JP4155786B2 - Dope for conductive aromatic polyamide fiber and method for adjusting the dope - Google Patents
Dope for conductive aromatic polyamide fiber and method for adjusting the dope Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、ドープの安定性及び紡糸・延伸時の工程安定性に優れた、導電性芳香族ポリアミド繊維を製造するに適したドープ及びその調整方法に関する。
【０００２】
【従来の技術】
従来、ポリパラフェニレンテレフタルアミドやポリメタフェニレンイソフタルアミドなどからなる芳香族ポリアミド繊維に各種の機能を付与する方法としては、紡糸した後の水で膨潤した状態にある繊維に、各種機能を付与する剤を含有する処理剤を接触させることにより、繊維中に該剤を含浸させる方法が知られている。（例えば特開昭６２−１８４１２７号公報、特開昭６３−１４５４１２号公報）しかし、かかる方法では十分な導電性を付与することはできない。
【０００３】
一方、繊維に導電性を付与する方法としては、乾式や湿式紡糸で繊維を形成する場合にはドープ中に導電性カーボン微粒子を添加する方法が知られている。しかし、ポリパラフェニレンテレフタルアミドを始めとするパラ配向型芳香族ポリアミドは硫酸などの強極性溶媒中にしか溶解し難いためと推定され、導電性カーボン微粒子の凝集に起因してドープの安定性が悪く、また細繊度糸が得がたいという問題がある。また、ポリメタフェニレンイソフタルアミドなどのアミド系極性溶媒に溶解する芳香族ポリアミドにおいても、その程度は上記よりも少ないものの、導電性カーボン微粒子の凝集に起因する同様の問題がある。
【０００４】
【特許文献１】
特開昭６２−１８４１２７号公報
【特許文献２】
特開昭６３−１４５４１２号公報
【０００５】
【発明が解決しようとする課題】
本発明は、かかる従来技術を背景になされたもので、その目的は、導電性カーボン微粒子の凝集がなく安定性に優れ、しかも紡糸時の工程安定性も良好な導電性芳香族ポリアミド繊維用として好適なドープ及びその調整方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、ドープ中の導電性カーボン粒子の凝集はドープのｐＨを制御することにより抑制できることを見出し本発明を完成するに至った。
【０００７】
かくして本発明によれば、第１の課題は、「ｐＨが４〜７である芳香族ポリアミドのアミド系極性溶媒溶液と、ｐＨが１０〜１３である導電性カーボン微粒子のアミド系極性溶媒分散体とを混合してなり、該芳香族ポリアミドのアミド系極性溶媒溶液中に、該芳香族ポリアミドの重量を基準として導電性カーボン微粒子が８〜４０重量％含まれるドープであって、該ドープのｐＨが６〜８であることを特徴とする導電性芳香族ポリアミド繊維用ドープ。」により達成することができる。
【０００８】
【発明の実施の形態】
以下、本発明の実施の形態について詳細に説明する。
本発明でいう芳香族ポリアミドとは、１種又は２種以上の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ポリマーであって、該芳香族基は２個の芳香環が酸素、硫黄又はアルキレン基で結合されたものであってもよい。また、これらの２価の芳香族基には、メチル基やエチル基などの低級アルキル基、メトキシ基、クロルキなどのハロゲン基等が含まれていてもよい。
【０００９】
かかる芳香族ポリアミドの具体例としては、ポリパラフェニレンテレフタルアミド、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、ポリメタフェニレンイソフタルアミドなどが挙げられる。なかでも、得られるドープの安定性及び紡糸時の工程安定性の観点から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が好ましい。
【００１０】
本発明で用いられるアミド系極性溶媒としては、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、ジメチルイミダゾリジノンなどを例示することができるが、特に、芳香族ポリアミドの重合からドープ調整、湿式紡糸工程に至るまでの取扱い性や安定性及び該溶媒の毒性等の点から、Ｎ−メチル−２−ピロリドンが好ましい。
【００１１】
上記芳香族ポリアミドとアミド系極性溶媒とからなる本発明のドープは、その芳香族ポリアミドの濃度はあまりに低すぎると紡糸時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、４〜７重量％の範囲が適当である。
【００１２】
次に、本発明で用いられる導電性カーボン微粒子は、それ自体が導電性を示すものであって繊維形成能を阻害しないものであれば特に限定されないが、通常平均粒径は０．１μｍ以下で、０．０１〜０．０５μｍ程度のものが用いられ、吸油量は２０ｍｌ／１００ｇ以上、好ましくは５０ｍｌ／１００ｇ以上のものが用いられる。
【００１３】
かかる導電性カーボン微粒子のドープ中含有量は、芳香族ポリアミドの重量を基準として８〜４０重量％、好ましくは１０〜２０重量％の範囲とする必要がある。該含有量が８重量％未満の場合には、得られる繊維の導電性が不十分となり、一方、４０重量％を超える場合には、ドープの曳糸性が低下し安定した紡糸が困難となるので好ましくない。
【００１４】
本発明のドープは、上記の要件に加えて、該ドープのｐＨが６〜８の範囲にあることが肝要である。該ドープのｐＨが６未満の場合には、ドープ中の導電性カーボン微粒子が凝集しやすくなるためと推定され、該微粒子の分散性に起因するドープの安定性に欠け、安定に紡糸することが困難となる。一方、８を超える場合には、該ｐＨを達成するために通常使用される剤（中和剤）の未反応物が微粒子として残存するため、紡糸パック内の圧力上昇を起こしやすくなり同じく安定に紡糸することが困難となる。
【００１５】
以上に説明した本発明のドープは、例えば以下の方法により調整することができる。すなわち、従来公知の方法にしたがって、アミド系極性溶媒中で芳香族ジカルボン酸クロライドと芳香族ジアミンとを反応させ、次いで、副生された塩酸を水酸化カルシウム微粒子等の中和剤で中和した、ｐＨが４〜７の芳香族ポリアミドのアミド系極性溶媒溶液を用い、これとｐＨが１０〜１３の導電性カーボン微粒子のアミド系極性溶媒分散体とを混合することにより容易に製造することができる。
【００１６】
ここで、芳香族ポリアミドのアミド系極性溶媒溶液のｐＨが４未満の場合には、芳香族ポリアミドの劣化が起こり易くなるので好ましくなく、一方、ｐＨが７を超える場合には、副生された塩酸を中和するために使用される水酸化カルシウム微粒子等の中和剤が未反応微粒子として残存しやすく、また、最終的に得られるドープのｐＨが８を越えやすくなるので好ましくない。
【００１７】
また、導電性カーボン微粒子は、アミド系極性溶媒中に均一に分散させた分散体として、芳香族ポリアミドのアミド系極性溶媒溶液と混合することが大切であり、例えば該微粒子を紛体のままで混合すると混合時に凝集体を形成しやすいので好ましくない。さらに、導電性カーボン微粒子をアミド系極性溶媒分散体として混合する際にも、該分散体のｐＨを１０〜１３の範囲にすることも必要である。該分散体のｐＨが１０〜１３の範囲外であっても、導電性カーボン微粒子の分散性が低下して均一に分散させることが困難となるので好ましくない。
【００１８】
なお、得られるドープのｐＨが６〜８の範囲となるように、さらに水酸化カルシウム微粒子等の中和剤のアミド系極性溶媒分散体を用いて調整しても構わない。
【００１９】
本発明のドープから、従来公知の芳香族ポリアミド繊維の製造方法により、容易に導電性芳香族ポリアミド繊維を得ることができる。例えば、半乾半湿式紡糸法により紡糸し、次いで、延伸倍率、延伸温度、熱セット温度等の延伸条件を適宜設定して配向・結晶状態を制御することにより、容易に比抵抗値（温度２０℃、湿度６５％で測定）が１０0Ω・ｃｍ〜１０8Ω・ｃｍの範囲の導電性を有するものが得られる。
【００２０】
【実施例】
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、実施例中の各特性値は下記の方法で測定した。
＜比抵抗値（体積固有抵抗値）ρ＞
東亜電波工業株式会社製の抵抗値測定機ＳＭ−８２１０極超絶縁計を用い、相対湿度３０％の条件下で、次のようにして測定した。長さ１０ｃｍの試料繊維の両端に１００（Ｖ）の電圧をかけて電気抵抗値Ｒ（Ω）を測定し、繊維の断面積をＳ（ｃｍ2）としてρ（Ω・ｃｍ）＝Ｒ×（Ｓ／１０）より求めた。なお、繊維の断面積は、繊維の密度を１．５ｇ／ｃｍ3として計算した。
【００２１】
［実施例１］
導電性カーボン微粒子としてＭＰＳ−１５０４ Ｂｌａｃｋ（Ｔ）（大日精化社製）を用い、Ｎ−メチル−２−ピロリドン（ＮＭＰ）中に分散させて、濃度１０重量％、ＰＨ１１．０の分散液を調整した。このカーボン微粒子分散液を、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（ＰＨを５．０に調整）中に、得られるドープ中のカーボン微粒子の含有量が芳香族ポリアミドの重量を基準として１５．０重量％となる割合で添加し、温度６０℃下４時間撹拌混合した。その際、得られるドープのｐＨが７．０となるように、水酸化カルシウム濃度が２２．５重量％のＮＭＰ分散液を微量添加して調製した。
【００２２】
得られたドープを用い、孔径０．３ｍｍ、孔数１００ホールの紡糸口金から毎分２０ｃｃの割合で吐出し、エアーギャップと呼ばれる空隙部分を介してＮＭＰ濃度３０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５３０℃下４．０倍に延伸した後８０ｍ／分の速度で巻き取って１３９ｄｔｅｘ／５０ｆｉｌの糸条を得た。得られた糸条の比抵抗値は５．０×１０3Ω・ｃｍであった。なお、ドープの安定性は良好で、長時間安定に紡糸延伸することができた。
【００２３】
［実施例２〜５、比較例１〜４］
導電性カーボン微粒子のＮＭＰ分散液のｐＨ、芳香族ポリアミドのＮＭＰ分散液のｐＨを表１に記載のとおりとし、かつ、導電性カーボン微粒子の含有量及びドープのｐＨを表１に記載のとおりとなるように調整する以外は実施例１と同様にして導電性芳香族ポリアミド繊維を得た。結果を表１にまとめて示す。
【００２４】
【表１】
【発明の効果】
本発明のドープによれば、ドープの安定性に優れているので、均一な品質の導電性繊維を安定して製造することができる。また、製糸の安定性が良好となっているので製糸条件の変更可能範囲が拡大し、容易に得られる導電性繊維の導電性を制御することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dope suitable for producing a conductive aromatic polyamide fiber having excellent dope stability and process stability during spinning and stretching, and a method for adjusting the dope.
[0002]
[Prior art]
Conventionally, as a method of imparting various functions to an aromatic polyamide fiber made of polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, etc., various functions are imparted to fibers that are swollen with water after spinning. There is known a method of impregnating a fiber with a treatment agent containing the agent by contacting the agent. (For example, JP-A-62-184127 and JP-A-63-145412) However, such a method cannot provide sufficient conductivity.
[0003]
On the other hand, as a method for imparting conductivity to the fiber, a method of adding conductive carbon fine particles to the dope is known when the fiber is formed by dry or wet spinning. However, it is presumed that para-oriented aromatic polyamides such as polyparaphenylene terephthalamide are difficult to dissolve only in strong polar solvents such as sulfuric acid, and the stability of the dope is caused by aggregation of conductive carbon fine particles. There is a problem that it is bad and it is difficult to obtain a fine yarn. An aromatic polyamide dissolved in an amide-based polar solvent such as polymetaphenylene isophthalamide also has the same problem due to aggregation of conductive carbon fine particles although the degree thereof is less than the above.
[0004]
[Patent Document 1]
JP 62-184127 A [Patent Document 2]
Japanese Patent Laid-Open No. 63-145212
[Problems to be solved by the invention]
The present invention has been made against the background of the prior art, and its purpose is for conductive aromatic polyamide fibers having excellent stability without aggregation of conductive carbon fine particles and having good process stability during spinning. An object is to provide a suitable dope and a method for adjusting the dope.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that aggregation of conductive carbon particles in the dope can be suppressed by controlling the pH of the dope, and have completed the present invention.
[0007]
Thus, according to the present invention, the first problem is that “ an amide polar solvent solution of an aromatic polyamide having a pH of 4 to 7 and an amide polar solvent dispersion of conductive carbon fine particles having a pH of 10 to 13”. becomes mixed bets, an amide based polar solvent solution of the aromatic polyamide, a doped conductive carbon particles is contained 8 to 40 wt% based on the weight of the aromatic polyamide, pH of the dope There as possible out be accomplished by conducting aromatic polyamide fiber dope. ", which is a 6-8.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The aromatic polyamide as used in the present invention is a polymer in which one or two or more divalent aromatic groups are directly linked by an amide bond, and the aromatic group has two aromatic rings as oxygen, It may be bonded with a sulfur or alkylene group. In addition, these divalent aromatic groups may include a lower alkyl group such as a methyl group or an ethyl group, a halogen group such as a methoxy group, or a chloro group.
[0009]
Specific examples of such aromatic polyamides include polyparaphenylene terephthalamide, copolyparaphenylene 3,4'-oxydiphenylene terephthalamide, and polymetaphenylene isophthalamide. Among these, from the viewpoint of the stability of the obtained dope and the process stability during spinning, copolyparaphenylene · 3,4′-oxydiphenylene terephthalamide is preferable.
[0010]
Examples of the amide polar solvent used in the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone and the like. N-methyl-2-pyrrolidone is preferred from the viewpoints of handleability and stability from polymerization of the aromatic polyamide to dope adjustment and wet spinning process, and toxicity of the solvent.
[0011]
The dope of the present invention consisting of the above aromatic polyamide and amide polar solvent tends to lower the discharge stability during spinning if the concentration of the aromatic polyamide is too low, while the dope viscosity is too high. In the same way, the dope discharge stability at the time of spinning deteriorates rapidly, and stable spinning is likely to be difficult due to a sudden rise in pressure in the spinning pack, so the range of 4 to 7% by weight is appropriate. .
[0012]
Next, the conductive carbon fine particles used in the present invention are not particularly limited as long as they are electrically conductive and do not impair the fiber forming ability, but the average particle diameter is usually 0.1 μm or less. The oil absorption amount is 20 ml / 100 g or more, preferably 50 ml / 100 g or more.
[0013]
The conductive carbon fine particle content in the dope needs to be 8 to 40% by weight, preferably 10 to 20% by weight, based on the weight of the aromatic polyamide. When the content is less than 8% by weight, the conductivity of the resulting fiber becomes insufficient. On the other hand, when it exceeds 40% by weight, the spinnability of the dope is lowered and stable spinning becomes difficult. Therefore, it is not preferable.
[0014]
In addition to the above requirements, it is important that the dope of the present invention has a pH of the dope in the range of 6-8. When the pH of the dope is less than 6, it is presumed that the conductive carbon fine particles in the dope are likely to aggregate, and the dope is not stable due to the dispersibility of the fine particles, so that stable spinning is possible. It becomes difficult. On the other hand, if it exceeds 8, the unreacted material of the agent (neutralizing agent) usually used to achieve the pH remains as fine particles, so that the pressure in the spin pack is likely to increase, and it is also stable. It becomes difficult to spin.
[0015]
The dope of the present invention described above can be adjusted, for example, by the following method. That is, according to a conventionally known method, an aromatic dicarboxylic acid chloride and an aromatic diamine are reacted in an amide polar solvent, and then the by-produced hydrochloric acid is neutralized with a neutralizing agent such as calcium hydroxide fine particles. It can be easily produced by using an amide polar solvent solution of an aromatic polyamide having a pH of 4 to 7 and mixing this with an amide polar solvent dispersion of conductive carbon fine particles having a pH of 10 to 13. it can.
[0016]
Here, when the pH of the amide-based polar solvent solution of the aromatic polyamide is less than 4, it is not preferable because the deterioration of the aromatic polyamide is likely to occur. On the other hand, when the pH exceeds 7, it is generated as a by-product. Neutralizing agents such as calcium hydroxide fine particles used for neutralizing hydrochloric acid are likely to remain as unreacted fine particles, and the pH of the finally obtained dope tends to exceed 8, which is not preferable.
[0017]
In addition, it is important that the conductive carbon fine particles are mixed with an amide polar solvent solution of an aromatic polyamide as a dispersion uniformly dispersed in an amide polar solvent. For example, the fine particles are mixed as a powder. This is not preferable because aggregates are easily formed during mixing. Furthermore, when the conductive carbon fine particles are mixed as an amide-based polar solvent dispersion, the pH of the dispersion needs to be in the range of 10-13. Even if the pH of the dispersion is outside the range of 10 to 13, it is not preferable because the dispersibility of the conductive carbon fine particles is lowered and it becomes difficult to disperse uniformly.
[0018]
In addition, you may adjust using the amide type | system | group polar solvent dispersion of neutralizing agents, such as calcium hydroxide microparticles | fine-particles, so that the pH of the dope obtained may be in the range of 6-8.
[0019]
From the dope of the present invention, a conductive aromatic polyamide fiber can be easily obtained by a conventionally known method for producing an aromatic polyamide fiber. For example, spinning is performed by a semi-dry semi-wet spinning method, and then the specific resistance value (temperature 20) is easily set by controlling the orientation / crystal state by appropriately setting the stretching conditions such as the stretching ratio, stretching temperature, and heat setting temperature. A product having a conductivity in the range of 10 0 Ω · cm to 10 8 Ω · cm is obtained.
[0020]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each characteristic value in an Example was measured with the following method.
<Specific resistance value (volume resistivity value) ρ>
Using a resistance value measuring device SM-8210 pole super insulation meter manufactured by Toa Denpa Kogyo Co., Ltd., measurement was performed as follows under the condition of a relative humidity of 30%. An electric resistance value R (Ω) is measured by applying a voltage of 100 (V) to both ends of a sample fiber having a length of 10 cm, and ρ (Ω · cm) = R × (where the cross-sectional area of the fiber is S (cm 2 ). S / 10). The cross-sectional area of the fiber was calculated by setting the fiber density to 1.5 g / cm 3 .
[0021]
[Example 1]
MPS-1504 Black (T) (manufactured by Dainichi Seika Co., Ltd.) is used as the conductive carbon fine particles and dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a dispersion having a concentration of 10% by weight and PH 11.0. It was adjusted. This carbon fine particle dispersion was mixed with an NMP solution of 6% by weight of copolyparaphenylene 3,4'-oxydiphenylene terephthalamide (aromatic polyamide having a copolymerization molar ratio of 1: 1) (PH adjusted to 5.0). The carbon fine particles in the resulting dope were added at a rate of 15.0% by weight based on the weight of the aromatic polyamide, and mixed with stirring at a temperature of 60 ° C. for 4 hours. At that time, an NMP dispersion having a calcium hydroxide concentration of 22.5% by weight was added in a small amount so that the pH of the resulting dope was 7.0.
[0022]
Using the obtained dope, it is discharged from a spinneret having a hole diameter of 0.3 mm and a hole number of 100 holes at a rate of 20 cc per minute, and is spun into an aqueous solution having an NMP concentration of 30% by weight through an air gap called an air gap. After being washed (semi-dry and semi-wet spinning method), washed with water, dried, then stretched 4.0 times at a temperature of 530 ° C., and then wound at a speed of 80 m / min to obtain a yarn of 139 dtex / 50 fil. The specific resistance value of the obtained yarn was 5.0 × 10 3 Ω · cm. The dope had good stability and could be spun and drawn stably for a long time.
[0023]
[Examples 2 to 5, Comparative Examples 1 to 4]
The pH of the NMP dispersion of conductive carbon fine particles and the pH of the NMP dispersion of aromatic polyamide are as shown in Table 1, and the content of conductive carbon fine particles and the pH of the dope are as shown in Table 1. A conductive aromatic polyamide fiber was obtained in the same manner as in Example 1 except that the adjustment was performed. The results are summarized in Table 1.
[0024]
[Table 1]
【The invention's effect】
According to the dope of the present invention, since the dope is excellent in stability, it is possible to stably produce conductive fibers of uniform quality. Moreover, since the stability of the yarn production is good, the changeable range of the yarn production conditions is expanded, and the conductivity of the conductive fibers that can be easily obtained can be controlled.
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