の製膜と同様に乾燥や延伸、リラックス、熱処理が
行なわれる。これらの処理は、一般に100〜500℃
で行なわれる。水中で縦延伸をすることにより孔径を変
えることができ、しかも残存無機塩量を10ppm以下
にすることが可能となった。製膜時の粘度は、100〜
1ooooポイズになるように製膜原液のポリマ濃度や
温度を調節することが好ましい。ここで粘度とは、回転
式B型粘度計で製膜時と同一条件(濃度、温度)で測定
した値をいう。Thereby, the shrinkage stress and humidity expansion coefficient can be set within the desired range. Thereafter, if an inorganic salt is added, water is passed through the film until the inorganic salt is completely removed from the film and until the residual rate of the aprotic polar solvent becomes 5% or less. The water temperature is preferably 0°C or more and 90°C or less, and more preferably 20°C or more and 80°C or less. Pore diameter and porosity can also be controlled by changing the water temperature. after that,
Drying, stretching, relaxing, and heat treatment are performed in the same way as in normal film formation. These treatments are generally carried out at temperatures between 100 and 500°C.
It will be held in By longitudinally stretching in water, the pore diameter can be changed, and the amount of residual inorganic salt can be reduced to 10 ppm or less. The viscosity during film formation is 100~
It is preferable to adjust the polymer concentration and temperature of the film-forming stock solution so that the poise becomes 100 poise. The viscosity here refers to a value measured using a rotating B-type viscometer under the same conditions (concentration, temperature) as during film formation.
金属ドラムやエンドレスの金属ベルトなどの支持体上に
キャストした場合はここで乾燥した後水中へ導いてもよ
い。この際溶媒が急激に飛散して面荒れを起こさないよ
うに調節する必要があり、一般に室温〜300℃、好ま
しくは50〜250℃で60分以内の範囲で行なわれる
。面倍率は、好ましくは0.8〜5.0倍、より好まし
くは1゜1〜3.0倍で延伸あるいはリラックスを行な
う。When cast onto a support such as a metal drum or an endless metal belt, it may be dried here and then introduced into water. At this time, it is necessary to control so that the solvent does not suddenly scatter and cause surface roughening, and the treatment is generally carried out at room temperature to 300°C, preferably 50 to 250°C, within 60 minutes. Stretching or relaxing is performed at an area magnification of preferably 0.8 to 5.0 times, more preferably 1°1 to 3.0 times.
面倍率とはフィルム縦方向(MD力方向の延伸倍率と横
方向(TD力方向の延伸倍率の積を言う。The areal magnification is the product of the stretching ratio in the longitudinal direction (MD force direction) of the film and the stretching ratio in the transverse direction (TD force direction).
面倍率を調節することでも孔径を自由に変えることがで
きる。The pore diameter can also be freely changed by adjusting the surface magnification.
[特性の評価法]
(1)機械特性(強度、伸度)
ASTM−D−882によるテンシロン型引張試験機に
試幅10mm、試技50mmとなるようにセットし、引
っ張り速度300mm/分で引っ張ってフィルムが破断
する時の強度、伸度を測定する。雰囲気は25℃、55
%RHである。[Method for evaluating properties] (1) Mechanical properties (strength, elongation) The specimen was set in a tensilon type tensile tester according to ASTM-D-882 with a test width of 10 mm and a test test of 50 mm, and pulled at a pulling speed of 300 mm/min. Measure the strength and elongation when the film breaks. Atmosphere is 25℃, 55
%RH.
(2)熱収縮率
試幅10mm、試技200mmになるようにフィルムを
切り出し、250℃のオーブン中で10分間加熱してか
ら試験片を取り出し放冷後下式により算出した。(2) Heat shrinkage rate A film was cut out to a test width of 10 mm and a test width of 200 mm, heated in an oven at 250° C. for 10 minutes, and then the test piece was taken out and allowed to cool, and then calculated using the formula below.
熱収縮率(%)=(加熱後の長さ一試技)/試技×10
0
(3)収縮応力
試幅10mm、試技100mmになるようにサンプルを
切り出し、0.25・kg/mm2の初期荷重をかけ、
定長に保つ。これを加熱炉で10℃/分の昇温速度で2
50℃まで昇温しで応力をチャートに書かせる。初期荷
重をかける前を零点として収縮応力を求める。Heat shrinkage rate (%) = (length after heating - trial) / trial × 10
0 (3) Shrinkage stress A sample was cut out with a trial width of 10 mm and a trial width of 100 mm, and an initial load of 0.25 kg/mm2 was applied.
Keep it at a constant length. Heat this in a heating furnace at a heating rate of 10℃/min for 2 hours.
Raise the temperature to 50°C and write the stress on a chart. Determine the shrinkage stress with the zero point before applying the initial load.
(4)熱膨張係数
熱収縮や吸脱湿の影響を除くため、フィルムを一旦15
0℃まで加熱し徐々に冷却し、ていった時の80〜15
0℃の領域における寸法変化から計算した。寸法変化量
は熱機械分析計(TMA)によって測定した。(4) Coefficient of thermal expansion In order to eliminate the effects of thermal contraction and moisture absorption and desorption, the film is
80-15 when heated to 0℃ and gradually cooled.
Calculated from dimensional changes in the 0°C region. The amount of dimensional change was measured using a thermomechanical analyzer (TMA).
(5)湿度膨張係数
恒温恒湿槽に試幅1 cm、試技15cmになるように
セットし、一定湿度(約30%RH)まで脱湿しフィル
ム長が一定になった後、加湿(約80%RH)すると吸
湿により伸び始める。約24時間後吸湿は平衡に達して
フィルムの伸びも平衡に達する。この時の伸び量から下
式により計算する。(5) Humidity Expansion Coefficient Set in a constant temperature and humidity chamber with a trial width of 1 cm and a trial width of 15 cm, dehumidify to a constant humidity (approximately 30% RH), and after the film length becomes constant, humidify (approximately 80% RH). %RH), it begins to elongate due to moisture absorption. After about 24 hours, moisture absorption reaches equilibrium and film elongation also reaches equilibrium. Calculate from the amount of elongation at this time using the formula below.
湿度膨張係数(cm/cm/%RH)=伸び量/(試技
×湿度差)
(6)吸湿率
フィルムを約100mmX 100mmに切り出し、1
50℃のオーブン中で1時間加熱脱湿後、乾燥デシケー
タ中で降温し脱湿時の重量を計る。このフィルムを75
%RH中に48時間放置後、取り出して飽和後の重量を
測定し、下式により計算する。Humidity expansion coefficient (cm/cm/%RH) = Amount of elongation/(Attempt x Humidity difference) (6) Cut the moisture absorption film to approximately 100 mm x 100 mm, and
After dehumidifying by heating in an oven at 50°C for 1 hour, the temperature is lowered in a dry desiccator, and the weight after dehumidification is measured. This film is 75
After being left in %RH for 48 hours, the sample was taken out, the weight after saturation was measured, and the weight was calculated using the following formula.
吸湿率(%)=(吸湿時の重量−脱湿時の重量)/脱湿
時の重量×100
(7)空孔率
試料(10X10cm)を流動パラフィンに24時間浸
漬し、表層の流動パラフィンを十分に拭き取った後の重
量と浸漬前の重量より下式により求める。Moisture absorption rate (%) = (Weight at moisture absorption - Weight at dehumidification) / Weight at dehumidification x 100 (7) Porosity Sample (10 x 10 cm) was immersed in liquid paraffin for 24 hours, and the liquid paraffin on the surface layer was immersed in liquid paraffin for 24 hours. Calculate the weight after wiping thoroughly and the weight before soaking using the formula below.
空孔率(%)=(浸漬後の重量−浸漬前の重量)/(見
かけ体積X流動パラフィンの密度)×100
(8)空孔径
水銀ポロシメータ(M I CROMERI T I
C8社製PORE 5IZER9300)i、:、J
:、す、空孔直径の分布を測定し、数平均を空孔径とし
た。Porosity (%) = (weight after immersion - weight before immersion) / (apparent volume x density of liquid paraffin) x 100 (8) Pore diameter mercury porosimeter (M I CROMERI T I
C8 company PORE 5IZER9300) i, :, J
: The distribution of pore diameters was measured, and the number average was taken as the pore diameter.
(9)流動パラフィン透過時間
JIS K 9003に規定された、37.8℃に
おける粘度が77±1センチストークスの流動パラフィ
ンを使用し、流動パラフィン及びサンプルを雰囲気温度
25℃にて24時間保持後、サンプルを水平面におき、
サンプル上5〜20mmの高さより流動パラフィンを0
,03〜0.06gを自然落下させる。このとき流動パ
ラフィンがサンプル面に接した時からサンプル面を透過
し反対面を湿すまでの時間を測定し流動パラフィン透過
時間とする。(9) Liquid paraffin permeation time Using liquid paraffin with a viscosity of 77 ± 1 centistokes at 37.8°C as specified in JIS K 9003, after holding the liquid paraffin and sample at an ambient temperature of 25°C for 24 hours, Place the sample on a horizontal surface,
Add liquid paraffin from a height of 5 to 20 mm above the sample.
,03-0.06g is allowed to fall naturally. At this time, the time from when the liquid paraffin comes into contact with the sample surface until it passes through the sample surface and wets the opposite surface is measured, and this is defined as the liquid paraffin permeation time.
(10)耐薬品性(強度保持率)
25℃の10重量%NaOH水溶液中に5日間浸した後
、上記の方法で強度を測り、下式により算出する。(10) Chemical resistance (strength retention) After being immersed in a 10% by weight NaOH aqueous solution at 25° C. for 5 days, the strength is measured using the method described above and calculated using the formula below.
強度保持率(%)=浸漬後の強度/浸漬前の強度×10
0
(11)素子巻テスト法
サンプルフィルムを4mm幅にスリットし、陽極化成ア
ルミ箔と陰極アルミ箔をサンプルフィルムと交互に重ね
て素子巻を作製する。この素子巻を、200℃で24時
間保存した後、サンプルフィルムを巻き出して様子を観
察する。評価は、次のような基準に従った。Strength retention rate (%) = Strength after immersion / Strength before immersion x 10
(11) Element winding test method A sample film is slit to a width of 4 mm, and anode chemical aluminum foil and cathode aluminum foil are alternately stacked on the sample film to produce an element winding. After storing this element roll at 200° C. for 24 hours, the sample film was unwound and observed. The evaluation was based on the following criteria.
・全く何の変化もなかったもの 二〇・実用上問題
がないと思われる程度の
変化のあったもの :○・フィルムもし
くはアルミ箔にしわが
はいり、実用上問題のあると思われ
るもの :X
[発明の効果]
本発明で得られる微孔性フィルムは、湿度膨張係数や吸
湿率が小さいため電池や電解コンデンサ、電気2重層コ
ンデンサのセパレータなどに用いた場合、多湿の雰囲気
下でも寸法変化が小さくしわなどが発生しないため性能
の劣化が起こらず、またフィルムをロール状で長期保存
した場合も良好な巻姿を保つことができる。特に、ニッ
ケルーカドミウム電池などのように水系の電解液を用い
る場合に効果がある。さらに、高温での収縮応力が小さ
いことから、100℃以上の高温で使用した場合でも、
しわなどが発生しないため性能の劣化が起こらず、特に
効果を発揮する。また機械特性も優れており薄膜化が可
能であり、前述の用途などの場合、よりコンパクトなも
のができるなどの効果がある。さらに、ミクロフィルタ
ー、透湿防水用途などにも優れた特性を発揮する。・Those with no change at all 20.Things that have changed to the extent that there is no practical problem: ○・Things that have wrinkles in the film or aluminum foil that may pose a practical problem: X [ Effects of the Invention] The microporous film obtained by the present invention has a small humidity expansion coefficient and moisture absorption rate, so when used for batteries, electrolytic capacitors, separators for electric double layer capacitors, etc., dimensional changes are small even in a humid atmosphere. Since wrinkles do not occur, there is no deterioration in performance, and even when the film is stored in roll form for a long period of time, it can maintain a good rolled shape. This is particularly effective when an aqueous electrolyte is used, such as in nickel-cadmium batteries. Furthermore, because the shrinkage stress at high temperatures is small, even when used at high temperatures of 100°C or higher,
Since wrinkles do not occur, there is no deterioration in performance, making it particularly effective. It also has excellent mechanical properties and can be made into a thin film, which has the effect of making it more compact for the above-mentioned applications. Furthermore, it exhibits excellent properties in microfilters, moisture permeable and waterproof applications, etc.
[実施例]
次に、本発明をより具体的に説明するために実施例を示
すが、これらに限定されるものではない。[Examples] Next, Examples will be shown to explain the present invention more specifically, but the present invention is not limited thereto.
実施例1
4.4′−ジアミノジフェニルメタン(DAM)と2−
クロロテレフタル酸クロリド(CTPC)から合成した
ポリマ溶液を水へ再沈澱し洗浄、乾燥して単離されたポ
リマを20重量%の濃度でN、N−ジメチルアセトアミ
ドに溶解し製膜原液とした。この原液を、下半分が水中
にあり回転している金属ドラム上にキャストし、25℃
の水中に導き自己支持性を持つや否やドラムより剥離し
、縦方向に1.4倍延伸した。さらに、フィルム中の残
存溶媒が5%以下になるまで水中を通した後、テンター
で280℃で乾燥しながら横方向に1.5倍延伸した。Example 1 4.4'-diaminodiphenylmethane (DAM) and 2-
A polymer solution synthesized from chloroterephthalic acid chloride (CTPC) was reprecipitated in water, washed, dried, and the isolated polymer was dissolved in N,N-dimethylacetamide at a concentration of 20% by weight to obtain a film-forming stock solution. This stock solution was cast onto a rotating metal drum with the lower half submerged in water and heated to 25°C.
As soon as it became self-supporting, it was peeled off from the drum and stretched 1.4 times in the machine direction. Further, the film was passed through water until the residual solvent in the film became 5% or less, and then stretched 1.5 times in the transverse direction while drying at 280° C. using a tenter.
厚み20μm1空孔径0. 7μm1空孔率70%の微
孔性フィルムが得られ、第1表に示すように収縮応力0
. 7 kg/mm2、湿度膨張係数30 X 10−
’cm/cm/%RHと熱、湿度に対して寸法安定性の
非常に優れたフィルムであった。また、素子巻きテスト
も良好であった。Thickness 20μm 1 pore diameter 0. A microporous film with a porosity of 7 μm and 70% was obtained, and as shown in Table 1, the shrinkage stress was 0.
.. 7 kg/mm2, humidity expansion coefficient 30 x 10-
The film had excellent dimensional stability with respect to 'cm/cm/%RH, heat, and humidity. Moreover, the element winding test was also good.
実施例2
NMP(N−メチルピロリドン)中で2−クロロ−p−
フェニレンジアミン(CPA)と2−クロロテレフタル
酸クロリド(CTPC)を反応させ炭酸リチウムで中和
して得られたままの溶液を製膜原液とした(濃度10重
量%)。水面の2cm上の口金よりこの製膜原液を押し
出し50℃の水中へ導き、直ちに1.2倍延伸し、実施
例1と同様の処理をして微孔性フィルムを得た。第1表
に示すように、熱・湿度寸法安定性に非常に優れたフィ
ルムであった。さらに、素子巻テストも非常に優れた結
果が得られた。Example 2 2-chloro-p- in NMP (N-methylpyrrolidone)
Phenylenediamine (CPA) and 2-chloroterephthalic acid chloride (CTPC) were reacted and neutralized with lithium carbonate, and the resulting solution was used as a membrane-forming stock solution (concentration: 10% by weight). This film-forming stock solution was extruded through a nozzle 2 cm above the water surface, introduced into water at 50°C, immediately stretched 1.2 times, and treated in the same manner as in Example 1 to obtain a microporous film. As shown in Table 1, the film had excellent heat and humidity dimensional stability. Furthermore, very excellent results were obtained in the element winding test.
実施例3
イソフタル酸クロリド(IPC)とメタフェニレンジア
ミン(MA)の界面重縮合により得られたポリマを15
重量%でNMPに溶解し、これに塩化カルシウムをポリ
マに対して20重量%添加して製膜原液とした。これを
実施例2と同様な方法で1.5倍の縦延伸を行ない、微
孔性フィルムを得た。第1表に示すような優れた特性を
有していた。Example 3 A polymer obtained by interfacial polycondensation of isophthalic acid chloride (IPC) and metaphenylenediamine (MA) was
It was dissolved in NMP at % by weight, and calcium chloride was added thereto in an amount of 20% by weight based on the polymer to obtain a membrane-forming stock solution. This was longitudinally stretched 1.5 times in the same manner as in Example 2 to obtain a microporous film. It had excellent properties as shown in Table 1.
比較例1
実施例3で水中での延伸を行なわない以外は同様な方法
でフィルムを得た。厚み40μm1空孔径0.1μm1
空孔率53%の微孔性フィルムが得られたが、第1表に
示すように収縮応力は0゜4 kg/mm2と小さいが
、湿度膨張係数が95×10−6cm/cm/%RHと
湿度寸法安定性の非常に悪いフィルムであった。Comparative Example 1 A film was obtained in the same manner as in Example 3 except that stretching in water was not performed. Thickness 40μm 1 pore diameter 0.1μm 1
A microporous film with a porosity of 53% was obtained, and as shown in Table 1, the shrinkage stress was as small as 0°4 kg/mm2, but the humidity expansion coefficient was 95 x 10-6 cm/cm/%RH. The film had very poor dimensional stability under humidity.
比較例2
実施例3で用いた製膜原液をガラス板上にキャストし、
−70℃の窒素雰囲気中で固化させ、ガラス板ごとドラ
イアイス−メタノール浴(−74℃)に浸し4時間抽出
した。その後、さらに室温で水中で脱塩脱溶媒した後、
乾燥して微孔性フィルムを得た。厚み50μm1空孔径
0.09μm1空孔率46%であったが、湿度膨張係数
が77X10−’cm/cm/%RHと湿度寸法安定性
に非常に劣り、収縮応力も1. 2 kg/mm2と大
きいフィルムであった。また、素子巻テストでも、しわ
がはいり、実用的には使用に耐えられないと考えられる
。Comparative Example 2 The film forming stock solution used in Example 3 was cast on a glass plate,
The mixture was solidified in a nitrogen atmosphere at -70°C, and the whole glass plate was immersed in a dry ice-methanol bath (-74°C) for extraction for 4 hours. Then, after further desalting and desolvation in water at room temperature,
A microporous film was obtained by drying. Although the thickness was 50 μm, the pore diameter was 0.09 μm, and the porosity was 46%, the humidity expansion coefficient was 77×10-' cm/cm/%RH, which was very poor in humidity dimensional stability, and the shrinkage stress was 1. It was a large film at 2 kg/mm2. In addition, wrinkles appeared in the element winding test, and it is considered that it cannot withstand practical use.
Claims (1)
て、少なくとも縦方向の湿度膨張係数が50×10^−
^6cm/cm/%RH以下、少なくとも縦方向の10
0〜300℃の温度範囲における収縮応力が2kg/m
m^2以下であることを特徴とする微孔性芳香族ポリア
ミドフィルム。An aromatic polyamide film having continuous micropores and having a humidity expansion coefficient of at least 50 x 10^- in the longitudinal direction.
^6cm/cm/%RH or less, at least 10 in the vertical direction
Shrinkage stress in the temperature range of 0 to 300℃ is 2kg/m
A microporous aromatic polyamide film characterized by having a diameter of m^2 or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4342789A JP2615976B2 (en) | 1989-02-23 | 1989-02-23 | Microporous aromatic polyamide film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4342789A JP2615976B2 (en) | 1989-02-23 | 1989-02-23 | Microporous aromatic polyamide film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02222430A true JPH02222430A (en) | 1990-09-05 |
JP2615976B2 JP2615976B2 (en) | 1997-06-04 |
Family
ID=12663402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4342789A Expired - Lifetime JP2615976B2 (en) | 1989-02-23 | 1989-02-23 | Microporous aromatic polyamide film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2615976B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10338809A (en) * | 1997-04-08 | 1998-12-22 | Sumitomo Chem Co Ltd | Composite film comprising low-permittivity resin and p-directing polyamide, prepreg thereof and use thereof |
JP2007204518A (en) * | 2006-01-31 | 2007-08-16 | Toray Ind Inc | Porous film containing aromatic polyamide or aromatic polyimide, separator for battery and method for producing the same |
JP2012180501A (en) * | 2011-02-07 | 2012-09-20 | Toray Ind Inc | Method for producing aromatic polyamide porous film, porous film obtained by the method, and battery separator using the aromatic polyamide porous film |
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 |
-
1989
- 1989-02-23 JP JP4342789A patent/JP2615976B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10338809A (en) * | 1997-04-08 | 1998-12-22 | Sumitomo Chem Co Ltd | Composite film comprising low-permittivity resin and p-directing polyamide, prepreg thereof and use thereof |
JP2007204518A (en) * | 2006-01-31 | 2007-08-16 | Toray Ind Inc | Porous film containing aromatic polyamide or aromatic polyimide, separator for battery and method for producing the same |
JP2012180501A (en) * | 2011-02-07 | 2012-09-20 | Toray Ind Inc | Method for producing aromatic polyamide porous film, porous film obtained by the method, and battery separator using the aromatic polyamide porous film |
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 |
Also Published As
Publication number | Publication date |
---|---|
JP2615976B2 (en) | 1997-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102712778B (en) | Aromatic polyamide porous film and separator for capacitor or battery using same | |
US3966686A (en) | Aromatic polyamide-type films | |
JP5636619B2 (en) | Composite porous membrane and method for producing the same | |
US20060138042A1 (en) | Heat-resistant film and composite ion-exchange membrane | |
WO2013122010A1 (en) | Battery separator, and battery separator manufacturing method | |
JPWO2013121971A1 (en) | Battery separator and battery separator manufacturing method | |
JP2008056905A (en) | Method for producing polymeric porous membrane and the resultant polymeric porous membrane | |
JPH02222430A (en) | Microcellular aromatic polyamide film | |
JP2553282B2 (en) | Aromatic polyamide film composite | |
JPH11250890A (en) | Porous polymer film for battery separator | |
JP5251055B2 (en) | Porous membrane containing aromatic polyamide | |
WO1997044182A1 (en) | Film of aromatic polyamide and/or aromatic polyimide and magnetic recording medium using the same | |
JP6264729B2 (en) | Porous film roll | |
JP2956129B2 (en) | Microporous film | |
CN109806774B (en) | Thin-layer composite membrane support, preparation method thereof and thin-layer composite membrane | |
WO1998042493A1 (en) | Aromatic polyamide film and magnetic recording medium made by using the same | |
KR101335950B1 (en) | Menufacturing Method of Meta-Aramid Based Porous Membrane for Secondary Battery and Porous Membrane thereby | |
JP4530652B2 (en) | Polyamideimide porous film with excellent chemical resistance and method for producing the same | |
JP2773382B2 (en) | Heat treatment method of aromatic polyamide film | |
JP4069725B2 (en) | Porous aromatic polyamide film and method for producing the same | |
JP5533265B2 (en) | Porous film containing aromatic polyamide and electricity storage device | |
JPH08230124A (en) | Laminated film roll | |
JPH0273832A (en) | Production of para oriented aromatic polyamide flame-retardant film | |
JPS6270022A (en) | Aromatic polymer film | |
JPH0427110A (en) | Heat-resistant capacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080311 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090311 Year of fee payment: 12 |
|
EXPY | Cancellation because of completion of term |