JP3911654B2 - Method for producing aramid filaments - Google Patents
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- JP3911654B2 JP3911654B2 JP36801797A JP36801797A JP3911654B2 JP 3911654 B2 JP3911654 B2 JP 3911654B2 JP 36801797 A JP36801797 A JP 36801797A JP 36801797 A JP36801797 A JP 36801797A JP 3911654 B2 JP3911654 B2 JP 3911654B2
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Description
【0001】
【発明の属する技術分野】
本発明は、高強度及び高弾性率を有するアラミド長繊維糸の製造方法に関する。
【0002】
【従来の技術】
アラミド繊維、特にパラ配向アラミド繊維は、高強度、高耐熱性等の優れた特性を有するため、産業用途、衣料用途に広く利用されている。
【0003】
パラアラミド繊維の基本的な製造方法については、米国特許第3,767,756号明細書にエアギャップ紡糸工程が提案され、硫酸98〜100.2%に溶かした芳香族ポリアミドの液晶を用いて、凝固、水洗、乾燥する工程で高強力、高弾性のアラミド繊維を得る方法が記載されている。この発明を基本として、さらに高強力糸を得る試みがなされ、一層の高強力糸が得られている。
【0004】
即ち、米国特許第3,767,756号明細書では、ポリマー粘度4.0以上、硫酸98〜100.2%に溶かした芳香族ポリアミドの溶液を用いて、紡糸、凝固、水洗、乾燥する工程で、洗浄張力が乾燥張力の1/3、即ち、2g/D以上(Dは繊維束で測定した単糸デニール)の張力で洗浄し、300℃以下の温度で乾燥することが記載されている。この中で、乾燥張力は、通常の2.5g/D以下に比べてはるかに高い3〜7g/Dにして、水分を少なくとも10%にすることにより、より高強力が得られることを示している。
【0005】
一方、米国特許第4726922号明細書には、低張力下で乾燥した後の水分は原糸の強度に影響しないが、高張力または中張力で乾燥すると、0.5g/D以上の強度上昇が得られ、弾性率も向上することが記載されている。また、水洗、中和の張力を増加させるとそれだけ乾燥張力を下げても高強度が得られることに着目し、原糸強度と弾性率が、実施例Iでは各々27.3g/D、799g/D、実施例IIでは27.4g/D、849g/D、また、26.2g/D、900g/Dの実施例もあり、さらに実施例IIIには強度27.8〜26.4g/D、弾性率869〜909g/Dの記載例もある。
【0006】
しかしながら、これらの乾燥張力は、米国特許第3767756号明細書では3〜7g/D、米国特許第4726922号明細書では3.7〜5.23g/Dと通常の1g/D以下の張力に対し、3〜7倍の張力で乾燥しており、商業生産としては、毛羽、タルミの発生が懸念され、品質の低下が避けられないので、このような方法ではこれ以上の高強度、高弾性糸を得るのは困難である。一方、米国特許第5173236号明細書では低張力(0.05〜0.35g/D)洗浄、乾燥で、口金と凝固浴の組合せにより、27.9〜26.5g/Dの強度を得ているが、弾性率は470〜483g/Dと低いレベルである。
【0007】
また、特開昭60−52617号公報および米国特許第4,560,743号明細書には、低張力乾燥(0.11〜0.45g/D)で、強度が35〜40.2g/d、弾性率540〜470g/dのアラミド繊維原糸を得たという記載がある。この方法では、強度は極めて高い水準になっているが、弾性率が不十分な水準である。
【0008】
上記のとおり、ポリ(pーフェニレンテレフタラミド)からなる従来のアラミド長繊維糸では、マルチフィラメント糸の強度が28.5g/Dを越えるものはなく、あるいは弾性率が950g/Dを越え、かつ強度が22g/D以上である高強度、高弾性糸もない。
【0009】
【発明が解決しようとする課題】
本発明は、商業生産に適応できるマルチフィラメントの物性向上を目的とし、極めて高い強度で、かつ十分な弾性率を有するか、または極めて高い弾性率で、かつ十分な強度を有するポリ(pーフェニレンテレフタラミド)からなるアラミド繊維の製造方法を提供することを課題とするものである。
【0010】
【課題を解決するための手段】
上記課題を解決する手段としての本発明は、ポリ(pーフェニレンテレフタラミド)の硫酸溶解溶液を口金を通してエアーギャップを経て凝固浴に紡出し、 水洗、中和、乾燥工程を経て、マルチフィラメントからなるアラミド長繊維糸を製造する方法において、口金吐出孔径を2.0mil以下とし、製造される長繊維糸の単糸繊度が0.3〜1.4dとなるようにし、凝固浴における単位時間当たりの凝固液量と通過糸質量の比( Mass Ratio) を250以上とし、かつ、乾燥工程における乾燥張力を2.0〜2.5g/Dとすることにより、単糸繊度が0.3〜1.4dで、強度が28.5g/Dを越え、かつ、弾性率が700〜1200g/Dであるアラミド長繊維糸の製造方法である。
さらにまた、ポリ(pーフェニレンテレフタラミド)の硫酸溶解溶液を口金を通してエアーギャップを経て凝固浴に紡出し、 水洗、中和、乾燥工程を経た後、熱処理して、マルチフィラメントからなるアラミド長繊維糸を製造する方法において、口金吐出孔径を2.0mil以下とし、製造される長繊維糸の単糸繊度が0.3〜1.4dとなるようにし、凝固浴における単位時間当たりの凝固液量と通過糸質量の比( Mass Ratio) を250以上とし、乾燥工程における乾燥張力を2.0〜2.5g/Dとし、かつ、熱処理温度を200〜300℃とすることにより、単糸繊度が0.3〜1.4dで、強度が22〜28.5g/D、かつ、弾性率が950〜1200g/Dであるアラミド長繊維糸の製造方法である。
【0012】
【発明の実施の形態】
アラミドは、芳香族ジアミンと芳香族ジカルボン酸がアミド結合した構造単位を有する重合体であり、芳香族ジアミンとしては、p−フェニレンジアミン、m−フェニレンジアミン、4,4´−ジアミノジフェニルエーテル、3,4´−ジアミノジフェニルエーテルまたはこれらの核置換化合物等が挙げられ、ジカルボン酸としては、テレフタル酸、イソフタル酸、2,6−ナフタレンジカルボン酸等が挙げられる。中でもp−フェニレンジアミンとテレフタル酸の組合せが好ましい。
【0014】
本発明法は、パラ系芳香族ポリアミドのホモポリマー、即ち、ポリ(pーフェニレンテレフタラミド)を使用し、米国特許第3,767,765号および4,965,033号明細書で示される液晶を用いたエアギャップ紡糸工程、即ち、乾湿式紡糸(液晶紡糸)工程で高強力糸を得るものである。
【0015】
すなわち、これらの特許が示すとおり、パラ系芳香族ポリアミド繊維の基本製造プロセスは、エアギャップ紡糸工程で液晶の性質を呈するポリマー硫酸溶解溶液(紡糸溶液)を口金吐出孔から押出して繊維の形態になってからエアギャップを通って凝固浴に導かれる。ここで、紡糸溶液中の溶媒に由来する繊維中の濃硫酸成分は、凝固浴である稀硫酸に移動する。その後、繊維は洗浄、中和、乾燥して巻き取られ、必要に応じてさらに熱処理される。凝固浴の技術に関しては米国特許第4,965,033号明細書に記載されている。
本発明法は上記した製造方法を基本とし、各工程における条件変更により商業的に高品質の高強力糸(強度28.5g/D以上、弾性率700〜1200g/D)および高弾性糸(弾性率950〜1200g/D、強度22〜28.5g/D)を製造可能としたものである。
【0016】
また、本発明法では、製造されるアラミド長繊維糸の単糸繊度(単位:d)が、通常商業生産されているアラミド長繊維糸より細いものとなるようにし、具体的には0.3〜1.4dとし、好ましくは0.5〜1.2dとする。
【0017】
本発明法において製造するアラミド長繊維糸の糸条繊度は50〜1000Dであることが好ましい。この長繊維糸の複数本を合糸すれば糸条繊度を50〜10000Dとすることができる。また、この長繊維糸は、通常の繊維の公知の交絡方法により、単繊維を交絡させて使用することも可能である。
【0018】
次に本発明のアラミド長繊維糸を得るための製造方法について、ポリ(パラフェニレンテレフタラミド)からなるマルチフィラメント糸の製造例に沿って説明する。
【0019】
ポリ(p−フェニレンテレフタラミド)を約19.50重量%溶液になるように硫酸に溶解し、凝固点以上の温度(約70℃)でその溶液(紡糸溶液)を紡糸工程に導く。この紡糸工程では、紡糸溶液を例えば孔径2.0milの口金を通し、エアギャップを経て低温(例えば3℃)の希流酸凝固浴中に導いて繊維状に形成し、ついで、水洗、中和工程を経て乾燥後、アラミド長繊維糸を巻取る。
【0020】
この乾湿式紡糸法において、アラミド長繊維糸の強度および弾性率を向上させるためには、繊維が口金から凝固浴に入るまでの間にいかに液晶ドメインを配向し、固定するかという点と、各単糸ごとにいかに均一な凝固を行なうかという点が重要なポイントとなる。
【0021】
また、その後の糸条の張力を種々変更することにより、強度と弾性率をある程度調整することも可能である。
【0022】
一般に、パラ系アラミド繊維は凝固液を通してポリマーを繊維状に凝固させるため、繊維の内外層に2層構造が形成されるが、この2層構造をできるだけ減少させ、表層部分を多くすることが重要である。
【0023】
以上の知見から、本発明のアラミド長繊維糸を製造するには次の条件を採ることが必要である。
【0024】
即ち、口金から吐出後の分子配向を十分高めるために吐出孔を細径化する手段を採用する。通常の吐出孔径が2.5milの吐出孔では十分な配向は得られないので、吐出孔径を2.0mil以下とする。さらに、単糸繊度が1.4d以下となるような細繊度とする。これにより、吐出後に急速かつ均一に凝固させ、高配向化させることができる。
【0025】
また、紡出糸が通過する凝固浴を均一化するためには、その凝固液量と通過糸質量の速度比(Mass Ratio)を250以上とする。これにより十分均一な凝固糸が得られる。この速度比( Mass Ratio )については、米国特許第4,965,033号明細書に記載されている。
【0026】
凝固液と紡出糸を接触させるための方法としては、中心に孔が開いたロート状トレーの凝固浴の孔に紡出糸を通過させ、凝固液を同時に流し込むトレー方式と、紡出糸に凝固液のジェットを噴射するジェット方式を組み合わせるのが好ましい。
【0027】
ジェット方式を採用する場合、凝固液のジェット速度と紡出糸の糸速度の比(Flow Ratio)は1.0〜1.5が好ましい。この範囲を保つことにより、弛みのない、高強度の糸が得られる。
【0028】
紡糸速度/口金吐出線速度の比を1.0〜7.0に保つことが好ましく、さらに1.1〜2.0が好ましく、これは、糸切れおよび単糸間の癒着の防止のために好ましい。
【0029】
また、紡糸速度が低速過ぎる場合にはポリマーの粘度低下が起こり、高速過ぎる場合には紡糸直後の張力が高くなり高強力糸が得られなくなる傾向がある。したがって、紡糸速度は繊度に応じた最適化することが望まれる。
【0030】
さらに、紡糸後、水洗、中和・乾燥にかかる張力も単糸強力に影響し、フィードロールと乾燥ロール間のストレッチ率は1.1〜1.5が好ましい。本発明法では単糸繊度を細径化することにより十分な高配向化を図っているので、乾燥張力は米国特許第4,726,922号明細書に示されるような3〜7g/dの高張力は必要なく、2.0〜2.5g/Dの乾燥張力とする。
【0031】
以上の条件で得られたアラミド長繊維糸は極めて高い強度と十分な弾性率を有する。これを熱処理することにより、さらに弾性率を向上させることができる。ただし、その際、強度は若干低下する。
【0032】
この時の熱処理条件は米国特許第4,726,922号明細書に記載されているように200℃以上、300℃以下の温度とする。好ましくは、230℃〜300℃の温度とする。
【0033】
こうした各製糸条件を選ぶことにより、本発明の高強力糸、高弾性糸を得ることができる。
【0034】
本発明のアラミド長繊維糸は、従来のアラミド長繊維糸と同様に加工することが可能であり、種々の加工品とすることができる。
【0035】
また、これらの加工品はマトリックス中に配備することにより、アラミド繊維強化物とすることができる。マトリックスとしては、天然ゴム、合成ゴム、ポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、ポリ塩化ビニル樹脂、PBT樹脂、PPS樹脂、PPO樹脂、ABS樹脂などの熱可塑性樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂、モルタル、セメント等の無機マトリックス等が挙げられる。
【0036】
マトリックス中に配備する方法としては、単繊維をマトリックス中に混練する方法、繊維糸条にマトリックスを含浸させる方法、繊維布帛にマトリックスを含浸させる方法などが挙げられる。
【0037】
また、本発明のアラミド長繊維糸は上記のような加工品や撚糸形態あるいは原糸を直接供給してベルト、タイヤコード、光ファイバーテンションメンバー、防弾具等の各種産業資材、建材、補強材等の工業材料、耐火服、手袋等の衣料などに利用できる。
【0038】
【実施例】
以下実施例により本発明を具体例に説明する。
【0039】
実施例1〜7
ポリ(p−フェニレンテレフタラミド)を硫酸に溶解して、ポリマー濃度19.50重量%の溶液とし、70℃の溶液状態で紡糸工程に導いた。エアーギャップを経た後の凝固液には、3℃の稀硫酸を用い、凝固液と紡出糸との接触にはトレー方式とジェット方式を併用した。紡出糸の凝固浴通過後、水洗、アルカリ洗浄、乾燥工程を経てアラミド長繊維糸を製造した。得られた長繊維糸の強度、弾性率および伸度を測定し、その結果を表1に示す。表1には、製糸条件も併記した。
【0040】
表1の実施例1〜7に示すとおり、強度28.5g/D以上で弾性率も700g/D以上の高性能原糸が得られた。
【0041】
比較例1〜2
実施例と同じポリマー、同じ製糸工程であるが、製糸条件は表1に示す公知の条件に変更してアラミド長繊維糸を製造した。得られた原糸物性を表1にまとめて示した。比較例1〜2で得られた長繊維糸は本発明に比べ、強度及び弾性率において劣っていた。
【0042】
【表1】
実施例8〜10、比較例3〜4
更に高弾性(950g/D以上)の原糸の実施例を表2に示す。
【0043】
表2の実施例8〜10は各々、表1の実施例5、6および7で得られたアラミド長繊維糸を、290℃もしくは300℃の温度で連続的に熱処理したものである。熱処理して得られた原糸物性を表2に示す。
【0044】
また、比較例3〜4も表2に示す。これは表1の比較例1、2で得られたアラミド長繊維糸を実施例10と同じ熱処理条件で熱処理したものである。
【0045】
実施例8〜10に示すとおり、弾性率は従来の750g/Dレベルに比べ飛躍的に向上している。
【0046】
【表2】
なお、製糸された長繊維糸の複数本を合糸することにより、所望の糸条繊度、例えば50〜10000Dなどとすることができる。
【0047】
【発明の効果】
本発明で得られるポリ(pーフェニレンテレフタラミド)からなるアラミド長繊維糸は、極めて高い強度で、かつ十分な弾性率を有するか、または、極めて高い弾性率で、かつ十分な強度を有するものであるため、従来のポリ(pーフェニレンテレフタラミド)からなるアラミド長繊維糸では適用困難であった各種用途に適用可能となる。 [0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an aramid continuous fiber yarn having high strength and high elastic modulus.
[0002]
[Prior art]
Aramid fibers, particularly para-oriented aramid fibers, have excellent properties such as high strength and high heat resistance, and are therefore widely used in industrial and clothing applications.
[0003]
The basic method for manufacturing a para-aramid fibers are proposed air gap spinning process is in U.S. Patent No. 3,767,756, a liquid crystal aromatic polyamide dissolved in 98 to 100.2% sulfuric acid, A method for obtaining high-strength and high-elasticity aramid fibers in the steps of coagulation, washing with water and drying is described. On the basis of this invention, an attempt to obtain a higher strength yarn has been made, and a higher strength yarn has been obtained.
[0004]
That is, in U.S. Patent No. 3,767,756, polymer viscosity of 4.0 or more, using a solution of aromatic polyamide dissolved in from 98 to 100.2 percent sulfuric acid, spinning, coagulation, washing with water, drying step The washing tension is 1/3 of the drying tension, that is, washing with a tension of 2 g / D or more (D is a single yarn denier measured with a fiber bundle), and drying is performed at a temperature of 300 ° C. or less. . Among them, the drying tension is 3-7 g / D which is much higher than the usual 2.5 g / D or less, and it is shown that higher strength can be obtained by making the moisture at least 10%. Yes.
[0005]
On the other hand, U.S. Patent No. 4726922, water and dried under low tension does not affect the strength of the yarn, and dried under high tension or medium tension, 0.5 g / D or more increase in strength is It is obtained that the elastic modulus is improved. Further, paying attention to the fact that high strength can be obtained even if the drying tension is lowered by increasing the tension of washing and neutralization, the raw yarn strength and elastic modulus are 27.3 g / D and 799 g / in, respectively, in Example I. D, Example II includes 27.4 g / D, 849 g / D, 26.2 g / D, and 900 g / D, and Example III has a strength of 27.8 to 26.4 g / D. There is also a description example of the elastic modulus 869 to 909 g / D.
[0006]
However, these drying tensions, to US Patent No. 3767756 Pat At 3 to 7 g / D, U.S. Patent No. At Pat 4726922 3.7~5.23g / D and less tension normal 1 g / D , It is dried at a tension of 3 to 7 times, and as a commercial production, there is concern about the occurrence of fluff and tarmi, and the deterioration of quality is unavoidable. Is difficult to get. On the other hand, US Patent No. 5173236 low tension (0.05~0.35g / D) washing, with drying, by a combination of the base and the coagulation bath, with the strength of 27.9~26.5g / D However, the elastic modulus is a low level of 470 to 483 g / D.
[0007]
In addition, the 60-52617 discloses and U.S. Patent No. 4,560,743 JP, at low tension drying (0.11~0.45g / D), strong degree 35~40.2G / d, it is described that give the aramid fiber yarns of elastic modulus 540~470g / d. In this method, the strength is extremely high, but the elastic modulus is insufficient.
[0008]
As described above, in the conventional aramid long fiber yarn made of poly (p-phenylene terephthalamide) , the strength of the multifilament yarn does not exceed 28.5 g / D, or the elastic modulus exceeds 950 g / D, and high strength strength is 22 g / D or more, high modulus yarns also have greens.
[0009]
[Problems to be solved by the invention]
The present invention aims to improve the properties of multifilaments that can be applied to commercial production, and has a very high strength and sufficient elastic modulus, or a very high elastic modulus and sufficient strength. it is an object of the present invention to provide a method for manufacturing aramid textiles consisting Terefutaramido).
[0010]
[Means for Solving the Problems]
The present invention as a means for solving the above problems, a poly (p-phenylene terephthalamide) sulfuric acid solution is spun into a coagulation bath through an air gap through an air gap, In a method for producing an aramid long fiber yarn composed of multifilaments through water washing, neutralization, and drying steps, the diameter of the nozzle discharge hole is set to 2.0 mil or less, and the single yarn fineness of the produced long fiber yarn is 0.3 to 1 4d, the ratio of the amount of coagulated liquid per unit time in the coagulation bath to the mass of the passing yarn ( mass ratio) is 250 or more, and the drying tension in the drying step is 2.0 to 2.5 g / D. This is a method for producing an aramid long fiber yarn having a single yarn fineness of 0.3 to 1.4 d, a strength exceeding 28.5 g / D, and an elastic modulus of 700 to 1200 g / D.
Furthermore, a sulfuric acid solution of poly (p-phenylene terephthalamide) is spun into a coagulation bath through an air gap through an air gap, In a method for producing an aramid long fiber yarn composed of multifilaments through water washing, neutralization, and drying steps, the diameter of the nozzle discharge hole is 2.0 mil or less, and the single yarn fineness of the produced long fiber yarn is 0.3 to 1.4d, the ratio of the amount of coagulated liquid per unit time in the coagulation bath to the mass of the passing yarn ( mass ratio) is 250 or more, and the drying tension in the drying step is 2.0 to 2.5 g. / D and a heat treatment temperature of 200 to 300 ° C., the single yarn fineness is 0.3 to 1.4 d, the strength is 22 to 28.5 g / D, and the elastic modulus is 950 to 1200 g / It is a manufacturing method of the aramid long fiber yarn which is D.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
A aramid, the aromatic diamine and an aromatic dicarboxylic acid is a polymer having a structural unit amide bond, the aromatic diamine, p- phenylenediamine, m- phenylenediamine, 4,4'-diaminodiphenyl ether, 3 4,4'-diaminodiphenyl ether or a nucleus-substituted compound thereof, and examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid . Of these, a combination of p-phenylenediamine and terephthalic acid is preferable.
[0014]
The present invention method is a homopolymer of para-aromatic polyamide, i.e., by using poly (p over phenylene terephthalamide), represented by U.S. Pat. No. 3,767,765 and 4,965,033 Pat A high tenacity yarn is obtained by an air gap spinning process using liquid crystal, that is, a dry and wet spinning process (liquid crystal spinning process) .
[0015]
That is, as shown in these patents, the basic manufacturing process of para-aromatic polyamide fibers is a method of extruding a polymer sulfuric acid solution (spinning solution) exhibiting liquid crystal properties in an air gap spinning process from a nozzle discharge hole into a fiber form. After that, it is led to the coagulation bath through the air gap. Here, the concentrated sulfuric acid component in the fiber derived from the solvent in the spinning solution moves to dilute sulfuric acid which is a coagulation bath. Thereafter, the fiber is washed, neutralized, dried and wound up, and further heat-treated as necessary. Respect of the coagulation bath techniques are described in U.S. Patent No. 4,965,033.
The method of the present invention is based on the above-described production method , and commercially high quality high strength yarn (strength 28.5 g / D or more, elastic modulus 700 to 1200 g / D) and high elasticity yarn (elasticity) by changing the conditions in each process . rate 950~1200g / D, in which the intensity 22~28.5g / D) was possible to manufacture.
[0016]
Further, in the present invention method, the single yarn fineness of the aramid filament yarn produced (unit: d) is generally to be those thinner than commercially produced Tei Ru aramid filament yarns, more specifically 0.3 and ~1.4d, good Mashiku is the 0.5~1.2d.
[0017]
Yarn fineness of Alami de filament yarn produced in the present invention method is preferably 50~1000D. If a plurality of these long fiber yarns are combined , the yarn fineness can be set to 50 to 10000D . Moreover, this long fiber yarn can also be used by entangled single fibers by a known entanglement method for ordinary fibers.
[0018]
Next, a production method for obtaining the aramid long fiber yarn of the present invention will be described along with a production example of a multifilament yarn made of poly (paraphenylene terephthalamide).
[0019]
Poly (p-phenylene terephthalamide) is dissolved in sulfuric acid so as to be an approximately 19.50% by weight solution, and the solution (spinning solution) is guided to the spinning process at a temperature above the freezing point (approximately 70 ° C.). In this spinning process, the spinning solvent solution for example through a die having a pore size of 2.0 mil, is formed into fibers led in Mareryu acid coagulation bath cold through an air gap (e.g., 3 ° C.), then washed with water, medium After drying through the summing process, the aramid long fiber yarn is wound up.
[0020]
In this dry-wet spinning method, in order to improve the strength and modulus of the aramid filament yarn, fibers oriented to how the liquid crystal domains until entering the coagulation bath from a nozzle, and that either a fixed, each An important point is how to perform uniform solidification for each single yarn.
[0021]
Further, the strength and elastic modulus can be adjusted to some extent by variously changing the tension of the subsequent yarn.
[0022]
In general, para-aramid fibers coagulate the polymer into a fibrous form through a coagulation solution, so a two-layer structure is formed in the inner and outer layers of the fiber. It is important to reduce this two-layer structure as much as possible and increase the surface layer portion. It is.
[0023]
From the above knowledge, the following conditions are required to produce the aramid long fiber yarn of the present invention .
[0024]
That is, to adopt a means for diameter reduction of the discharge holes in order to increase the molecular orientation after ejection from a die sufficiently. Since a normal orientation can not be obtained with a normal discharge hole diameter of 2.5 mil, the discharge hole diameter is set to 2.0 mil or less . Further, the fineness is such that the single yarn fineness is 1.4 d or less . Thus, rapid and is uniformly solidified after discharge, it is Rukoto to high orientation.
[0025]
Further, in order to equalize the coagulating bath spun yarn passes, its coagulating liquid volume and passing yarn mass velocity ratio of the (Mass Ratio) 2 50 or more. Thereby, a sufficiently uniform coagulated yarn can be obtained. This speed ratio (Mass Ratio) are described in U.S. Patent No. 4,965,033.
[0026]
As a method for contacting the coagulating solution and spun yarn, passes the spun yarn into the hole of the coagulation bath funneled tray hole is opened in the center, the tray system for pouring coagulating liquid at the same time to the spun yarn It is preferable to combine a jet system in which a jet of coagulating liquid is injected.
[0027]
In the case of adopting the jet method, the ratio (Flow Ratio) between the jet speed of the coagulation liquid and the yarn speed of the spun yarn is preferably 1.0 to 1.5. By maintaining this range, a high-strength yarn with no slack can be obtained.
[0028]
It is preferable to maintain the ratio of spinning speed / die discharge linear speed at 1.0 to 7.0. 1 to 2.0 is preferred, which is preferred for the prevention of adhesions between yarn breakage and single yarn.
[0029]
Further, when the spinning speed is too slow to occur decrease the viscosity of the polymer, if too fast tend to not be obtained high tenacity yarn becomes high tension immediately after spinning. Therefore, it is desirable to optimize the spinning speed in accordance with the fineness .
[0030]
Furthermore, the tension applied to washing, neutralization and drying after spinning also affects the single yarn strength, and the stretch ratio between the feed roll and the drying roll is preferably 1.1 to 1.5. Since the present invention method is aimed sufficiently high orientation by the fineness slender, dry tension of 3 to 7 g / d, as shown in U.S. Patent No. 4,726,922 high tension forces required Ku, a dry tension of 2.0~2.5g / D.
[0031]
The aramid long fiber yarn obtained under the above conditions has extremely high strength and sufficient elastic modulus . By heat-treating this, the elastic modulus can be further improved. However, the strength slightly decreases at that time.
[0032]
Heat treatment conditions in this U.S. Pat. No. 4,726,922 Pat has been that way 200 ° C. or higher according to, to 300 ° C. or lower. Preferably, the temperature is 230 ° C to 300 ° C.
[0033]
By selecting each of these yarn making conditions, the high strength yarn and the high elastic yarn of the present invention can be obtained.
[0034]
The aramid long fiber yarn of the present invention can be processed in the same manner as a conventional aramid long fiber yarn, and can be made into various processed products.
[0035]
Moreover, these processed goods can be made into an aramid fiber reinforced material by disposing in a matrix. As the matrix, natural rubber, synthetic rubber, polyamide resin, polyester resin, polyolefin resin, polyvinyl chloride resin, PBT resin, PPS resin, PPO resin, ABS resin and other thermoplastic resins, epoxy resin, phenol resin, melamine resin, Examples thereof include thermosetting resins such as unsaturated polyester resins, and inorganic matrices such as mortar and cement.
[0036]
Examples of the method of disposing in the matrix include a method of kneading single fibers in the matrix, a method of impregnating the fiber yarn with the matrix, a method of impregnating the fiber fabric with the matrix, and the like.
[0037]
Further, the aramid long fiber yarn of the present invention can be directly supplied with the processed product or twisted yarn form or the raw yarn as described above, such as various industrial materials such as belts, tire cords, optical fiber tension members, bulletproof devices, building materials, reinforcing materials, etc. It can be used for clothing such as industrial materials, fireproof clothing and gloves.
[0038]
【Example】
Hereinafter, the present invention will be described by way of specific examples.
[0039]
Examples 1-7
Poly (p-phenylene terephthalamide) was dissolved in sulfuric acid to obtain a solution having a polymer concentration of 19.50% by weight , and the solution was introduced into the spinning process at 70 ° C. The coagulation liquid after passing through the air gap, using a dilute sulfuric acid of 3 ° C., in combination with the tray system and jet system in contact with the coagulating liquid and the spun yarn. After spinning out coagulation bath of yarn passage, washed with water, alkali washing, to produce aramid filament yarn through a drying step. The strength, elastic modulus, and elongation of the obtained long fiber yarn were measured, and the results are shown in Table 1. Table 1 also shows the yarn production conditions.
[0040]
As shown in Examples 1 to 7 in Table 1, high-performance raw yarns having a strength of 28.5 g / D or more and an elastic modulus of 700 g / D or more were obtained.
[0041]
Comparative Examples 1-2
Aramid long fiber yarns were produced by changing the spinning conditions to the known conditions shown in Table 1 with the same polymer and the same spinning process as in the examples . The obtained raw yarn physical properties are summarized in Table 1. Long fiber yarn obtained in Comparative Examples 1 and 2 compared with the present invention, were inferior in the strength of and elastic modulus.
[0042]
[Table 1]
Examples 8-10, Comparative Examples 3-4
Table 2 shows examples of yarns having higher elasticity (950 g / D or more).
[0043]
The examples in Table 2 8-10 respectively, in which the aramid filament yarns obtained in Examples 5, 6 and 7 of Table 1 was continuously heat-treated at a temperature of 290 ° C. or 300 ° C.. Table 2 shows the properties of the raw yarn obtained by the heat treatment .
[0044]
Comparative examples 3 to 4 are also shown in Table 2. This is obtained by heat treatment with the same heat treatment conditions as aramid filament yarns Example 10 obtained in Comparative Examples 1 and 2 of Table 1.
[0045]
As shown in Examples 8 to 10, the elastic modulus is dramatically improved compared to the conventional 750 g / D level.
[0046]
[Table 2]
Note that by doubling a plurality of the long fiber yarn which is reeling, Ru can be, eg desired yarn fineness, for example 50~10000D.
[0047]
【The invention's effect】
The aramid long fiber yarn made of poly (p-phenylene terephthalamide) obtained in the present invention has a very high strength and a sufficient elastic modulus, or has a very high elastic modulus and a sufficient strength. for those, the applicable available-for application which was difficult various applications in aramid filament yarns made of conventional poly (p over phenylene terephthalamide).
Claims (7)
Priority Applications (1)
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JP36801797A JP3911654B2 (en) | 1997-12-25 | 1997-12-25 | Method for producing aramid filaments |
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JP36801797A JP3911654B2 (en) | 1997-12-25 | 1997-12-25 | Method for producing aramid filaments |
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JP3911654B2 true JP3911654B2 (en) | 2007-05-09 |
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Families Citing this family (18)
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JP2004009758A (en) * | 2002-06-03 | 2004-01-15 | Yokohama Rubber Co Ltd:The | Pneumatic radial tire |
JP3929356B2 (en) * | 2002-06-05 | 2007-06-13 | 帝人テクノプロダクツ株式会社 | Multi-row wholly aromatic polyamide multifilament yarn with excellent splitting properties |
US7976943B2 (en) * | 2007-10-09 | 2011-07-12 | E. I. Du Pont De Nemours And Company | High linear density, high modulus, high tenacity yarns and methods for making the yarns |
EP2053147A1 (en) * | 2007-10-23 | 2009-04-29 | Teijin Aramid B.V. | Method for spinning and washing aramid fiber and recovering sulfuric acid |
CN102644127A (en) * | 2008-03-31 | 2012-08-22 | 可隆工业株式会社 | Para-aramid fiber |
WO2009134063A2 (en) * | 2008-04-29 | 2009-11-05 | 주식회사 코오롱 | Aramid tire cord and manufacturing method thereof |
KR101310142B1 (en) * | 2008-04-30 | 2013-09-23 | 코오롱인더스트리 주식회사 | Aramid multi-filament and method of manufacturing the same |
KR101310139B1 (en) * | 2008-04-30 | 2013-09-23 | 코오롱인더스트리 주식회사 | Method of manufacturing aramid multi-filament |
KR100924909B1 (en) * | 2008-05-21 | 2009-11-03 | 주식회사 코오롱 | Aramid Fiber and method of making the same |
WO2010094620A1 (en) | 2009-02-17 | 2010-08-26 | Teijin Aramid B.V. | Method for producing a filament yarn from an aromatic polyamide |
KR101219213B1 (en) * | 2010-12-21 | 2013-01-07 | 코오롱인더스트리 주식회사 | Method for manufacturing aramid fiber |
KR101432865B1 (en) * | 2010-12-28 | 2014-08-26 | 코오롱인더스트리 주식회사 | Method for manufacturing Aramid staple fiber |
CN102154726B (en) * | 2011-05-23 | 2012-11-21 | 蓝星(成都)新材料有限公司 | Middle modulus poly (p-phenyl-terephthalamide) fiber and preparation method thereof |
KR101360988B1 (en) * | 2012-10-19 | 2014-02-11 | 주식회사 효성 | Aromatic polyamide multi filament having high-strength and process for preparing the same |
JP6284749B2 (en) * | 2013-11-19 | 2018-02-28 | 東レ・デュポン株式会社 | Polyparaphenylene terephthalamide fiber with excellent splitting properties |
JP6320119B2 (en) * | 2014-03-31 | 2018-05-09 | 東レ・デュポン株式会社 | Toothed belt fabric |
JP6685071B2 (en) * | 2015-03-27 | 2020-04-22 | 東レ・デュポン株式会社 | Crimped aramid staple fiber, high-strength spun yarn made of the same, fiber structure and protective material |
CN112105765B (en) * | 2018-05-10 | 2023-03-14 | 帝人株式会社 | Wholly aromatic polyamide fiber |
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