JPS61102413A - Production of poly-paraphenylene terephthalamide yarn - Google Patents

Abstract

PURPOSE:To obtain the titled yarn having high strength, high elongation, improved mechanical properties by the use of an aqueous solution of sulfuric acid as a coagulating solution, by inserting the bottom end of a capillary into a flow tube and feeding a secondary coagulating solution from the top of the end face of the capillary. CONSTITUTION:A solution of >=30g based on 100ml solvent of poly-parphenylene terephthalamide polymer in 98.0-100.2% sulfuric acid showing optical anisotropy, is passed through an uncoagulable fluid layer into the >=10wt% aqueous solution of sulfuric acid (coagulating solution) 21. The bottom end of the capillary 11 (length/inner diameter >=0.5) set at the bottom of the coagulating bath 20 is inserted into the flow tube 12, a secondary coagulation solution is fed from the top of the end face of the capillary 11 through the feed pipe 13 for the secondary coagulating solution, the velocity of the coagulating solution in the flow tube is made >=80% yarn velocity, so that spinning tension is reduced. A cross section ratio of the flow tube and the capillary is >=2, and the length of the flow tube is set to make the yarn therein have >=10mm seconds retaining time.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、ポリ−パラフェニレンテレフタルアミド（以
下、・ＰＰＴＡと略称する）糸繊維の製造方法に関する
。史に詳しくは、改良された機械的性質を持つＰＰＴＡ
系繊維全繊維東的Ｉ／Ｃｇ利な硫酸水＃液の凝固浴を用
いて製造する紡糸法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing poly-paraphenylene terephthalamide (hereinafter abbreviated as PPTA) yarn fiber. For more details on the history, see PPTA with improved mechanical properties.
The present invention relates to a spinning method for producing whole fibers using a coagulating bath of aqueous sulfuric acid.

従来の技術 芳香族ジアミンと芳香族ジカルメン酸、及び／又は芳香
族アミノカルダン酸から全芳香族ポリアミドが誘導され
ることは公知であシ、またこれら芳香族ポリアミドから
繊維が得られることも既に公知である。さらに、かかる
芳香族ポリアミドのうち特に、ＰＰＴＡ系ポリマーから
、その剛直な分子構造から期待される通り、高い融点、
優れた結品性、高い強度、高いヤング率等の好ましい物
性を有する繊維が得られることも既に知られている。BACKGROUND OF THE INVENTION It is known that fully aromatic polyamides can be derived from aromatic diamines, aromatic dicarmenic acids, and/or aromatic aminocardic acids, and it is also already known that fibers can be obtained from these aromatic polyamides. It is. Furthermore, among such aromatic polyamides, PPTA-based polymers in particular have a high melting point, as expected from their rigid molecular structure.
It is also already known that fibers having favorable physical properties such as excellent binding properties, high strength, and high Young's modulus can be obtained.

例えば、％開明４７−３９４５８提案によれば、少くと
も９８％以上の濃度の濃硫酸に溶解しｆｄ’ＰＴＡ系ポ
リマーの光学的異方性を示す溶液を、オリフィスを通し
て、不活性な非凝固性流体中に押し出し、次いで凝固浴
中全通すことによって、好まし７１　　　　　　　　　
　・　　　　　　　　　　　　　　　　　　　　　　　
　　”　　　　　　”　・・□□ｔ ７Ｉア４＝−一一一４＝＝＝＝＝＝＝＝＝＝；＝＝＝＝
＝；＝＝＝＝；＝＝＝＝＝；＝＝＝＝；＝＝＝＝＝；１
＝−一一一一一一一一一ニニーーーーーーーーーーーー
ーーーーー−一□ ― 子２２２２２２２２２２２２２−＝＝＝＝＝＝＝＝＝＝
＝＝＝＝＝＝；＝＝＝＝＝＝＝−＝＝＝＝＝＝＝＝；＝
＝＝＝＝＝＝−＝＝＝＝＝＝＝＝；エエエエエエエエエ
エエエエエエエエエエエエシ桐　イ１へ　２ 性質に優れたＰＰＴＡ繊維を得ることは困難であった。For example, according to the proposal of % Kaimei 47-39458, a solution of an optically anisotropic fd'PTA polymer dissolved in concentrated sulfuric acid with a concentration of at least 98% is passed through an orifice to form an inert, non-coagulable polymer. Preferably 71 by extrusion into a fluid and then passing through a coagulation bath.
・
” ・・□□t 7Ia4=-1114==========;====
=;====;=====;====;=====;1
=-11111111 Ninny---------------------------------------1□ - Child 2222222222222-==========
======;=======-========;=
======-========; EEEEEEEEEEEEEEEEEEEEEEEEEEES Kiri 1. 2. It was difficult to obtain PPTA fibers with excellent properties.

かかる方法に対し、紡糸張力を低減する方法として、凝
固浴下部に特定のスピンチューブ（細孔）を設け、糸条
と凝固液を同時に落下させつつ紡糸する方法（特開昭５
３−７８３２０号報）が提案されたが、１ＯＩ４以上の
硫酸水溶液を用いては、張力−Ｉイン−ニー′□−一さ
−−１＝−コー、−１５，・１１１１１１１１１−■■
■■■■■■■■■■■■■■−■■■■■■■−■■
■■■■■■−■■■■■■■−■■■■■■■■−■
■■■■■■−，，，，，０，，。In contrast to this method, as a method to reduce the spinning tension, a specific spin tube (pore) is provided at the bottom of the coagulation bath, and the yarn and coagulation liquid are simultaneously dropped while spinning (Japanese Patent Laid-Open No. 5
3-78320) was proposed, but when using a sulfuric acid aqueous solution of 1OI4 or more, the tension -Iin-knee'
■■■■■■■■■■■■■−■■■■■■■−■■
■■■■■■−■■■■■■■−■■■■■■■■−■
■■■■■■−,,,,,0,,.

□ □ □ Ｃ４し　（Ｖ題Ｑ６ しかしながら、かかる方法においては、凝固浴中の凝固
液と走行する糸条との摩擦抵抗により、糸条に大きな引
き取シ張力、即ち紡糸張力がかかる。この紡糸張力は、
凝固液の硫酸濃度を高めると溶液の粘度、比重の増加で
増大するため、紡糸張力の低い、即ち硫酸濃度の低い＃
８固液を用いた場合は没れた機械的性質を有する繊維を
与えるが、硫酸製置の上昇に伴って、得られる繊維の強
度・伸度が著しく低下する。促って、各課として用いる
硫酸の回収面において工業的にＭ利な１０％以上の滅酸
水浴液を一次凝固液として用いて機械的ビンナユーフ以
降の自由落下域においては、重力加速度の働きにより落
下液の速度が逐次高まるため、凝固途中の糸条に抵抗履
歴を与え、高次構造の破壊を引き起こす結果、強度及び
伸度の低下を招き、充分に高い性能を有するｌ！雄は得
られない。□ □ □ C4 (V Question Q6 However, in this method, a large pulling tension, that is, spinning tension, is applied to the yarn due to the frictional resistance between the coagulating liquid in the coagulation bath and the running yarn. This spinning tension teeth,
When the sulfuric acid concentration of the coagulating solution is increased, the viscosity of the solution increases as the specific gravity increases, so spinning tension is low, that is, # with a low sulfuric acid concentration.
When 8 solid-liquid is used, fibers with excellent mechanical properties are obtained, but as the sulfuric acid production rate increases, the strength and elongation of the obtained fibers decrease significantly. In order to promote the recovery of sulfuric acid used in each section, a 10% or more acid-depleted water bath solution, which is industrially advantageous in terms of M, is used as the primary coagulation liquid. As the velocity of the liquid increases gradually, it imparts a resistance history to the yarn during solidification, causing destruction of the higher-order structure, resulting in a decrease in strength and elongation. I can't get a male.

特［１０％以上の硫酸水溶液を一次凝固液に用いた場合
は、凝固がよυ不完全となり、見掛けの張力を低下させ
ても凝固途中の糸条への抵抗が蛮骨／）　ｒＬ　ｕ王ソ
１いない。Special [If a 10% or more sulfuric acid aqueous solution is used as the primary coagulation liquid, the coagulation will be incomplete, and even if the apparent tension is lowered, the resistance to the threads during coagulation will be extremely high. 1 is not there.

更に、凝固液と糸条の速度差によって生じる摩擦抵抗を
低減するために、凝固浴液を加圧し、スピンチューブか
らの凝固液速を加速する方法（特開昭５３−７８．３２
１号報ｌ１或いは、スピンチューブを通して落下する糸
条と凝固液流に、複数の小径ノズル或いはスリットから
噴出させた別の凝固液を、糸条の引き取り方向に当てて
加速する方法（特開昭５６−１２８３１２号報）が提提
案れた。Furthermore, in order to reduce the frictional resistance caused by the speed difference between the coagulating liquid and the yarn, a method of pressurizing the coagulating bath liquid and accelerating the speed of the coagulating liquid from the spin tube (JP-A-53-78-32
No. 111 Alternatively, a method of accelerating the yarn and coagulating liquid falling through a spin tube by applying another coagulating liquid jetted from a plurality of small-diameter nozzles or slits in the yarn take-up direction (Japanese Patent Laid-Open No. 56-128312) was proposed.

この方法により、−次凝固液に硫酸水溶液を用いても、
凝固液を加速することによって、見＋Ｊｔ　Ｉｒｆ上、
紡糸張力を低減することは可能であるか、スとして用い
製造する方法について、ＰＰＴＡ系ポリマーの濃硫酸溶
液（以下、単にドープと略称する）からの凝固過程にお
ける糸条の形成と、得られるＰＰＴＡ繊維の物性及び構
造とを対応させつつ長期間の研究を続けてきた。その結
果、ドープを非凝固性の流体層を通して凝固浴に導く湿
式紡糸法において、ちる特定の条件を満たす流管中で基
因愼オ斧堝をにおいでのみ、惠帽１λつ高伸廖空気又は
非凝固性の流体層を通して少なくとも１０％硫酸水溶液
の一次凝固液に導き、次いで凝固浴下部に設けられた細
管中に糸条を導き走行させたのち、該糸条を洗浄、乾燥
等の仕上げ工程に供する湿式紡糸法によシ繊維を製造す
るにあたり、該細管は長さと内径の比が０．５以上であ
って、かつ、該細管の下端部が挿入される球に流管を設
置し、その際該流管は細管の断面積の２倍以上の断面積
になるような内径、及び走行する糸条が１０ｊＥＩ１秒
以上滞留出来るような長さを有し、かつ、流管中の凝固
液速度が糸条速度の少なくとも８０％になるように、該
細管の下端面の上部から二次凝固液を供給することを特
徴とする。With this method, even if a sulfuric acid aqueous solution is used as the secondary coagulation liquid,
By accelerating the coagulation liquid, on +Jt Irf,
Is it possible to reduce the spinning tension? Regarding the manufacturing method using the process, we will discuss the formation of threads during the coagulation process of a PPTA-based polymer from a concentrated sulfuric acid solution (hereinafter simply referred to as dope), and the resulting PPTA We have been conducting long-term research while matching the physical properties and structure of fibers. As a result, in the wet spinning method in which the dope is introduced into the coagulation bath through a non-coagulable fluid layer, it is possible to carry out a high elongation air or The yarn is guided through a non-coagulable fluid layer to a primary coagulation solution of at least 10% sulfuric acid aqueous solution, then the yarn is guided and run through a thin tube provided at the bottom of the coagulation bath, and then the yarn is subjected to finishing processes such as washing and drying. In producing fibers by a wet spinning method, the capillary has a length-to-inner diameter ratio of 0.5 or more, and a flow tube is installed in a sphere into which the lower end of the capillary is inserted; In this case, the flow tube has an inner diameter that has a cross-sectional area that is at least twice the cross-sectional area of the thin tube, and a length that allows the traveling thread to stay for 10jE1 second or more, and the coagulation liquid in the flow tube. It is characterized in that the secondary coagulation liquid is supplied from the upper part of the lower end surface of the thin tube so that the speed is at least 80% of the yarn speed.

本発明において、ＰＰＴＡ系ポリマーとは、ポリ−パラ
フェニレンテレフタルアミドならびにそ単位１０モルチ
以下が、それぞれ他の芳香族ジアミノ残基又は／及び他
の芳香族ジカルゼキシル残より成るコポリアミドを総称
する。これらＰＰＴＡ系ｌリマーは単独、または混合物
のいずれであっても本発明法に用いることかでさる。In the present invention, the PPTA-based polymer is a general term for poly-paraphenylene terephthalamide and copolyamides in which 10 moles or less of the units thereof are each composed of other aromatic diamino residues or/and other aromatic dicarzexyl residues. These PPTA-based remers may be used alone or as a mixture in the method of the present invention.

本発明法のＰＰＴＡ系繊維の製造法においては、少くと
も強度が１ｓ、９／ｄ以上、伸度が３ｓ以上、かつ初期
モジュラスが２ｓｏＮ／ｄ以上を示す如き高性能７１１
維が対象とされるべきであり、そのためには、使用され
るＰＰＴＡ系ポリマーの重合度が一定の値以上のもので
なければならず、固有粘度（η１ｎｈ）で表わして３．
５以上、特に４．５以上であることが望ましい。In the method for producing PPTA fiber according to the present invention, high performance 711 fibers exhibiting at least a strength of 1 s, 9/d or more, an elongation of 3 s or more, and an initial modulus of 2 soN/d or more are used.
For this purpose, the degree of polymerization of the PPTA-based polymer used must be above a certain value, and the degree of polymerization, expressed in intrinsic viscosity (η1nh), must be 3.
It is desirable that it be 5 or more, especially 4.5 or more.

かかるＰＰＴＡ系ポリマーから、本発明法に用いられる
紡糸用ド□−プは、既に公矧の方法によって調製さｎる
。その際、溶剤としては、工業的には濃硫酸が有利に用
いられる。濃硫酸の濃度は、９８〜１０　ｏ、鑓ｉｉｔ
　％が好ましく、特に扁い固有粘度を有するＰＰＴＡ系
ポリマーを高濃度に溶解する場合には９９重ｉ％以上の
ものが用いられる。The spinning dope used in the method of the present invention is prepared from such a PPTA polymer by a known method. In this case, concentrated sulfuric acid is industrially advantageously used as the solvent. The concentration of concentrated sulfuric acid is 98-10 o,
% is preferable, and in particular, when dissolving a PPTA-based polymer having a low intrinsic viscosity at a high concentration, 99% by weight or more is used.

紡糸用ドープは、溶媒１０〇−当り少なくとも３０ＩＩ
のＰＰＴＡ系ポリマーを含むように調製することが好ま
しい。更に好ましくは３３．９以上のＰＰＴＡ系ポリマ
ーを含むように調製する。The spinning dope should contain at least 30 II per 100 of the solvent.
It is preferable to prepare it so that it contains a PPTA-based polymer. More preferably, it is prepared to contain a PPTA polymer having a molecular weight of 33.9 or more.

しかしながら、ポリマー濃度が高すぎるとドードーゾの
粘度が高くなりすぎるため、ドープ温度を高く設定する
必要があシ、紡糸操作上困難を伴いやすい。従って、高
過ぎないよう選ばれるべきである。ドープの調製および
使用に当っては、上記４リマ一濃度範囲においては、ド
ープは室温付近では固化する場合があるため、室温から
８０℃程度の温度で取扱えばよい。しかしながら、ポリ
マーの分解を可及的に回避する観点から、固化しない限
りなるべく低い温度を選ぶことが好ましい。However, if the polymer concentration is too high, the viscosity of the dodozo will become too high, so it is necessary to set the dope temperature high, which tends to cause difficulties in the spinning operation. Therefore, it should be chosen not to be too expensive. When preparing and using the dope, the dope may solidify near room temperature in the above-mentioned 4-lima concentration range, so it may be handled at a temperature from room temperature to about 80°C. However, from the viewpoint of avoiding decomposition of the polymer as much as possible, it is preferable to select a temperature as low as possible unless it solidifies.

このようにして調製された紡糸用ドープは、上記のポリ
マー濃度、ドープ温度範囲で光学的異方性を有すること
が認められる。かかるドープが本発明法において便用さ
れ、紡糸口金を通して一旦窒気又は、非凝固性の流体層
、通常空気中に押し出され、ついで凝固浴中に導びかれ
る。その際、凝固浴中の凝固しつつある、または凝固し
た糸条はほとんど引き伸ばしが行なわれないため、吐出
されたドープは非凝固性のＪｃ体！−において、引き取
シのドラフト（引き伸ばし）がかかり、引き伸ばされる
。この引き伸ばしにおいて、引き伸ばし率が低いと充分
に繊維の物性ケ高めることが出来ず、また、高すぎると
この間でドープ流が切断されるため、通常は、引き伸ば
し率は４〜１５倍、好ましくは５〜１２倍の間に設定さ
れる。It is recognized that the spinning dope thus prepared has optical anisotropy within the above polymer concentration and doping temperature ranges. Such a dope is conveniently used in the process of the present invention, once forced through a spinneret into a layer of nitrogen or a non-coagulable fluid, usually air, and then introduced into a coagulation bath. At that time, the coagulating or coagulated yarn in the coagulation bath is hardly stretched, so the discharged dope is a non-coagulable Jc form! At -, the draft (stretching) of the take-off sheet is applied and the material is stretched. In this stretching, if the stretching rate is low, the physical properties of the fiber cannot be sufficiently enhanced, and if the stretching rate is too high, the dope flow will be cut off in this stretch, so the stretching rate is usually 4 to 15 times, preferably 5 times. It is set between ~12 times.

ドープの引き伸ばしが行なわれる空気又は非凝固性の流
体層の長さ、即ちドープの吐出される紡糸用口金の面か
ら凝固浴液表面までの距離は、通常約１〜５０１１麓、
好適には３〜２０朋の範囲に設定されるが、これに限定
されるものではない。具体的には、紡糸用口金からのド
ープの吐出速度、上記のドラフト率、フィラメントの融
合機会を少くすること等を考慮して決定される。The length of the air or non-coagulable fluid layer in which the dope is stretched, that is, the distance from the surface of the spinning nozzle from which the dope is discharged to the surface of the coagulating bath, is usually about 1 to 50 mm,
It is preferably set in the range of 3 to 20, but is not limited to this. Specifically, it is determined in consideration of the dope discharging speed from the spinning nozzle, the above-mentioned draft rate, reducing the chance of filament fusion, etc.

また、ドープの吐出に際して用いられる紡糸用口金の孔
径は、製造しようとする繊維の太さ、及び上記のドラフ
ト率の設定によυ遠足されるべきであって、通常は０．
０５〜０．１０１ｍ＋　　の範囲のものが選択されるが
、これに限られるものではない。更に紡糸用口金に設け
られる孔数は、製造しようとする繊維の構成によって決
定されるべきものであシ、特に本発明法ｆ：実施する九
当って格別限定されるものではない。In addition, the hole diameter of the spinning nozzle used for discharging the dope should be adjusted depending on the thickness of the fiber to be manufactured and the above-mentioned draft rate setting, and is usually 0.
05 to 0.101 m+, but is not limited thereto. Further, the number of holes provided in the spinning nozzle should be determined depending on the structure of the fiber to be produced, and is not particularly limited to the number of holes to be carried out in method f of the present invention.

本発明の効果を充分に発揮させるためには、−次凝固液
として１０係以上のｆｆｃ酸水溶液が用いられ、該硫酸
濃度は高けれは鍋い程その効果が大きい。しかし７０係
を超えると糸条は凝固の遅れが著しくなシ、僅かな抵抗
で高次構造の破壊をきたすため、二次凝固液の硫酸濃度
を一次凝固液の硫酸濃度より低くシ、凝固を早めること
が好ましい。In order to fully exhibit the effects of the present invention, an FFC acid aqueous solution with a coefficient of 10 or more is used as the secondary coagulation liquid, and the higher the sulfuric acid concentration, the greater the effect. However, if the temperature exceeds 70, the coagulation of the yarn will be significantly delayed, and even the slightest resistance will cause destruction of the higher-order structure. It is preferable to start early.

工業的に有利な硫酸水溶液を騨固液に用いて、高性能の
ＰＰＴＡ系繊維を製造するための本発明法においては、
前記の様にして吐出され、引き伸ばされたドープを一次
錠固液中に導き、糸条を形成しつつ、凝固浴下部に設け
られた細管に導き、更に紡速の少なくとも８０幅の速度
で凝固液が流れる流管中へ糸条を走行させることに最大
の特徴がある。In the method of the present invention for producing high-performance PPTA fibers using an industrially advantageous sulfuric acid aqueous solution as a solid solution,
The dope discharged and stretched as described above is introduced into the primary tablet solid liquid, and while forming threads, is introduced into a thin tube provided at the bottom of the coagulation bath, and further coagulated at a speed of at least 80% of the spinning speed. The main feature is that the thread runs through the flow tube through which the liquid flows.

ＰＰＴＡ系繊維の形成過程においては、凝固によって形
成される高次構造の破壊、配向の進行等の変化を伴ない
ながら繊維が形成されるが、これらは単に張力のみの作
用をうけるものではなく、その張力が付与された糸条の
凝固状態によっても大きく変化するものでめる為、各凝
固状態での張力履歴が最終製品糸の構造及び機械的な物
性に反映することは、理解されるべきである。In the process of forming PPTA fibers, fibers are formed with changes such as destruction of the higher-order structure formed by coagulation and progress of orientation, but these are not simply affected by tension; Since the tension varies greatly depending on the coagulation state of the yarn to which it is applied, it should be understood that the tension history in each coagulation state will be reflected in the structure and mechanical properties of the final product yarn. It is.

ＰＰＴＡ系ｆＲ雄を１０係以上の誠酸水溶液で一次凝固
させ製造する場合にあっては、硫酸濃度の上昇と共に該
水溶液の粘度、及び比重の増加による紡糸張力の増大、
更に凝固糸条中の硫酸濃度と凝固液の硫酸濃度の差の減
少によシ凝固の遅れが同時に起こることによって、凝固
不完全な未凝固糸条は、より低い張力で構造破壊を生じ
る。従って紡糸張力を低減することが重要であり、この
為には一次凝固液の速度を糸条速度まで加速する必要が
ある。しかしながら、単ＫＭ固浴下部に細管又は細孔を
設け、糸条と共に一次凝固欣を重力の加速度によって加
速する方法、或いは、強制的Ｋ例えば下向きのジェット
流などによシニ次凝固液の速度を加速する方法において
は、見掛は上引取時に計測される紡糸張力は低減される
ものの、自由落下域で重力の加速度が働き、二次凝固液
の落下速度が逐次高まり、糸条と落下液との速度差を一
定に保つことが出来なかった。この結果、凝固途中の糸
条に抵抗Ｈ歴を与え高次構造の破壊を引き起し充分に高
い強度及び伸度を合せ持つＰＰＴＡ系繊維を得るには至
らない。In the case of manufacturing PPTA-based fR male by primary coagulation with an aqueous solution of true acid having a modulus of 10 or more, an increase in the spinning tension due to an increase in the viscosity and specific gravity of the aqueous solution as the concentration of sulfuric acid increases;
Furthermore, due to the simultaneous delay in coagulation caused by the decrease in the difference between the sulfuric acid concentration in the coagulated yarn and the sulfuric acid concentration in the coagulating solution, the incompletely coagulated uncoagulated yarn causes structural failure at a lower tension. Therefore, it is important to reduce the spinning tension, and for this purpose it is necessary to accelerate the speed of the primary coagulation liquid to the yarn speed. However, there is a method in which a thin tube or pore is provided at the bottom of the single KM solid bath, and the primary coagulation liquid is accelerated together with the yarn by the acceleration of gravity, or the velocity of the secondary coagulation liquid is increased by forced KM, such as a downward jet flow. In the acceleration method, although the apparent spinning tension measured at the time of top take-up is reduced, the acceleration of gravity acts in the free fall region, and the falling speed of the secondary coagulation liquid increases gradually, causing the yarn and falling liquid to It was not possible to keep the speed difference constant. As a result, a resistance H history is imparted to the yarn during coagulation, causing destruction of the higher-order structure, making it impossible to obtain a PPTA fiber having sufficiently high strength and elongation.

従って、１０係以上の硫酸水溶液を凝固液として強度及
び伸度共に優れた高性能のＰＰＴＡ系繊維を製造するた
めには、凝固の完成度の低い未凝固糸条においても繊維
構造の破壊を引き起さない様に１更に、伸度の低下を招
く配向の進行を抑制する様に１凝固状態に応じて張力を
低減すると同時に、その低張力の状態を一定時間維持す
ることが必要である。その為には、糸条に随伴する二次
凝（６）液の流速を加速して糸条と二次凝固液との摩擦
抵抗を減少せしめ、かつ、−一旦加速された凝固液は一
定速度を保たせることによって、この間で糸条にかかる
張力を極めて低い状態に保ちつつ凝固を進行させ繊維を
形成することが出来るのである。Therefore, in order to produce high-performance PPTA fibers with excellent strength and elongation using a sulfuric acid aqueous solution with a coefficient of 10 or higher as a coagulation liquid, it is necessary to prevent destruction of the fiber structure even in uncoagulated yarns with a low degree of coagulation. In order to prevent this from occurring, it is also necessary to reduce the tension according to the solidification state and maintain the low tension state for a certain period of time so as to suppress the progress of orientation that would lead to a decrease in elongation. To do this, the flow rate of the secondary coagulating liquid (6) accompanying the yarn is accelerated to reduce the frictional resistance between the yarn and the secondary coagulating liquid, and - once accelerated, the coagulating liquid has a constant velocity. By maintaining this, it is possible to proceed with coagulation and form fibers while keeping the tension on the yarn extremely low during this period.

ここに、直管を設け、二次凝固液を一定速度で流す本発
明法の一つの重要な意義があることは理解されなければ
ならない。また、糸条束又は糸条の一部が前記直管の影
響を受ける領域を走行することは、張力増加につながる
為さける必要がある。It must be understood here that there is one important significance of the method of the present invention in which a straight pipe is provided and the secondary coagulation liquid is caused to flow at a constant speed. Furthermore, it is necessary to avoid running a yarn bundle or a portion of the yarn through an area affected by the straight pipe, as this will lead to an increase in tension.

従って、直管の上部に細管を設け、糸条を流管中に導く
前に＃細管に該糸条を一端導くことに、本発明のもう一
つの重要な意義があることも理解されなければならない
。Therefore, it must be understood that another important significance of the present invention lies in providing a thin tube at the upper part of the straight tube and guiding one end of the yarn into the thin tube before guiding the yarn into the flow tube. No.

上述した様に、強度及び伸度共に優れた高性能ＰＰＴＡ
系繊維を製造するには、糸条の凝固状態に応じて、紡糸
張力の低減を図る必要があり、かつ、該低張力の状態を
一定時間維持する必要がある。％Ｉｃ、３００ｍ／Ｉｃ
上の紡糸速度を採用して、強度及び伸度共ＫｌれたＰＰ
ＴＡ系繊維を製造するには、凝固浴下部に設けられた細
管を経由して、少なくとも紡糸速度の８０％、好ましく
は９０係、更に好ましくは９５係以上の速度で凝固液が
流れる流管中へ糸条が導かれる。特に、−次凝固液の硫
酸製置が高ければ高い程糸条の凝固が遅れる為、その時
かかる張力は更に低いものとする必要があシ、流管中の
凝固液の速度を紡糸速度により近づけることが好ましい
。As mentioned above, high-performance PPTA with excellent strength and elongation.
In order to produce fibers, it is necessary to reduce the spinning tension depending on the coagulation state of the yarn, and it is necessary to maintain the low tension state for a certain period of time. %Ic, 300m/Ic
Adopting the above spinning speed, PP with low strength and elongation
In order to produce TA-based fibers, the coagulating liquid flows through a flow tube at a speed of at least 80% of the spinning speed, preferably 90 parts, more preferably 95 parts or more of the spinning speed, through a thin tube provided at the bottom of the coagulation bath. The yarn is guided. In particular, the higher the concentration of sulfuric acid in the secondary coagulation liquid, the slower the coagulation of the yarn, so the tension applied at that time needs to be lowered, and the speed of the coagulation liquid in the flow tube should be brought closer to the spinning speed. It is preferable.

また、紡糸速ｋを旨めた場合も同様のことが言えるし、
流管中に供給される二次凝固浴の硫酸濃度が高ければ高
めた場合も同様である。逆に、凝固の完成度が高い糸条
、例えば１０％硫酸水溶液の一次凝固浴で３００　ｙ＠
　７分で紡糸されている糸条では、張力の比較的高い状
態、又は流管中の凝固液の速度が紡糸速度より速い状態
においても繊維の高次構造の破壊が抑制される為、該凝
固液の速度を紡糸速度の１５０９Ｊもの大きさまでする
ことができ、更に、該凝固液と糸条とを分離する工程に
細孔を設ける、あるいは気体を噴射する等の糸重量の工
夫をすることで、該凝固液の速度を更に高めることも出
来る。The same thing can be said when the spinning speed k is increased.
The same holds true when the sulfuric acid concentration of the secondary coagulation bath supplied into the flow tube is increased. On the other hand, for yarns with a high degree of coagulation, for example, in a primary coagulation bath of 10% sulfuric acid aqueous solution,
For yarn spun in 7 minutes, destruction of the higher-order structure of the fiber is suppressed even when the tension is relatively high or when the speed of the coagulating liquid in the flow tube is faster than the spinning speed. The speed of the liquid can be increased up to the spinning speed of 1509 J, and furthermore, by creating pores in the process of separating the coagulated liquid from the yarn, or by injecting gas, etc., the yarn weight can be adjusted. , it is also possible to further increase the speed of the coagulating liquid.

一方流管の設計に当っては、前述した様にａＬ管中を走
行する糸条が該流管の壁面の影響全極力受けない様に、
該流管の上端に設けた細管の断面積の２倍以上の断面積
になるような径を有する流管を採用することが重要であ
シ、上記断面積比が２倍未満になると走行糸条に流管の
壁面の悪影砕が及ぼされ、高強度のＰＰＴＡｍ維が得ら
れない。On the other hand, when designing the flow tube, as mentioned above, the yarn running in the aL tube should be designed so that it is not affected by the wall surface of the flow tube as much as possible.
It is important to adopt a flow tube with a diameter that is at least twice the cross-sectional area of the thin tube provided at the upper end of the flow tube.If the cross-sectional area ratio is less than twice, the running yarn Due to the negative shadow fracture of the flow tube wall surface, high-strength PPTAm fibers cannot be obtained.

流管の径を大きくすることは、供給する凝固液の量が増
大しエネルギーの増加につながる為、コストの面から該
流管の径の上限が決定される。Increasing the diameter of the flow tube increases the amount of coagulation liquid to be supplied, leading to an increase in energy, so the upper limit of the diameter of the flow tube is determined from the cost perspective.

また、流管中を走行する糸条が管壁の影響をうけないた
めには、該流管の形状が実質的に直管であることが好ま
しい。しかし、該流管が大きい内径を鳴している及び／
または短かい場合は、該流管中を走行する糸条が管壁の
影響をうけにくいため、曲管であってもよい。Further, in order to prevent the thread running through the flow tube from being affected by the tube wall, it is preferable that the flow tube has a substantially straight shape. However, the flow tube has a large inner diameter and/or
Alternatively, if the flow tube is short, it may be a curved tube because the thread running in the flow tube is less affected by the tube wall.

上記流管の長さは、不発明法において住めて重要な要件
の一つである。即ち、糸条の凝固の完成度が極めて低い
状態で流管中より糸条が自由落下域に引き出されること
は、わずかな張力及び／又は抵抗変化で糸条の高次構造
の破壊を招き、繊細性能の低下につながる為、少なくと
も１０ｆ１秒以上走行する糸条が滞留出来るような流管
長を有することが必要であ）、該流管長はこ、紡糸速度
の高速化及び／又は−次、二次凝固液の硫酸濃度の高濃
度化に伴なり長く設定することが肝要である。The length of the flow tube is one of the important requirements under the Non-Invention Act. In other words, if the yarn is pulled out from the flow tube into the free-fall region in a state where the degree of coagulation of the yarn is extremely low, a slight change in tension and/or resistance will cause the destruction of the higher-order structure of the yarn, resulting in a delicate structure. (To avoid this, it is necessary to have a flow tube length that allows threads running for at least 10 f1 seconds to stay there. As the sulfuric acid concentration of the coagulation solution increases, it is important to set the time longer.

本発明における細管は、糸条を収束させて前記流管に導
く役目があると同時に、該流管中から凝固浴表面に向か
って流れる二次凝固液の急激な噴出を防ぐ役目を有して
いる。従って、該細管は、長さと内径の比が０．５以上
に設計すると同時に、かつ、該細管の下端部が少なくと
も挿入される様に流管を設置することが重要であシ、該
条件が一方でも満たされなければ、紡浴表面及び内部に
不安定な流れを生じ、長時間安定して紡糸することが出
来ない。The thin tube in the present invention has the role of converging the threads and guiding them to the flow tube, and at the same time has the role of preventing sudden jetting of the secondary coagulation liquid flowing from the flow tube toward the surface of the coagulation bath. There is. Therefore, it is important to design the capillary to have a length-to-inner diameter ratio of 0.5 or more, and to install the flow tube so that at least the lower end of the capillary is inserted. If either one of these conditions is not satisfied, unstable flow will occur on the surface and inside of the spinning bath, making it impossible to stably spin the fiber for a long period of time.

本発明法の典型的な操作を第１図の紡糸装置で示す。こ
の装置では、細管１１を上端に有する流管１２が紡浴下
部に設けられている。−次凝固液は供給ノズル２２を通
して紡浴中に液の供給がなされ、二次凝固液は供給ノズ
ル１３を通して液の供給がなされる。本発明法に係る細
管と流管との位置関係は、第２図Ａに示すように細管の
下端面と流管の上端面とが少なくとも又わる関係にあり
、特に第２図Ｂのように両端面が重なる位置関係がよシ
好ましい。A typical operation of the method of the invention is illustrated in the spinning apparatus of FIG. In this device, a flow tube 12 having a capillary tube 11 at its upper end is provided at the bottom of the spinning bath. - The secondary coagulation liquid is supplied into the spinning bath through the supply nozzle 22, and the secondary coagulation liquid is supplied through the supply nozzle 13. The positional relationship between the capillary and the flow tube according to the method of the present invention is such that the lower end surface of the capillary and the upper end surface of the flow tube are at least crossed as shown in FIG. 2A, and especially as shown in FIG. 2B. A positional relationship in which both end surfaces overlap is more preferable.

更に、流管の中心と細管の中心とが一致するように設置
することが好ましいが、一致しなくても特に問題はない
。細管及び流管の断面形状は、通常円形のものが用いら
れるが、本発明法においては特に限定されるものではな
く、例えば矩形、三角形状あるいは橢円状など、いずれ
であってもよい。Furthermore, although it is preferable to install the flow tube so that the center of the flow tube and the center of the thin tube coincide with each other, there is no particular problem even if they do not coincide with each other. The cross-sectional shapes of the thin tubes and flow tubes are usually circular, but are not particularly limited in the method of the present invention, and may be, for example, rectangular, triangular, or oval.

更に、上記断面形状が第３図Ｂのように長さ方向で変化
していてもよいが、細管の最小断面積の少なくとも２倍
以上の断面積になるような最小径を有する流管とするこ
とが必要である。Furthermore, the cross-sectional shape may vary in the length direction as shown in FIG. 3B, but the flow tube should have a minimum diameter that is at least twice the minimum cross-sectional area of the thin tube. It is necessary.

本発明の実施に当っては、流管の上端に設けられた細管
は凝固浴液表面から２００ｍｙｘ以内の深さに設置され
ることが好ましく、通常は１０〜１５０間、特に好まし
くはｌＯ〜１００ＩＸの範囲に設置される。In carrying out the present invention, the thin tube provided at the upper end of the flow tube is preferably installed at a depth within 200 myx from the surface of the coagulation bath, usually between 10 and 150 myx, particularly preferably between lO and 100 Ix. be installed within the range of

本発明法によって凝固形成された糸条は、流管から、例
えばネルソンロール等の引き取り手段によって６００ｒ
ｎ／分以上の極めて高い速度で引き取られ、付着する凝
固液あるいは残存する溶剤硫酸の中和、洗浄、乾燥等の
仕上工程に供される。The yarn coagulated by the method of the present invention is removed from the flow tube for 600 rpm by a pulling means such as a Nelson roll.
It is taken off at an extremely high rate of n/min or more, and subjected to finishing processes such as neutralization of the adhering coagulating liquid or remaining solvent sulfuric acid, washing, and drying.

その際、形成された糸条繊維中に含有される酸の中和、
洗浄、または中和によって生じた塩の洗浄は、最終的に
得られるＰＰＴＡ系繊維の品質上特に徹底して行われる
ことが好ましく、これらの処理に長時間を必要とする。At that time, neutralization of the acid contained in the formed yarn fibers,
In view of the quality of the PPTA fibers finally obtained, it is preferable that the salts generated by washing or neutralization be thoroughly washed, and these treatments require a long time.

このような徹底した中和又は洗浄を長時間に埋シ実施す
る方法として、多数のロールを組み合わせて滞留時間を
長くとる方法であっても差支えないが、特に、特公唄５
５−９０８８提案による、ネットコンベヤー上にＰＰＴ
Ａ系繊維を堆積して水洗、中和、乾燥する方法が、工業
的にも且つ高品質の繊維を得る上からも好ましく用いら
れる。更には、本発明法の実施に当って例えば特公昭５
４−３６６９８号報にて提案されたネットコンベヤー上
での乾燥後さらに熱処理を行うこと等の処理を行なうこ
とも許される。As a method for carrying out such thorough neutralization or cleaning over a long period of time, it is possible to use a method in which a large number of rolls are combined to increase the residence time.
5-9088 proposal, PPT on net conveyor
A method in which A-type fibers are deposited, washed with water, neutralized, and dried is preferably used industrially and from the viewpoint of obtaining high-quality fibers. Furthermore, in implementing the method of the present invention, for example,
It is also permissible to perform further heat treatment after drying on a net conveyor as proposed in No. 4-36698.

本発明は、すべてのＰＰＴＡ系繊維の製造に対して有効
であるが、ＰＰＴＡＰＰＡ系繊維高い結晶性の故か、Ｗ
ｌ、雄がフィブリル化しやすかったシ、割れやすいこと
もあって、単繊維の太さは、太すぎないことが望ましい
。通常は大略１０デニール以下、好ましくは３デニール
以下に設定される。The present invention is effective for the production of all PPTA fibers, but perhaps because of the high crystallinity of PPTAPPA fibers, W
1. The male fibers tend to fibrillate and break easily, so it is desirable that the thickness of the single fibers is not too thick. Usually, it is set to about 10 denier or less, preferably 3 denier or less.

総繊維の線密度は２０〜４５００デニール、通常、５０
〜３０００　デニールであることが好ましい。The linear density of the total fiber is 20-4500 denier, usually 50
~3000 denier is preferred.

実施例 以下、実施例によって本発明を更に詳細に説明するが、
これらの実施例は何ら本発明を限定するものでない。Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.
These examples do not limit the invention in any way.

実施例中、特にことわシのない限９「係」は重量ノぐ−
セントを表わす。また、本発明法において用いられる種
々の、Ｒラメ−ターの主なものは以下の様にして測定さ
れたものである。In the examples, unless otherwise specified, 9.
Represents cents. Further, the various R rammeters used in the method of the present invention are mainly measured as follows.

固有粘此の測定法： 固有粘匿（ηｌｎｈ　）は、９８．５重ｔ％の濃硫酸に
製置（Ｃ）　＝　０．５　／ｉ／　ｄｉ　でポリマーま
たは繊維を溶かした溶液を３０℃にて常法によシ測定す
る。Intrinsic viscosity measurement method: Intrinsic viscosity (ηlnh) is determined by dissolving a polymer or fiber solution in 98.5 wt% concentrated sulfuric acid (C) = 0.5 /i/di and heating it to 30°C. and then measure using the usual method.

繊維の強伸度特性の測定法； 繊維糸条の強度、伸度およびヤング率の測定はＪＩＳ規
格に準じ、測定に先立って１０ｍ当シ、８回の撚りを加
えた糸条について、定速伸長型強伸度試験機だより、把
握長２０ｃｍ、引張シ速度５０チ／分にて、荷重−伸長
率典線を描き、それより読み取り、または算出したもの
で、測定数２０個の平均値で表わす。Measuring method for strength and elongation properties of fibers; The strength, elongation and Young's modulus of fiber yarns are measured in accordance with JIS standards. Prior to measurement, yarns that have been twisted 8 times per 10m are twisted at a constant speed. Newsletter from an elongation type strength and elongation tester, with a grip length of 20 cm and a tensile speed of 50 inches/min, draw a load-elongation rate typical line, read or calculate from it, and average value of 20 measurements. It is expressed as

流管と細管の断面積比； 流管の内径をＤｌ、細管の内径をＤ−とすると共に円形
のものを用いた場合は、次式によシ計算され流管中の凝
固液の速度ニ 一次凝固液の供給量と該凝固液をＭする紡浴からのオー
バーフロー量との運から細管部の吸引量（条件によって
は、噴出量）と二次凝固液の供給量よシ、流管中を通る
凝固液量を求め、該凝固液量を流管の断面積で除した値
、即ち平均流速を流管中の凝固液速度とする。The cross-sectional area ratio of the flow tube and the capillary; when the inner diameter of the flow tube is Dl, the inner diameter of the capillary is D-, and a circular one is used, the velocity ratio of the coagulating liquid in the flow tube is calculated using the following formula. Based on the relationship between the supply amount of the primary coagulation liquid and the overflow amount from the spinning bath that Mates the coagulation liquid, the suction amount (depending on the conditions, the ejection amount) of the thin tube section and the supply amount of the secondary coagulation liquid are determined in the flow tube. The amount of coagulated liquid passing through the tube is determined, and the value obtained by dividing the amount of coagulated liquid by the cross-sectional area of the flow tube, that is, the average flow velocity, is taken as the velocity of the coagulated liquid in the flow tube.

参考例 低温溶液重合法によυ次の如（ＰＰＴＡポリマーを得た
。Reference Example The following PPTA polymer was obtained by low temperature solution polymerization method.

特公、昭５３−４３９８６号公報に示された重合装置中
でＮ−メチルピロリド７１０００部に無水塩化カルシウ
ム７０部を溶解し、次いでバラフエニレ／ジアミン４８
．６部を溶解した。８℃に冷却した後、テレフタル酸ジ
クロライド９１．４部を粉末状で一度加えた。数分後に
重合反応物はチーズ状に固化したので、特公昭５３−４
３９８６号公報記載の方法にしたがって重合装置より重
合反応物を排出し、直ちに２軸の密閉型ニーダ−に移し
、同ニーダ−中で重合反応物を微粉砕した。次に微粉砕
物をヘンシェルミキサー中に移し、はぼ等景の水を加え
てさらに粉砕した後、濾過し、数回温水中で洗浄して、
１１０℃の熱風中で乾燥した。固弔粘粘度が６．２の淡
黄色のＰＰＴＡポリマー９５部を得た。In the polymerization apparatus shown in Japanese Patent Publication No. 53-43986, 70 parts of anhydrous calcium chloride was dissolved in 71,000 parts of N-methylpyrrolid, and then 48 parts of rose elm/diamine was dissolved.
．． 6 parts were dissolved. After cooling to 8°C, 91.4 parts of terephthalic acid dichloride was added once in powder form. After a few minutes, the polymerization reaction product solidified into a cheese-like shape, so the
The polymerization reaction product was discharged from the polymerization apparatus in accordance with the method described in Japanese Patent No. 3986, and immediately transferred to a twin-screw closed kneader, and the polymerization reaction product was pulverized in the same kneader. Next, the finely ground material was transferred to a Henschel mixer, added with water for further grinding, filtered, washed several times in hot water,
It was dried in hot air at 110°C. 95 parts of pale yellow PPTA polymer having a solid viscosity of 6.2 was obtained.

なお、異なった固有粘度のポリマーは、Ｎ−メチルピロ
リドンとモノマー（ハラフェニレンジアミ／およびテレ
フタル酸ジクロライド）の比、または／および七ツマー
間の比等を変えることによって容易に得ることができる
。Incidentally, polymers having different intrinsic viscosities can be easily obtained by changing the ratio of N-methylpyrrolidone and monomers (halaphenylene diamide/and terephthalic acid dichloride), or the ratio between heptamers, etc.

実施例１ 参考例に従って製造した固有粘度（η１ｎｈ）が６．９
のポリ−／ぞラフエニレンテレフタルアミトヲ、ポリマ
ー濃度が１９．２　％になるように９９．７　％の濃硫
酸に、温度を８０℃に保ちながら溶解し、紡糸用のポリ
マー溶液（以下ドープと略称）を調製した。このドープ
は、光学的異方性を示すことが、直又ニコル下の偏光顕
微鏡観察で確認された。Example 1 Manufactured according to Reference Example with an intrinsic viscosity (η1nh) of 6.9
The poly-/zo-rough ethylene terephthalamide was dissolved in 99.7% concentrated sulfuric acid to a polymer concentration of 19.2% while maintaining the temperature at 80°C, and a polymer solution for spinning (hereinafter referred to as dope) was obtained. ) was prepared. It was confirmed by polarizing microscopy observation under direct Nicol conditions that this dope exhibits optical anisotropy.

このドープを真空下４時間靜置脱泡稜、紡糸にｊ　　用
いた。ドープをギアポンプを通して３００メツシユステ
ンレス金鋼を８重に巻いたキャンドルフィルターを逃し
て濾過後、第１図に示す紡糸用装置に設置された０、０
口１の孔径、１００個の孔数を有する紡糸用口金から５
絹の空気中を通して４０係硫酸水溶液の一次凝固液中に
押し出した。This dope was left under vacuum for 4 hours for degassing and used for spinning. The dope is passed through a gear pump, passed through a candle filter made of 300 mesh stainless steel wrapped eight times, and filtered.
5 from a spinning nozzle with a hole diameter of 1 and a number of holes of 100.
The silk was passed through air and extruded into a primary coagulation solution of a 40% sulfuric acid aqueous solution.

流管中に供給する二次凝固液は、同じく３０係硫酸水溶
液で、凝固液の温度は一次、二次凝固液共に２℃であっ
た。The secondary coagulating liquid supplied into the flow tube was also a 30% aqueous sulfuric acid solution, and the temperature of the coagulating liquid was 2° C. for both the primary and secondary coagulating liquids.

流管中から取出された糸条は、変向ロールにて変向後、
ネルノンロールによシ引き取シ、次いでワイングーによ
りｚビン上１ｃ捲き取り、このゼビンを流れ中に２夜浸
漬して糸条を洗浄後、１００℃の熱風乾燥機中で乾燥し
た。After the yarn taken out from the flow tube is changed direction by a direction change roll,
The yarn was taken up with a flannel roll, then rolled up on a Z-bin using a wine goo, and the yarn was immersed in a stream for two nights to wash the yarn, and then dried in a hot air dryer at 100°C.

この際紡糸に用いた装置は第１図に示すものであり、−
次凝固液で満たされた凝固浴槽（直径２０Ｇ朋、深さ１
００Ｂ）と上端に細管（直径２關ダ、長さ１０１ｍ＋）
を有する流管（直径６朋グ、長さ４００ｍｇ）とからな
るものである。The apparatus used for spinning at this time is shown in Fig. 1, and -
Next, a coagulation bath filled with coagulation liquid (diameter 20G, depth 1
00B) and a thin tube at the upper end (2 diameters, 101m+ length)
(diameter 6 mm, length 400 mg).

流管には、二次凝固液を供給するための、供給ノズル１
３が付してあシ、細管１１の下端面と流管１２の上端面
とは、２關の重なり部を有するように調整されており、
−次凝固液の表面から６０薦諺の深さに細管が設けられ
ている。The flow tube includes a supply nozzle 1 for supplying the secondary coagulation liquid.
3, the lower end surface of the thin tube 11 and the upper end surface of the flow tube 12 are adjusted so as to have two overlapping parts,
- A capillary is provided at a depth of 60 mm from the surface of the coagulating liquid.

紡糸に当っては、流管中の液速か設定速度になるように
二次供給水量°を調整した。During spinning, the secondary supply water amount was adjusted so that the liquid velocity in the flow tube was the same as the set speed.

以上の手段で、ドラフト率（ドープの吐出線速／糸条の
引き取り速度）を＆７で一定とし七、各紡糸速度及び液
速（流管中）で紡糸し、得られた繊維の物性を第１表に
示す。Using the above method, the draft rate (dope discharge linear speed/yarn take-up speed) was kept constant at &7, and spinning was performed at each spinning speed and liquid speed (in the flow tube), and the physical properties of the obtained fibers were evaluated as follows. It is shown in Table 1.

比鮫例としては、管長を２００とし、凝固が極めて不完
全のまま自由落下域に引き出す公知の紡糸方法で製造さ
れた繊維物性を示した。な訃、この時の流管径は４　Ｍ
Ｌｙｊで、二次凝固液の供給水量が５１７分、細管部の
吸水量がｏ、ｓｓｌ／分であった。As an example, the physical properties of a fiber manufactured using a known spinning method with a tube length of 200 mm and drawn into a free fall region with very incomplete coagulation are shown. The diameter of the flow tube at this time was 4 M.
In Lyj, the amount of water supplied to the secondary coagulation liquid was 517 minutes, and the amount of water absorbed by the thin tube portion was o, ssl/minute.

以下余白 第１表からも明らかな様に、本発明法においては、同一
紡速の公知の紡糸法（比較例１）よりも繊維の強度及び
伸度共に優れた繊維が得られることが確認された。As is clear from Table 1 below, it has been confirmed that the method of the present invention yields fibers with superior fiber strength and elongation compared to the known spinning method (Comparative Example 1) at the same spinning speed. Ta.

また、各紡速で流管中の液速が紡速の８０１に満たない
条件下で製造されたｆｌ維は、繊維物性が極めて低く、
該液速が紡速の８０９６以上においては高強度及び高伸
度を有する優れた繊維を得た。In addition, fl fibers produced under conditions where the liquid velocity in the flow tube is less than 801% of the spinning speed at each spinning speed have extremely low fiber properties;
When the liquid speed was above the spinning speed of 8096, excellent fibers with high strength and high elongation were obtained.

実施例２ 固有粘度（η１ｎｈ）が７．２４のポリー／＃５７エ二
しンテレフタルアミドｔ−９９，８９６の濃硫識中に、
ポリマー濃度が１９．５％になるように、７０℃で２時
間溶解した。溶解は真空下で行ない、次いで２時間の静
置脱泡を行なった後紡糸に使用した。Example 2 During concentration of poly/#57 enylene terephthalamide t-99,896 with an intrinsic viscosity (η1nh) of 7.24,
The polymer was dissolved at 70° C. for 2 hours so that the polymer concentration was 19.5%. The dissolution was carried out under vacuum, and the mixture was left to stand for 2 hours for degassing before being used for spinning.

このドープを、孔径０．０７關ダ、孔数５００個を有す
る紡糸用口金から、ドラフト率が７．９となるように押
出し、細管の形状の違いを除いては実施例１と同じ第１
図に示す装置を用いて、一旦ＩＱｇの空間を走行させた
のち、温度を０〜３℃に保った２０チ硫酸水溶液を一次
凝固液と二次凝固液として用いて、第２表の紡糸条件で
紡糸を行なった。その際、流雪上端の細管の形状は、第
３図Ａのような内径４朋ダ長さｌＯｍと内径６朋ダ長さ
１０駄の形状であシ、流管の上端面と該細管の下端面と
は、４間の重なり部を有していた。This dope was extruded from a spinning nozzle with a hole diameter of about 0.07 and a number of holes of 500 so that the draft rate was 7.9.
Using the apparatus shown in the figure, after once traveling through a space of IQg, a 20-thiosulfuric acid aqueous solution kept at a temperature of 0 to 3°C was used as the primary coagulation liquid and secondary coagulation liquid, and the spinning conditions were as shown in Table 2. Spinning was performed with At this time, the shape of the thin tube at the upper end of the drifting snow is a shape with an inner diameter of 4 mm and a length of 1 Om and an inner diameter of 6 mm and a length of 10 mm, as shown in Figure 3A. The lower end surface had a four-way overlapped portion.

糸条は、−次凝固液の表面から３０ｍの深さに設置され
た細管、更に設定速度で二次凝固液が流れる流管（内径
１２　［０）を通って、ｌｌ１Ｉｉｌ管よシ下方４００
１１１に設けた変向ロールにて変向後、ネルソンロール
にて引き取シ、次いで、第４図に示すＰ　Ｐ　Ｔ　Ａｆ
！［（７）連ｆｆｌ製造装置Ｃ４？公昭５ｓ−９０８８
号公報に記載）により、即ち糸条を一対のギヤーニップ
ロール（歯車状のロールが浅く噛み合い、その間で糸条
を送シ出す）により反転ネット上に振シ込み、次いて６
理コンベアー上に反転させて乗せた。処理コンベアー上
に乗せられた先山は、シャワ一方式による水洗水によシ
洗浄された後、乳化剤によシボ中に分散させた鉱物油を
ｉｓ金含有る油剤液を給付され、次いで２００℃の熱風
乾燥を行った後、コンペア−上から取り上げられ、ワイ
ンダーによりゼピン上に捲きとられた。The thread passes through a thin tube installed at a depth of 30 m from the surface of the secondary coagulation liquid, and further through a flow tube (inner diameter 12[0]) through which the secondary coagulation liquid flows at a set speed, and then passes through the ll1Iil tube 400 meters below.
After changing the direction with the change-of-direction roll provided at 111, it is taken up with the Nelson roll, and then the P P T Af shown in FIG.
! [(7) Continuous ffl manufacturing equipment C4? Kosho 5s-9088
In other words, the yarn is transferred onto a reversing net by a pair of gear nip rolls (gear-shaped rolls are shallowly engaged and the yarn is fed between them), and then
It was inverted and placed on a processing conveyor. The first pile placed on the processing conveyor is washed with water using a single shower system, and then is supplied with an oil solution containing gold, which is mineral oil dispersed in the grain using an emulsifier, and then heated at 200°C. After drying with hot air, it was taken up from the top of the comparator and rolled onto a zepine with a winder.

以下余白 この様にして得られた繊維の性能は第２表に示す。Margin below The performance of the fibers thus obtained is shown in Table 2.

本発明法における繊維の性能は６００ｍ／分以上の高い
紡糸速度においても、糸条の滞留時間が少なくとも１０
朋秒以上になる様な流管長を有すると、２０チの硫酸水
溶液を一次及び二次凝固液として用いても、高強度及び
高伸度を有する繊維が得られた。The performance of the fiber in the method of the present invention is such that even at high spinning speeds of 600 m/min or more, the residence time of the yarn is at least 10 m/min.
When the flow tube length was longer than 10 seconds, fibers with high strength and elongation were obtained even when a 20-inch sulfuric acid aqueous solution was used as the primary and secondary coagulation liquid.

実施例３ 固有粘度（７１ｎｈ）が７．９１のポリ−パラフェニレ
ンテレフタルアミドｆ、９９．７％の濃硫酸中に、ポリ
マー濃度が１９．３係になるように、７０℃で２時間溶
解した。溶解は真空下で行ない、ついで２時間の静置脱
泡を行なったのち紡糸に使用した。Example 3 Poly-paraphenylene terephthalamide f having an intrinsic viscosity (71nh) of 7.91 was dissolved in 99.7% concentrated sulfuric acid at 70°C for 2 hours so that the polymer concentration was 19.3%. . The dissolution was carried out under vacuum, and the mixture was left to stand for 2 hours for degassing before being used for spinning.

このドープを孔径０．０７ｍ５ｚｆ、孔数５００個を有
する紡糸用口金から、ドラフト率′が８，０となるよう
に押出し、実施例１と同じ第１図に示す装置を用いて、
一旦ｔｏｔｒｇの空間を走行させたのち、温度を０〜３
℃に保った３５チ硫酸水溶液を一次及び二次凝固液とし
て用いて、第３表に示す紡糸を行なった。その際、流管
上端の細管は内径６Ｒｄで該細管の下端面と流管の上端
面とは、いずれもＩＩＩＩＩＩの重なシ部を有していた
。This dope was extruded from a spinning nozzle with a hole diameter of 0.07 m5zf and a number of holes of 500 so that the draft rate was 8.0, and using the same apparatus as in Example 1 shown in FIG. 1,
After running in the totrg space, the temperature is set to 0 to 3.
The spinning shown in Table 3 was carried out using a 35% sulfuric acid aqueous solution kept at 0.degree. C. as the primary and secondary coagulation liquids. At that time, the thin tube at the upper end of the flow tube had an inner diameter of 6 Rd, and the lower end surface of the thin tube and the upper end surface of the flow tube both had an overlapping part of III.

糸条は、−次凝固浴の表面から３０朋の架さに設置され
た細管、更に設定速度で二次凝固液が流れる流管を通っ
て、細管よシ下方５００　ｍｍに設けた変向ロールにて
変向後、ネルソンロールにて引き取り、ついで実施例２
と同様の工程を経てゼピン上に捲き取られた。The yarn is passed through a thin tube installed on a rack 30 mm from the surface of the secondary coagulation bath, and then through a flow tube through which the secondary coagulation liquid flows at a set speed, and then passed through a direction changing roll installed 500 mm below the thin tube. After changing direction at , it was picked up at Nelson roll, and then Example 2
After going through the same process as above, it was rolled up onto Zepin.

この様にして得られた繊確の性能を第３表に示す。Table 3 shows the performance of the fibers obtained in this way.

即ち、−次及び二次凝固液＆Ｃ３５％硫酸水溶液を用い
ても、流管の断面積と細管の断面積との比を少なくとも
２以上にすることで、高強度及び高伸度を有する繊維が
得られた。In other words, even when using secondary and secondary coagulation liquid &C 35% sulfuric acid aqueous solution, by setting the ratio of the cross-sectional area of the flow tube to the cross-sectional area of the capillary to at least 2 or more, fibers with high strength and high elongation can be obtained. Obtained.

一方、細管の長さと内径の比が０．５に満たないと、−
次凝固液の浴中が安定せず糸条を安定して引き取ること
が出来なかった。On the other hand, if the ratio of the length of the tubule to the inner diameter is less than 0.5, -
The next coagulation solution was not stable in the bath, and the yarn could not be drawn off stably.

比較例２ 細管の下端面と流管の上端面との重なり部が全くないこ
とを除いては、実施例３〜６と同じ条件で紡糸を試みた
が、−次凝固液の紡浴中が不安定となり、糸条を安定し
て引き取ることが出来なかった。Comparative Example 2 Spinning was attempted under the same conditions as in Examples 3 to 6, except that there was no overlap between the lower end surface of the capillary tube and the upper end surface of the flow tube. It became unstable, and the yarn could not be taken off stably.

比較例３ 実施例３に用いられたものと同じ紡糸用ドープを用い、
同一の吐出条件で空間に吐出後、−次凝固浴中に導いた
。Comparative Example 3 Using the same spinning dope as that used in Example 3,
After discharging into the space under the same discharging conditions, it was introduced into a second coagulation bath.

次いで一次凝固液表面から３０關の深さに設置された細
管（内径６Ｈグ、長さ６龍）を通して糸条及び−次凝、
固液を落下させ、細管から５００認下方で変向ロールに
て糸条１ｋｆ向させ友後、実施例２と同様の工程を経て
繊維を得た。得られた繊維の物性を第２表に併記したが
、本発明の繊維に比較して性能面で著しく劣るものであ
った。Next, the thread and the second coagulate were passed through a thin tube (inner diameter 6 mm, length 6 mm) installed at a depth of 30 mm from the surface of the primary coagulate liquid.
The solid liquid was allowed to fall, and the yarn was directed by a direction changing roll for 1 kf at a position 500 mm below the capillary. After that, the same process as in Example 2 was carried out to obtain fibers. The physical properties of the obtained fibers are also listed in Table 2, and they were significantly inferior in performance compared to the fibers of the present invention.

発明の効果 本発明によるＰＰＴＡＰＴＡ系繊維法によれば該ポリマ
ーを溶解するための溶媒として用いる硫酸の回収面で工
業的に有利な１０％以上の硫酸水溶液を一次凝固液とし
て製造される従来の繊維の物性に対し、強度の１０〜２
０％以上の向上に加えて、特に伸度の約１５〜３０チ以
上の向上ｋｍ成することが全てのＰ　ＰＴＡ系繊維の製
造に対して可能である。なお、かかる本発明法の著しい
効果は、ａｏｏｍ／分以上の紡糸速度において顕著に現
われる。Effects of the Invention According to the PPTAPTA fiber method according to the present invention, conventional fibers are manufactured using a 10% or more sulfuric acid aqueous solution as the primary coagulation liquid, which is industrially advantageous in terms of recovering sulfuric acid used as a solvent for dissolving the polymer. physical properties, strength of 10 to 2
In addition to improvements of more than 0%, in particular improvements in elongation of about 15 to 30 cm or more are possible for the production of all PPTA-based fibers. Note that the remarkable effects of the method of the present invention are noticeable at spinning speeds of aoom/min or more.

このように本発明法によって得られたＰＰＴＡＰＴＡ系
繊維度及び伸度の両方に優れた繊維であって、これらの
侵れた特性は、該繊維の実使用に当って消費性能上極め
て有利である。As described above, the PPTAPTA-based fiber obtained by the method of the present invention has excellent both fiber density and elongation, and these eroded characteristics are extremely advantageous in terms of consumption performance when the fiber is actually used. .

本発明によって得られたＰＰＴＡＰＴＡ系繊維の優れた
特性によって、衣料用、産業資材用を問わず使用される
が、特にブレードホース、コンベアベルト、タイヤ、エ
アパックなどのゴムの補強材、プラスチックの強化繊維
素材など、特に高強度かつ高伸度の特徴が十分に活用さ
れる分野で有用である。Due to the excellent properties of the PPTAPTA-based fibers obtained by the present invention, they are used for both clothing and industrial materials, but are particularly useful as reinforcement materials for rubber such as braided hoses, conveyor belts, tires, and air packs, and for reinforcing plastics. It is especially useful in fields such as textile materials where the characteristics of high strength and high elongation are fully utilized.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明法に好適な紡糸装置の一例を示す。第２
図及び第３図は、第１図の細管と流管上端部の例を示す
図である。第４図は、ＰＰＴＡ繊維の連続製造装置を示
す。 １１・・細管、１２・・流管、１３・・二次凝固液供給
ノズル、２０・・凝固液槽、２１・・次凝固液、２２・
・次凝固液供給ノズル、３０・・糸条変向用ロールガイ
ド、４０・・紡糸用口金、５０・・糸条及び凝固液流、
６０・・糸条、７４・・引き取り用ネルソンロール、７
５・・ギヤーニップロール、７６・・反転ネット、７７
・・糸山を送る為のコンベアーネット、７８・・水洗用
ジャワトレイ、７９・・熱風乾燥機、８０・・捲き取り
用ワイングー、８１・・糸山おさえ用カックーネット。 特許出願人　旭化成工業株式会社 第１図 第２図 第３図 （Ａ）　　　　　　　（Ｂ）FIG. 1 shows an example of a spinning apparatus suitable for the method of the present invention. Second
The figure and FIG. 3 are diagrams showing an example of the capillary tube and the upper end portion of the flow tube in FIG. 1. FIG. 4 shows an apparatus for continuous production of PPTA fibers. 11. Thin tube, 12. Flow tube, 13. Secondary coagulation liquid supply nozzle, 20. Coagulation liquid tank, 21. Secondary coagulation liquid, 22.
・Next coagulation liquid supply nozzle, 30.. Roll guide for yarn direction change, 40.. Spinneret, 50.. Yarn and coagulation liquid flow,
60... Yarn, 74... Nelson roll for take-up, 7
5. Gear nip roll, 76. Inversion net, 77
・・Conveyor net for sending the yarn pile, 78・・Java tray for washing, 79・・Hot air dryer, 80・・Wine goo for winding up, 81・・Cuckoo net for holding down the yarn pile. Patent applicant: Asahi Kasei Industries, Ltd. Figure 1 Figure 2 Figure 3 (A) (B)

Claims (2)

【特許請求の範囲】[Claims] （１）溶媒１００ｍｌ当り、少なくとも３０ｇのポリ−
パラフエニレンテレフタルアミド系ポリマーを含む９８
．０〜１００．２％硫酸の光学的異方性を示す溶液を、
空気又は非凝固性の流体層を通して少なくとも１０％硫
酸水溶液の一次凝固液に導き、次いで凝固浴下部に設け
られた細管中に糸条を導き走行させた後、該糸条を洗浄
、乾燥等の仕上げ工程に供する湿式紡糸法により繊維を
製造するにあたり、該細管は長さと内径の比が０．５以
上であつて、かつ、該細管の下端部が挿入される様に流
管を設置し、その際該流管は細管の断面積の２倍以上の
断面積になるような内径、及び走行する糸条が１０ｍｍ
秒以上滞留出来るような長さを有し、かつ、流管中の凝
固液速度が糸条速度の少なくとも８０％になるように、
該細管の下端面の上部から二次凝固液を供給することを
特徴とするポリ−パラフェニレンテレフタルアミド系繊
維の製造方法(1) At least 30 g of polycarbonate per 100 ml of solvent.
98 containing paraphenylene terephthalamide polymers
．． A solution showing optical anisotropy of 0 to 100.2% sulfuric acid,
The yarn is introduced into a primary coagulation solution of at least 10% sulfuric acid aqueous solution through air or a non-coagulable fluid layer, and then the yarn is guided and run through a thin tube provided at the bottom of the coagulation bath, and then the yarn is washed, dried, etc. When producing fibers by the wet spinning method for the finishing process, the flow tube is installed so that the ratio of the length to the inner diameter of the capillary is 0.5 or more, and the lower end of the capillary is inserted, In this case, the flow tube has an inner diameter that has a cross-sectional area more than twice that of the thin tube, and a running thread of 10 mm.
It has a length such that it can stay there for more than a second, and the velocity of the coagulated liquid in the flow tube is at least 80% of the thread velocity.
A method for producing poly-paraphenylene terephthalamide fibers, characterized in that a secondary coagulation liquid is supplied from the upper part of the lower end surface of the capillary. （２）紡糸速度が少なくとも３００ｍ／分である特許請
求の範囲第１項記載の製造方法(2) The manufacturing method according to claim 1, wherein the spinning speed is at least 300 m/min.