DE60124546T2 - A method of making a crimped animal fiber of reduced cross-section - Google Patents

Description

BACKGROUND OF THE INVENTION

1. Field of the invention

The The present invention relates to a thinned animal fiber, made thinner by stretching and temporarily or permanently maintains the resulting state, and a process for the preparation thereof and a spun yarn, the obtained by mixing with the animal fiber.

2. Description of the state of the technique

Several conventional Attempts to subject an animal fiber to a stretching treatment have been made to a voluminous or light animal fiber to improve the heat retention capacity and make a spun yarn with a finer yarn size. In the Japanese Patent publication No. Sho 44-15136 discloses a method in which a sliver, after a wool-combed train according to a Turning process for a single-ply combed drawstring, a two-ply combed drawstring and a multi-layered one Corkscrew was twisted, a stretch of 30% in an aqueous solution of a penetrant and a nonionic surfactant at 70 ° C and then the sliver stretched and fixed at 50 ° C for 1 h and subsequently cooled in water, turned on and dried. Because the task of the above Processing in the fixation of a temporarily stretched state, become the ripples the wool fibers restored by the temporary fixation relieved in a subsequent relaxation process.

In Japanese Patent Publication No. Sho 46-33141, a method is disclosed in which, in the case of Scallop of 20 g / m, after wool-combing by means of a turning process for one one-ply combed drawstring, a two-ply combed drawstring and a multi-layered one Worsted rotation of about 0.05 to 0.4 turns / cm lent a draw is given a stretch of 30% in water at 100 ° C is fixed, the sliver for about 1 h in water or the Crumb of a stretch of 20% in an aqueous solution of 2% monoethanolamine hydrogen sulfite at 80 ° C is subjected and fixed for 40 minutes and then the sliver in Washed, turned up and dried in air or dried, whereby a latent contraction or latent ripples are obtained. However, this is not a method of reduction the fiber diameter of a wool fiber and to increase the Fiber length.

In Japanese Unexamined Patent Publication No. Hei 5-500989 is a complicated one Stretching device and a stretching method by means of a false twisting process for the formation of thinner listed wool staple fibers, and in this document is described as having an untwisted sliver or roving of 50 to 110 g / m treated with 0.25 to 1 g / l of a wetting agent and that a plasticizer to produce a mercaptoanion in protein fibers, 1 to 75 g / l of sulfite, hydrogen sulfite or metahydrogen sulfite of Sodium, ammonium or potassium, an alkali as such, an alkali salt, Sodium thioglycolate or ammonium thioglycolate can be used. The formation of a mercaptoanion by means of the one described above Procedure is only possible under alkaline conditions. Even though there described a stretching of protein fibers in the presence of an alkali is, therefore, are a sufficient dive time and a comparatively high temperature required for softening. Under the conditions a dive time of about several seconds at low temperature Even though a sliver bundle is 100%, it practically converts 60%, stretched, a tearing of individual fibers and leads in that the stretched sliver contains many short fibers. At the Method of this document, wherein the sliver for softening the protein fibers of the untwisted sliver at a speed of 13.2 m / min, 3 m / min or 6 m / min introduced into a dip, a Rotation rate of about 120 or 180 by means of a false-twist spinning method, used widely in the spinning process of a synthetic fiber is lent, and the sliver is stretched by 100% and then reduced by steam with a residence time of 2 min and subsequently obtained in an untwisted state and in a hydrogen peroxide bath oxidized and rinsed and dried, an oxidation / reduction fixation is imparted, to stabilize a permanent fixation, wherein a neutralization treatment with an acid or base is not applied. Therefore, the fiber, because the obtained elongated protein fibers are basic, in a following heat treatment a tendency to yellowing.

Japanese Laid-Open Publication No. Hei 7-3556 describes the following method untwisted sliver of animal fibers having a fiber length of 30 mm or more is contained in hot water of 80 ° C or in aqueous solutions of 80 ° C containing 1.0% by weight of thioglycolic acid and 1.5 moles of urea and containing 25% iger aqueous ammonia solution are adjusted to a pH of 2.5, or in an aqueous solution of 80 ° C containing 2.0 wt .-% thioglycolic acid and 1.5 moles of urea and with 28% aqueous ammonia solution to a pH is set at 3.7, dipped and treated, and then first stretched by 1.05 times between six press rolls, each using a small diameter press rolls. Subsequently, the sliver between the six nip rolls is stretched by 1.49 times, and a reduction fixation by means of a steam treatment at a steam pressure of 2 kg / cm ^{2 is} applied. In the next method, the sliver is oxidized in an aqueous solution at pH 7 at 40 ° C for 10 minutes with 1% hydrogen peroxide using a drawstring dyeing machine, and then washed in a slub-draw washing and troweling machine and dried. However, in this method, because a roll pulls on the untwisted sliver, it has several problems in the operation, such as a fiber wound on the roll surface and slippage of the sliver in the roll drawing system, low productivity and high cost, for example, those described above described defect are due to.

JP 2001-003238 discloses a method for obtaining a long and thin Animal hair fiber by swelling and softening the fiber.

SUMMARY THE INVENTION

in the Case of natural Wool, the finest fibers have a diameter of 15 to 16 microns. Because such Wool fibers a substance produced in an extremely low amount and are very expensive, an industrial technology is desired can support the supply of such wool fibers at a very low cost. It is known that a single fiber of an animal fiber, in particular a wool fiber, which is completely swollen in water is up to 50% to 60% can be stretched. A procedure to get a thinner made fiber, which increases the fiber length and the stretched state permanently preserved without destroying the bilateral structure, is not known. The present invention does the above described thinner made animal fiber with the properties of a lesser Fiber contraction in boiling water, low alkali solubility and a high urea-bisulfite (UB) solubility and so forth in addition to the properties described above and a method of preparation available.

The The present invention relates to a process for the preparation of thinner made, curled fibers at a rate of percentage reduction in tensile strength for undyed spun yarn of not less than 10%, a shrinkage of the fiber in boiling Water of not more than 1%, an alkali solubility of not more than 22 wt .-% and a UB solubility greater than 35% by weight, with the thinned, crimped ones animal fibers are produced by virtually the same 1.20 to 1.60 times stretched after the animal, from a bilateral structure existing fibers anisotropic Sources using basic softening and swelling agents were subjected.

• a) ein Verfahren, bei dem einem Faserband aus tierischer Faser eine echte Drehung verliehen wird,
• b) ein Verfahren, bei dem ein gedrehtes Faserband aus tierischer Faser mit einer basischen wässrigen Lösung quellen gelassen und weichgemacht wird und anschließend ein anisotropes Quellen auf die aus einer bilateralen Struktur bestehende tierische Faser einwirken gelassen wird,
• c) ein, Reduktionsverfahren, bei dem eine Disulfidbindung in der anisotrop gequollenen und weichgemachten Faser gespalten wird,
• d) ein Streckverfahren, bei dem die reduzierte und anisotrop gequollene und weichgemachte Faser um das praktisch 1,20- bis 1,60fache gestreckt wird,
• e) ein Verfahren, bei dem die gestreckte tierische Faser oxidiert wird, wodurch eine Disulfidbindung wieder gebildet wird,
• f) ein Verfahren, bei dem die Faser mit einer Säure neutralisiert wird, damit sie entquillt,
• g) ein Verfahren zum Trocknen bis zu einem spannungslosen Zustand, wobei ein Tauchen und Zusammenpressen unter Verwendung von wenigstens drei Paaren von Presswalzen, die jeweils in einem Oxidationsbehandlungsbad, einem Neutralisationsbehandlungsbad und Heißwasser-Waschbädern, die jeweils vor und nach den beiden zuvor erwähnten

The method for producing the thinned, crimped animal fiber described above comprises the following steps:

• a) a process in which a sliver of animal fiber is given a true rotation,
• b) a method in which a twisted sliver of animal fiber is allowed to swell and soften with a basic aqueous solution and then an anisotropic swelling is applied to the animal fiber consisting of a bilateral structure,
• c) a reduction method in which a disulfide bond in the anisotropically swollen and plasticized fiber is split,
• d) a stretching process in which the reduced and anisotropically swollen and softened fiber is stretched by substantially 1.20 to 1.60 times,
• e) a method in which the stretched animal fiber is oxidized, thereby re-forming a disulfide bond,
• f) a process in which the fiber is neutralized with an acid to make it deflow,
• g) a method of drying to a de-energized state, wherein dipping and compressing using at least three pairs of press rolls, each in an oxidation treatment bath, a neutralization treatment bath and hot water baths, respectively before and after the two aforementioned

Baths are mounted, are formed, repeated and wherein the oxidation treatment at 15 to 25 ° C is performed.

SUMMARY THE DRAWINGS

1 Fig. 12 is a schematic view of a drawing process for producing a thinned animal fiber and one of the examples of a device used in the present invention.

2 Fig. 10 is a schematic view of a manufacturing method and apparatus used in the present invention.

3 is a schematic view of the press roll in a processing step.

4 Fig. 10 is a schematic view of a drying process in a process for producing a thinned animal fiber and an example of a device used in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The thinned obtained by the process of the present invention animal fiber is reduced by practically 1.20 to 1.60 times or 1.20 times stretched to 1.30 times, and as a result, the thinner state temporary or permanently fixed. The thinner ones made animal fiber is a fiber made with a thinner Shape, resulting in a substantially permanently fixed state and has a degree of fineness that is natural animal fibers can not be found and beyond the ripples which has a natural animal fiber.

Usually When stretching a fiber, perfect plastic deformation takes place never, and a total deformation partially includes an elastic Deformation, and therefore the proportion of elastic deformation recovers after stretching to the original one Shape. Accordingly, a distinction the applied extension from the practical extension, which remains in the fiber. Because these two extensions to be distinguished in the present invention, the real stretching extension of the twisted fiber bundle by adding term "practical".

Furthermore means the state of "permanent Fixation of the thinner made form ", that the thinner made form as a result of general treatment or processing of fibers such as by a spinning process and a dyeing process not lost.

Furthermore means a "permanent Fixation of the thinner made form ", that, because the thinner form is not fixed permanently or semi-permanently, the thinner made form the possibility has, in some cases lost due to a relaxation process.

Furthermore means the "property the recovery the ripple "that an animal Fiber a ripple, they originally could recover through a relaxation treatment.

When Relaxation method for recovery the ripple and discharge from a temporary fixed thinner condition is a treatment with warm water, hot water, Steam etc. mentioned. In particular, a method for relaxation processing by hot Water or steam preferred.

• 1) Eine tierische Faser besteht aus einem Zellgewebe in Spindelform und besteht aus einem Parakortex, der aus einem dichten Gewebe besteht, und einem Orthokortex, der aus einem Gewebe mit einer geringeren Dichte und einer geringeren Regelmäßigkeit besteht. Daher hat der Parakortex eine höhere Dichte (höher als 1,280) als der Orthokortex (niedriger als 1,280) und eine bilaterale Struktur und steht im engen Zusammenhang mit der Bildung einer Kräuselung. Der Parakortex stellt immer das Innere einer Krümmung der Kräuselung und der Orthokortex andererseits das Äußere dar. Und der Orthokortex nimmt quantitativ einen größeren Teil als der Parakortex ein. Der Orthokortex wird von basischen Farbstoffen leicht gefärbt, und andererseits wird der Parakortex leicht mit sauren Farbstoffen gefärbt. Von diesem Standpunkt aus ist der Orthokortex basophil, und der Parakortex ist acidophil. Wenn eine tierische Faser in eine wässrige Lösung von basischen Reagenzien wie Natriumhydroxid, Natriumcarbonat oder ein organisches Amin und dergleichen getaucht wird, werden die basischen Reagenzien natürlicherweise selektiv vom basophilen Orthokortex statt vom acidophilen Parakortex absorbiert (d.h., dass ein aniosotropes Quellen erfolgt), und der Orhtokortex quillt ungefähr um das 2fache in Längsrichtung der Faser. Als Ergebnis erfolgt eine Relaxation in der Bindung der makromolekularen Kette des Keratinproteins. Die vorliegende Erfindung macht von diesem Phänomen vollständig Gebrauch.
• 2) Weil der Parakortex mehr Cystin als der Orthokortex einschließt, hat der Parakortex natürlicherweise eine höhere Cystin-Vernetzungsdichte, und daher ist es schwierig, den Parakortex weichzumachen und quellen zu fassen. Durch die Spaltung einer vernetzenden Bindung von Cystin mittels Reduktionsmitteln wie Natriumhydrogensulfit, das die Cystinvernetzung spaltet, kann die Streckeigenschaft einer Faser jedoch verbessert werden. Die gespaltene Vernetzung wird mittels einer Austauschreaktion von Cystin/Cystein (-SS-/-SN) durch die Wirkung eines Oxidationsmittels im Verfahren nach den Strecken wieder vernetzt, und als Ergebnis ist die Struktur der dünner gemachten tierischen Faser fixiert.
• 3) Um eine Wollfaser dünner zu machen, muss ein starkes Strecken im Wesentlichen um das 1,2- bis 1,6fache angewandt werden, und daher sollte eine Weichmacher- und Quellbearbeitung bei einer hohen Temperatur und für einen langen Zeitraum vorsichtig durchgeführt werden. Ein Tauchen in eine wässrige Lösung von Weichmacher- und Quellreagenzien bei Normaltemperatur für mehrere Sekunden kann der Faser kein ausreichendes Strecken verleihen, sondern zum Reißen vieler Faser führen. Folglich wird als Ergebnis einer solchen Herstellung ein gestrecktes Faserband mit einem hohen Gehalt an gerissenen, kurzen Fasern erhalten.
• 4) Weil eine Weichmacher- und Quellbearbeitung unter basischen Bedingungen durchgeführt wird, ist eine neutralisierende Verarbeitung eine wesentliche Bedingung zur Stabilisierung der Polypeptidstruktur von Keratinproteinmolekülen. Darüber hinaus ist eine Neutralisierung einer sauren und einer basischen Behandlung eine notwendige und ausreichende Bedingung zur weiteren Stabilisierung der Struktur. Daher müssen, je basischer die verwendeten Chemikalien oder Reagenzien sind, umso saurere Chemikalien oder Reagenzien verwendete werden.
• 5) Die Kortexzelle einer tierischen Faser ist eine spindelförmige Zelle. Die Länge der spindelförmigen Zelle des Orthokortex ist ein wenig größer als diejenige des Parakortex, und dieser Längenunterschied beeinflusst die Krümmung der Kräuselung. Durch eine reduzierende Bearbeitung unter basischen Bedingungen quillt die Zelle auf der Seite des Orthokortex in Querrichtung auf, und als Ergebnis schrumpft sie in der Längsrichtung. Infolge eines Entquellens des Orthokortex durch eine Neutralisation mit einer Säure zieht der Orthokortex sich durch ein Entquellen in Querrichtung zusammen und dehnt sich gleichzeitig in Längsrichtung aus. Sowohl die Länge als auch die Kräuselung nehmen den ursprünglichen Zustand wieder ein.
• 6) Wenn eine Oxidationsbehandlung angewandt wird, nachdem einem Faserband aus tierischer Faser eine echte Drehung verliehen wurde, das Faserband in eine Weichmacher- und Quelllösung getaucht und dann stark gestreckt wird, wird auf jede Faser im Faserbündel aufgrund einer hohen Verdrehung und einem starken Strecken ein Querdruck ausgeübt. Folglich werden die Fasern so verformt, dass sie eine flache Form einnehmen. Klebende Stoffe zwischen den Zellen mit einem löslichen Protein mit einem niedrigen Fließen von Cystin aus dem Inneren der Faser bedecken die Oberfläche der Faser, wodurch eine Abnahme des Oberflächenglanzes bewirkt wird.

The treatment for softening and swelling the animal fiber is the most important method in the present invention for continuously carrying out a stretching work and permanently fixing the thinned state, and is essential for a process for producing a thinned animal fiber of the present invention. Hereinafter, a technique and thought will be described, which constitute the basis of the present invention.

• 1) An animal fiber consists of a spindle-shaped cell tissue and consists of a paracortex consisting of a dense tissue and an orthocortex consisting of a tissue having a lower density and a lower regularity. Therefore, the paracortex has a higher density (higher than 1.280) than the orthocortex (lower than 1.280) and a bilateral structure and is closely related to the formation of a crimp. The paracortex always represents the inside of a curvature of curling and the orthocortex on the other hand the exterior. And the orthocortex quantitatively occupies a greater part than the paracortex. The orthocortex is slightly colored by basic dyes, and on the other hand, the paracortex is easily stained with acid dyes. From this point of view, the orthocortex is basophilic, and the paracortex is acidophilic. When an animal fiber is dipped in an aqueous solution of basic reagents such as sodium hydroxide, sodium carbonate or an organic amine and the like, the basic reagents are naturally selectively absorbed by the basophilic orthocortex rather than by the acidophilic paracortex (ie an anisotropic swelling occurs), and the Orhtocortex swells approximately 2 times in the longitudinal direction of the fiber. As a result, relaxation occurs in the binding of the macromolecular chain of the keratin protein. The present invention makes full use of this phenomenon.
• 2) Because the paracortex includes more cystine than the orthocortex, the paracortex naturally has a higher cystine crosslink density, and therefore it is difficult to soften and swell the paracortex. However, by cleaving a crosslinking bond of cystine with reducing agents such as sodium hydrogen sulfite, which cleaves the cystine crosslink, the stretch property of a fiber can be improved. The cleaved crosslink is re-crosslinked by means of an exchange reaction of cystine / cysteine (-SS - / - SN) by the action of an oxidizing agent in the process after the stretching, and as a result, the structure of the thinned animal fiber is fixed.
• 3) To thin a wool fiber, a strong stretching must be applied substantially by 1.2 to 1.6 times, and therefore plasticizing and swelling processing should be performed cautiously at a high temperature and for a long period of time. Dipping in an aqueous solution of softening and swelling reagents at normal temperature for several seconds can not impart sufficient stretch to the fiber, but result in cracking of many fibers. Consequently, as a result of such manufacture, a stretched sliver having a high content of cracked short fibers is obtained.
• 4) Because plasticizer and swelling processing is conducted under basic conditions, neutralizing processing is an essential condition for stabilizing the polypeptide structure of keratin protein molecules. In addition, neutralization of acidic and basic treatment is a necessary and sufficient condition for further stabilization of the structure. Therefore, the more basic the chemicals or reagents used, the more acidic chemicals or reagents must be used.
• 5) The cortical cell of an animal fiber is a spindle-shaped cell. The length of the spindle-shaped cell of the orthocortex is slightly larger than that of the paracortex, and this difference in length affects the curvature of the curl. By reducing under basic conditions, the cell swells on the side of the orthocortex in the transverse direction, and as a result shrinks in the longitudinal direction. As a result of deswelling the orthocortex by neutralization with an acid, the orthocortex contracts by swelling in the transverse direction and at the same time expands longitudinally. Both the length and the ripple resume their original state.
• 6) When an oxidation treatment is applied after real rotation has been given to an animal fiber sliver, the sliver is dipped in a softening and swelling solution, and then strongly stretched, it is applied to each fiber in the fiber bundle due to high twisting and stretching Transverse pressure exerted. As a result, the fibers are deformed to take a flat shape. Adhesive substances between the cells with a soluble protein with a low flow of cystine from the inside of the fiber cover the surface of the fiber, causing a decrease in surface gloss.

Furthermore adhere to the fibers of the bundle made of animal fiber back together when the sticky substances to be dried, the fiber bundle gets stiffened, and then the separation between fibers becomes very difficult by means of panting, and therefore tearing takes place of fibers. At this stage, through both treatments, the one with a swelling agent and that with an acid as modifier for a Protein, for example formic acid, the adhesive substances that cover the fiber surface are removed, causing the surface gloss is restored. This treatment with an acid like formic acid is a groundbreaking system that also has the simultaneous effect the neutralization of the reduction process described above under basic conditions.

When animal fiber used in the present invention be a fiber that includes a protein fiber, such as wool, mohair, Alpaca, Kashmir, Lama, Vikunja and Camel mentioned. In particular, are wool, Mohair and alpaca preferred.

• a) ein Verfahren, bei dem einem Faserband aus tierischer Faser eine echte Drehung verliehen wird,
• b) ein Verfahren, bei dem ein gedrehtes Faserband aus tierischer Faser mit einer basischen wässrigen Lösung quellen gelassen und weichgemacht wird und anschließend ein anisotropes Quellen auf die Faser einwirken gelassen wird,
• c) ein Reduktionsverfahren, bei dem eine Disulfidbindung in der anisotrop gequollenen und weichgemachten Faser gespalten wird,
• d) ein Streckverfahren, bei dem die reduzierte und gequollene und weichgemachte Faser um das praktisch 1,20- bis 1,60fache gestreckt wird,
• e) ein Verfahren, bei dem die gestreckte tierische Faser oxidiert wird, wodurch eine Disulfidbindung wieder gebildet wird,
• f) ein Verfahren, bei dem die Faser mit einer Säure neutralisiert wird, damit sie entquillt,
• g) ein Verfahren zum Trocknen bis zu einem relaxierten Zustand.

A thinned animal fiber can be prepared by the method of the following items a) to g):

• a) a process in which a sliver of animal fiber is given a true rotation,
• b) a method in which a twisted sliver of animal fiber with a basic aqueous Lö swelling and softening and then allowing anisotropic swelling to act on the fiber,
• c) a reduction process in which a disulfide bond in the anisotropically swollen and plasticized fiber is split,
• d) a stretching process in which the reduced and swollen and softened fiber is stretched by virtually 1.20 to 1.60 times,
• e) a method in which the stretched animal fiber is oxidized, thereby re-forming a disulfide bond,
• f) a process in which the fiber is neutralized with an acid to make it deflow,
• g) a method of drying to a relaxed state.

The present invention is characterized in that the diving and the pressing are repeated, wherein at least three pairs of Press rolls are used, each in the oxidation treatment bath, in the neutralization treatment bath and in hot water wash baths, the each mounted before and after the previously listed two baths are present, and the oxidation treatment at 15 to 25 ° C is performed.

A superior thinner made animal fiber that has never been previously obtained at a rate of percentage reduction in tensile strength for undyed spun yarn of not less than 10%, a shrinkage of the fiber in boiling Water of not more than 1%, an alkali solubility of not more than 22 wt .-% and a UB solubility of more than 35% by weight becomes by the use of the above-mentioned press rolls and through the implementation an oxidation at a low temperature of 15 to 25 ° C. Here, a rate of percentage reduction in tensile strength means that of the tensile strength of the treated fiber in relation to the Tensile strength of an untreated animal fiber.

in the Generally it is for the removal of processing agents and residues in the preceding method, a washing method, preferably a washing process with warm water after a stretching process, to provide an oxidation process and a neutralization process. When washing with warm water is performed, a fiber is preferred treated in the stretched state, to prevent the relaxed Structure by the heat the warm water shrinks.

At the The first method is an animal fiber in sliver state one real turn given. By doing that the sliver before stretching A true twist may be given by winding up fibers on the roll surface and slipping of a sliver can be prevented, thereby one of these disorders caused decrease in productivity is avoided.

In In the present invention, the rotating method and the type are Twisting machine subjected to no special restriction. In the one Case in which a sliver of wool fiber by means of a fly-ply twisting machine For example, the weight is given a true turn the sliver to about 20 to 40 g / m, for example about 37 g / m, set, and it is desirable that gave 16 turns / m to 25 turns / m of true rotation become. When mohair and alpaca are, because the fiber itself is a bad one cohesion has, for example, a rotation of about 20 turns / min to 30 Turns / min for a sliver of about 37 g / m is required.

At the second method, the twisted animal fiber is a source and softening by means of a base. As described above is an animal fiber pulls in the longitudinal direction due to a swelling softening, whereby the diameter increases, together. The outside the ripple The animal fiber consists of an orthocortex component, and On the other hand, the inside of a crimp mainly consists of a paracortex component, and these two form a bilateral one Structure. About that In addition, because of an orthocortex to basic reagents a has higher affinity Swelling and softening by basic reagents stronger than at the orthocortex (anisotropic swelling). Therefore, if basic reagents used as a swelling agent, the orthocortex that swells on the outside the ripple is located in the transverse direction of the fiber stronger, and vice versa pulls the Fiber lengthwise together. Therefore, the ripple goes lost, and the fiber takes a straight line or a similar one Shape.

In In the present invention, it is the degree of the required Quellens prefers that the volume swelling degree is at least 2.0 times and even more preferably 2.0 to 2.5 times, and most preferably which is 2.0 to 2.1 times.

The examples for a useful swelling agent in the present invention is a Carbonate of an alkali metal, sodium, ammonium or potassium, Sodium hydroxide, a bicarbonate of an alkali metal or of Ammonium and potassium hydroxide.

Furthermore are examples of Softening agents Amines such as monoethanolamine and diethanolamine. These funds can independently or used in combination.

Preferably becomes an aqueous solution used both monoethanolamine with a concentration of 1 to 3 g / l as well as sodium hydroxide with a concentration of contains about 8 to 13 g / l, whereby the pH is adjusted to 7.5 to 9.0. Especially preferred is an aqueous solution used, the monoethanolamine with a concentration of 2 g / l and sodium hydroxide at a concentration of 10 g / l. These aqueous solutions will be in a big surplus across from the processed animal fiber used, or the processing agent always gets a watery solution is added so that the concentration of the aqueous solution is kept constant. The immersion temperature is in the range of 30 to 60 ° C, preferably 40 ° C, and the dive time is in the range of 20 to 50 minutes, preferably 30 minute

In front Stretching is the swollen and softened animal fiber subjected to reduction processing to cleave the disulfide bond, "-S-S-" in the cortex. examples for Reducing agents for the Reduction processing can be used are sulfite, hydrogen sulfite or metahydrogen sulfite of alkali metals, sodium, potassium or Ammonium, sodium thioglycolate, ammonium thioglycolate, monoethanolamine sulfide and monoethanolamine hydrogen sulfite. Preferably, sodium hydrogen sulfite or sodium sulfite. The state of the reduction processing by these reducing agents varies depending on the type and the concentration of the reducing agent and is usually 1 to 3 minutes at 60 to 100 ° C, preferably 1 to 2 minutes at 80 to 100 ° C. About that addition is the concentration of the reducing agent in the aqueous solution is 10 to 50 g / l, preferably 20 to 40 g / l.

Of the The degree of reduction is preferably in a range in which at least 25% of all disulfide bonds, and more preferably 25 to 40% be split. Most preferably, it is 25 to 30%.

The animal fiber used in the softening and swelling process or continue to undergo the reduction processing is fully, then with a true stretch ratio of not less than 1.20, preferably 1.20 to 1.60 and always even more preferably from 1.30 to 1.60 stretched. When the stretching in hot Water at 80 to 100 ° C or in steam from 90 to 95 ° C carried out can be stretching with a low fiber rippling roving respectively. Stretching can be done between rollers that come with different surface speeds rotate. The stretching does not necessarily need in one step carried out but can be done in many stages. Usually allows one Stretch that according to the latter Procedure, a more stable and higher draw ratio.

Around Removing swelling agents and softening agents and reducing agents, The animal fiber after stretching is usually in warm or hot water from 30 to 60 ° C or preferably 45 to 50 ° C washed. It is preferred that the washing be in the stretched state takes place so that the stretched state can not relax. at In hot water washing, hot water is repeated penetrate into the animal fiber and then with at least three or more pairs of press rolls pressed out. This causes a sufficient washing action and allows the following oxidation process a high performance.

The Animal fiber becomes after stretching and washing with hot water treated with an oxidizing agent to the oxidation-reduction state in the fiber namely to balance the cystine / cysteine (- SS - / - SH) ratio in the range of 900 (.Mu.mol / g Wool) / 10 (μmol / g Wool) to 700/50, preferably from 800/10 to 700/30 becomes. The relationship changes more or less dependent from the sheep species. When a large amount of fiber is reduced, it is natural essential to increase the amount of oxidation, and thus possible a balanced relationship the reduction / oxidation the permanent determination of a chemical Fixation. Through this treatment, the "-S-S -" crosslinking becomes the previous one Reduction process was broken, reformed, and it forms a cross-linked state, almost the state of an untreated Fiber comes close.

In oxidation processing, the oxidizing agent is repeatedly allowed to penetrate into the animal fiber and then pushed out with at least three nip rolls. Thus, the efficient and sufficient oxidation processing enables a treatment to be carried out at a low temperature of 15 to 25 ° C. Because by the press rolls sufficient impregnation and Oxidati On low temperature treatment of the animal fiber, the fiber suffers little damage, and hence, a superior thinned fiber having a rate of percentage lowering of tensile strength for undyed spun yarn of not less than 10% shrinks the fiber boiling water of not more than 1%, an alkali solubility of not more than 22% by weight, and a UB solubility of more than 35% by weight.

When Oxidizing agents can Hydrogen peroxide, potassium bromate, sodium bromate, sodium borate, potassium borate etc. are used. Hydrogen peroxide is preferred. hydrogen peroxide is preferred because of the remaining remaining in the fiber Share can be easily removed. When hydrogen peroxide as Oxidizing agent is used, the concentration of hydrogen peroxide in the aqueous solution preferably 1 to 3% by weight and more preferably 2.8% by weight. In the case where the hydrogen peroxide concentration for example 2.8% by weight, is the processing time is 90 to 150 s and at 15 to 25 ° C preferably 120 s.

Usually will the animal fiber, the above-described processing with the oxidizing agent is treated with hot or warm water of 40 to 60 ° C washed to remove the oxidizing agent in the fiber. at This washing treatment will also be impregnated with animal fiber Water and a subsequent Pressing out, wherein at least three or more pairs of press rolls are used, to increase the efficiency for removing the oxidizing agent.

Then the animal fiber is neutralized with a Acid, to neutralize the remaining basic substances and then the on the fiber surface isolated soluble Protein that bleeds out of the interior of the fiber during the stretching process, to remove.

Also in the neutralization processing, at least three or more Press roll pairs used to accelerate the neutralization and perfect to complete.

When Neutralizing agents are an inorganic acid such as hydrochloric acid and sulfuric acid and an organic acid like acetic acid, formic acid and oxalic acid prefers. formic acid is particularly preferred. The processing conditions of diving and washing for 40 to 80 s in the solution with a pH of 2.0 to 4.5 is preferably carried out at room temperature. When the laundry under a preferred condition with in an aqueous formic acid solution a pH of 2.5 room temperature for 30s, the neutralizes basic chemicals contained in this fiber, and at the same time, the bleeding of the soluble protein from the inside also becomes eliminated the fiber, and as a result, a shiny, thinner obtained fiber.

at the thinner made animal fiber is the true rotation of the fiber after neutralization and washing, and the fiber becomes dried tension-free. The animal fiber, in the transverse direction swollen and in the longitudinal direction has contracted, contracts in the transverse direction and is simultaneously in the longitudinal direction stretched, because the source state is lifted when it dries. On This is done by thinning Fiber swelling in animal fiber with bilateral structure not even. Because the swelling especially on the orthocortex side of the cross section animal fiber, i. in the outer area the original one ripple the animal fiber, is the degree of stretching of the length means a swelling on the Orthokortex side also larger. Accordingly, a crimp becomes By eviscerating restored so that the orthocortex side to the outside becomes. Thus, a thinner made animal fiber, without the real length itself changed Has.

By the above operation takes the fiber diameter, although this from the type of animal fiber depends on about 15 to 20%, and the fiber length elevated by about 35 to 45%.

Hereinafter, the present invention will be explained in more detail based on the accompanying drawings as examples. 1 to 4 FIG. 10 are schematic views of the method of thinning an animal fiber. FIG. A true rotation of 16 turns / m in the Z-direction is given to an animal sliver ( 1 ) with a twisting machine ( 2 ) and the twisted sliver is wound on a yarn carrier ( 1 ). As in 2 is the twisted sliver of animal fiber, after a coil rack ( 4 ) was loaded, pulled out and placed in a pretreatment bath ( 5 ) for softening and swelling. The plasticized and swollen fiber is from a press roll group consisting of upper rolls ( 6 ) and ( 7 ) and lower rollers ( 8th ) 9 ) 10 ) and ( 11 ) is pressed. Between these press roll groups and the press roll groups coming from the upper rolls ( 12 ) 13 ) and the lower rollers ( 14 ) 15 ) and ( 16 ), the animal fiber is stretched, the speed difference between the two groups of rolls while passing through a reduction processing bath ( 17 ) and a steam processing machine ( 18 ), which are mounted between the roller groups, is guided. With this device, the stretch extension with the draw ratio of 1.4 times (virtually 1.20 times) to 2.5 times (virtually 1.80 times) can be varied. Next, the stretched animal fiber is placed in the hot water bath ( 19 ), and to prevent relaxation, which is usually carried out in a hot-water bath, the sliver between a roller ( 13 ) and a roller ( 23 ) stretched 1.01 times.

And then the sliver gets into the oxidation baths ( 24 ) 29 ) and ( 34 ) and subjected to an oxidation treatment by placing it in each oxidation bath between the rolls ( 23 ) and ( 28 ) 28 ) and ( 33 ) and ( 33 ) and ( 38 ) is stretched 1.01 times and then it becomes a neutralizing bath ( 39 ). The sliver is then also in the neutralization between the rollers ( 38 ) and ( 43 ) stretched about 1.01 times. The fiber that is allowed to neutralize is in ( 44 ) and ( 49 ) introduced. The sliver is held in a state in which a slight tension is applied by moving it between the rollers (FIG. 43 ) 48 ) and ( 48 ) 53 ) is stretched about 1.01 times in a hot water bath. Furthermore, it is between the rollers ( 53 ) and ( 54 ) stretched 1.01 times, followed by a cancellation of the true rotation by means of a twisting device ( 55 ) of the rotary can type and a drying. When dried in a de-energized condition, an in 3 illustrated dryer of suction type ( 56 ) used.

In the method described above, with an upper roller pair and two lower rollers, a load of 600 to 1000 kg is allowed to act on the two ends of the rollers, ie in each case on the upper roller ( 6 ) / the lower rollers ( 8th ) 9 ), the upper roller ( 7 ) / the lower rollers ( 10 ) / ( 11 ) and the upper roller ( 12 ) / the lower rollers ( 14 ) 15 ). The diameter of the upper rollers ( 6 ) 7 ) and ( 12 ) is 80 mm, for example, and it is preferable that the surface is coated with a rubber layer having a hardness of about 80 °. As the lower rolls, a roll of stainless steel having recesses formed in the transverse direction of the surface is preferable. Thus, the roller has a structure that prevents slipping even in the case where the roller extends by 1.4 to 2.2 times (practically 1.20 to 1.60 times) by means of roller stretching. The pretreatment bath ( 5 ) is equipped with a storage tank ( 57 ) equipped with processing solution, and a metering pump delivers a treatment agent. And the same liquid as in the pretreatment bath ( 5 ) is taken from a storage tank ( 58 ) from a metering pump to the reduction processing bath ( 17 ). Furthermore, the oxidation baths ( 24 ) 29 ) and ( 34 ) with storage tanks ( 59 ) 60 ) 61 ) and metering pumps, and the neutralization bath ( 39 ) is equipped with a storage bath ( 62 ) and a dosing tank.

The sliver of animal fiber is placed in the pre-treatment bath ( 5 ) under basic conditions so softened and swollen that it can be stretched to a high degree. And in the reduction processing bath ( 17 ) comprising the above-mentioned reducing agent and the damping device ( 18 ), the cystine crosslinking bond of an animal fiber is cleaved with this reducing agent, and the fiber is stretched by about 1.4 to 2.2 times (practically by 1.20 to 1.60 times), thereby making it thinner becomes. The cystine crosslinking is achieved by oxidation with an oxidizing agent in the oxidation baths ( 24 ) 29 ) and ( 34 ), and as a result, the molecular structure of the protein of the animal fiber is stabilized in a state where the fiber is made thinner. In neutralization bath ( 39 ), the base absorbed by the animal fiber is almost neutralized with formic acid, etc. to neutral state, and at the same time, the soluble protein eluted at that fiber surface and covering the fiber surface is removed, and these methods lead to the production of a thinned fiber a property of recovery of curl and a high gloss. Preferably, the anisotropic swelling and softening process and the reduction process are carried out in one process.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples

example 1

This in 1 The listed process diagram is followed. The Wool-Kammzug, which was obtained by a merino wool-combing with 37 g / m ( 1 ) having an average fiber diameter of 18.7 μm and an average fiber length of 77.2 mm (the length of the longest fiber was 150 mm) was rotated 16 turns / m at a speed of 1.3 m / min the pre-treatment bath ( 5 ) and soft for 30 minutes at 40 ° C in the working fluid of the following composition subjected to machining and source processing. sodium bisulfite 30 g / l Monoethanolamine 2 g / l sodium hydroxide about 10 g / l (to adjust the working fluid to a pH of 8.0)

Next, the sliver was placed in the reducing bath ( 17 ), which contained a solution of the same composition as the pre-treatment bath solution described above, and further plasticized and swelled for 30 seconds at 80 ° C and then for 70 s at 95 ° C in the damper ( 18 ) subjected to steam processing. At the same time, the sliver with the roll groups ( 12 ) and ( 13 ) with a surface velocity of 2.1 times in relation to one of the roll groups ( 6 ) and ( 7 ) by 2.1 times (practically 1.40 times). The sliver was then bathed for 30s with warm water at 25 ° C in a hot water bath ( 19 ) washed.

In this treatment, the sliver is repeatedly subjected to pressing / dipping in the processing liquid by means of the press rolls (FIG. 20 ) 21 ) and ( 22 ). Thus, sufficient fluid displacement has been achieved. Then in the oxidation baths ( 24 ) 29 ) and ( 34 ), in which the press roller pairs ( 25 ) 26 ) and ( 27 ) 30 ) 31 ) and ( 32 ) 35 ) 36 ) and ( 37 ) were mounted in an equivalent manner, an oxidation treatment was carried out at 25 ° C. for 40 seconds, using an aqueous solution containing 2.8% by weight of hydrogen peroxide in each processing bath. Also in this method, the wool fiber tape is subjected to a sufficient oxidation effect by a liquid displacement effect by the press roller pairs in the baths as in the hot water washing bath mentioned above. Thereafter, in neutralization bath ( 39 ), in which the press roller pairs ( 40 ) 41 ) and ( 42 ) were similarly neutralized at 25 ° C for 30 seconds using an aqueous solution adjusted to pH 2.5 with formic acid, and then washing with warm water at 25 ° C ° C in the hot water wash baths ( 44 ) and ( 49 ), in which the press roller pairs ( 45 ) 46 ) and ( 47 ); ( 50 ) 51 ) and ( 52 ) were mounted in a comparable manner. Also in these neutralization and hot water washing baths, sufficient neutralization and effect of the warm water washing were achieved by the liquid displacement effect of the roller pairs mounted in the baths as in the above-mentioned hot water washing baths and the oxidizing baths. Finally, the sliver was twisted by means of a twisting device of the rotary can type and by means of the Saugtrommeltrockners ( 56 ) dried.

The Stretched wool fiber tape obtained by the above method was hacked and combed, whereby listed in Table 1 Result was obtained.

It it turned out that the stretched wool fiber sliver described above to that effect it was modified to be thinner made and a white one and shining Wool fiber with a ripple was.

[Table 1]

The stretched wool fiber described above was also spun to obtain a yarn having a yarn count of 1/30 and a twist of Z 440, as shown in Table 2. by virtue of By decreasing the fiber diameter and increasing the number of fibers constituting a yarn by the thinning treatment, the tensile strength of the yarn does not decrease so much as compared with an untreated yarn.

[Table 2]

Comparative Example 1

in the Compared to example, the machining became according to the machining conditions of Example 1, except that the press rolls, which were at that time mounted in each of the oxidation baths, not used The slivers were hackled and combed back, resulting in the table 3 listed Results were obtained.

[Table 3]

And The stretched wool fiber described above was spun, thereby a yarn with a yarn count of 1/30 and a twist of Z 440, as shown in Table 4. In the data of Rate of shrinking in hot Water means a minus (-) a shrinking.

When the working was carried out without using the press rolls mounted in each of the oxidizing baths and the hydrogen peroxide solution was penetrated into the wool-kneading train at a working temperature of only 25 ° C, the blocking effect on the -SH group by hydrogen peroxide was not fully achieved , Therefore, the fixing effect was insufficient, and as a result, the fiber diameter was compared to the thicker obtained in Example 1, and the fiber length was also short. Moreover, in the test spun yarn described above, as compared with Example 1, it was also observed that boiling water contraction was stronger as compared with Example 1. Namely, in order to fully fix the shape of the fiber after stretching by the use of an aqueous solution containing 2.8% by weight of hydrogen peroxide, it was found to be essential to force-circulate by means of the liquid-displacing action using the press rollers mounted in the baths to carry out the aqueous hydrogen peroxide solution.

Comparative Example 2

When Comparison to Example 1 was made except that the temperature the hydrogen peroxide liquid 80 ° C was and those in each of the oxidation baths mounted press rolls were not used, the machining according to the processing conditions of Example 1 performed. The sliver was hacked and combed, making it a table 5 listed Result was obtained.

[Table 5]

And the stretched woolen combing described above became the same Woven as in Example 1, whereby a yarn with a yarn count of 1/30 and one turn of Z 440, and the data of the yarn are listed in Table 6.

If the processing at 80 ° C carried out without the press rolls used in each of the oxidation baths were to use, although the appearance of the fiber after stretching similar to that of the stretched wool fiber of Example 1, both the mean fiber length as well as the length the longest Shorter fiber as in Example 1. In addition, an increase in the amount of short fibers was also observed. This result shows that by the oxidation treatment at high Temperature the fiber brittle and the short fiber in this wool-scabbard by the panting and combing was formed. The alkali solubility and the UB solubility, with which the degree of damage As a result, the damage of the fiber is determined stretched wool fiber through the processing conditions of Comparative Example 2 is higher compared to the stretched wool-combed draw of Example 1.

Also in the spun fiber yarn tested above are compared to yarn, which is made using the stretched wool-combed of Example 1, the strength and elongation of the Yarns, using the stretched wool-combed under the working conditions of Comparative Example 2 were obtained, lower and the result described above was supported. It means that to obtain a stretched wool fiber, in which damage to the Fiber suppressed becomes, the watery Hydrogen peroxide solution at a low temperature in the sliver of wool fiber of a forced circulation must be subjected to and the oxidation treatment by means of in the baths mounted press rolls must be done. This fact shows that the press rolls in the baths, used in the present invention, an important Element for obtaining a stretched wool fiber with a low wool content damage of fibers.

Example 2 (no part representing the invention

The fiber sliver from wool fibers of 37 g / m ( 1 ) having an average fiber diameter of 27.0 μm and an average fiber length of 70.0 mm was rotated by 16 turns / m with a flyer type twisting machine. This sliver was treated in the same manner as Example 1 except for the following treatment condition.

[Different from example 1 Conditions]

• 1) The composition of the treatment solution and the treatment temperature and the duration of the plasticizer and source pretreatment bath ( 5 Sodium bicarbonate 30 g / l Sodium carbonate 0.15 g / l Immersion condition 10 min at 60
• 2) stretch ratio: 1.7 times (practical stretch ratio: 1.25 fold)
• 3) Instead of the treatment bath ( 24 . 29 . 34 ) water of 80 ° C without a passage through the reduction processing bath ( 17 ) and omitting oxidation processing by means of hydrogen peroxide.
• 4) The neutralization treatment was carried out at a pH of 4.5 using acetic acid instead of formic acid in the neutralizing bath ( 39 ) carried out.

The obtained fiber had a structure whose ability to recover the ripple temporarily fixed is. The mean fiber diameter and the mean fiber length before and after treatment are listed in Table 7. The mixture of 70% by weight Woolen fiber tape obtained by a thinning treatment and 30% by weight of an unstretched sliver of 27.0 μm became 3/4 Nm spun and subjected to a relaxation treatment by means of steam. The specific volume of the obtained yarn was measured, and the result is shown in Table 8.

[Table 7]

[Table 8]

In the examples and comparative examples described above the alkali solubility and the UB solubility an animal fiber measured on the basis of the test method, which under "7.21.1 Alkali solubility "and" 7.21.2 Solubility in urea-sodium bisulfate (UB solubility) "under" 7.21 degree of fiber damage "of JIS-L-1081 are.

According to the present Invention it is possible that the fiber diameter of an animal fiber is reduced can, the fiber length be enlarged can, and that the animal fiber is capable of, modified to that effect to be that thinner fiber obtained without the rippling property that the natural Owns fiber, gets lost. Because the wool fiber is a natural fiber is inevitable in terms of fineness (fiber diameter) and length (fiber length) restrictions is subject to the production of a spun yarn with a fine Garnfeinheit therefore also limited. On the one hand, the present invention an industrial production of a thinner animal Fiber by overcoming the limitations described above. And on the other hand allows the present invention is an industrial production of a thinned Fiber to give light products of animal fibers, whose volume has a high air content and a high Heat retaining property by having a mild condition during stretching, i. the fixing conditions about a temporary Fixation, to be used.

Claims (8)

Method for producing a thinned, ruffled animal fiber with a solid, thinned form with a Rate of lowering of tensile strength for undyed spun yarn of non less than 10%, a shrinkage of the fiber in boiling water of not more than 1%, an alkali solubility of not more than 22 wt .-% and a urea-bisulfite (UB) solubility greater than 35% by weight, comprising: a) a procedure in which: gave a true twist to a sliver of animal fiber becomes, b) a method in which a twisted sliver of animal fiber with a basic aqueous solution swollen and softened and then an anisotropic swelling on those consisting of a bilateral structure animal fiber is allowed to act, c) a reduction process, in which a disulfide bond in the anisotropically swollen and plasticized fiber is split, d) a stretching method in which the reduced and anisotropically swollen and softened fiber around the practical 1.20 to 1.60 times stretched, e) a procedure whereby: the stretched animal fiber is oxidized, creating a disulfide bond is formed again, f) a method in which the fiber with an acid is neutralized, so that it depletes, g) a method for Dry to an unstretched state, taking a dip and Compress using at least three pairs of Press rolls, each in an oxidation treatment bath, a Neutralization treatment bath and one before the oxidation treatment bath mounted hot water wash and a hot water wash bath mounted after the neutralization treatment bath are formed, repeated and wherein the oxidation treatment at 15 to 25 ° C is carried out. Process for the preparation of thinned animal fiber The method of claim 1, wherein the method of anisotropic swelling and plasticizing and the reduction process in one process carried out become. A method of making the thinned animal fiber of claim 1, wherein the treat the anisotropically swelling plasticizing is carried out by adding the twisted fiber sliver in a basic, aqueous, swelling agent and a plasticizer-containing solution having a pH of 7.6 to 10.5 at 30 to 80 ° C 5 to 40 is dipped for a long time. Method for producing a thinned animal fiber according to one of the claims 1 to 3, wherein the means for the anisotropically swelling, softening treatment is a base, from that of a monoethanolamine, a carbonate of an alkali metal or of ammonium and a hydrogencarbonate of an alkali metal or ammonium group. Method for producing a thinned animal fiber according to claim 1, wherein the reducing agent is one of a Hydrogen sulfite of an alkali metal or of ammonium and a sulfite an alkali metal or ammonium group is selected. Process for the preparation of thinned animal fiber according to one of the claims 1 to 3, wherein the stretching treatment in hot water or in heated Steam takes place. Method for producing a thinned animal fiber according to claim 1, wherein the oxidation of the stretched animal Fiber is carried out using hydrogen peroxide. Method for producing a thinned animal fiber according to one of the claims 1 to 3, wherein the neutralization method using formic acid carried out becomes.