JP4351552B2 - Method for producing para-type wholly aromatic polyamide fiber - Google Patents
Method for producing para-type wholly aromatic polyamide fiber Download PDFInfo
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- JP4351552B2 JP4351552B2 JP2004040991A JP2004040991A JP4351552B2 JP 4351552 B2 JP4351552 B2 JP 4351552B2 JP 2004040991 A JP2004040991 A JP 2004040991A JP 2004040991 A JP2004040991 A JP 2004040991A JP 4351552 B2 JP4351552 B2 JP 4351552B2
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- fiber
- aromatic polyamide
- carbon black
- wholly aromatic
- type wholly
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- 239000000835 fiber Substances 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000004760 aramid Substances 0.000 title description 23
- 229920003235 aromatic polyamide Polymers 0.000 title description 23
- 239000006229 carbon black Substances 0.000 claims description 26
- 239000004753 textile Substances 0.000 claims 2
- 235000019241 carbon black Nutrition 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 12
- 238000009987 spinning Methods 0.000 description 10
- 239000003607 modifier Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- Artificial Filaments (AREA)
Description
本発明は、パラ型全芳香族ポリアミド繊維の製造方法に関するものである。さらに詳しくは、熱融着性を有するパラ型全芳香族ポリアミドからなる繊維を、高温下で熱延伸および／または熱処理する際の工程安定性を改善し、品位に優れたパラ型全芳香族ポリアミド繊維を生産性よく製造する方法に関するものである。 The present invention relates to a method for producing para-type wholly aromatic polyamide fibers. More specifically, the para-type wholly aromatic polyamide is superior in quality by improving process stability when heat-stretching and / or heat-treating a fiber made of para-type wholly aromatic polyamide having heat-fusibility at high temperature. The present invention relates to a method for producing fibers with high productivity.
パラ型全芳香族ポリアミド繊維は、優れた耐熱性、耐薬品性、高強度、高弾性率といった種々の優れた特性を有することから、工業的に各種マトリックスの補強材やロープなどに用いられている。しかしながら、該パラ型全芳香族ポリアミド繊維の高強力・高弾性率化を達成するために、高温下での延伸および／または熱処理を施すと該工程で単繊維同士が融着して安定に製糸できないとか、得られる繊維の機械的特性が低下するという問題がある。さらには、単繊維同士がわずかに融着しても、糸条としては柔軟性が低下して取扱い性が悪いものになるという問題もある。 Para-type wholly aromatic polyamide fiber has various excellent properties such as excellent heat resistance, chemical resistance, high strength, and high modulus of elasticity, so it is industrially used for various matrix reinforcements and ropes. Yes. However, in order to achieve high strength and high elastic modulus of the para-type wholly aromatic polyamide fiber, when subjected to drawing and / or heat treatment at a high temperature, the single fibers are fused to each other in this step to stably produce the yarn. There is a problem that the mechanical properties of the obtained fiber are deteriorated. Furthermore, even if the single fibers are slightly fused, there is a problem that the flexibility of the yarn is lowered and the handleability is poor.
このような問題を改善するため、従来種々の方法が提案されている。例えば特許文献１には、熱延伸および／または熱処理時に融着性を有する合成繊維の表面に、親水ゲル形成性無機化合物のコロイドと疎水コロイドとの混合物を付与して融着性を改善する技術が、また、特許文献２には、熱延伸および／または熱処理時に融着性を有する合成繊維の表面に、親水ゲル形成性無機化合物のコロイドと界面活性剤を付与して融着性を改善する技術が提案されている。さらに、特許文献３には、芳香族コポリアミド繊維表面に繊維間滑り摩擦を低下させる粒状無機物質を付与して熱延伸性を改善する技術が提案されている。このように、従来のパラ型全芳香族ポリアミド繊維は、熱延伸および/または熱処理を施す前に、融着性を改善する目的で繊維表面に種々の処理剤を付与することが不可欠であるとされている。 In order to improve such problems, various conventional methods have been proposed. For example, Patent Document 1 discloses a technique for improving the fusing property by imparting a mixture of a colloid of a hydrophilic gel-forming inorganic compound and a hydrophobic colloid to the surface of a synthetic fiber having a fusing property during heat drawing and / or heat treatment. However, in Patent Document 2, a colloid of a hydrophilic gel-forming inorganic compound and a surfactant are imparted to the surface of a synthetic fiber having a fusibility during hot drawing and / or heat treatment to improve the fusibility. Technology has been proposed. Furthermore, Patent Document 3 proposes a technique for improving the heat stretchability by applying a granular inorganic substance that reduces inter-fiber sliding friction to the surface of an aromatic copolyamide fiber. As described above, it is indispensable that the conventional para-type wholly aromatic polyamide fiber is imparted with various treatment agents on the fiber surface for the purpose of improving the fusibility before the hot drawing and / or heat treatment. Has been.
しかしながら、このような表面改質剤を繊維表面に付与する方法では、該改質剤を繊維表面に均一に付着させる必要があるだけでなく、該改質剤を繊維に付着させた後は、該改質剤の繊維からの工程への脱落や堆積等が問題となりやすいため、管理が非常に煩雑であるだけでなく困難である。さらには、この表面改質剤が生産された繊維表面に残った場合には、繊維そのものが有する特性を下げる可能性もあるので好ましくない。この問題を解決するには、熱延伸および／または熱処理後に該改質剤を除去するための工程が必要となるだけでなく、その除去の過程で毛羽が発生するなど、繊維がダメージを受けやすいという問題もある。 However, in the method of applying such a surface modifier to the fiber surface, not only the modifier needs to be uniformly attached to the fiber surface, but also after the modifier is attached to the fiber, Since the dropping of the modifier from the fiber into the process, accumulation, and the like are likely to be problematic, management is not only very complicated but also difficult. Furthermore, if this surface modifier remains on the produced fiber surface, the properties of the fiber itself may be lowered, which is not preferable. In order to solve this problem, not only a process for removing the modifier after hot drawing and / or heat treatment is required, but also the fiber is easily damaged, such as generation of fluff during the removal process. There is also a problem.
本発明は、上記従来技術を背景になされたもので、その目的は、高温下で熱延伸および／または熱処理する際の工程安定性を改善し、品位に優れたパラ型全芳香族ポリアミド繊維が生産性よく製造できる方法を提供することにある。 The present invention has been made against the background of the above-described prior art, and its purpose is to improve the process stability when heat-drawing and / or heat-treating at a high temperature, and to provide a para-type wholly aromatic polyamide fiber excellent in quality. The object is to provide a method capable of producing with high productivity.
本発明者の研究によれば、上記課題は、「カーボンブラックを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重量に対して５．０〜４０重量％配合し、３００℃以上で全延伸倍率６倍以上に熱延伸することを特徴とする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繊維の製造方法。」により達成できることが見いだされた。 According to the inventor's research, the above-mentioned problem is that “carbon black is blended in an amount of 5.0 to 40% by weight based on the weight of copolyparaphenylene · 3,4′- oxydiphenylene terephthalamide , It has been found that this can be achieved by "a method for producing copolyparaphenylene-3,44'-oxydiphenylene terephthalamide fiber, characterized in that it is heat-drawn to a draw ratio of 6 times or more ."
本発明の方法によれば、表面改質剤を付与しなくとも、高温度下での熱延伸および／または熱処理時に従来発生しやすかった繊維間の融着を抑制することができ、工程が簡略化されるだけでなく、品位の良好な繊維を安定して製造することができる。 According to the method of the present invention, it is possible to suppress fusion between fibers, which has been easy to occur at the time of heat stretching and / or heat treatment at a high temperature without adding a surface modifier, and the process is simplified. It is possible to stably produce high-quality fibers.
本発明におけるパラ型全芳香族ポリアミドは、パラ型の芳香族ジカルボン酸、芳香族ジアミン、芳香族アミノカルボン酸などを、カルボキシル基とアミノ基とが略等モルとなる割合で重縮合して得られるものを対象とし、特に繊維の強度や弾性率を高めるために高温度下で熱延伸または熱処理が施されるものが好ましい。具体的なパラ型全芳香族ポリアミド繊維としては、ポリパラフェニレンテレフタルアミド繊維、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繊維などを例示することができる。特に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繊維は、高強力繊維を得るためには未延伸糸を３００℃以上、好ましくは３５０〜５５０℃の高温に加熱して６倍以上に熱延伸する必要があるので、単繊維が軟化し互いに融着して延伸性が悪化しやすく、また、後述するカーボンブラックを紡糸用ドープに分散させる際、該ドープは光学的に等方性で取扱いやすいので、本発明が対象とする繊維としては好適である。 The para-type wholly aromatic polyamide in the present invention is obtained by polycondensing para-type aromatic dicarboxylic acid, aromatic diamine, aromatic aminocarboxylic acid, etc. at a ratio such that the carboxyl group and amino group are approximately equimolar. In particular, those that are subjected to heat stretching or heat treatment at high temperatures in order to increase the strength and elastic modulus of the fibers are preferred. Specific examples of para-type wholly aromatic polyamide fibers include polyparaphenylene terephthalamide fibers and copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fibers. In particular, the copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber is heated to a high temperature of 300 ° C. or higher, preferably 350 to 550 ° C. to obtain a high tenacity fiber. Since it is necessary to heat-draw, the single fibers are softened and fused to each other, and the drawability is liable to deteriorate, and when the carbon black described later is dispersed in the spinning dope, the dope is optically isotropic. Since it is easy to handle, it is suitable as a fiber targeted by the present invention.
本発明においては、上述のように高温度での熱延伸または熱処理中に単繊維同士が融着しやすいパラ型全芳香族ポリアミド繊維の熱延伸または熱処理において、予め繊維中にカーボンブラックを配合しておき、引続いて該繊維を高温下で熱処理および／または熱処理する。このように、カーボンブラックを配合することにより、該熱延伸、熱処理工程での単繊維間の融着現象を抑制することができ、容易に引張強度が１８ｃＮ／ｄｔｅｘ以上の繊維を得ることができる。 In the present invention, as described above, carbon black is preliminarily blended in the fiber in the heat-stretching or heat-treatment of the para-type wholly aromatic polyamide fiber, in which the single fibers are easily fused during heat-stretching or heat-treatment at a high temperature as described above. Then, the fiber is subsequently heat-treated and / or heat-treated at a high temperature. Thus, by blending carbon black, it is possible to suppress the fusion phenomenon between single fibers in the heat drawing and heat treatment steps, and it is possible to easily obtain fibers having a tensile strength of 18 cN / dtex or more. .
ここで使用するカーボンブラックは特に限定する必要はなく、従来公知のものを任意に使用することができる。なかでも、アセチレンブラック、ケッチェンブラックなどの導電性カーボンブラックは、本発明の目的である製糸性改善のほかに、導電性能も改善された体積抵抗率が１０１０Ω・ｃｍ以下の繊維が得られるので好ましい。 The carbon black used here is not particularly limited, and any conventionally known carbon black can be used. Among these, conductive carbon blacks such as acetylene black and ketjen black provide fibers with a volume resistivity of 10 10 Ω · cm or less with improved electrical conductivity in addition to the improvement in yarn production, which is the object of the present invention. This is preferable.
カーボンブラックの平均粒子径は、繊維の単糸直径と比較して十分に小さければ特に問題はないが、５μｍ以下、特に０．０１〜０．５０μｍの範囲であることが好ましい。 The average particle diameter of carbon black is not particularly problematic as long as it is sufficiently smaller than the single yarn diameter of the fiber, but is preferably 5 μm or less, particularly preferably in the range of 0.01 to 0.50 μm.
カーボンブラック粒子の配合量は、パラ型全芳香族ポリアミド重量に対して５．０〜４０重量％、好ましくは８．０〜３０．０重量％、特に１０．０〜２０．０重量％の範囲とする必要がある。カーボンブラックの配合量が５．０重量％未満の場合には、繊維間の融着抑制効果が不十分となり本発明の目的を達成することができない。一方４０重量％を越える場合には、ドープの粘度が高くなりすぎて紡糸性が低下するだけでなく、延伸性も低下して得られる繊維の引張強度も低下するので好ましくない。 The compounding amount of the carbon black particles is 5.0 to 40% by weight, preferably 8.0 to 30.0% by weight, particularly 10.0 to 20.0% by weight, based on the weight of the para-type wholly aromatic polyamide. It is necessary to. When the blending amount of carbon black is less than 5.0% by weight, the effect of suppressing fusion between fibers becomes insufficient and the object of the present invention cannot be achieved. On the other hand, if it exceeds 40% by weight, not only the viscosity of the dope becomes too high and the spinnability is lowered, but also the tensile strength of the fiber obtained by lowering the stretchability is unfavorable.
なお、カーボンブラックをパラ型全芳香族ポリアミド中に導入する方法は任意であり、特に限定されるものではない。例えば、繊維の紡糸用ドープに、直接カーボンブラックを添加して分散させてもよいし、予め紡糸用の溶媒にカーボンブラックを分散させておき、この分散体を紡糸用ドープに混合してもかまわない。 The method for introducing carbon black into the para-type wholly aromatic polyamide is arbitrary, and is not particularly limited. For example, carbon black may be added and dispersed directly in a fiber spinning dope, or carbon black may be dispersed in a spinning solvent in advance, and this dispersion may be mixed with the spinning dope. Absent.
以下、パラ型全芳香族ポリアミドがコポリパラフェニレン・３、４’−オキシジフィニレンテレフタルアミドである場合を例にあげ、紡糸延伸について説明する。まず該ポリアミドおよびカーボンブラックを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、ジメチルイミダゾリジノンなどのアミド系極性溶媒に溶解・分散させたドープを調整する。なかでも、ドープ調整、紡糸工程に至るまでの取扱い性や安定性および該溶媒の毒性などの点から、Ｎ−メチル−２−ピロリドンが好ましい。 In the following, spinning drawing will be described by taking as an example the case where the para-type wholly aromatic polyamide is copolyparaphenylene-3,4'-oxydifinylene terephthalamide. First, a dope is prepared by dissolving and dispersing the polyamide and carbon black in an amide polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone. Among these, N-methyl-2-pyrrolidone is preferable from the viewpoints of handling and stability up to the dope adjustment and spinning process, toxicity of the solvent, and the like.
ドープ濃度は、あまりに低すぎると湿式または半乾半湿式で紡糸する際の吐出安定性が低下しやすく、一方、あまりに高すぎるとドープの粘性が急激に増加して同様に紡糸時のドープの吐出安定性が悪くなるうえ、紡糸パック内の急激な圧上昇により安定した紡糸が困難になりやすいので、適当な範囲に設定する。 If the dope concentration is too low, the discharge stability during spinning by wet or semi-dry semi-wet tends to decrease, while if it is too high, the viscosity of the dope increases abruptly, and similarly the dope discharge during spinning The stability is deteriorated, and stable spinning is likely to be difficult due to a rapid pressure increase in the spinning pack.
なお、ここでいう湿式とは、紡糸口金から直接凝固浴中に糸条を押出す方式をいい、半乾半湿式とは、紡糸口金と凝固浴の間にエアーギャップを設け、紡糸口金から押出された糸条はエアー中を通過した後に凝固浴中を通過させる方法をいう。この際、エアーギャップ距離（紡糸口金面と凝固液面との距離）は、通常吐出孔間距離の６倍以下とされる。 Here, wet refers to a method in which the yarn is extruded directly from the spinneret into the coagulation bath, and semi-dry and semi-wet refers to an air gap provided between the spinneret and the coagulation bath, and extrusion from the spinneret. The formed yarn refers to a method of passing through the coagulation bath after passing through the air. At this time, the air gap distance (the distance between the spinneret surface and the coagulation liquid surface) is usually 6 times or less the distance between the discharge holes.
凝固された糸条は水洗した後に乾燥させるが、乾燥する前の段階、好ましくは水洗する前の工程で、凝固糸条を湿潤状態で１．０５〜３．０倍に延伸することが好ましい。該湿潤状態での延伸方法は、空気中等の不活性ガス中で行うこともできるが、安定な延伸調子を得るためには水洗浴中、特に温水浴中で実施することが好ましい。特に、水洗前の段階に温水浴中で延伸すると、該延伸中に、糸条中に残存する溶剤を物理的に低下させることができ、水洗効率をさらに向上させることができるので好ましい。 The coagulated yarn is washed with water and dried, but it is preferable to stretch the coagulated yarn in a wet state by 1.05 to 3.0 times before drying, preferably before washing with water. The stretching method in a wet state can be performed in an inert gas such as air, but it is preferably performed in a washing bath, particularly in a warm water bath, in order to obtain a stable stretching condition. In particular, stretching in a warm water bath before washing with water is preferable because the solvent remaining in the yarn can be physically reduced during the drawing and the washing efficiency can be further improved.
水洗後の糸条は乾燥し、次いで熱延伸する。ここで熱延伸の条件は、通常３００℃以上の温度で全延伸倍率６倍以上、好ましくは３５０〜５５０℃の高温範囲で全延伸倍率８〜１２倍の範囲で延伸すればよい。なお、該熱延伸の方法は特に限定する必要はなく、熱板に接触させつつ延伸する方法、高温の不活性ガス（例えばスチーム、窒素、あるいは空気等）の雰囲気中で延伸する方法等、従来公知の方法のいずれをも採用することができる。さらには、該延伸を２段階以上の複数回に分けて行ってもよい。 The yarn after washing with water is dried and then hot drawn. Here, the conditions for the heat stretching are usually stretching at a temperature of 300 ° C. or higher and a total stretching ratio of 6 times or more, preferably 350 to 550 ° C. in a high temperature range of 8 to 12 times. The method of hot stretching is not particularly limited, and a conventional method such as a method of stretching while contacting a hot plate, a method of stretching in an atmosphere of a high-temperature inert gas (for example, steam, nitrogen, air, etc.), etc. Any of the known methods can be employed. Furthermore, the stretching may be performed in two or more steps.
熱延伸後の単繊維繊度は０．５〜１０ｄｔｅｘの範囲、特に０．７〜８ｄｔｅｘの範囲が好適である。また、紡出されるフィラメント数は２５０〜３０００本、好ましくは５００〜２５００本、特に好ましくは１０００〜２０００本の範囲である場合が好適である。 The single fiber fineness after hot drawing is preferably in the range of 0.5 to 10 dtex, particularly in the range of 0.7 to 8 dtex. The number of filaments to be spun is 250 to 3000, preferably 500 to 2500, and particularly preferably 1000 to 2000.
以下、実施例をあげて本発明をさらに具体的に説明する。なお、実施例中における各物性値は下記の方法で測定した。
（１）繊度、引張強度
ＪＩＳ−Ｌ１０１３に準拠して測定した。
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each physical-property value in an Example was measured with the following method.
(1) Fineness and tensile strength Measured according to JIS-L1013.
（２）カーボンブラック平均粒径
島津製作所製 レーザ回折式粒度分布測定装置ＳＡＬＤ−２００Ｖ ＥＲを使用し、カーボンブラックのアミド系極性溶媒分散体を、同じ極性溶媒で希釈してカーボンブラック濃度を０．０５重量％とし、これを測定に供した。
(2) Carbon black average particle diameter Using a laser diffraction particle size distribution analyzer SALD-200V ER manufactured by Shimadzu Corporation, an amide-based polar solvent dispersion of carbon black is diluted with the same polar solvent to reduce the carbon black concentration to 0. 0. This was used for measurement.
（３）繊維の体積固有抵抗値（体積低効率）
東亜電波工業社製の抵抗値測定機 ＳＭ−８２１０極超絶縁計を使用し、相対湿度６５ＲＨ％雰囲気中において測定した。具体的には繊維の試料長を１０ｃｍ（Ｌ（ｃｍ））とし、この試料長間に０．５ＫＶの電圧をかけ、そのときの電気抵抗値Ｒ（Ω）を測定し、導電糸の断面積をＳ（ｃｍ２）としてρ（Ω・ｃｍ）＝Ｒ×(Ｓ／Ｌ)より求めた。ここにＳは繊維の密度ｄ=１．５ｇ／ｃｍ３とみなし、Ｄは総繊度値（ｄｔｅｘ）をそのまま重量に読み替えた値として、Ｓ＝Ｄ／（１００００００×ｄ）より求めた。また、この時の繰り返し測定数は１０とし、その平均値を体積固有抵抗値とした。
(3) Fiber volume resistivity (volume low efficiency)
The resistance value measuring machine SM-8210 pole super insulation meter made by Toa Denpa Kogyo Co., Ltd. was used, and measurement was performed in an atmosphere with a relative humidity of 65 RH%. Specifically, the fiber sample length is 10 cm (L (cm)), a voltage of 0.5 KV is applied between the sample lengths, the electrical resistance value R (Ω) at that time is measured, and the cross-sectional area of the conductive yarn is measured. Was determined from ρ (Ω · cm) = R × (S / L) as S (cm 2 ). Here, S was regarded as a fiber density d = 1.5 g / cm 3, and D was obtained from S = D / (1000000 × d), where the total fineness value (dtex) was directly replaced by weight. The number of repeated measurements at this time was 10, and the average value was defined as the volume resistivity.
［実施例１］
カーボンブラックとして、三菱化学社製＃２６００を用い、Ｎ−メチル−２−ピロリドン（ＮＭＰ）中に、浅田鉄工社製ビーズミル（Ｎａｎｏ Ｇｒａｉｎ Ｍｉｌｌ）を使用し、濃度１０重量％のカーボンブラックのＮＭＰ分散体を調整した。この時、メディアとして、０．３ｍｍのジルコニアビーズを使用した。この分散体のカーボンブラックの平均粒径は、０．３５μｍであった。
[Example 1]
As carbon black, # 2600 manufactured by Mitsubishi Chemical Corporation was used, and NMP dispersion of carbon black having a concentration of 10% by weight was used in N-methyl-2-pyrrolidone (NMP) using a bead mill manufactured by Asada Iron Works (Nano Grain Mill). I adjusted my body. At this time, 0.3 mm zirconia beads were used as media. The average particle size of carbon black of this dispersion was 0.35 μm.
このカーボンブラック分散体、およびＮＭＰを、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（共重合モル比が１：１の芳香族ポリアミド）の濃度６重量％のＮＭＰ溶液中に、得られるドープ中のカーボンブラックの含有量が芳香族ポリアミドの重量を基準として５重量％となる割合で添加し、温度８０℃下４時間撹拌混合した。得られたドープを用い、孔径０．３ｍｍ、孔数１０００ホールの紡糸口金から吐出し、エアーギャップ約１０ｍｍを介してＮＭＰ濃度４５重量％の水溶液中に紡出し凝固した後（半乾半湿式紡糸法）、水洗、乾燥し、次いで、温度５００℃下で１０倍に延伸した後、巻き取り芳香族ポリアミド繊維を得た。この時、熱処理前に繊維の表面改質を目的とした表面処理を施さなかったが安定に製糸することができた。 This carbon black dispersion and NMP were obtained in an NMP solution having a concentration of 6% by weight of copolyparaphenylene 3,4'-oxydiphenylene terephthalamide (aromatic polyamide having a copolymerization molar ratio of 1: 1). The carbon black content in the resulting dope was added at a ratio of 5% by weight based on the weight of the aromatic polyamide, and the mixture was stirred and mixed at a temperature of 80 ° C. for 4 hours. The obtained dope was discharged from a spinneret having a hole diameter of 0.3 mm and a hole number of 1000 holes, and spun into an aqueous solution having an NMP concentration of 45% by weight through an air gap of about 10 mm and solidified (semi-dry and semi-wet spinning). Method), washed with water, dried, and then stretched 10 times at a temperature of 500 ° C. to obtain a wound aromatic polyamide fiber. At this time, the surface treatment for the surface modification of the fiber was not performed before the heat treatment, but the yarn could be stably produced.
得られたパラ型全芳香族ポリアミド繊維は、総繊度１６７０ｄｔｅｘ、フィラメント数１０００フィラメント、単糸繊度１．６７ｄｅｔｘ／フィラメントであり、引張強度は２５．１ｃＮ／ｄｔｅｘであった。 The obtained para type wholly aromatic polyamide fiber had a total fineness of 1670 dtex, a filament count of 1000 filaments, a single yarn fineness of 1.67 dtex / filament, and a tensile strength of 25.1 cN / dtex.
［実施例２、３］
実施例２では、カーボンブラックの含有量を、パラ型全芳香族ポリアミド重量を基準として２０重量％とし、実施例３では、使用するカーボンブラックを、導電性のカーボンブラック（＃３０５０ 三菱化学社製）とし、その含有量を１０重量％とする以外は、実施例１と同様ににして、パラ型全芳香族ポリアミド繊維を得た。その結果を表１にまとめて示す。なお、実施例３で得られた導電性芳香族ポリアミド繊維の抵抗値は、８．３８×１０８Ω・ｃｍであり、良好な導電性を示すことが確認された。
[Examples 2 and 3]
In Example 2, the carbon black content was 20% by weight based on the weight of the para-type wholly aromatic polyamide. In Example 3, the carbon black used was conductive carbon black (# 3050 manufactured by Mitsubishi Chemical Corporation). And a para-type wholly aromatic polyamide fiber was obtained in the same manner as in Example 1 except that the content was 10% by weight. The results are summarized in Table 1. In addition, the resistance value of the conductive aromatic polyamide fiber obtained in Example 3 was 8.38 × 10 8 Ω · cm, and it was confirmed that good conductivity was exhibited.
［比較例１］
カーボンブラックを配合することなく実施例１記載の方法でパラ型芳香族ポリアミド繊維の製糸を試みたところ、繊維の融着が頻繁に見られ、その引張破断強度は１７．５ｃＮ／ｄｔｅｘであった。結果をあわせて表１に示す。
[Comparative Example 1]
An attempt was made to produce para-aromatic polyamide fibers by the method described in Example 1 without blending carbon black. As a result, fiber fusion was frequently observed, and the tensile strength at break was 17.5 cN / dtex. . The results are shown in Table 1.
以上に説明した本発明のパラ型全芳香族ポリアミド繊維の製造方法によれば、繊維表面に改質剤を付与しなくとも、高温度下での熱延伸および／または熱処理が容易にでき、また得られる繊維の品位も良好なので、その工業的価値は極めて大である。 According to the method for producing a para-type wholly aromatic polyamide fiber of the present invention described above, it is possible to easily perform heat stretching and / or heat treatment at a high temperature without adding a modifier to the fiber surface. Since the quality of the resulting fiber is good, its industrial value is extremely high.
Claims (3)
引張強度が１８ｃＮ／ｄｔｅｘ以上である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繊維。 A fiber obtained by the method for producing a copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber according to claim 1,
Ru der tensile strength 18cN / dtex or more co polyparaphenylene-3,4'-diphenylene terephthalamide textiles.
体積抵抗率が１０１０Ω・ｃｍ以下である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繊維。 A fiber obtained by the method for producing a copolyparaphenylene 3,4'-oxydiphenylene terephthalamide fiber according to claim 1,
Volume resistivity of Ru der less 10 10 Omega-cm copoly paraphenylene-3,4'-diphenylene terephthalamide textiles.
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