JP2007023430A - Method for producing conductive aromatic polyamide fiber - Google Patents
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- JP2007023430A JP2007023430A JP2005207945A JP2005207945A JP2007023430A JP 2007023430 A JP2007023430 A JP 2007023430A JP 2005207945 A JP2005207945 A JP 2005207945A JP 2005207945 A JP2005207945 A JP 2005207945A JP 2007023430 A JP2007023430 A JP 2007023430A
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- 239000004760 aramid Substances 0.000 title claims abstract description 55
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000010419 fine particle Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- 238000006116 polymerization reaction Methods 0.000 description 4
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- KDISMIMTGUMORD-UHFFFAOYSA-N 1-acetylpiperidine Chemical compound CC(=O)N1CCCCC1 KDISMIMTGUMORD-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013351 cheese Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-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
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006017 homo-polyamide Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
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- GXMIHVHJTLPVKL-UHFFFAOYSA-N n,n,2-trimethylpropanamide Chemical compound CC(C)C(=O)N(C)C GXMIHVHJTLPVKL-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- REPVNSJSTLRQEQ-UHFFFAOYSA-N n,n-dimethylacetamide;n,n-dimethylformamide Chemical compound CN(C)C=O.CN(C)C(C)=O REPVNSJSTLRQEQ-UHFFFAOYSA-N 0.000 description 1
- VIJUZNJJLALGNJ-UHFFFAOYSA-N n,n-dimethylbutanamide Chemical compound CCCC(=O)N(C)C VIJUZNJJLALGNJ-UHFFFAOYSA-N 0.000 description 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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Abstract
Description
本発明は，導電性芳香族ポリアミド繊維の製造方法に関する。さらに詳しくは、熱処理することで、導電性微粒子の添加量を増やすことなく、優れた導電性を有する芳香族ポリアミド繊維の熱処理を加える製造方法に関する。 The present invention relates to a method for producing a conductive aromatic polyamide fiber. More specifically, the present invention relates to a production method in which heat treatment is performed to heat-treat aromatic polyamide fibers having excellent conductivity without increasing the amount of conductive fine particles added.
従来、芳香族ジカルボン酸成分と芳香族ジアミン成分とからなる芳香族ポリアミド繊維、特にパラ系の芳香族ポリアミド繊維は、その強度、高弾性率、高耐熱性といった特性を生かして産業用途、衣料用途に広く用いられている。 Conventionally, aromatic polyamide fibers composed of an aromatic dicarboxylic acid component and an aromatic diamine component, especially para-type aromatic polyamide fibers, are used in industrial and clothing applications by taking advantage of their strength, high elastic modulus, and high heat resistance. Widely used in
一方、従来から除電性能に優れた導電性芳香族ポリアミド繊維については、種々提案がなされており、例えば繊維表面に金属メッキを施して導電性を付与するものや、導電性カーボンブラックを樹脂やゴム類に分散させ、これを繊維表面にコートすることによって導電性被覆層を形成させたもの、導電性微粒子などを充填剤として用いるものなどがある。しかし、これらは、製造工程が複雑で技術的に困難であったり、実使用における摩耗や繰り返し洗濯といった外的作用によって導電性が容易に低下してしまったり、良好な導電性能を得るために多量の導電性微粒子を添加することで、紡糸工程での安定性が悪くなるという問題があった。 On the other hand, various proposals have been made for conductive aromatic polyamide fibers that have been excellent in static elimination performance. For example, a conductive metal black is applied to the fiber surface to impart conductivity, or conductive carbon black is used as a resin or rubber. There are those in which a conductive coating layer is formed by being dispersed on a fiber and coated on the fiber surface, and those using conductive fine particles as a filler. However, the manufacturing process is complicated and technically difficult, the conductivity easily decreases due to external effects such as wear and repeated washing in actual use, and a large amount for obtaining good conductivity performance. There was a problem that the stability in the spinning process was deteriorated by adding the conductive fine particles.
また、特許文献１（特開昭６２−１８４１２７号公報）には、芳香族ポリアミド繊維を水で膨潤させた状態で水溶性の導電性物質を接触させることにより、導電性芳香族ポリアミド繊維を提供する方法が提案されているが、上記提案と同じく実使用における摩耗や繰り返し洗濯といった外的作用によって導電性が容易に低下してしまうという問題があった。
さらに、特許文献２（特開２００１−０４９５３２号公報）には、導電性カーボンブラックを含有する熱可塑性ポリアミドからなる導電ポリマー層と熱可塑性ポリアミドからなる保護ポリマー層とが複合されてなり、かつ導電ポリマー層が繊維表面に露出している導電性繊維が提案されている。しかし、この場合、導電性能を向上するためには、熱可塑性ポリアミド中の導電性カーボンブラックの含有量を増やすことが必要となるが、その場合、紡糸性が極端に悪化するという問題があった。
Patent Document 1 (Japanese Patent Application Laid-Open No. 62-184127) provides a conductive aromatic polyamide fiber by bringing a water-soluble conductive substance into contact with the aromatic polyamide fiber swollen with water. However, as with the above proposal, there has been a problem that the electrical conductivity is easily lowered by an external action such as wear or repeated washing in actual use.
Further, Patent Document 2 (Japanese Patent Application Laid-Open No. 2001-049532) is composed of a composite of a conductive polymer layer made of thermoplastic polyamide containing conductive carbon black and a protective polymer layer made of thermoplastic polyamide, and conductive. Conductive fibers have been proposed in which a polymer layer is exposed on the fiber surface. However, in this case, in order to improve the conductive performance, it is necessary to increase the content of the conductive carbon black in the thermoplastic polyamide. In this case, there is a problem that the spinnability is extremely deteriorated. .
このように、従来においては、外的作用に強く、長期に亘り導電性を有し、紡糸工程において安定的に生産可能な芳香族ポリアミド繊維は得られていないのが実情である。
本発明の目的は、外的作用に強く、長期の使用に耐えうる、熱処理を加えることで工程安定性に優れる導電性芳香族ポリアミド繊維の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a conductive aromatic polyamide fiber that is resistant to external action and can withstand long-term use, and is excellent in process stability by applying heat treatment.
本発明は、導電性微粒子を含有する導電性芳香族ポリアミド繊維を、温度４５０〜５５０℃の雰囲気下で、張力１．０ｃＮ／ｄｔｅｘ以下、時間０．５秒以上熱処理することを特徴とする導電性芳香族ポリアミド繊維の製造方法に関する。
ここで、導電性微粒子の導電性芳香族ポリアミド繊維中における含有量は、導電性芳香族ポリアミド繊維を構成する芳香族ポリアミドに対して、好ましくは５〜３０重量％である。
また、上記導電性微粒子としては、好ましくは導電性カーボンブラック微粒子が挙げられる。
さらに、本発明の熱処理後の導電性芳香族ポリアミド繊維の、温度２０℃、湿度６５％における体積固有抵抗値は、好ましくは１×１０-1〜１０８Ω・ｃｍである。
The present invention is characterized in that a conductive aromatic polyamide fiber containing conductive fine particles is heat-treated in an atmosphere at a temperature of 450 to 550 ° C., a tension of 1.0 cN / dtex or less, and a time of 0.5 seconds or more. The present invention relates to a method for producing a reactive aromatic polyamide fiber.
Here, the content of the conductive fine particles in the conductive aromatic polyamide fiber is preferably 5 to 30% by weight with respect to the aromatic polyamide constituting the conductive aromatic polyamide fiber.
Further, the conductive fine particles are preferably conductive carbon black fine particles.
Furthermore, the volume specific resistance value of the conductive aromatic polyamide fiber after the heat treatment of the present invention at a temperature of 20 ° C. and a humidity of 65% is preferably 1 × 10 −1 to 10 8 Ω · cm.
本発明によれば、帯電防止繊維、保護衣料、フィルターなどの用途として長期間に亘り優れた除電性能を有し、安定的に生産可能な導電性繊維の熱処理を加える製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method which adds the heat processing of the conductive fiber which has the excellent static elimination performance over a long period of time as uses, such as an antistatic fiber, protective clothing, and a filter, and can be produced stably. it can.
本発明は、導電性微粒子を含有する芳香族ポリアミド繊維を特定の条件下で熱処理することにより、外的作用に強く、長期の使用に耐えうる導電性芳香族ポリアミド繊維を得るものである。
本発明で用いる芳香族ポリアミドとは、ポリアミドを構成する繰り返し単位の８０モル％以上(好ましくは９０モル％以上)が、下記式(1)で表される芳香族ホモポリアミド、または、芳香族コポリアミドからなるものである。
−ＮＨＡｒ１ＮＨＣＯＡｒ２ＣＯ− ・・・（１）
ここで、Ａｒ１、Ａｒ２は芳香族基を表し、なかでも下記式(２)から選ばれた同一の、または相異なる芳香族基からなるものが好ましい。ただし、芳香族基の水素原子は、ハロゲン原子、低級アルキル基、フェニル基などで置換されていてもよい。
The present invention provides a conductive aromatic polyamide fiber that is resistant to external action and can withstand long-term use by heat-treating an aromatic polyamide fiber containing conductive fine particles under specific conditions.
The aromatic polyamide used in the present invention is an aromatic homopolyamide represented by the following formula (1) or an aromatic copolyamide in which 80 mol% or more (preferably 90 mol% or more) of the repeating units constituting the polyamide is used. It is made of polyamide.
-NHAr 1 NHCOAr 2 CO- (1)
Here, Ar 1 and Ar 2 represent an aromatic group, and among them, those composed of the same or different aromatic groups selected from the following formula (2) are preferable. However, the hydrogen atom of the aromatic group may be substituted with a halogen atom, a lower alkyl group, a phenyl group, or the like.
このような芳香族ポリアミドの製造方法や特性については、例えば、英国特許第１５０１９４８号明細書、米国特許第３７３３９６４号明細書、同第３７６７７５６号明細書、同第３８６９４２９号明細書、特開昭４９-１００３２２号公報、特開昭４７-１０８６３号公報、特開昭５８-１４４１５２号公報、特開平４-６５５１３号公報などに記載されており、具体的には、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、あるいはポリメタフェニレンイソフタルアミドなどが例示される。 With respect to the production method and characteristics of such aromatic polyamides, for example, British Patent No. 1501948, US Pat. Nos. 3,733,964, 3,767,756, and 3,869,429, JP-A-4949 No.-100322, JP-A-47-10863, JP-A-58-144152, JP-A-4-65513 and the like. Specifically, polyparaphenylene terephthalamide, copolypara Examples include phenylene 3,4′-oxydiphenylene terephthalamide, polymetaphenylene isophthalamide, and the like.
一方、導電性微粒子とは、金属微粒子ないしはカーボンブラックなど、それ自体が導電性能を示す物質であって、繊維形成を阻害するようなものでなければ特に限定されないが、製造技術から見て本発明においてはカーボンブラックが好ましく使用される。 On the other hand, the conductive fine particles are not particularly limited as long as they are substances that themselves exhibit conductive performance, such as metal fine particles or carbon black, and do not inhibit fiber formation. In this case, carbon black is preferably used.
本発明で用いる導電性カーボンブラック微粒子としては、ＡＳＴＭ Ｄ２４１４−６５Ｔに準じて測定したジブチルフタレート（ＤＢＰ）吸油量が２０ｍＬ/１００g以上である導電性カーボンブラック微粒子が好ましく用いられ、ＤＢＰ吸油量が５０ｍＬ/１００g以上である高導電性カーボンブラック微粒子がより好ましく用いられる。 As the conductive carbon black fine particles used in the present invention, conductive carbon black fine particles having a dibutyl phthalate (DBP) oil absorption measured in accordance with ASTM D2414-65T of 20 mL / 100 g or more are preferably used, and the DBP oil absorption is 50 mL. Highly conductive carbon black fine particles having a weight of 100 g or more are more preferably used.
また、導電性カーボンブラック微粒子としては、その体積固有抵抗値が、温度２０℃および湿度６５％条件下で測定したときに、１×１０〜１８ｍΩである電気抵抗値を有するものが好ましく用いられ、１１〜１５ｍΩであるものがより好ましく用いられる。なお、本発明でいう「体積固有抵抗値」とは、後述する測定法での測定値をいう。 Further, as the conductive carbon black fine particles, those having an electric resistance value of 1 × 10 to 18 mΩ when the volume resistivity value is measured under the conditions of a temperature of 20 ° C. and a humidity of 65% are preferably used. Those having 11 to 15 mΩ are more preferably used. The “volume resistivity value” as used in the present invention refers to a value measured by a measurement method described later.
導電性微粒子の導電性芳香族ポリアミド繊維中における含有量は、該導電性芳香族ポリアミド繊維を構成する芳香族ポリアミドに対する含有量として、導電性能と紡糸の安定性から５〜３０重量％の範囲が好ましく、さらに好ましくは１０〜２０重量％である。含有量が５重量％より低いと繊維の比抵抗値はカーボンブラック未添加糸と殆ど変わらず、導電性能を示さない。一方、含有量が４０重量％を超えるときには、紡糸時の糸切れが頻発し連続的な紡糸が不可能である。 The content of the conductive fine particles in the conductive aromatic polyamide fiber ranges from 5 to 30% by weight in terms of the conductive performance and spinning stability as the content of the aromatic polyamide constituting the conductive aromatic polyamide fiber. Preferably, it is 10 to 20% by weight. When the content is lower than 5% by weight, the specific resistance value of the fiber is almost the same as that of the carbon black non-added yarn, and does not show conductive performance. On the other hand, when the content exceeds 40% by weight, yarn breakage frequently occurs during spinning, and continuous spinning is impossible.
本発明の導電性芳香族ポリアミド繊維は、上記芳香族ポリアミドを有機溶媒に溶解させて等方性のドープになし、例えばこれに同じ有機溶媒に分散させたカーボンブラック微粒子などの導電性微粒子を添加して湿式紡糸する。ここで、ドープは、芳香族ポリアミドが溶解している限り、溶液重合を行った後の有機溶媒ドープそのままでも、別途得られた芳香族ポリアミドを有機溶媒に溶解させたものでもよい。特に、溶液重合反応を行った後のそのままのものが好ましい。 The conductive aromatic polyamide fiber of the present invention is obtained by dissolving the aromatic polyamide in an organic solvent to form an isotropic dope. For example, conductive fine particles such as carbon black fine particles dispersed in the same organic solvent are added thereto. And wet spinning. Here, as long as the aromatic polyamide is dissolved, the dope may be an organic solvent dope after solution polymerization is performed as it is, or a separately obtained aromatic polyamide may be dissolved in an organic solvent. In particular, the one after the solution polymerization reaction is preferable.
重合溶媒あるいは有機の再溶解溶媒としては、一般に公知の非プロトン性有機極性溶媒を用いるが、例を挙げるとＮ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、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，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルプロピオンアミド、Ｎ，Ｎ−ジメチルブチルアミド、Ｎ，Ｎ−ジメチルイソブチルアミド、Ｎ−メチルカプロラクタム、Ｎ，Ｎ−ジメチルメトキシアセトアミド、Ｎ−アセチルピロリジン、Ｎ−アセチルピペリジン、Ｎ−メチルピペリドン−２、Ｎ，Ｎ’−ジメチルエチレン尿素、Ｎ，Ｎ’−ジメチルプロピレン尿素、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルマロンアミド、Ｎ−アセチルピロリドン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル尿素、ジメチルスルホキシドなどである。 As a polymerization solvent or an organic redissolving solvent, generally known aprotic organic polar solvents are used. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylformamide N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N, N-dimethylbutyramide, N, N-dimethylisobutyramide, N-methylcaprolactam, N, N-dimethylmethoxy Acetamide, N-acetylpyrrolidine, N-acetylpiperidine, N-methylpiperidone-2, N, N′-dimethylethyleneurea, N, N′-dimethylpropyleneurea, N, N, N ′, N′-tetramethylmalonamide N-acetylpyrrolidone, N, N, N ′, N′-tetramethylurea, dimethyl Sulfoxide, and the like.
本発明における芳香族ポリアミドの重合度は特に制限されないが、該ポリマーが溶媒に溶けるならば、成形加工性を損なわない範囲内で重合度は大きい方が好ましい。本発明の芳香族ポリアミドを溶液重合する場合、酸成分とジアミン成分の比は実質的に等モルで反応させるが、重合度制御のためいずれかの成分を過剰に用いることもできる。また、末端封鎖剤として単官能性の酸成分、アミン成分を使用しても良い。 The degree of polymerization of the aromatic polyamide in the present invention is not particularly limited. However, if the polymer is soluble in a solvent, it is preferable that the degree of polymerization is large as long as the moldability is not impaired. When the aromatic polyamide of the present invention is subjected to solution polymerization, the ratio of the acid component to the diamine component is reacted in substantially equimolar amounts, but either component can be used in excess for controlling the degree of polymerization. Moreover, you may use a monofunctional acid component and an amine component as a terminal blocker.
上記のごとくして得られる等方性のドープは、湿式紡糸される。この場合、該ドープを凝固浴の中に直接吐出しても良いし、あるいはエアギャップを設けてもよい。凝固浴は、芳香族ポリアミドの貧溶媒が用いられるが、芳香族ポリアミドドープの溶媒が急速に抜け出して芳香族ポリアミド繊維に欠陥ができないように、通常は良溶媒を添加して凝固速度を調節する。一般には、貧溶媒としては水、良溶媒としては芳香族ポリアミドドープ用の溶媒を用いるのが好ましい。良溶媒／貧溶媒の比は、芳香族ポリアミドの溶解性や凝固性にも依るが、１５／８５から４０／６０が一般的に好ましい。 The isotropic dope obtained as described above is wet-spun. In this case, the dope may be discharged directly into the coagulation bath, or an air gap may be provided. For the coagulation bath, a poor solvent for aromatic polyamide is used, but usually a good solvent is added to adjust the coagulation rate so that the aromatic polyamide dope solvent quickly escapes and the aromatic polyamide fiber is not defective. . In general, it is preferable to use water as the poor solvent and an aromatic polyamide dope solvent as the good solvent. The ratio of good solvent / poor solvent is generally preferably 15/85 to 40/60, although it depends on the solubility and coagulability of the aromatic polyamide.
得られた繊維は、この段階では充分に配向していないので、この後、熱延伸して広角Ｘ線回折より求めた結晶配向度が８９％以上、結晶化度が７４％以上と高度に配向および結晶化させることが好ましい。これより、結晶配向度、結晶化度のどちらか一方または両方が低い場合には、本発明の熱処理を施しても得られる繊維の機械的物性が不充分となりやすい。熱延伸の温度は、芳香族ポリアミドのポリマー骨格にもよるが、３００℃以上５５０℃以下であることが好ましく、また、延伸倍率は１０倍以上が好ましい。 Since the obtained fiber is not sufficiently oriented at this stage, the crystal orientation degree determined by wide-angle X-ray diffraction after hot drawing is 89% or more, and the degree of crystallinity is 74% or more. And it is preferably crystallized. Accordingly, when one or both of the degree of crystal orientation and the degree of crystallinity are low, the mechanical properties of the fiber obtained even when the heat treatment of the present invention is performed tend to be insufficient. The temperature of hot stretching depends on the polymer backbone of the aromatic polyamide, but is preferably 300 ° C. or higher and 550 ° C. or lower, and the draw ratio is preferably 10 times or higher.
本発明は、上記のように等方性のドープを湿式紡糸して得られる導電性芳香族ポリアミド繊維を、下記条件で緊張熱処理することに最大の特徴を有するもので、かくすることにより、外的作用に強く、長期にわたり導電性を有する、本発明の導電性芳香族ポリアミド繊維が得られる。 The present invention has the greatest feature in tension heat treatment of the conductive aromatic polyamide fiber obtained by wet spinning the isotropic dope as described above under the following conditions. It is possible to obtain the conductive aromatic polyamide fiber of the present invention, which is strong in action and has conductivity over a long period of time.
すなわち、本発明の熱処理によれば、このようにして、湿式紡糸−延伸された導電性芳香族ポリアミド繊維を、さらに温度４５０〜５５０℃の雰囲気下で、張力１．０ｃＮ／ｄｔｅｘ以下、時間０．５秒以上、熱処理する。
導電性芳香族ポリアミド繊維を熱処理することで、体積固有抵抗値の制御が容易となる。熱処理温度は、導電性能から４５０〜５５０℃の範囲が必要であり、好ましくは５２０〜５５０℃である。熱処理温度が４５０℃より低いと繊維の体積固有抵抗値は熱処理前と殆ど変わらず、熱処理をする優位性がない。一方、熱処理温度が５５０℃を超えるときには芳香族ポリアミドの熱劣化が起こり、高強力繊維としてのアラミド繊維の特徴が無くなる。
また、熱処理における張力は、１．０ｃＮ／ｄｔｅｘ以下であることが必要であり、好ましくは０．０１〜０．８ｃＮ／ｄｔｅｘである。張力が１．０ｃＮ／ｄｔｅｘを超えると繊維が延伸され、さらなる抵抗値の上昇を招くため好ましくない。さらに、熱処理時間は０．５秒以上であることが必要であり、好ましくは１．０〜３．０秒である。熱処理時間が０．５秒より短いと繊維に伝わる熱量が不足するため、体積固有抵抗値の制御が困難となるため好ましくない。
That is, according to the heat treatment of the present invention, the wet-spun and stretched conductive aromatic polyamide fiber is further subjected to a tension of 1.0 cN / dtex or less for a time 0 in an atmosphere at a temperature of 450 to 550 ° C. Heat treatment for 5 seconds or more.
By heat-treating the conductive aromatic polyamide fiber, the volume specific resistance value can be easily controlled. The heat treatment temperature needs to be in the range of 450 to 550 ° C., preferably 520 to 550 ° C., from the viewpoint of the conductive performance. When the heat treatment temperature is lower than 450 ° C., the volume resistivity value of the fiber is almost the same as that before the heat treatment, and there is no superiority to the heat treatment. On the other hand, when the heat treatment temperature exceeds 550 ° C., the aromatic polyamide is thermally deteriorated, and the characteristics of the aramid fiber as the high-strength fiber are lost.
Moreover, the tension in the heat treatment needs to be 1.0 cN / dtex or less, and preferably 0.01 to 0.8 cN / dtex. When the tension exceeds 1.0 cN / dtex, the fiber is stretched and further increases in resistance value, which is not preferable. Furthermore, the heat treatment time needs to be 0.5 seconds or more, and preferably 1.0 to 3.0 seconds. When the heat treatment time is shorter than 0.5 seconds, the amount of heat transmitted to the fiber is insufficient, and it is difficult to control the volume resistivity value, which is not preferable.
導電性芳香族ポリアミド繊維を、上記温度、張力、処理時間にて熱処理を行うことにより、温度２０℃、湿度６５％における体積固有抵抗値を１０−１〜１０８Ω・ｃｍに制御することが可能である。 By conducting heat treatment of the conductive aromatic polyamide fiber at the above temperature, tension, and treatment time, the volume resistivity value at a temperature of 20 ° C. and a humidity of 65% can be controlled to 10 −1 to 10 8 Ω · cm. Is possible.
ここで、体積固有抵抗値ρ（Ω・cm）の測定は、東亜電波工業株式会社製の抵抗値測定機 ＳＭ−８２１０極超絶縁計を用いて、相対湿度３０%の条件下で測定した。さらに具体的には、導電性芳香族ポリアミド繊維の試料長Ｌ（ｃｍ）を１０ｃｍとし、この１０ｃｍ間に１００（Ｖ）の電圧をかけてそのときの電気抵抗値Ｒ（Ω）を測定し、繊維の断面積をＳ（ｃｍ２）としてρ（Ω・ｃｍ）＝Ｒ×（Ｓ／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は総繊度値をそのまま重量に読み替えた値として、
Ｓ＝Ｄ／（１,０００,０００×ｄ）より求めた。
Here, the volume resistivity value ρ (Ω · cm) was measured under the condition of a relative humidity of 30% using a resistance value measuring device SM-8210 pole super insulation meter manufactured by Toa Denpa Kogyo Co., Ltd. More specifically, the sample length L (cm) of the conductive aromatic polyamide fiber is 10 cm, a voltage of 100 (V) is applied between the 10 cm, and the electrical resistance value R (Ω) at that time is measured. The cross-sectional area of the fiber was determined as ρ (Ω · cm) = R × (S / L) with S (cm 2 ). Here, S is regarded as a fiber density d = 1.5 g / cm 3, and D is a value obtained by replacing the total fineness value with the weight as it is,
It calculated | required from S = D / (1,000,000 * d).
以下、実施例を挙げて本発明をさらに具体的に説明する。
実施例１
導電性カーボンブラックとして、ＭＰＳ−１５０４ Ｂｌａｃｋ（Ｔ）（大日精化社製、ＤＢＰ吸油量：１４０ｍｌ／１００ｇ、体積固有抵抗値：１４ｍΩ）に、Ｎ−メチルピロリドンを添加、混合して該カーボンブラックが１０重量％のＮ−メチルピロリドン分散液を調製した。このカーボンブラック分散液を、コポリパラフェニレン・３，４'−オキシジフェニレン・テレフタルアミドの６重量％のＮ−メチルピロリドン溶液に対して、カーボンブラックが１４．９重量％となるように添加、攪拌混合し紡糸原液を調製した。
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
As a conductive carbon black, N-methylpyrrolidone was added to and mixed with MPS-1504 Black (T) (manufactured by Dainichi Seika Co., Ltd., DBP oil absorption: 140 ml / 100 g, volume resistivity: 14 mΩ), and the carbon black A 10% by weight N-methylpyrrolidone dispersion was prepared. This carbon black dispersion was added to a 6 wt% N-methylpyrrolidone solution of copolyparaphenylene 3,4′-oxydiphenylene terephthalamide so that the carbon black would be 14.9 wt%, A spinning dope was prepared by stirring and mixing.
上記紡糸原液を、半乾半湿式紡糸機を用い、孔径０．３ｍｍでホール数１００の紡糸ノズルから毎分２０ｃｃ／分の吐出条件でエアーギャップと呼ばれる空隙部分を通じてＮ−メチルピロリドン３０重量％水溶液で温度５０℃の凝固浴中に紡出し凝固したのち、５０℃で水洗、２００℃で乾燥し、次いで５３０℃で４倍に延伸し、熱処理温度５５０℃、張力０．６ｃＮ／ｄｔｅｘ、処理時間１．０秒で熱処理し、８０ｍ／ｍｉｎで２８０ｄｔｅｘ／１００fをチーズに巻き取り糸条を得た。このチーズの表層よりサンプリングをし、導電性能を評価したところ、体積固有抵抗値は５．０×１００Ω・ｃｍであった。 Using a semi-dry and semi-wet spinning machine, the above spinning dope is 30% by weight of N-methylpyrrolidone through a void portion called an air gap under a discharge condition of 20 cc / min from a spinning nozzle having a hole diameter of 0.3 mm and a hole number of 100 at a rate of 20 cc / min. After spinning and coagulating in a coagulation bath at a temperature of 50 ° C., washing with water at 50 ° C., drying at 200 ° C., and then stretching 4 times at 530 ° C., heat treatment temperature 550 ° C., tension 0.6 cN / dtex, treatment time Heat treatment was performed for 1.0 second, and 280 dtex / 100f was wound around cheese at 80 m / min to obtain a yarn. Sampling was performed from the surface layer of this cheese, and the electrical conductivity was evaluated. As a result, the volume specific resistance value was 5.0 × 10 0 Ω · cm.
実施例２
熱処理における処理温度が５４０℃であること以外は、実施例１と全く同じとしたときの体積固有抵抗値は２．０×１０２Ω・ｃｍであった。
Example 2
Except that the treatment temperature in the heat treatment was 540 ° C., the volume resistivity value was 2.0 × 10 2 Ω · cm when exactly the same as in Example 1.
実施例３
熱処理における張力が１．０ｃＮ／ｄｔｅｘｇであること以外は、実施例２と全く同じとした時の体積固有抵抗値は９．０×１０４Ω・ｃｍであった。
Example 3
Except that the tension in the heat treatment was 1.0 cN / dtexg, the volume resistivity value was 9.0 × 10 4 Ω · cm when exactly the same as in Example 2.
実施例４
熱処理における処理時間が０．５秒であること以外は、実施例２と全く同じとしたときの体積固有抵抗値は６．０×１０２Ω・ｃｍであった。
Example 4
Except that the treatment time in the heat treatment was 0.5 seconds, the volume resistivity value was 6.0 × 10 2 Ω · cm when exactly the same as in Example 2.
実施例５
熱処理における処理温度が５００℃であること以外は、実施例１と全く同じとしたときの体積固有抵抗値は４．０×１０６Ω・ｃｍであった。
Example 5
Except that the treatment temperature in the heat treatment was 500 ° C., the volume resistivity value was 4.0 × 10 6 Ω · cm when exactly the same as in Example 1.
実施例６
熱処理における処理温度が４５０℃であること以外は、実施例１と全く同じとしたときの体積固有抵抗値は８．０×１０７Ω・ｃｍであった。
Example 6
Except that the treatment temperature in the heat treatment was 450 ° C., the volume resistivity value was 8.0 × 10 7 Ω · cm when exactly the same as in Example 1.
比較例１
熱処理を行わないこと以外は、実施例１と全く同じとしたときの体積固有抵抗値は９．０×１０９Ω・ｃｍであった。
Comparative Example 1
The volume resistivity value was 9.0 × 10 9 Ω · cm when exactly the same as Example 1 except that no heat treatment was performed.
比較例２
熱処理における処理温度が４００℃であること以外は、実施例１と全く同じとしたときの体積固有抵抗値は８．０×１０９Ω・ｃｍであった。
Comparative Example 2
Except that the treatment temperature in the heat treatment was 400 ° C., the volume resistivity value was 8.0 × 10 9 Ω · cm when exactly the same as in Example 1.
比較例３
熱処理における処理温度が６００℃であること以外は実施例１と全く同じとしたとき、芳香族ポリアミドの熱劣化により、繊維形状を保たなかった。そのため、抵抗値測定は出来なかった。
Comparative Example 3
When the treatment temperature in the heat treatment was exactly the same as in Example 1 except that the treatment temperature was 600 ° C., the fiber shape was not maintained due to thermal degradation of the aromatic polyamide. Therefore, the resistance value could not be measured.
比較例４
熱処理における張力が１．５ｃＮ／ｄｔｅｘｇであること以外は、実施例２と全く同じとした時の体積固有抵抗値は３．０×１０１０Ω・ｃｍであった。
Comparative Example 4
Except that the tension in the heat treatment was 1.5 cN / dtexg, the volume resistivity value was 3.0 × 10 10 Ω · cm when exactly the same as in Example 2.
比較例５
熱処理における処理時間が０．４秒であること以外は、実施例２と全く同じとしたときの体積固有抵抗値は６．０×１０９Ω・ｃｍであった。
以上の結果を表１に示す。
Comparative Example 5
Except that the treatment time in the heat treatment was 0.4 seconds, the volume resistivity value was 6.0 × 10 9 Ω · cm when exactly the same as in Example 2.
The results are shown in Table 1.
本発明により得られる導電性芳香族ポリアミド繊維は、長期間にわたり優れた除電性能を有し、安定的に生産可能な導電性繊維であるので、帯電防止繊維、保護衣料、フィルターなどの用途として有用である。
The conductive aromatic polyamide fiber obtained by the present invention is a conductive fiber that has excellent static elimination performance over a long period of time and can be stably produced, and is therefore useful for applications such as antistatic fibers, protective clothing, and filters. It is.
Claims (4)
The conductive aromatic fragrance according to any one of claims 1 to 3, wherein the conductive aromatic polyamide fiber after heat treatment has a volume specific resistance value of 1 x 10 -1 to 10 8 Ω · cm at a temperature of 20 ° C and a humidity of 65%. For producing an aromatic polyamide fiber.
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