JP6154101B2 - Separator made of aromatic polyamide nanofiber structure - Google Patents
Separator made of aromatic polyamide nanofiber structure Download PDFInfo
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- JP6154101B2 JP6154101B2 JP2012046668A JP2012046668A JP6154101B2 JP 6154101 B2 JP6154101 B2 JP 6154101B2 JP 2012046668 A JP2012046668 A JP 2012046668A JP 2012046668 A JP2012046668 A JP 2012046668A JP 6154101 B2 JP6154101 B2 JP 6154101B2
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- 239000002121 nanofiber Substances 0.000 title claims description 66
- 239000004760 aramid Substances 0.000 title claims description 33
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 33
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 claims description 32
- 239000000835 fiber Substances 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000003990 capacitor Substances 0.000 claims description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 42
- 238000009987 spinning Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 31
- 238000001523 electrospinning Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012776 electronic material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 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 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 description 1
- LNTGGPJSADTYSG-UHFFFAOYSA-N 2-(2-carbonochloridoylphenoxy)benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(Cl)=O LNTGGPJSADTYSG-UHFFFAOYSA-N 0.000 description 1
- WEEOFHJAGVFCFD-UHFFFAOYSA-N 2-n-chlorobenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NCl WEEOFHJAGVFCFD-UHFFFAOYSA-N 0.000 description 1
- RPKCLSMBVQLWIN-UHFFFAOYSA-N 2-n-methylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1N RPKCLSMBVQLWIN-UHFFFAOYSA-N 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- LHSXSRQUGCHBPG-UHFFFAOYSA-N 4-(aminomethoxy)aniline Chemical compound NCOC1=CC=C(N)C=C1 LHSXSRQUGCHBPG-UHFFFAOYSA-N 0.000 description 1
- IWRVPXDHSLTIOC-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1N=NC1=CC=CC=C1 IWRVPXDHSLTIOC-UHFFFAOYSA-N 0.000 description 1
- HPFMWXQXAHHFAA-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=CC(C(Cl)=O)=C1 HPFMWXQXAHHFAA-UHFFFAOYSA-N 0.000 description 1
- CGXXBHCRXCEKCP-UHFFFAOYSA-N 5-methoxybenzene-1,3-dicarbonyl chloride Chemical compound COC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 CGXXBHCRXCEKCP-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000005859 cell recognition Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VIUHYPPHBQZSPF-UHFFFAOYSA-N naphthalene-1,4-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1 VIUHYPPHBQZSPF-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、芳香族ポリアミドナノファイバー繊維構造体及びセパレータに関するものである。さらに詳しくは、ポリマーの主骨格をなす構成単位とは異なる第３成分の芳香族ジアミン、または芳香族ジカルボン酸ハライドを共重合させることによって、アルカリ金属塩を添加せずに紡糸溶液の安定性を向上させ、該紡糸溶液からエレクトロスピニング法によって好適に生産される、アルカリ金属塩を含まない芳香族ポリアミドナノファイバー構造体に関する。 The present invention relates to an aromatic polyamide nanofiber fiber structure and a separator. More specifically, the stability of the spinning solution can be improved without adding an alkali metal salt by copolymerizing an aromatic diamine or aromatic dicarboxylic acid halide as a third component different from the structural unit constituting the main skeleton of the polymer. The present invention relates to an aromatic polyamide nanofiber structure containing no alkali metal salt, which is preferably produced by electrospinning from the spinning solution.
ナノファイバーを成形する手段として、メルトブロー法、海島型混合紡糸繊維法、エレクトロスピニング法などがあり、なかでもエレクトロスピニング法は１９３０年代頃から知られた技術であり、数ｎｍ〜数μｍ径の繊維のウェブとすることが可能であり、従って、他の方法に比べて体積に対する表面積の比が大きく高い多孔性を有するウェブの製造が可能である。又室温でも紡糸が可能である上、簡素な装置構成にてナノファイバーを直接成形できることから、生体高分子などの熱に弱い高分子も含め、非常に幅広いポリマーのナノファイバー化が現在でも盛んに応用研究されている。 As means for forming nanofibers, there are a melt blow method, a sea-island type mixed spinning fiber method, an electrospinning method, etc. Among them, the electrospinning method is a technique known since the 1930s, and has a diameter of several nm to several μm. Therefore, it is possible to produce a web having a high porosity with a large surface area to volume ratio compared to other methods. In addition, spinning at room temperature is possible, and nanofibers can be directly molded with a simple device configuration, so a wide range of polymer nanofibers, including biopolymers that are vulnerable to heat, are still popular today. Applied research has been conducted.
ナノファイバーの微小な繊維径や広い表面積が発現する効果、例えば優れた透湿効果やスリップ効果、細胞認識効果などは、自動車、建築、医療などの幅広い産業分野で期待されている。
このエレクトロスピニング法については工業生産用設備のみならず、ナノファイバー製造方法についても、多数の技術開示がなされている。
The effects of nanofibers such as the fine fiber diameter and wide surface area, such as excellent moisture permeability effect, slip effect, and cell recognition effect, are expected in a wide range of industrial fields such as automobiles, architecture, and medicine.
With respect to this electrospinning method, many technical disclosures have been made not only on industrial production equipment but also on nanofiber manufacturing methods.
ポリビニルアルコール（ＰＶＡ）、ポリアクリロニトリル（ＰＡＮ）、ポリアミド（ＰＡ）は、とくに多くの研究内容が開示されており、エレクトロスピニング法やナノファイバーに関する特許実施例および技術文献において容易に見出すことが可能である（特許文献１、非特許文献１）。
芳香族ポリアミドは、耐熱性、難燃性、耐薬品性、絶縁性に優れた繊維として有用であることは公知であり、織物、編物、湿式／乾式不織布といった繊維構造体が産業用途製品に幅広く開発展開がなされている。一方で、芳香族ポリアミドを主成分とするナノファイバーに関しては、その成形が可能との一文が特許文献に記載はあるものの、実施例がなく詳細が不明であるものが多い（特許文献２）。
Polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and polyamide (PA) have been disclosed in particular, and can be easily found in patent examples and technical literature related to electrospinning and nanofibers. Yes (Patent Document 1, Non-Patent Document 1).
Aromatic polyamide is known to be useful as a fiber excellent in heat resistance, flame retardancy, chemical resistance and insulation, and fiber structures such as woven fabrics, knitted fabrics and wet / dry nonwoven fabrics are widely used in industrial products. Development development has been made. On the other hand, regarding nanofibers mainly composed of aromatic polyamide, although there is a description in the patent literature that the molding is possible, there are many examples and details are unknown (Patent Document 2).
数少ない芳香族ポリアミドナノファイバー化の実施例が記載されている特許や技術文献については、アルカリ金属塩等の塩を含んだ紡糸溶液を使用している（特許文献３、非特許文献２）。アルカリ金属塩を芳香族ポリアミド紡糸溶液に添加することは、ポリマーの溶解を助け、かつ紡糸溶液の安定性を保持できることから、アルカリ金属塩の存在は非常に重要である。しかしながら、アルカリ金属塩を含む紡糸溶液からエレクトロスピニング法により成形したナノファイバーは、電子材料部品や超高性能フィルター用途においては、アルカリ金属塩などのイオン性コンタミネーションを極力減らすことが必要で、先の文献に記載の方法では適用させることが困難である。また、上記紡糸溶液からのエレクトロスピニングでは、目的とするコレクター上に均一に積層させにくく、アルカリ金属塩が高濃度になるほど顕著となり、仮に均一な積層を達成し、水洗浄が必要で水洗浄を施したとしても、芳香族ポリアミドナノファイバー中のアルカリ金属塩を完全に除去できないという問題がある。 For patents and technical documents describing a few examples of aromatic polyamide nanofiber formation, a spinning solution containing a salt such as an alkali metal salt is used (Patent Document 3, Non-Patent Document 2). The presence of the alkali metal salt is very important because adding the alkali metal salt to the aromatic polyamide spinning solution can help dissolve the polymer and maintain the stability of the spinning solution. However, nanofibers formed by electrospinning from a spinning solution containing an alkali metal salt need to reduce ionic contamination such as alkali metal salt as much as possible in electronic material parts and ultra-high performance filter applications. It is difficult to apply the method described in the above document. In addition, in the electrospinning from the spinning solution, it is difficult to uniformly laminate on the target collector, and the higher the concentration of the alkali metal salt, the more prominent it is. Even if applied, there is a problem that the alkali metal salt in the aromatic polyamide nanofiber cannot be completely removed.
このアルカリ金属塩の問題に対しては、特許文献４にはアルカリ金属塩を含まない芳香族ポリアミドナノファイバーが記載されているが、目標としていた電子材料部品において明確な効果が得られていない。特にリチウムイオン二次電池のセパレータにおいては、高耐熱かつ低温での放電負荷特性の更なる向上が求められている。こうした点に鑑み、エレクトロスピニング法により成形可能な、アルカリ金属塩を含まず、かつ良好な性能を有する電子材料部品としてのナノファイバー構造体の開発が望まれている。 Regarding the problem of this alkali metal salt, Patent Document 4 describes an aromatic polyamide nanofiber that does not contain an alkali metal salt, but a clear effect has not been obtained in the targeted electronic material part. In particular, a separator for a lithium ion secondary battery is required to further improve discharge load characteristics at high heat resistance and low temperature. In view of these points, it is desired to develop a nanofiber structure as an electronic material part that can be molded by an electrospinning method and does not contain an alkali metal salt and has good performance.
本発明は、アルカリ金属塩を含まず、高温環境下での構造体や細孔の形態保持に優れ、
電子材料部品のセパレータとしたとき優れた性能を発揮する芳香族ポリアミドナノファイバー構造体を提供することにある。
The present invention does not contain an alkali metal salt and is excellent in maintaining the form of the structure and pores in a high temperature environment.
An object of the present invention is to provide an aromatic polyamide nanofiber structure that exhibits excellent performance when used as a separator for electronic material parts.
本発明者が検討した結果、特定の共重合芳香族ポリアミドを用い、エレクトロスピニング法によりナノファイバー構造体を成形し、その際、ある繊維径の範囲として平均細孔径を制御し適正化したとき、電池等の電子材料部品としてセパレータを用いた際に内部短絡が発生し難く、高温や低温とした加工または使用環境変化でも性能低下が少ないことを見出し本発明に到達した。 As a result of investigation by the present inventors, using a specific copolymerized aromatic polyamide, a nanofiber structure is formed by an electrospinning method, and at that time, when the average pore diameter is controlled and optimized as a certain fiber diameter range, When a separator is used as an electronic material part such as a battery, an internal short circuit is unlikely to occur, and it has been found that there is little deterioration in performance even when processing is performed at high or low temperatures or when the usage environment changes.
かくして本発明によれば、繊維軸方向に直行する断面直径が５００ｎｍより大きく１０００ｎｍ以下であるエレクトロスピニング芳香族ポリアミドナノファイバーのみからなる構造体において、該芳香族ポリアミドが、下記の式（１）で示される反復構造単位を含む芳香族ポリアミド骨格中に、反復構造の主たる構造単位とは異なる芳香族ジアミン成分、または芳香族ジカルボン酸ハライド成分を第３成分として芳香族ポリアミドの反復構造単位の全量に対し１〜１０ｍｏｌ％となるように共重合させた芳香族ポリアミドであり、該構造体の平均細孔径が１．５〜４．０μｍである芳香族ポリアミドナノファイバー構造体のみからなるセパレータが提供される。
−（ＮＨ−Ａｒ１−ＮＨ−ＣＯ−Ａｒ１−ＣＯ）− ・・・式（１）
ここで、Ａｒ１はメタ配位又は平行軸方向以外に結合基を有する２価の芳香族基である。
Thus, according to the present invention, in a structure composed only of electrospun aromatic polyamide nanofibers having a cross-sectional diameter perpendicular to the fiber axis direction of more than 500 nm and not more than 1000 nm, the aromatic polyamide is represented by the following formula (1): In the aromatic polyamide skeleton containing the recurring structural unit shown, the aromatic diamine component different from the main structural unit of the recurring structure or the aromatic dicarboxylic acid halide component is used as the third component to the total amount of the recurring structural unit of the aromatic polyamide. A separator comprising only an aromatic polyamide nanofiber structure, which is an aromatic polyamide copolymerized so as to be 1 to 10 mol%, and whose average pore diameter of the structure is 1.5 to 4.0 μm, is provided. The
-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
本発明によれば、特定の第３成分を共重合した芳香族コポリアミド溶液とすることにより、紡糸溶液がアルカリ金属塩を使用しなくても安定化され、エレクトロスピニング法によりアルカリ金属塩を含まない芳香族コポリアミドナノファイバーが提供されるため、電子材料部品用途などの、イオンを含まないことが望まれる製品への開発応用が可能となる。文献などによって、既に公開されている芳香族コポリアミドナノファイバーの成形方法にしたがって紡糸すると、蛍光Ｘ線分析を行った際に、アルカリ金属塩由来の例えばＣａ２＋イオンが検出されるが、本発明の方法では、このようなイオンは検出されない。 According to the present invention, by using an aromatic copolyamide solution copolymerized with a specific third component, the spinning solution is stabilized without using an alkali metal salt, and an alkali metal salt is contained by electrospinning. Since no aromatic copolyamide nanofibers are provided, it is possible to develop and apply to products that are desired to be free of ions, such as electronic material component applications. When spinning according to a method for forming an aromatic copolyamide nanofiber that has already been published in literatures, for example, Ca 2+ ions derived from alkali metal salts are detected when fluorescent X-ray analysis is performed. In this method, such ions are not detected.
さらに、芳香族ポリアミドナノファイバーの持つ高耐熱性により、高温環境下での形態保持に優れ、かつ該ナノファイバーの繊維径を制御することで、構造体としての平均細孔径を制御し、電子材料部品用セパレータとして良好な性能を得ることができる。 Furthermore, due to the high heat resistance of aromatic polyamide nanofibers, it has excellent shape retention under high-temperature environments, and by controlling the fiber diameter of the nanofibers, the average pore diameter as a structure is controlled, and an electronic material Good performance can be obtained as a separator for parts.
ナノファイバーとは数ｎｍ〜数μｍの断面径を有する繊維の総称であり、エレクトロスピニング法で安定に製造でき、かつアルカリ金属塩を含まない芳香族ポリアミドナノファイバーを得るため鋭意検討し本発明に到達したものである。 Nanofiber is a general term for fibers having a cross-sectional diameter of several nanometers to several micrometers, and has been intensively studied to obtain an aromatic polyamide nanofiber that can be stably produced by an electrospinning method and does not contain an alkali metal salt. It has been reached.
本発明でいう芳香族ポリアミドとは、１種類以上の２価の芳香族基が直接アミド結合により連結されている繊維形成性ポリマーであって、下記式（１）で示される繰り返し単位を骨格とする芳香族ポリアミドである。中でもポリメタフェニレンイソフタルアミドなどが好適に用いられる。
−（ＮＨ−Ａｒ１−ＮＨ−ＣＯ−Ａｒ１−ＣＯ）− ・・・式（１）
Ａｒ１：メタ配位又は平行軸方向以外に結合基を有する２価の芳香族基
The aromatic polyamide as used in the present invention is a fiber-forming polymer in which one or more kinds of divalent aromatic groups are directly linked by an amide bond, and the repeating unit represented by the following formula (1) is a skeleton. Is an aromatic polyamide. Among them, polymetaphenylene isophthalamide is preferably used.
-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Ar1: a divalent aromatic group having a linking group other than in the meta-coordinate or parallel axis direction
本発明のエレクトロスピニング法で安定に製造でき且つアルカリ金属塩を含まない芳香族ポリアミドナノファイバーを得るための重要な構成要素は、芳香族コポリアミドナノファイバー中の第３成分の使用であり、その含有率が１〜１０ｍｏｌ％であることが必要であり、さらに好ましくは２〜５ｍｏｌ％である。 An important component for obtaining an aromatic polyamide nanofiber that can be stably produced by the electrospinning method of the present invention and does not contain an alkali metal salt is the use of a third component in the aromatic copolyamide nanofiber, The content is required to be 1 to 10 mol%, and more preferably 2 to 5 mol%.
第３成分の含有率が１〜１０ｍｏｌ％であると分子鎖構造が乱れて結晶性が低下し、アルカリ金属塩を加えずとも安定に存在することとなるため、ゲル化が生じない。紡糸溶液の安定性が長時間にわたって要求される生産工程においては、前述の効果は極めて有効である。 When the content of the third component is 1 to 10 mol%, the molecular chain structure is disturbed, the crystallinity is lowered, and the presence of the alkali metal salt is stable, so that gelation does not occur. In the production process where the spinning solution is required to be stable over a long period of time, the above-described effects are extremely effective.
第３成分の含有率が１ｍｏｌ％未満であると、紡糸溶液にゲル化が生じるためアルカリ金属塩を添加する必要があり、また１０ｍｏｌ％を超えると、紡糸溶液の粘度が上昇し、得られたナノファイバーの繊維径のバラツキが大きくなり、かつ目的の平均細孔径が得られない。 When the content of the third component is less than 1 mol%, gelation occurs in the spinning solution, so it is necessary to add an alkali metal salt. When the content exceeds 10 mol%, the viscosity of the spinning solution is increased and obtained. The variation in the fiber diameter of the nanofiber is increased, and the target average pore diameter cannot be obtained.
芳香族コポリアミドナノファイバーの繊維径は５００ｎｍより大きく１０００ｎｍ以下であることが必要である。繊維径が５００ｎｍ以下であると、構造体としての強力が小さくなり取扱い性が低下し、後述する平均細孔径が得られ難くなる。一方、ナノファイバーの繊維径が１０００ｎｍを超えると、電界紡糸中の溶媒の揮発が妨げられ、ナノファイバー同士が融着することで、良好な平均細孔を得られ難くなる。繊維径は、好ましくは５００ｎｍより大きく９９０ｎｍ以下、より好ましくは５００ｎｍより大きく９５０ｎｍ以下、さらに好ましくは５０５ｎｍ〜８００ｎｍ、よりさらに好ましくは５５０〜７００ｎｍである。 The fiber diameter of the aromatic copolyamide nanofiber needs to be larger than 500 nm and not larger than 1000 nm. When the fiber diameter is 500 nm or less, the strength as a structure is reduced, the handleability is lowered, and the average pore diameter described later is difficult to obtain. On the other hand, if the fiber diameter of the nanofiber exceeds 1000 nm, volatilization of the solvent during electrospinning is hindered, and it becomes difficult to obtain good average pores by fusing the nanofibers together. The fiber diameter is preferably greater than 500 nm and less than or equal to 990 nm, more preferably greater than 500 nm and less than or equal to 950 nm, more preferably 505 nm to 800 nm, and even more preferably 550 to 700 nm.
また、構造体における平均細孔径は、１．５〜４．０μｍであることが必要である。平均細孔径が１．５μｍ未満であると、イオンの透過が妨げられセパレータとしての性能が劣る。一方、平均細孔径が４．０μｍを超えると電池等の電子材料部品としてセパレータを用いた際に内部短絡を発生させる頻度が高くなる。平均細孔径は、好ましくは１．７〜３．５μｍ、より好ましくは２．０〜３．０μｍである。 Moreover, the average pore diameter in a structure needs to be 1.5-4.0 micrometers. When the average pore diameter is less than 1.5 μm, the permeation of ions is hindered and the performance as a separator is inferior. On the other hand, when the average pore diameter exceeds 4.0 μm, the frequency of generating an internal short circuit increases when a separator is used as an electronic material part such as a battery. The average pore diameter is preferably 1.7 to 3.5 μm, more preferably 2.0 to 3.0 μm.
なお、繊維径の細い繊維の製造方法には、例えば、ポリマー溶液をバーストして細化させる爆裂紡糸法（国際公開第２００２／０５２０７０号パンフレット）や、一般に熱溶融性ポリマーで行われているメルトブロー技術を、ポリマー溶液を用いた紡糸にも応用する紡糸法を検討したが、エレクトロスピニング法において前記芳香族コポリアミドポリマーを用い前記繊維径のナノファイバーとしたとき、上記のようなセパレータ等に適した平均細孔径を有するナノファイバー構造体が容易に得られるだけでなく、該構造体において、高温で処理したときの収縮が小さく、平均細孔径の変化率も小さくなる、繊維径や平均細孔径があることを見出したものである。よって、本発明の要件を満足する芳香族コポリアミドを選定しない場合、または、本発明で規定する繊維径としない場合は、かかる十分な効果が得られない。 In addition, as a method for producing a fiber having a small fiber diameter, for example, an explosive spinning method (International Publication No. 2002/052070 pamphlet) in which a polymer solution is burst and thinned, or a melt blow generally performed with a heat-meltable polymer is used. We have studied a spinning method that applies the technology to spinning using a polymer solution. When the aromatic copolyamide polymer is used in the electrospinning method and the nanofiber has the above fiber diameter, it is suitable for the above-mentioned separator. In addition to easily obtaining a nanofiber structure having an average pore diameter, the structure has a small shrinkage when treated at a high temperature, and the change rate of the average pore diameter is small. It has been found that there is. Therefore, when an aromatic copolyamide that satisfies the requirements of the present invention is not selected, or when the fiber diameter is not defined in the present invention, such a sufficient effect cannot be obtained.
具体的には、ナノファイバー構造体の特性としては、２５０℃における寸法変化率が５％未満であることが好ましい。また、２００℃にて１時間加熱した際の平均細孔径の変化率が３０％以下であることが好ましい。上記構造体としたとき、電池、キャパシタ、コンデンサ等への加工や使用環境において高温にさらされても、加工性や性能低下が少なく高性能の電子部品を得ることができ望ましく、本発明の前記要件を満たすナノファイバー構造体は、上記熱安定性を容易に実現できる。 Specifically, as a characteristic of the nanofiber structure, the dimensional change rate at 250 ° C. is preferably less than 5%. Moreover, it is preferable that the change rate of the average pore diameter at the time of heating at 200 degreeC for 1 hour is 30% or less. When the above structure is used, it is desirable to obtain a high-performance electronic component with little deterioration in workability and performance even when exposed to high temperatures in processing and use environments such as batteries, capacitors and capacitors. A nanofiber structure that satisfies the requirements can easily achieve the thermal stability.
本発明のナノファイバー構造体は、以下に説明する芳香族コポリアミド紡糸溶液を用いたエレクトロスピニング法により製造することができる。
紡糸溶液中の芳香族コポリアミド濃度は、５〜２５重量％、好ましくは１０〜２０重量％であることが好ましい。濃度が５重量％未満であると、ゲル化は起こりにくくなり、紡糸溶液の安定性は向上するが、同紡糸溶液からエレクトロスピニング法によって紡糸すると、フィルム様の積層体が大部分を占めるようになり、また生産性も低くなるため、好ましくない。濃度が２５重量％を超えると、紡糸溶液としての安定性が低下し、室温ではゲル化が発生してしまう。
The nanofiber structure of the present invention can be produced by an electrospinning method using an aromatic copolyamide spinning solution described below.
The concentration of the aromatic copolyamide in the spinning solution is 5 to 25% by weight, preferably 10 to 20% by weight. If the concentration is less than 5% by weight, gelation is less likely to occur and the stability of the spinning solution is improved. However, when the spinning solution is spun by electrospinning, the film-like laminate occupies the majority. Further, the productivity is also low, which is not preferable. When the concentration exceeds 25% by weight, the stability as a spinning solution is lowered, and gelation occurs at room temperature.
次に固有粘度ＩＶは１．０〜４．０であり、さらに好ましくは１．５〜３．５である。固有粘度ＩＶが１．０未満の紡糸溶液を使用してエレクトロスピニングを実施すると、成形物の大部分がフィルム化しやすくなるか、ビーズと呼ばれる節糸状のポリマーの塊が、該ナノファイバー上に多数出現する。ビーズの出現数は、目的とする性能が達成できる範囲であれば良いが、頻出すると目的とする性能が低下するばかりでなく、残存溶媒量の増加にもつながるため好ましくない。固有粘度ＩＶが４．０を超えると、繊維径のバラつきが大きくなり、目的の繊維径を有するナノファイバーを得にくく、好ましくない。
ポリマーの重合方法としては、とくに限定する必要はないが、特公昭３５−１４３９９号公報、米国特許第３３６０５９５号、特公昭４７−１０８６３号公報などに記載される溶液重合法、界面重合法を用いても良い。
Next, intrinsic viscosity IV is 1.0-4.0, More preferably, it is 1.5-3.5. When electrospinning is performed using a spinning solution having an intrinsic viscosity IV of less than 1.0, a large part of the molding is easily formed into a film, or a large number of nodular polymer clusters called beads are formed on the nanofiber. Appear. The number of beads may be within a range where the target performance can be achieved. However, if it appears frequently, not only the target performance is lowered but also the residual solvent amount is increased, which is not preferable. When the intrinsic viscosity IV exceeds 4.0, the variation in the fiber diameter becomes large, and it is difficult to obtain nanofibers having the target fiber diameter, which is not preferable.
The polymerization method of the polymer is not particularly limited, but a solution polymerization method and an interfacial polymerization method described in Japanese Patent Publication No. 35-14399, US Pat. No. 3,360,595, Japanese Patent Publication No. 47-10863, and the like are used. May be.
第３成分として共重合させる、式（２）、（３）に示した芳香族ジアミンの具体例としては、例えば、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、クロロフェニレンジアミン、メチルフェニレンジアミン、アセチルフェニレンジアミン、アミノアニシジン、ベンジジン、ビス（アミノフェニル）エーテル、ビス（アミノフェニル）スルホン、ジアミノベンズアニリド、ジアミノアゾベンゼン等が挙げられる。式（４）、（５）に示すような芳香族ジカルボン酸ジクロライドの具体例としては、例えば、テレフタル酸クロライド、イソフタル酸クロライド、１，４−ナフタレンジカルボン酸クロライド、２，６−ナフタレンジカルボン酸クロライド、４，４’−ビフェニルジカルボン酸クロライド、５−クロルイソフタル酸クロライド、５−メトキシイソフタル酸クロライド、ビス（クロロカルボニルフェニル）エーテルなどが挙げられる。 Specific examples of aromatic diamines represented by formulas (2) and (3) to be copolymerized as the third component include m-phenylenediamine, p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, and acetylphenylene. Examples include diamine, aminoanisidine, benzidine, bis (aminophenyl) ether, bis (aminophenyl) sulfone, diaminobenzanilide, and diaminoazobenzene. Specific examples of the aromatic dicarboxylic acid dichloride represented by the formulas (4) and (5) include, for example, terephthalic acid chloride, isophthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, and 2,6-naphthalenedicarboxylic acid chloride. 4,4′-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, bis (chlorocarbonylphenyl) ether, and the like.
紡糸溶液としては、とくに限定するものではないが、上記溶液重合や界面重合などで得られた、芳香族コポリアミドポリマーを含むアミド系溶媒溶液から塩類を除去したものを用いても良いし、上記重合溶液から該ポリマーを単離し、これをアミド系溶媒に溶解したものを用いても良い。
ここで用いられるアミド系溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシドなどを例示することができるが、とくにＮ，Ｎ−ジメチルアセトアミドが好ましい。
The spinning solution is not particularly limited, but a solution obtained by removing salts from an amide solvent solution containing an aromatic copolyamide polymer obtained by the above solution polymerization or interfacial polymerization may be used. A polymer obtained by isolating the polymer from the polymerization solution and dissolving it in an amide solvent may be used.
Examples of the amide solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like, and in particular, N, N-dimethylacetamide. Is preferred.
エレクトロスピニング法によるナノファイバーの作製は適宜な装置を用いて行うことができるが、ノズルなどの紡糸溶液吐出部から、上記紡糸液を電界によって曳糸することが一般的であり、特に限定するものではないが、電圧は１０〜７０ｋＶ、紡糸距離は５．０〜５０ｃｍであるのが好ましい。
曳糸したナノファイバーは積層して繊維ウエッブのような繊維構造体にすることが好ましい。均一に積層する方法として特に限定はないが、例えば、ノズル部やナノファイバーのコレクター部をトラバースさせる方法や、ノズル部周辺からコレクター部において均一な気流を発生させる方法が挙げられる。
本発明においては、さらにカレンダーロールにて２７０〜３５０℃にて、ロール間距離を５〜２０μｍとしてプレス処理することが好ましい。
Nanofibers can be produced by an electrospinning method using an appropriate apparatus. However, it is common to spin the spinning solution by an electric field from a spinning solution discharge section such as a nozzle. However, it is preferable that the voltage is 10 to 70 kV and the spinning distance is 5.0 to 50 cm.
The twisted nanofibers are preferably laminated to form a fiber structure such as a fiber web. The method of uniformly laminating is not particularly limited, and examples thereof include a method of traversing the nozzle part and the nanofiber collector part and a method of generating a uniform air flow from the periphery of the nozzle part in the collector part.
In the present invention, it is preferable that the calender roll is pressed at 270 to 350 ° C. and the distance between the rolls is 5 to 20 μm.
本発明のナノファイバー構造体を用いた、電池、キャパシタ、コンデンサは、前記のようにアルカリ金属塩等の塩を含まず、電極等の劣化が少なく長寿命化が可能である。また、本発明のナノファイバー構造体は、上記用途のセパレータに用い、高温下でのセパレータ自体の寸法安定に優れるだけでなく、細孔の大きさの変化も極めて小さく、高温での加工や使用における性能低下が少なく、かつ、低温負荷特性にも優れている。 A battery, a capacitor, and a capacitor using the nanofiber structure of the present invention do not contain a salt such as an alkali metal salt as described above, and the life of the electrode can be extended with little deterioration. In addition, the nanofiber structure of the present invention is used for the separator for the above-mentioned applications, and not only is excellent in dimensional stability of the separator itself at high temperature, but also the change in pore size is extremely small, and processing and use at high temperature. There is little degradation in performance and excellent low temperature load characteristics.
以下、実施例に基づいて本発明をさらに詳細に説明する。しかし、以下の例によって、本発明が限定されることはない。なお、実施例中の各特性値は下記の方法で測定した。 Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the following examples. In addition, each characteristic value in an Example was measured with the following method.
＜固有粘度ＩＶ＞
重合溶液から芳香族コポリアミドポリマーを単離して乾燥させた後、ポリマー濃度／濃硫酸が１００ｍｇ／１００ｍｌとなるようにポリマーを溶解させ、３０℃においてオストワルド粘度計にて測定した。
<Intrinsic viscosity IV>
After the aromatic copolyamide polymer was isolated from the polymerization solution and dried, the polymer was dissolved so that the polymer concentration / concentrated sulfuric acid was 100 mg / 100 ml, and measured at 30 ° C. with an Ostwald viscometer.
＜繊維径＞
ナノファイバーを任意に５０本サンプリングし、走査型電子顕微鏡ＪＳＭ６３３０Ｆ（ＪＥＯＬ社製）にて測定し、繊維径の平均値を求めた。なお測定は、２０，０００倍の倍率で行った。
<Fiber diameter>
50 nanofibers were sampled arbitrarily and measured with a scanning electron microscope JSM6330F (manufactured by JEOL), and the average value of the fiber diameters was determined. The measurement was performed at a magnification of 20,000 times.
＜平均細孔径＞
ナノファイバー構造体をCapillary Flow Porometer CFP-1200-AEXL（Porous Materials, Inc.製）を用いて、任意に２０ケの細孔径を測定し、平均細孔径を求めた。
<Average pore diameter>
The nanofiber structure was arbitrarily measured for 20 pore diameters using a Capillary Flow Porometer CFP-1200-AEXL (manufactured by Porous Materials, Inc.) to obtain an average pore diameter.
＜アルカリ金属塩含有率＞
ナノファイバーを成形した後、蛍光Ｘ線分析装置システム３２７０（リガク製）にて、含有元素を分析した。
<Alkali metal salt content>
After forming the nanofibers, the contained elements were analyzed with a fluorescent X-ray analyzer system 3270 (manufactured by Rigaku).
＜寸法変化率＞
ナノファイバー構造体から、それぞれ任意に縦方向、横方向にそれぞれ５ｍｍ×２５ｍｍの大きさで１０ヶ所サンプリングし、ＴＭＡ４０００ＳＡ（Ｂｒｕｋｅｒ ＡＸＳ社製）で、チャック間長を２０ｃｍとして３０℃から２５０℃まで昇温速度１０℃／分にて熱処理し、以下式から縦方向、横方向の寸法変化率（％）を求め、それらの平均値を算出した。
縦方向の寸法変化率（％）＝（熱処理前の縦方向のサンプル長さ−熱処理後の縦方向のサンプル長さ）／熱処理前の縦方向のサンプル長さ
横方向の寸法変化率（％）＝（熱処理前の横方向のサンプル長さ−熱処理後の横方向のサンプル長さ）／熱処理前の横方向のサンプル長さ
<Dimensional change rate>
The nanofiber structure was sampled at 10 locations of 5 mm x 25 mm in the vertical and horizontal directions, respectively, and increased from 30 ° C to 250 ° C with a TMA4000SA (Bruker AXS) with a length between chucks of 20 cm. Heat treatment was performed at a temperature rate of 10 ° C./min, and the dimensional change rate (%) in the vertical direction and the horizontal direction was obtained from the following formula, and the average value thereof was calculated.
Dimensional change rate in the vertical direction (%) = (longitudinal sample length before heat treatment−longitudinal sample length after heat treatment) / longitudinal sample length before heat treatment lateral dimensional change rate (%) = (Sample length in the horizontal direction before heat treatment-sample length in the horizontal direction after heat treatment) / sample length in the horizontal direction before heat treatment
＜平均細孔径変化＞
ナノファイバー構造体を、任意に２０ｃｍ×２０ｃｍの大きさでサンプリングし、２００℃に設定した乾燥機に、その内壁面にナノファイバー構造体が接触しないように吊り下げた状態で、１時間熱処理を実施した。その後、前記方法で平均細孔径を測定し、さらに変化率を求めた。
平均細孔径変化率（％）＝（熱処理前の平均細孔径−熱処理後の平均細孔径）／熱処理前の平均細孔径
<Average pore diameter change>
The nanofiber structure is arbitrarily sampled at a size of 20 cm × 20 cm, and heat treatment is performed for 1 hour in a state where the nanofiber structure is suspended from a dryer set to 200 ° C. so that the nanofiber structure does not contact the inner wall surface. Carried out. Thereafter, the average pore diameter was measured by the above method, and the rate of change was further determined.
Average pore diameter change rate (%) = (average pore diameter before heat treatment−average pore diameter after heat treatment) / average pore diameter before heat treatment
＜紡糸溶液の安定性＞
得られたポリマーから、下記の実施例、及び比較例の如く調整した紡糸溶液を２０℃／６０％ＲＨにて２４時間静置し、目視観察にて白濁のないものを○、白濁したものを×で評価した。また、紡糸溶液全体の白濁はないが、０．５ｍｍ以上の白い固形成分が観察されたものについても×で評価した。
<Stability of spinning solution>
From the obtained polymer, the spinning solution prepared as in the following examples and comparative examples was allowed to stand at 20 ° C./60% RH for 24 hours, and the one having no white turbidity was visually observed. It evaluated by x. Moreover, although there was no cloudiness of the whole spinning solution, it evaluated by x also about what the white solid component of 0.5 mm or more was observed.
＜低温負荷特性試験＞
正極材料にマンガン酸リチウム、負極材料に天然黒鉛、電解液に１．０Ｍ−ＬｉＰＦ６−ＥＣ／ＥＭＣ＝３／７を用いて、設計容量６０ｍＡｈのラミネートセルを作成し、２０℃環境下で１．０Ｃ、４．２Ｖの定電流・定電圧充電（１．５時間）後、１．０Ｃ、２．７Ｖカットオフの定電流放電を実施し、２０℃環境下での電池容量を確認した後、再度、１．０Ｃ、４．２Ｖの定電流・定電圧充電（１．５時間）を実施し、その後−２０℃環境下で１０時間放置し、１．０Ｃ、２．７Ｖカットオフの定電流放電を実施し２０℃環境下対比での容量保持率を算出した。
<Low temperature load characteristic test>
A laminate cell with a design capacity of 60 mAh was prepared using lithium manganate as the positive electrode material, natural graphite as the negative electrode material, and 1.0M-LiPF 6 -EC / EMC = 3/7 as the electrolyte solution. 0.0C, 4.2V constant current / constant voltage charge (1.5 hours), 1.0C, 2.7V constant current discharge was performed, and the battery capacity in a 20 ° C environment was confirmed. Then, 1.0C, 4.2V constant current / constant voltage charging (1.5 hours) was performed again, and then left at −20 ° C. for 10 hours to obtain a constant 1.0C, 2.7V cutoff. Current discharge was carried out, and the capacity retention rate was calculated in comparison with a 20 ° C. environment.
［実施例１］
特公昭４７−１０８６３号公報記載の方法に準じた下記の界面重合法により以下のポリマーを製造した。
イソフタル酸ジクロライド２５．１３ｇ（９９ｍｏｌ％）と第３成分としてテレフタル酸ジクロライド０．２５ｇ（１ｍｏｌ％）を水分含有率２ｍｇ／１００ｍｌのテトラヒドロフラン１２５ｍｌに溶解し、−２５℃に冷却した。これを撹拌しながらメタフェニレンジアミン１３．５２ｇ（１００ｍｏｌ％）を、上記テトラヒドロフラン１２５ｍｌに溶解した溶液を細流として約１５分間にわたって添加し、白色の乳濁液（Ａ）を作製した。これとは別に無水炭酸ナトリウム１３．２５ｇを水２５０ｍｌに室温で溶かし、これを撹拌しながら５℃まで冷却して炭酸ナトリウム水和物結晶を析出させ分散液（Ｂ）を作製した。上記乳濁液（Ａ）と分散液（Ｂ）とを激しく混合した。更に２分間混合を続けた後、２００ｍｌの水を加えて希釈し、生成重合体を白色粉末として沈殿させた。重合終了系からろ過、水洗、乾燥して目的とするポリマーを得た。得られた芳香族コポリアミドポリマーについて測定した固有粘度ＩＶを表１に示す。
[Example 1]
The following polymers were produced by the following interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863.
25.13 g (99 mol%) of isophthalic acid dichloride and 0.25 g (1 mol%) of terephthalic acid dichloride as a third component were dissolved in 125 ml of tetrahydrofuran having a water content of 2 mg / 100 ml and cooled to −25 ° C. While stirring this, 13.52 g (100 mol%) of metaphenylenediamine was added over about 15 minutes as a trickle of a solution obtained by dissolving 125 ml of the above tetrahydrofuran to prepare a white emulsion (A). Separately, 13.25 g of anhydrous sodium carbonate was dissolved in 250 ml of water at room temperature, and this was cooled to 5 ° C. with stirring to precipitate sodium carbonate hydrate crystals to prepare a dispersion (B). The emulsion (A) and dispersion (B) were mixed vigorously. After further mixing for 2 minutes, 200 ml of water was added for dilution, and the resulting polymer was precipitated as a white powder. Filtration, washing with water and drying were carried out from the polymerization completed system to obtain the desired polymer. The intrinsic viscosity IV measured for the resulting aromatic copolyamide polymer is shown in Table 1.
得られた芳香族コポリアミドポリマーをＮ，Ｎ−ジメチルアセトアミドに、１５重量％となるように溶解させエレクトロスピニング用の紡糸溶液とした。エレクトロスピニングは特開２００６−３３６１７３号公報記載の方法に準じ、下記の通りナノファイバーを製造した。上記の芳香族コポリアミドポリマーをＮ，Ｎ−ジメチルアセトアミドに、１５重量％となるように溶解させ、１ｋＶ／ｃｍとなるように電界を作用させて、エレクトロスピニングを実施して、ナノファイバーを成形し、これを紡糸液吐出ノズル部からコレクターまでの距離を４０ｃｍとして集積し、ナノファイバー不織布を得た。
さらに、このナノファイバー不織布を、金属製カレンダーロールにて温度３００℃、ロール間距離１０μｍとして加圧熱処理し、目付１２ｇ／ｍ２のナノファイバー構造体を得た。結果を表１に示す。
The obtained aromatic copolyamide polymer was dissolved in N, N-dimethylacetamide so as to be 15% by weight to obtain a spinning solution for electrospinning. Electrospinning produced nanofibers as follows according to the method described in JP-A-2006-336173. The above-mentioned aromatic copolyamide polymer is dissolved in N, N-dimethylacetamide so as to be 15% by weight, an electric field is applied so as to be 1 kV / cm, and electrospinning is performed to form nanofibers. This was accumulated with the distance from the spinning solution discharge nozzle part to the collector being 40 cm to obtain a nanofiber nonwoven fabric.
Furthermore, this nanofiber nonwoven fabric was subjected to pressure heat treatment with a metal calender roll at a temperature of 300 ° C. and a distance between rolls of 10 μm to obtain a nanofiber structure having a basis weight of 12 g / m 2 . The results are shown in Table 1.
［実施例２〜４］
実施例１と同様の製造方法に従い、第３成分の添加率を表１に記載の通りに変更する以外は、実施例１と同様の操作を行った。結果を表１に示す。
[Examples 2 to 4]
According to the same production method as in Example 1, the same operation as in Example 1 was performed except that the addition ratio of the third component was changed as shown in Table 1. The results are shown in Table 1.
［実施例５〜６］
実施例１と同様の製造方法に従い、紡糸溶液のポリマー濃度及びエレクトロスピニングでの紡糸条件を変更して、ナノファイバーの平均繊維径を表１に記載の通りに変更する以外は、実施例１と同様の操作を行った。結果を表１に示す。
[Examples 5 to 6]
According to the same production method as in Example 1, except that the polymer concentration of the spinning solution and the spinning conditions in electrospinning were changed, and the average fiber diameter of the nanofiber was changed as described in Table 1, Example 1 and The same operation was performed. The results are shown in Table 1.
［比較例１］
実施例１と同様の製造方法に従い、テレフタル酸ジクロライドを添加することなしに、イソフタル酸ジクロライド２５．２５ｇ（１００ｍｏｌ％）、メタフェニレンジアミン１３．２５ｇ（１００ｍｏｌ％）にて重合する以外は、実施例１と同様の操作を行った。結果を表１に示した。上記条件では、溶液の安定性が悪く長時間の紡糸はできなかった。
[Comparative Example 1]
According to the same production method as in Example 1, except that polymerization was carried out with 25.25 g (100 mol%) of isophthalic acid dichloride and 13.25 g (100 mol%) of metaphenylenediamine without adding terephthalic acid dichloride. The same operation as 1 was performed. The results are shown in Table 1. Under the above conditions, the solution was not stable and could not be spun for a long time.
［比較例２］
塩化カルシウムを添加する以外は、実施例１と同様の操作を行った。結果を表１に示した。紡糸溶液の安定性は非常に良好であるが、繊維の水洗浄を十分に行っても塩化カルシウムが抜けきらなかった。
[Comparative Example 2]
The same operation as in Example 1 was performed except that calcium chloride was added. The results are shown in Table 1. Although the stability of the spinning solution was very good, calcium chloride could not be completely removed even after the fiber was sufficiently washed with water.
［比較例３〜４］
実施例１と同様の製造方法に従い、第３成分の添加率を表１に記載の通り変更する以外は、実施例１と同様の操作を行った。結果を表１に示す。
[Comparative Examples 3 to 4]
According to the same production method as in Example 1, the same operation as in Example 1 was performed except that the addition ratio of the third component was changed as shown in Table 1. The results are shown in Table 1.
［比較例５］
実施例１と同様の製造方法に従い、紡糸溶液のポリマー濃度及びエレクトロスピニングでの紡糸条件を変更して、ナノファイバーの平均繊維径を表１に記載の通りに変更する以外は、実施例１と同様の操作を行った。結果を表１に示す。
[Comparative Example 5]
According to the same production method as in Example 1, except that the polymer concentration of the spinning solution and the spinning conditions in electrospinning were changed, and the average fiber diameter of the nanofiber was changed as described in Table 1, Example 1 and The same operation was performed. The results are shown in Table 1.
［比較例６］
特公昭４７−１０８６３号公報記載の方法に準じた界面重合法により製造した固有粘度ＩＶ１．３５のポリメタフェニレンイソフタルアミド粉未２０重量部を、−１０℃に冷却したジメチルアセトアミド（ＤＭＡｃ）８０重量部中に懸濁させ、スラリー状にした後、４５℃まで昇温して溶解させ、透明なポリマー溶液を得た。
上記のポリマー溶液を、ギアポンプを使って特願２００９−１９４９１７号の紡糸装置に供給し、紡糸温度３５℃として紡糸を行った。凝固液として水を使用し、吐出後のポリマー溶液に吹き付け、ポリマー溶液を固化させて連続繊維とし、これを積層し、さらに金属製カレンダーロールにて温度２５０℃、線圧設定５０ｋｇ／ｃｍとして加圧熱処理し、目付２０ｇ／ｍ２のナノファイバー構造体を得た。結果を表１に示す。
[Comparative Example 6]
80 parts by weight of dimethylacetamide (DMAc) cooled to −10 ° C. with 20 parts by weight of polymetaphenylene isophthalamide powder having an intrinsic viscosity of IV1.35 produced by an interfacial polymerization method according to the method described in Japanese Patent Publication No. 47-10863 After suspending in a part and making it into a slurry state, the temperature was raised to 45 ° C. and dissolution was performed to obtain a transparent polymer solution.
The above polymer solution was supplied to a spinning device of Japanese Patent Application No. 2009-94917 using a gear pump, and spinning was performed at a spinning temperature of 35 ° C. Water is used as the coagulation liquid, sprayed onto the polymer solution after discharge, the polymer solution is solidified to form continuous fibers, laminated, and further heated at a temperature of 250 ° C. and a linear pressure setting of 50 kg / cm with a metal calender roll. The heat treatment was performed to obtain a nanofiber structure having a basis weight of 20 g / m 2 . The results are shown in Table 1.
［比較例７］
ポリマー溶液として実施例２で用いた芳香族ポリアミドコポリマーを用いた以外は、比較例６と同様にして、ナノファイバー構造体を得た。結果を表１に示す。
[Comparative Example 7]
A nanofiber structure was obtained in the same manner as in Comparative Example 6 except that the aromatic polyamide copolymer used in Example 2 was used as the polymer solution. The results are shown in Table 1.
表中の略号の説明
ＴＰＣ：テレフタル酸ジクロライド
ＰＰＤ：パラフェニレンジアミン
ＤＭＡｃ：Ｎ，Ｎ−ジメチルアセトアミド
Explanation of abbreviations in the table TPC: terephthalic acid dichloride PPD: paraphenylenediamine DMAc: N, N-dimethylacetamide
本発明によれば、無塩の芳香族コポリアミドナノファイバーを積層させた構造体を、安定的に成形することが可能となるため、アルカリ金属塩等のイオン性コンタミネーションを好まない電子部品用のセパレータへの応用展開が可能である。また、本発明のナノファイバー構造体によって、電池、キャパシタ、コンデンサ、特にアルミニウム電解コンデンサに適したセパレータを実現できたものであり、実用面で優れており、産業利用上の可能価値が極めて高いものである。 According to the present invention, it is possible to stably form a structure in which salt-free aromatic copolyamide nanofibers are laminated. For electronic parts that do not like ionic contamination such as alkali metal salts. Can be applied to other separators. The nanofiber structure of the present invention has realized a separator suitable for a battery, a capacitor, a capacitor, particularly an aluminum electrolytic capacitor, is excellent in practical use, and has a very high potential value for industrial use. It is.
Claims (10)
−（ＮＨ−Ａｒ１−ＮＨ−ＣＯ−Ａｒ１−ＣＯ）− ・・・式（１）
ここで、Ａｒ１はメタ配位又は平行軸方向以外に結合基を有する２価の芳香族基である。 In a structure consisting only of electrospun aromatic polyamide nanofibers having a cross-sectional diameter perpendicular to the fiber axis direction of more than 500 nm and not more than 1000 nm, the aromatic polyamide includes a repeating structural unit represented by the following formula (1) In the aromatic polyamide skeleton, the aromatic diamine component or the aromatic dicarboxylic acid halide component different from the main structural unit of the repeating structure is used as the third component to be 1 to 10 mol% with respect to the total amount of the repeating structure unit of the aromatic polyamide. A separator comprising only an aromatic polyamide nanofiber structure, which is an aromatic polyamide copolymerized as described above, and having an average pore size of 1.5 to 4.0 μm.
-(NH-Ar1-NH-CO-Ar1-CO) -... Formula (1)
Here, Ar1 is a divalent aromatic group having a bonding group other than in the meta-coordinate or parallel axis direction.
Ｈ２Ｎ−Ａｒ２−ＮＨ２ ・・・式（２）
Ｈ２Ｎ−Ａｒ２−Ｙ−Ａｒ２−ＮＨ２ ・・・式（３）
ＸＯＣ−Ａｒ３−ＣＯＸ ・・・式（４）
ＸＯＣ−Ａｒ３−Ｙ−Ａｒ３−ＣＯＸ ・・・式（５）
ここで、Ａｒ２はＡｒ１とは異なる２価の芳香族基、Ａｒ３はＡｒ１とは異なる２価の芳香族基、Ｙは酸素原子、硫黄原子、アルキレン基からなる群から選ばれる少なくとも１種の原子又は官能基であり、Ｘはハロゲン原子を表す。 The separator according to claim 1, wherein the aromatic diamine as the third component is represented by formulas (2) and (3), or the aromatic dicarboxylic acid halide is represented by formulas (4) and (5).
H 2 N—Ar 2 —NH 2 Formula (2)
H 2 N-Ar2-Y- Ar2-NH 2 ··· formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Here, Ar2 is a divalent aromatic group different from Ar1, Ar3 is a divalent aromatic group different from Ar1, Y is at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group Or it is a functional group and X represents a halogen atom.
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