JP4354831B2 - Para-type aromatic polyamide fiber, fiber structure and production method thereof - Google Patents
Para-type aromatic polyamide fiber, fiber structure and production method thereof Download PDFInfo
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- JP4354831B2 JP4354831B2 JP2004006441A JP2004006441A JP4354831B2 JP 4354831 B2 JP4354831 B2 JP 4354831B2 JP 2004006441 A JP2004006441 A JP 2004006441A JP 2004006441 A JP2004006441 A JP 2004006441A JP 4354831 B2 JP4354831 B2 JP 4354831B2
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- 239000000835 fiber Substances 0.000 title claims description 105
- 239000004760 aramid Substances 0.000 title claims description 29
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 40
- 208000012886 Vertigo Diseases 0.000 description 10
- 239000002657 fibrous material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 230000005686 electrostatic field Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- -1 polymetaphenylene isophthalamide Polymers 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000561 Twaron Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Description
本発明はパラ型芳香族ポリアミド系繊維、繊維構造体およびその製造方法に関する。 The present invention relates to a para-type aromatic polyamide fiber, a fiber structure, and a method for producing the same.
最近の急速な高密度情報技術の発達にともない、電子回路用積層基板に用いる誘導体には寸法安定性や加工性の他、より一層の薄型化や低誘電率化が求められるようになってきた。 With the recent rapid development of high-density information technology, derivatives used for multilayer substrates for electronic circuits have been required to be thinner and have a lower dielectric constant in addition to dimensional stability and processability. .
芳香族ポリアミド繊維紙は、他素材からなる紙素材に比べて、耐熱性、電気絶縁性、耐熱寸法安定性、軽量性などの点で優れているため、最近では、電気回路板用積層物の基材にも活用されつつある。例えば、ポリメタフェニレンイソフタルアミド短繊維（帝人テクノプロダクツ株式会社製、商標；コーネックス）とポリメタフェニレンイソフタルアミドパルプからなる電気絶縁紙が提案されている（例えば、特許文献１、２参照。）。また、ポリパラフェニレンテレフタルアミド短繊維（帝人トワロン株式会社製、商標；トワロン）やコポリパラフェニレン−３，４’−オキシジフェニレン−テレフタルアミド短繊維（帝人テクノプロダクツ株式会社製、商標;テクノーラ）と有機系樹脂バインダーからなる芳香族ポリアミド繊維紙などが提案されている（例えば、特許文献３、４参照。）。
Aromatic polyamide fiber paper is superior to other paper materials in terms of heat resistance, electrical insulation, heat-resistant dimensional stability and light weight. It is also being used for base materials. For example, an electrical insulating paper made of polymetaphenylene isophthalamide short fiber (manufactured by Teijin Techno Products Co., Ltd., trademark: Conex) and polymetaphenylene isophthalamide pulp has been proposed (see, for example,
しかしながら、上記繊維紙を構成する繊維径を小さくするには限界があり、繊維紙の薄型化には限界があった。 However, there is a limit to reducing the fiber diameter of the fiber paper, and there is a limit to thinning the fiber paper.
本発明の目的は、上記従来技術が有していた問題点を解消し、極めて小さな繊維径を有するパラ型芳香族ポリアミドからなる繊維を提供することにある。 An object of the present invention is to solve the problems of the prior art and provide a fiber made of para-type aromatic polyamide having an extremely small fiber diameter.
また、本発明の他の目的は、極めて小さな繊維径を有するパラ型芳香族ポリアミドからなる繊維を含む繊維構造体を提供することにある。 Another object of the present invention is to provide a fiber structure including fibers made of para-type aromatic polyamide having an extremely small fiber diameter.
さらに本発明の他の目的は、極めて簡便な方法で上記繊維構造体を製造する方法を提供することにある。 Furthermore, the other object of this invention is to provide the method of manufacturing the said fiber structure by a very simple method.
本発明者らは、上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。
すなわち本発明の目的は、
パラ型芳香族ポリアミドの全繰り返し単位を基準として８０モル％以上が下記一般式（Ｉ）で表される繰り返し単位で占められ、繊維径が１μm以下であり、更に繊維長が２０μｍ以上である、パラ型芳香族ポリアミド系繊維によって達成される。
As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, the object of the present invention is to
80 mol% or more is occupied by the repeating unit represented by the following general formula (I) based on all repeating units of the para-type aromatic polyamide, the fiber diameter is 1 μm or less, and the fiber length is 20 μm or more. This is achieved by para-type aromatic polyamide fiber.
また、本発明の他の目的は、
上述のパラ型芳香族ポリアミド系繊維を少なくとも含む繊維構造体によって達成される。
Another object of the present invention is to
This is achieved by a fiber structure including at least the above-described para-type aromatic polyamide fiber.
さらに、本発明の他の目的は、
パラ型芳香族ポリアミドが有機溶媒に溶解した溶液を製造する段階と、前記溶液を静電紡糸法にて紡糸する段階と、前記紡糸によって捕集基板に累積される繊維構造体を得る段階を含む、繊維構造体の製造方法によって達成される。
Furthermore, another object of the present invention is to
Including a step of producing a solution in which a para-type aromatic polyamide is dissolved in an organic solvent, a step of spinning the solution by an electrostatic spinning method, and a step of obtaining a fiber structure accumulated on a collection substrate by the spinning. This is achieved by a method for manufacturing a fiber structure.
本発明の繊維を含む繊維構造体は、優れた耐熱性や電気絶縁性を維持したまま、薄型化が可能であり、透過性の良いフィルターや電子回路板用積層物の基材などに良好に用いることができる。 The fiber structure containing the fiber of the present invention can be thinned while maintaining excellent heat resistance and electrical insulation, and is suitable for a base material of a filter or a laminate for an electronic circuit board having good permeability. Can be used.
また、得られる繊維構造体はそのまま使用することもできるし、また取り扱い性やその他の要求事項に合わせて他の部材と組み合わせて用いることもできる。 Moreover, the obtained fiber structure can be used as it is, and can also be used in combination with other members in accordance with handling properties and other requirements.
以下、本発明について詳細に説明する。
本発明のパラ型芳香族ポリアミド系繊維は、該パラ型芳香族ポリアミドの全繰り返し単位を基準として、８０モル％以上が下記一般式（Ｉ）で表される繰り返し単位で占められることが必要である。
Hereinafter, the present invention will be described in detail.
In the para-type aromatic polyamide fiber of the present invention, it is necessary that 80 mol% or more is occupied by the repeating unit represented by the following general formula (I) based on all repeating units of the para-type aromatic polyamide. is there.
本発明の繊維の平均径は１μｍ以下であることが必要である。繊維の平均径が１μｍを越えると、それによって得られる繊維構造体の柔軟性が乏しくなり、好ましくない。該繊維構造体を構成する繊維の平均径は好ましくは、０．０１〜０．５μｍの範囲にあることである。 The average diameter of the fiber of the present invention is required to be 1 μm or less. When the average diameter of the fibers exceeds 1 μm, the flexibility of the fiber structure obtained thereby is not preferable. The average diameter of the fibers constituting the fiber structure is preferably in the range of 0.01 to 0.5 μm.
本発明の繊維は、繊維長が２０μｍ以上であることが必要である。繊維長が２０μｍ以下であると、それによって得られる繊維構造体の力学強度が不十分なものとなる。繊維長は、好ましくは、４０μｍ以上であり、更に好ましくは１ｍｍ以上である。 The fiber of the present invention needs to have a fiber length of 20 μm or more. When the fiber length is 20 μm or less, the mechanical strength of the fiber structure obtained thereby is insufficient. The fiber length is preferably 40 μm or more, more preferably 1 mm or more.
本発明において、パラ型芳香族ポリアミド系繊維としては、本発明の目的を奏する範囲内で、他のポリマーを併用（例えば共重合、ポリマーブレンド等）して繊維化しても良い。 In the present invention, the para-type aromatic polyamide fiber may be made into a fiber by using another polymer in combination (for example, copolymerization, polymer blend, etc.) within the scope of the object of the present invention.
本発明の繊維構造体は、上記パラ型芳香族ポリアミド系繊維を含むことを特徴とするが、ここで、本発明において「繊維構造体」とは、繊維が、織り、編み、積層などの操作を受けることによって、形成された三次元の構造体をいい、好ましい例として不織布を挙げることができる。 The fiber structure of the present invention is characterized by including the above-mentioned para-type aromatic polyamide fiber. Here, in the present invention, the “fiber structure” means that the fiber is an operation such as weaving, knitting, or laminating. Is a three-dimensional structure formed, and a preferred example is a nonwoven fabric.
本発明の繊維構造体における、該パラ型芳香族ポリアミド系繊維の含有量は特に限定されないが、５０重量％以上含まれると該パラ型芳香族ポリアミド系繊維の特徴を活かすことができ、好ましい。より好ましくは８０重量％以上であり、実質的に該パラ型芳香族ポリアミド系繊維のみで構成された繊維構造体がさらに好ましい。 The content of the para-type aromatic polyamide fiber in the fiber structure of the present invention is not particularly limited. However, if it is contained in an amount of 50% by weight or more, the characteristics of the para-type aromatic polyamide fiber can be utilized, which is preferable. More preferably, it is 80% by weight or more, and a fiber structure substantially composed of only the para-type aromatic polyamide fiber is further preferred.
特に、該繊維構造体を形成する繊維の平均径が１μm以下であり、更に繊維長２０μｍ以下の繊維を実質的に含まないようにすることが好ましい。 In particular, it is preferable that the average diameter of the fibers forming the fiber structure is 1 μm or less and that fibers having a fiber length of 20 μm or less are not substantially contained.
本発明の繊維構造体を製造するには、前述の繊維が得られる手法であればいずれも採用することができるが、前述のパラ型芳香族ポリアミドが有機溶媒に溶解した溶液を製造する段階と、前記溶液を静電紡糸法にて紡糸する段階と、前記紡糸によって捕集基板に累積される繊維構造体を得る段階を含むことが、製造方法の好ましい一態様として挙げることができる。 Any method can be used to produce the fiber structure of the present invention as long as the above-mentioned fibers can be obtained, and a step of producing a solution in which the above-mentioned para-type aromatic polyamide is dissolved in an organic solvent; A preferred embodiment of the production method includes a step of spinning the solution by an electrostatic spinning method and a step of obtaining a fiber structure accumulated on a collection substrate by the spinning.
ここで、静電紡糸法とは繊維形成性の化合物を溶解させた溶液を電極間で形成された静電場中に吐出し、溶液を電極に向けて曳糸し、形成される繊維状物質を捕集基板上に累積することによって繊維構造体を得る方法であって、繊維状物質とは、繊維形成性化合物を溶解させた溶媒が留去している状態のみならず、該溶媒が繊維状物質に含まれている状態も示している。 Here, the electrostatic spinning method is a method in which a solution in which a fiber-forming compound is dissolved is discharged into an electrostatic field formed between electrodes, the solution is spun toward the electrodes, and the formed fibrous substance is A method of obtaining a fibrous structure by accumulating on a collection substrate, wherein the fibrous substance is not only in a state where a solvent in which a fiber-forming compound is dissolved is distilled off, but also in a fibrous state. The state contained in the substance is also shown.
次いで、静電紡糸法で用いる装置について説明する。
前述の電極は、金属、無機物、または有機物のいかなるものでも導電性を示しさえすれば用いることができ、また、絶縁物上に導電性を示す金属、無機物、または有機物の薄膜を持つものであっても良い。
Next, an apparatus used in the electrostatic spinning method will be described.
The above-described electrode can be used as long as it has conductivity, and any metal, inorganic, or organic material has a thin film of conductive metal, inorganic, or organic material on an insulator. May be.
また、静電場は一対又は複数の電極間で形成されており、いずれの電極に高電圧を印加しても良い。これは、例えば電圧値が異なる高電圧の電極が２つ（例えば１５ｋＶと１０ｋＶ）と、アースにつながった電極の合計３つの電極を用いる場合も含み、または３つを越える数の電極を使う場合も含むものとする。 The electrostatic field is formed between a pair or a plurality of electrodes, and a high voltage may be applied to any of the electrodes. This includes, for example, the case where two high voltage electrodes with different voltage values (for example, 15 kV and 10 kV) and a total of three electrodes connected to the ground are used, or when more than three electrodes are used. Shall also be included.
次に静電紡糸法による本発明の繊維構造体を構成する繊維の製造手法について順を追って説明する。 Next, the production method of the fibers constituting the fiber structure of the present invention by the electrostatic spinning method will be described step by step.
まず前述のパラ型芳香族ポリアミドが有機溶媒に溶解した溶液を製造するが、ここで、溶液中のパラ型芳香族ポリアミドの濃度は１〜３０重量％であることが好ましい。該濃度が１重量％より小さいと、濃度が低すぎるため繊維構造体を形成することが困難となり好ましくない。また、３０重量％より大きいと、得られる繊維の平均径が大きくなり好ましくない。より好ましい濃度は２〜２０重量％である。 First, a solution in which the above-mentioned para-type aromatic polyamide is dissolved in an organic solvent is produced. Here, the concentration of the para-type aromatic polyamide in the solution is preferably 1 to 30% by weight. If the concentration is less than 1% by weight, it is not preferable because the concentration is too low, making it difficult to form a fiber structure. On the other hand, if it is larger than 30% by weight, the average diameter of the resulting fiber is undesirably large. A more preferred concentration is 2 to 20% by weight.
また、前記のパラ型芳香族ポリアミドを溶解させるための溶媒としては、パラ型芳香族ポリアミドを溶解し、かつ静電紡糸法にて紡糸する段階で蒸発し、繊維を形成可能なものであれば特に限定されないが、溶解性、取り扱い性の点からアミド系溶媒が好ましく、さらに好ましくはＮ−メチル−２−ピロリドン（以下、ＮＭＰと略記することがある。）、ジメチルフォルムアミド（以下、ＤＭＦと略記することがある。）、ジメチルアセトアミド（以下、ＤＭＡｃと略記することがある。）である。 In addition, the solvent for dissolving the para-type aromatic polyamide is not particularly limited as long as it can dissolve the para-type aromatic polyamide and evaporate at the stage of spinning by an electrostatic spinning method to form a fiber. Although not particularly limited, an amide solvent is preferable from the viewpoint of solubility and handleability, and more preferably N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), dimethylformamide (hereinafter referred to as DMF). And dimethylacetamide (hereinafter sometimes abbreviated as DMAc).
これらの溶媒は単独で用いても良く、複数の溶媒を組み合わせた混合溶媒として用いても良い。特に静電紡糸法においては、溶液の粘度と溶媒蒸発速度が形成される繊維の平均径に大きな影響を与えるため、ＮＭＰとＤＭＦおよび／またはＤＭＡｃを混合して溶液の粘度と溶媒蒸発速度を調整することで、平均径を制御することができ、より好ましい。 These solvents may be used alone or as a mixed solvent in which a plurality of solvents are combined. Especially in the electrospinning method, NMP, DMF and / or DMAc are mixed to adjust the viscosity of the solution and the solvent evaporation rate because the viscosity of the solution and the solvent evaporation rate greatly affect the average fiber diameter. By doing so, the average diameter can be controlled, which is more preferable.
次に前記溶液を静電紡糸法にて紡糸する段階について説明する。該溶液を静電場中に吐出するには、任意の方法を用いることが出来、例えば、溶液をノズルに供給することによって、溶液を静電場中の適切な位置に置き、そのノズルから溶液を電界によって曳糸して繊維化させればよい。 Next, the step of spinning the solution by the electrostatic spinning method will be described. Any method can be used to eject the solution into the electrostatic field, for example, by supplying the solution to a nozzle, placing the solution in a suitable position in the electrostatic field, and applying the solution from the nozzle to the electric field. Can be made into a fiber by stringing.
以下、図１を用いて本発明の繊維構造体を製造するための好ましい態様について更に具体的に説明する。
注射器の筒状の溶液保持槽（図１中３）の先端部に適宜の手段、例えば高電圧発生器（図１中６）にて電圧をかけた注射針状の溶液噴出ノズル（図１中１）を設置して、溶液（図１中２）を溶液噴出ノズル先端部まで導く。接地した繊維状物質捕集電極（図１中５）から適切な距離で該溶液噴出ノズル（図１中１）の先端を配置し、溶液（図１中２）が該溶液噴出ノズル（図１中１）の先端部から噴出させ、このノズル先端部分と繊維状物質捕集電極（図１中５）との間で繊維状物質を形成させることができる。
Hereinafter, the preferable aspect for manufacturing the fiber structure of this invention using FIG. 1 is demonstrated more concretely.
An injection needle-like solution ejection nozzle (in FIG. 1) in which voltage is applied to the tip of the cylindrical solution holding tank (3 in FIG. 1) of the syringe by an appropriate means, for example, a high voltage generator (6 in FIG. 1). 1) is installed, and the solution (2 in FIG. 1) is guided to the tip of the solution ejection nozzle. The tip of the solution ejection nozzle (1 in FIG. 1) is disposed at an appropriate distance from the grounded fibrous material collecting electrode (5 in FIG. 1), and the solution (2 in FIG. 1) is placed in the solution ejection nozzle (FIG. 1). It is ejected from the tip of the middle 1), and a fibrous material can be formed between the nozzle tip and the fibrous material collecting electrode (5 in FIG. 1).
また他の態様として、図２を以って説明すると、該溶液の微細滴（図示せず。）を静電場中に導入することもでき、その際の唯一の要件は溶液（図２中２）を静電場中に置いて、繊維化が起こりうるような距離に繊維状物質捕集電極（図２中５）から離して保持することである。例えば、溶液噴出ノズル（図２中１）を有する溶液保持槽（図２中３）中の溶液（図２中２）に直接、繊維状物質捕集電極に対抗する電極（図２中４）を挿入することもできる。 As another embodiment, referring to FIG. 2, fine droplets (not shown) of the solution can be introduced into the electrostatic field, and the only requirement is that the solution (2 in FIG. 2). ) In an electrostatic field and kept away from the fibrous material collection electrode (5 in FIG. 2) at such a distance that fiberization can occur. For example, an electrode (4 in FIG. 2) that directly opposes the fibrous material collecting electrode in a solution (2 in FIG. 2) in a solution holding tank (3 in FIG. 2) having a solution ejection nozzle (1 in FIG. 2). Can also be inserted.
該溶液をノズルから静電場中に供給する場合、数個のノズルを並列的に用いて繊維状物質の生産速度を上げることもできる。また、電極間の距離は、帯電量、ノズル寸法、溶液のノズルからの噴出量、溶液濃度等に依存するが、１０ｋＶ程度のときには５〜２０ｃｍの距離が適当であった。また、印加される静電気電位は、一般に３〜１００ｋＶ、好ましくは５〜５０ｋＶ、一層好ましくは５〜３０ｋＶである。所望の電位は従来公知の任意の適切な方法で作れば良い。 When supplying the solution from the nozzle into the electrostatic field, several nozzles can be used in parallel to increase the production rate of the fibrous material. Further, the distance between the electrodes depends on the charge amount, the nozzle size, the ejection amount of the solution from the nozzle, the solution concentration, etc., but when it is about 10 kV, the distance of 5 to 20 cm is appropriate. The applied electrostatic potential is generally 3 to 100 kV, preferably 5 to 50 kV, and more preferably 5 to 30 kV. The desired potential may be generated by any appropriate method known in the art.
上記二つの態様は、電極が捕集基板を兼ねる場合であるが、電極間に捕集基板となりうる物を設置することで、電極と別に捕集基板を設け、そこに繊維積層体を捕集することも出来る。この場合、例えばベルト状物質を電極間に設置して、これを捕集基板とすることで、連続的な生産も可能となる。 The above two embodiments are cases where the electrode also serves as a collection substrate, but by installing an object that can be a collection substrate between the electrodes, a collection substrate is provided separately from the electrode, and the fiber laminate is collected there. You can also In this case, for example, continuous production is also possible by installing a belt-like substance between the electrodes and using it as a collection substrate.
次に捕集基板に累積される繊維構造体を得る段階について説明する。本発明においては、該溶液を捕集基板に向けて曳糸する間に、条件に応じて溶媒が蒸発して繊維状物質が形成される。通常の室温であれば捕集基板上に捕集されるまでの間に溶媒は完全に蒸発するが、もし溶媒蒸発が不十分な場合は減圧条件下で曳糸しても良い。この捕集基板上に捕集された時点では少なくとも前記繊維平均径と繊維長とを満足する繊維構造体が形成されている。また、曳糸する温度は溶媒の蒸発挙動や紡糸液の粘度にあわせて調整すれば良く、通常は、０〜１００℃の範囲である。 Next, the step of obtaining the fiber structure accumulated on the collection substrate will be described. In the present invention, while spinning the solution toward the collection substrate, the solvent evaporates depending on conditions to form a fibrous material. At normal room temperature, the solvent completely evaporates until it is collected on the collection substrate. However, if the solvent evaporation is insufficient, the solvent may be drawn under reduced pressure. When collected on the collection substrate, a fiber structure satisfying at least the fiber average diameter and fiber length is formed. The spinning temperature may be adjusted according to the evaporation behavior of the solvent and the viscosity of the spinning solution, and is usually in the range of 0 to 100 ° C.
本発明の製造方法によって得られる繊維構造体は、単独で用いても良いが、取り扱い性やその他の要求事項に合わせて、他の部材と組み合わせて使用しても良い。例えば、捕集基板として支持基材となりうる不織布や織布、フィルム等を用い、その上に繊維積層体を形成することで、支持基材と該繊維積層体を組み合わせた部材を作成することも出来る。 The fiber structure obtained by the production method of the present invention may be used alone, but may be used in combination with other members in accordance with handleability and other requirements. For example, a non-woven fabric, woven fabric, film, or the like that can serve as a support substrate is used as a collection substrate, and a fiber laminate is formed thereon, thereby creating a member that combines the support substrate and the fiber laminate. I can do it.
また、得られた繊維構造体に対して熱処理や化学処理を施しても良く、さらに、紡糸以前の任意の段階で、前述のパラ型芳香族ポリアミドに、エマルジョン、有機物もしくは無機物の粉末、フィラー等を混合しても良い。 In addition, the obtained fiber structure may be subjected to heat treatment or chemical treatment. Furthermore, at any stage before spinning, the above-mentioned para-type aromatic polyamide is added to an emulsion, organic or inorganic powder, filler, etc. May be mixed.
例えば本発明の繊維構造体に各種触媒を担持させることにより、触媒担持基材として用いることもできる。 For example, by supporting various catalysts on the fiber structure of the present invention, it can also be used as a catalyst supporting substrate.
以下、本発明を実施例によりさらに具体的に説明するが、本発明は、これらの実施例に何等限定を受けるものではない。また実施例中における各値は下記の方法で求めた。
（１）繊維の平均径：
得られた繊維構造体の表面を走査型電子顕微鏡（株式会社日立製作所製「Ｓ−２４００」）により撮影（倍率２００００倍）して得た写真から無作為に２０箇所を選んで繊維の径を測定し、すべての繊維径（ｎ＝２０）の平均値を求めて、繊維の平均径とした。
（２）繊維長２０μｍ以下の繊維の存在確認：
得られた繊維構造体の表面を走査型電子顕微鏡（株式会社日立製作所製「Ｓ−２４００」）により撮影（倍率８０００倍）して得た写真を観察し、繊維長２０μｍ以下の繊維が存在するかどうか確認した。
（３）固有粘度：
固有粘度は、濃硫酸中、０.５g／ｄＬ、２５℃で測定した。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Average fiber diameter:
The surface of the obtained fiber structure was photographed with a scanning electron microscope ("S-2400" manufactured by Hitachi, Ltd.) (magnification: 20000 times), and 20 spots were randomly selected from the photos. The average value of all the fiber diameters (n = 20) was determined and used as the average fiber diameter.
(2) Confirmation of the presence of fibers having a fiber length of 20 μm or less:
A photograph obtained by photographing the surface of the obtained fiber structure with a scanning electron microscope (“S-2400” manufactured by Hitachi, Ltd.) (magnification 8000 times) is observed, and fibers having a fiber length of 20 μm or less are present. Confirmed whether or not.
(3) Intrinsic viscosity:
Intrinsic viscosity was measured in concentrated sulfuric acid at 0.5 g / dL at 25 ° C.
［実施例１］
３，４’−ジアミノフェニルエーテル６．６３部とｐ−フェニレンジアミン３．５６部をＮＭＰ２９０部に溶解し、これに塩化テレフタロイル１３．３７部を加えて窒素気流下で４時間重合した。これに水酸化カルシウム粉末を４．８８部加えて中和し、パラ型芳香族ポリアミドの６％ＮＭＰ溶液を得た。このとき、得られたパラ型芳香族ポリアミドの固有粘度は３．２であった。
[Example 1]
6.63 parts of 3,4′-diaminophenyl ether and 3.56 parts of p-phenylenediamine were dissolved in 290 parts of NMP, and 13.37 parts of terephthaloyl chloride was added thereto, followed by polymerization under a nitrogen stream for 4 hours. This was neutralized by adding 4.88 parts of calcium hydroxide powder to obtain a 6% NMP solution of para-type aromatic polyamide. At this time, the intrinsic viscosity of the obtained para-type aromatic polyamide was 3.2.
この溶液にＮＭＰとＤＭＦを加え、パラ型芳香族ポリアミド３ｗｔ％、ＮＭＰ７７ｗｔ％、ＤＭＦ２０ｗｔ％の溶液を作成した。 NMP and DMF were added to this solution to prepare a solution of 3 wt% para-type aromatic polyamide, 77 wt% NMP, and 20 wt% DMF.
次いで、図１に示す装置を用いて、該溶液を繊維状物質捕集電極（図中５）に８時間吐出した。噴出ノズル（図中１）の内径は０．８ｍｍ、溶液供給速度は２μｌ／分、電圧は１５ｋＶ、噴出ノズル１から繊維状物質捕集電極５までの距離は１５ｃｍであった。得られた繊維構造体の目付は４g／ｍ２であった。得られた繊維構造体を走査型電子顕微鏡で測定したところ、平均繊維径は０．０８μｍであり、繊維長２０μｍ以下の繊維は観察されなかった。得られた繊維構造体表面の走査型電子顕微鏡写真図を図３に示す。
Next, using the apparatus shown in FIG. 1, the solution was discharged to a fibrous material collecting electrode (5 in the figure) for 8 hours. The inner diameter of the ejection nozzle (1 in the figure) was 0.8 mm, the solution supply speed was 2 μl / min, the voltage was 15 kV, and the distance from the
１ 溶液噴出ノズル
２ 溶液
３ 溶液保持槽
４ 電極
５ 繊維状物質捕集電極
６ 高電圧発生器
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