EP2719801A1 - Bain de filage et procédé de renforcement d'un corps de formage - Google Patents

Bain de filage et procédé de renforcement d'un corps de formage Download PDF

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Publication number
EP2719801A1
EP2719801A1 EP12187870.6A EP12187870A EP2719801A1 EP 2719801 A1 EP2719801 A1 EP 2719801A1 EP 12187870 A EP12187870 A EP 12187870A EP 2719801 A1 EP2719801 A1 EP 2719801A1
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EP
European Patent Office
Prior art keywords
liquid
coagulation
coagulation bath
bath
liquid container
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12187870.6A
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German (de)
English (en)
Inventor
Stefan Zikeli
Friedrich Ecker
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Aurotec GmbH
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Aurotec GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aurotec GmbH filed Critical Aurotec GmbH
Priority to EP12187870.6A priority Critical patent/EP2719801A1/fr
Priority to TW102136592A priority patent/TWI609899B/zh
Priority to RU2015116641A priority patent/RU2649270C2/ru
Priority to US14/434,625 priority patent/US10208402B2/en
Priority to KR1020157012140A priority patent/KR102105865B1/ko
Priority to CN201380062926.7A priority patent/CN104838048B/zh
Priority to EP13776771.1A priority patent/EP2906742B1/fr
Priority to PCT/EP2013/071135 priority patent/WO2014057022A1/fr
Publication of EP2719801A1 publication Critical patent/EP2719801A1/fr
Priority to ZA2015/02381A priority patent/ZA201502381B/en
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the present invention relates to coagulation baths for spinning processes.
  • Celluose and other polymers can be dissolved in suitable solvents and converted by controlled solidification into a desired shaped body.
  • this shaped article is filaments, fibrils and the like, it is also referred to as a spinning process.
  • cellulose is dissolved in aqueous solutions of amine oxides, particularly solutions of N-methyl-morpholine-N-oxide (NMMO), to produce spin products such as filaments, staple fibers, films, etc. from the resulting dope. This is done by precipitation of the extrudates in water or dilute amine oxide solutions after the extrudates of the extrusion die are passed through an air gap in the precipitation bath.
  • NMMO N-methyl-morpholine-N-oxide
  • the US 4,416,698 relates to an extrusion or spinning process for cellulose solutions to form cellulose into filaments.
  • a fluid spinning material a solution of cellulose and NMMO (N-methylmorpholine-N-oxide) or other tertiary amines - formed by extrusion and placed in a precipitation bath for solidification and expansion. This method is also known as the "lyocell” method.
  • the US 4,246,221 and the DE 2913589 describe processes for producing cellulosic filaments or films wherein the cellulose is drawn in fluid form. It describes a spinning process in which cellulose is dissolved in tertiary amine oxide, wherein the resulting cellulose solution is forced through a nozzle tool, extruded through an air gap into a spinning funnel and drawn off at the end of the spinning funnel as an endless thread.
  • the inserted spinning funnel is equipped with a supply means and a laxative for the spinning bath.
  • the US 4,261,943 relates to a process for the production of shaped cellulose articles, wherein the surface of the spun threads is treated with a non-solvent.
  • the WO 93/19230 A1 describes a further development of the lyocell process, in which the cellulose-containing spinning material is cooled immediately after molding before introduction into the precipitation bath.
  • the WO 94/28218 A1 describes a process for producing cellulose filaments in which a cellulose solution is formed into a plurality of strands via a die. These strands are brought through a gas-flow gap in a precipitation bath and discharged continuously.
  • the DE 555183 relates to spinning vessels for the wet spinning process, wherein a spider yarn passes through several vertical baths.
  • the WO 92/4871 describes a process for making a cellulosic fiber with reduced fibrillation tendency.
  • the reduced fibrillation is achieved by allowing all the baths, with which the fiber comes into contact before the first drying, to have a maximum pH of 8.5. This control in a continuous bath is very complicated and requires chemicals for pH control.
  • CA 2057133 A1 describes a process for the production of cellulose filaments wherein a dope is extruded and introduced via an air gap into a cooled NMMO containing water bath.
  • the water bath contains a cycle for bath fluid regeneration with a spin bath supply and an outlet for controlling the NMMO components.
  • Michels and Kosan (Lenzinger Berichte, 86 (2006) 144-153 ) is concerned with the coagulation process of cellulose fibers with or without the addition of additives from spinning solutions consisting of NMMO or ionic liquids.
  • the aim of these investigations is to determine the water retention capacity and the strength of the resulting fibers.
  • the strength of the fibers produced is according to the examples largely independent of the solvent used, however, cause additional components (in admixture with cellulose) usually a significant decrease in strength.
  • the examples also show a clear Influence on the water retention capacity of the "never dried" fiber. However, these differences are largely offset by one-off drying.
  • the invention relates to a coagulation bath with a Koagulations practickeitszulauf, wherein the Koagulations practickeitszulauf has one or more orifices, which are below the Koagulations continuekeits regulates the coagulation or at least one Koagulations slimkeitszulauf, below the Koagulations crampkeitscludes the coagulation bath is arranged.
  • the present invention is further set forth by further aspects and by methods in which the inventive devices are used, which are all combinable with each other.
  • the invention is further defined as set out in the claims. According to the invention, the elongation of the molding is optimally controlled by the gentle and controlled precipitation in every aspect of the invention.
  • the present invention provides a coagulation bath having a coagulating liquid inlet and a molded article entry area solidified in the coagulation bath, the entrance area being provided at a position where the coagulating liquid is coagulated with coagulating liquid, the coagulating liquid inlet being one or more Has orifices, which are below the inlet area and are directed to introduced into the coagulation bath molded body, so that the moldings in operation with supplied or fresh Coagulation be flowed.
  • the shaped bodies according to the invention are preferably filaments. Accordingly, according to the invention, the coagulation bath is also referred to as spin bath. Spinning bath and coagulation bath are used interchangeably herein.
  • the shaped bodies can also be foils or other shaped bodies with any desired cross section.
  • the moldings are manufacturedichnchively formed by extrusion and are therefore also referred to as continuous moldings with indefinite length.
  • the present invention relates to a spinning bath having a coagulating liquid inlet and a filament entry area solidified in the spinning bath, the entrance area being provided at a position where the coagulating liquid is filled with coagulating liquid is the liquid surface of the coagulating liquid, characterized in that the Koagulations whatsoeverkeitszulauf has one or more orifices, which lie below the inlet region and are directed to introduced into the spinning spinneret filaments, so that the filaments are flown in operation with supplied coagulation liquid.
  • a spin bath according to the invention is usually positioned under an extrusion apparatus in which the still fluid moldings or filaments are extruded.
  • the filaments pass through an air gap in which the threads can optionally be supplied with air, and then enter the spinning bath.
  • the air gap height may, for example, be between 5 mm and 40 mm, in particular between 10 mm and 30 mm.
  • the shaped bodies or spun yarns can be stretched, which improves the textile properties of the obtained solidified products in some cases. In the invention, stretching is optional and may or may not be performed.
  • the moldings enter the bath and coagulate as determined by the coagulation liquid, which is usually a non-solvent of the molded body mass.
  • the molding composition is preferably cellulose.
  • Spinning baths usually have a Koagulations practickeitszulauf to renew the coagulation liquid in the spinning bath. Since the moldings contain solvents, the composition of the spinning bath could be changed without a controlled feed, which results in a time-varying Coagulation property could affect the consistency of the moldings.
  • Coagulation is usually discharged with the moldings from the bath.
  • the bath can also have a separate outlet for coagulation fluid.
  • the flow of the fluid moldings serves the purpose of exchanging solvent and non-solvent between the fluid moldings and the Koagulationsbad and can be accomplished via various devices.
  • the mouths of the Koagulations practickeitszulaufs are positioned within the spinning bath and below the inlet region of the moldings.
  • the mouths are directed in particular on introduced into the coagulation bath moldings, so that the moldings are flown in operation with coagulation liquid.
  • This provides constant coagulation conditions, thereby increasing consistency and allowing accurate control of coagulation conditions, e.g. to influence the fibrillation tendency as desired.
  • the moldings do not completely shock-like coagulate, but only the surface is coagulated.
  • the threads are further or completely solidified by expulsion of the solvent. In the meantime, the threads can remain in a gel-like state. This second stage can still be done in this first spin bath or in another separate spin bath.
  • the mouths of the coagulating fluid inlet are, in preferred embodiments, laterally onto the shaped bodies, e.g. Spun threads, directed in the spinning bath.
  • the lateral flow causes an unimpeded passage of the shaped body through the spinning bath, which is supplied by the flow coagulation liquid or fresh coagulation liquid is taken from the threads.
  • the coagulation is accomplished at least on the surface of the moldings to controlled conditions.
  • the orifices are preferably arranged centrally in the spinning bath, in particular preferably in a horizontal orientation.
  • the exact position in the spinning bath is not essential, but there is a position to distinguish at the edge of the spinning bath, which is not or only negligible to direct Influx of the moldings is suitable to achieve the effects of the invention.
  • the mouths of the liquid supply line are directed in preferred embodiments obliquely against the extrusion direction of the spun yarns or in the direction of the liquid surface of the spinning bath (up), but may also be directed perpendicular to the extrusion direction of the filaments or even obliquely downward (in the extrusion direction). Also, a horizontal or horizontal arrangement (e.g., substantially parallel to the liquid surface) is possible.
  • the angle between the transport / extrusion direction of the moldings and the flow direction of the supplied coagulation liquid at the mouths is preferably between -90 ° (down) and + 90 ° (up) between -40 ° (down) and 80 ° (upwards), more preferably between -30 ° and 70 °, in particular preferably between -25 ° and 65 °, between -30 ° and 60 ° or between -35 ° and 55 °.
  • liquid feed lines in addition to a first liquid feed line, further liquid feed lines may be provided which are positioned both below and above the liquid surface and are either supplied together with the first liquid feed line or else fed separately.
  • the orifices are positioned in further preferred embodiments at a distance of 1 mm to 50 mm from the molded bodies transported through the coagulation bath.
  • the distance is the geometrically least possible distance, e.g. determined by a normal to the spinning direction (extrusion direction) or the direction in which the shaped bodies are transported away by the spinning bath (for example, pulled over a deflection roller). More preferably, the distance is from 2 mm to 45 mm, from 3 mm to 40 mm, from 4 mm to 35 mm, from 5 mm to 30 mm from 6 mm to 25 mm, from 7 mm to 20 mm or from 8 mm to 15 mm.
  • a mixing of the supplied coagulation liquid with coagulation liquid already present in the spinning bath which is Deutschenmengt with introduced through the moldings solvents, reduced.
  • deflecting elements can also be provided in the spinning bath in the region of the orifices.
  • the baffles shield the flow of coagulating liquid supplied to the Spinning bath introduced molding, in particular in said inlet region on the surface of the coagulation, before the influx of coagulation located in the spinning bath from.
  • the orifices are provided below the surface (also referred to as level) of the coagulating liquid in the spinning bath and, in this function, are also suitable for effecting an external level control of the coagulating liquid in the spinning bath.
  • the orifices are 1 mm to 500 mm below the surface or level, in particularly preferred embodiments, these are 2 mm to 400 mm, 3 mm to 300 mm, 4 mm to 250 mm, 5 mm to 200 mm, 6 mm to 150 mm, 8 mm to 100 mm, 10 mm to 80 mm, 12 mm to 60 mm, 14 mm to 40 mm or even 15 mm to 30 mm below the surface or the level of the coagulating liquid in the spinning bath.
  • the orifices are in vertical alignment in the upper half of the Koagulations whatsoever crampkeitsstandes, which is necessary for the operation.
  • a coagulation bath is provided with a liquid container, e.g. a trough provided with a fluid conduit into the fluid reservoir having one or more ports below a predetermined level of fluid in the fluid reservoir, and a fluid level regulator external to the fluid reservoir hydraulically communicating with the fluid in the fluid reservoir via the fluid conduit, the fluid level governor Contains opening at a predetermined level.
  • a liquid level controller is provided outside the liquid container of the coagulation bath filled with coagulating liquid (also referred to herein as spinning bath).
  • Spinning baths usually have a Koagulations practickeitszulauf to compensate for at least the liquid container by Mittransport with the transported through the spinning bath molding.
  • the spinning bath can also be a separate Have fluid outlet.
  • no separate liquid outlet is provided in the spin bath.
  • the coagulation liquid is usually contaminated by various substances, solvents and non-solvents of the molding material mass or other substances of the production process.
  • Contaminating substances can be, for example, metal ions which can be dissolved out of the extrusion apparatus (eg from steel, stainless steel, ceramics, sintered metals, aluminum, plastic, non-ferrous metals or precious metals).
  • Preferred materials are all iron, iron alloys, chromium-nickel steels, nickel steels (eg Hastelloy materials, titanium, tantalum).
  • the external liquid level controller offers a possibility to supply only as much liquid to the spinning bath as is taken from the coagulation tank due to drag losses caused by the discharged filament ribbon. This allows a particularly gentle and turbulence-free supply of coagulation with coagulation liquid.
  • the liquid level controller is preferably combined with the liquid feed.
  • the liquid level controller on the liquid inlet.
  • the amount of inflow into the bath is controlled by the position of the opening and thus the level in the bath.
  • a line from the liquid level controller into the spinning bath then passes the coagulating liquid into the spinning bath.
  • the line into the bath opens in particular below the Koagulations practickeitsheys as described above - in particular to accomplish the hydraulic connection with the liquid level controller, but also to feed in preferential embodiments as described above, the entering into the spinning bath moldings directly with supplied (fresh) coagulation liquid. Therefore, the liquid line preferably leads into the interior of the liquid container, such as a tub, wherein the Mouths lie in the interior of the liquid container. Particularly preferably, the openings are in the middle, that is not on the edge of the liquid container as described above.
  • the height of the opening in the liquid level controller is height adjustable.
  • the height of the opening can be designed to be height-adjustable by rotation of a rotatable element.
  • the level differences from 5 mm to 200 mm, preferably from 10 mm to 150 mm, from 15 mm to 100 mm or from 20 mm to 50 mm vary.
  • the overflow from the opening can be used to feed a subsequent washing stage.
  • a subsequent washing step may be another bath into which the shaped bodies are introduced after coagulation.
  • the invention in another aspect, relates to a coagulation bath apparatus comprising at least one coagulating liquid container and a subsequent washing container, a first liquid container (“coagulating liquid container”) having a first coagulating liquid, and a second liquid container (“washing container”) having a second coagulating liquid, and a shaped body -Umlenkvoriques for directing moldings from the coagulation tank in the washing container, wherein the first coagulating liquid may have a different concentration of coagulants than the second coagulation and / or another temperature.
  • coagulating liquid container having a first coagulating liquid
  • washing container a second liquid container having a second coagulating liquid
  • a shaped body -Umlenkvoriques for directing moldings from the coagulation tank in the washing container, wherein the first coagulating liquid may have a different concentration of coagulants than the second coagulation and / or another temperature.
  • the coagulating liquid container in combination with the subsequent washing container can be used to produce other coagulation conditions.
  • the first container only the surface of the moldings can be solidified and the complete solidification can be carried out in the second container (for example by thorough washing out of the solvents remaining in the moldings).
  • the amounts of solvent are reciprocal to the amount of coagulant.
  • the first container has a higher solvent concentration or a lower coagulant concentration than the second container or the other way around.
  • gentle or rapid coagulation can be carried out in the first and / or second container.
  • product parameters such as fibrillation can be controlled in a controlled manner, depending on the shape of the molded body and the cross-sectional dimension.
  • solvent e.g. a tertiary amine oxide, particularly preferably NMMO
  • the concentration of solvent in the first coagulation bath in the range from 15% to 50%, preferably from 20% to 40% (all percentages in% by weight).
  • solvent e.g. a tertiary amine oxide, particularly preferably NMMO
  • the concentration of solvent e.g. a tertiary amine oxide, particularly preferably NMMO
  • the concentration of solvent e.g. a tertiary amine oxide, particularly preferably NMMO
  • the concentration of solvent e.g. a tertiary amine oxide, particularly preferably NMMO
  • the concentration of solvent e.g. a tertiary amine oxide, particularly preferably NM
  • the shaped bodies are not completely solidified in the first coagulation bath, but converted into a gel-like state.
  • the shaped bodies are still drawn in the first coagulation bath, which due to the different degrees of coagulation in the inner and outer region of the moldings causes particularly interesting properties of the resulting finished shaped body, in particular threads.
  • the second liquid container has a separate liquid inlet from the first liquid container.
  • the second liquid container may have a liquid drain separately from the molded article discharge.
  • the liquid drain can be an overflow.
  • the liquid which is drained from the first coagulation container through the shaped bodies, such as filament bundles, is introduced into the second liquid container. This efficiently reuses expensive solvents or coagulation fluids.
  • the liquid inlet of the first and / or second liquid container outside the liquid container with an external liquid level controller, in particular as already described above.
  • the invention relates to further methods for solidifying shaped articles using any of those described herein Coagulation baths or devices.
  • the invention relates to a process for the solidification of moldings, wherein the fluid moldings are passed into a coagulation bath with a coagulating liquid, wherein in the coagulation bath, the moldings are supplied with coagulation liquid supplied into the coagulation bath.
  • coagulation liquid lines can open into the coagulation bath, so that the openings are directed onto the shaped bodies as already described herein.
  • the invention also relates to a process for the solidification of moldings, the fluid moldings being passed into a coagulation bath with a liquid container having a coagulating liquid, wherein the level of coagulation liquid is predetermined by a liquid level controller located outside the liquid container, preferably with an external liquid level controller as described above , Preferably, coagulation liquid supplied to the bath is supplied via the liquid level controller.
  • the liquid is fed into the regulator and connected via a hyrdaulische connection through another line to the bathroom. Through this connection, liquid flows from the regulator into the bath, depending on the level in the bath to equalize the liquid with the level of the opening.
  • the invention relates to a method for solidifying shaped bodies in a coagulation bath apparatus with at least two separate liquid containers (eg trays), wherein in a first liquid container moldings are partially solidified and in a second liquid container, preferably after application from the first liquid container via a deflecting and / or bundling apparatus, and in the second liquid container the shaped bodies are additionally washed out and further solidified.
  • a first liquid container moldings are partially solidified and in a second liquid container, preferably after application from the first liquid container via a deflecting and / or bundling apparatus, and in the second liquid container the shaped bodies are additionally washed out and further solidified.
  • different conditions can be set, by different temperatures in particular hot-melt moldings can be cooled and solidified in two controlled stages.
  • the solvents may be washed out of the moldings in at least two stages from the moldings under various conditions.
  • the outlet openings on Extruders are chosen in any form. Possible are elongated openings for forming films or small, round openings for forming filaments or threads. Preferably, the openings are a maximum of 2 mm, a maximum of 1.5 mm, a maximum of 1.2 mm, a maximum of 1.1 mm, a maximum of 1 mm narrow or in diameter.
  • the openings may be at least 0.1 mm, at least 0.2 mm, at least 0.3 mm, at least 0.4 mm, at least 0.5 mm, at least 0.6 mm, at least 0.7 mm, at least 0.8 mm , be at least 0.9 mm narrow or in diameter.
  • a plurality of extrusion openings on the extruder or a plurality of moldings are provided side by side.
  • the extrusion openings may be on a cambered, i. curved, extrusion plate may be provided, wherein preferably the curvature angle a at the edge of the extrusion plate to the extrusion is an acute angle.
  • the curvature angle ⁇ is preferably less than 85 °, in particular less than 80 °, less than 75 °, less than 70 °, less than 65 °, less than 60 °, less than 55 °.
  • the profile of the attachment of the extrusion openings can be adapted to the profile of the surface of a liquid in the coagulation.
  • media, liquids and / or temperatures can be provided in which the shaped bodies solidify.
  • liquids or solutions can be used in which the material is insoluble and thus fails.
  • lower temperatures may be selected at which the material solidifies.
  • the shaped bodies according to the invention for example filaments, threads or films, can be produced.
  • the moldings can be discharged continuously or discontinuously from the coagulation bath.
  • the liquid in the coagulation bath can also be renewed continuously or discontinuously.
  • the collecting bath can be heated to a certain temperature, for example by heating or Cooling elements or by controlling the medium change.
  • the shaped bodies can consist of a thermoplastic mass, in particular of a viscous fluid which is solidified in the coagulation bath.
  • the composition is selected from cellulose solutions, solidifiable fluids, especially "hot-melts", such as polymers, polycarbonates, polyesters, polyamides, polylactic acid, polypropylene, etc.
  • Cellulose solutions are in particular cellulose-amine oxide solutions, in particular solutions of tertiary amine oxide solutions.
  • An example is a cellulose-NMMO (N-methylmorpholine-N-oxide) solution, as in US 4,416,698 or the WO 03/057951 A1 described.
  • cellulose solutions ranging from 4% to 23% cellulose are used for processing into extrusion products.
  • the shaped bodies preferably contain solidified cellulose in a coagulation liquid.
  • the solution may be a mixture of water and a tertiary amine oxide such as NMMO, most preferably aqueous solutions.
  • the solvent eg NMMO, should be present in the spin bath (or baths) in a concentration sufficiently low to precipitate cellulose.
  • the solvent is introduced into the spinning bath (s) by the moldings and should be maintained at a low enough level by renewing the coagulating liquid through the feed to achieve the desired degree of coagulation in the respective spinning bath.
  • the solution of the molding material may be an aqueous solution.
  • the solution may be a thixotropic fluid, in particular a spinning solution.
  • the spinning solution may contain NMMO and cellulose, wherein the mass ratio of NMMO to cellulose is between 12 and 3, preferably between 10 and 4, or more preferably between 9 and 5.
  • the mass ratio a) ("input") of NMMO to cellulose in the molding prior to introduction into the coagulation liquid between 12 and 3, preferably between 10 and 4 or between 9 and 5.
  • the mass ratio b ) ("output") of NMMO adhering in and on the shaped body to cellulose in the shaped body when applied from the (first) coagulation bath is between 10 and 0.5, preferably between 8 and 1, in particular between 6 and 3.
  • the ratio is particularly preferred of the Massverphase ntisse a) and b) ("input: output”), wherein the Masseverophophentisse a) and b) are as defined above, between 0.2 and 25, preferably between 0.3 and 10, in particular between 0.5 and 3.
  • the mass ratios NMMO to cellulose in the molding can be selected by appropriate mixing of the substances (before extrusion and, associated with this before introduction into the coagulation bath).
  • the output mass ratio b) can be controlled by the amount of NMMO in the coagulating liquid and / or the flow rate and withdrawal speed of the molded articles, and in particular by devices for deflaking or draining liquid adhering to the molded article.
  • "In or on the molding adhering NMMO" is to be understood that the molding after treatment in the coagulation still contains solvent, especially in the core, and was coagulated only superficially ("im") and optionally on the molding liquid of the coagulation bath adheres (" at the").
  • Coagulation fluid may still have relatively high levels of solvent (NMMO).
  • NMMO solvent
  • These amounts of discharged quantities are preferably balanced by delivery via the Koagulations intermediarkeitszulauf. If the ratio a: b> 1, NMMO must additionally be added to the coagulation liquid, since the amount of NMMO fed in via the fluidized moldings is insufficient for export and otherwise the amount of NMMO in the bath would decrease (which would also be a less preferred but nevertheless possible embodiment).
  • the additional NMMO delivery is preferably made via the coagulation fluid feed.
  • Special materials have a melting temperature of at least about 40 ° C, at least 50 ° C, at least 55 ° C, at least 60 ° C, at least 65 ° C, at least 70 ° C, at least 75 ° C.
  • the material may be at exemplary temperatures of at least about 40 ° C, at least 50 ° C, at least 55 ° C, at least 60 ° C, at least 65 ° C, at least 70 ° C, at least 75 ° C, at least about 80 ° C , at least 85 ° C, at least 90 ° C, at least 95 ° C, extruded and passed into the coagulation bath.
  • the temperature of the first and / or second Koagulationsbads is preferably between 5 ° C and 60 ° C, more preferably between 10 ° C and 50 ° C or between 15 ° C and 40 ° C.
  • the temperature of the second coagulation bath is at least 1 ° C, preferably at least 5 ° C cooler than the first coagulation bath.
  • the shaped bodies can be conveyed via a deflecting and / or bundling element, e.g. a pulley (fixed or rotating) can be removed from the coagulation bath (or baths).
  • a deflecting and / or bundling element e.g. a pulley (fixed or rotating) can be removed from the coagulation bath (or baths).
  • the take-off speed for removing the moldings from the first or second coagulation bath - which can be selected independently of one another - between 5 m / min and 100 m / min, particularly preferably between 10 m / min and 80 m / min, is particularly preferred between 20 m / min and 60 m / min, in particular between 25 m / min and 50 m / min.
  • first and / or second coagulation bath additives can be added to achieve certain product properties.
  • crosslinking agents, emulsifiers, surfactants, detergents or even colorants or dyes also "colorless” dyes
  • the shaped articles may be subjected to treatment with an emulsifiable polymer, e.g. Polyethylene or polyvinyl acetate, or even be crosslinked with glyoxal.
  • the Fibrillationsreduzi für uzi für uzi für spun cellulosic moldings can be achieved with Bire effetfarbstoffen, glyoxal, a glycol, glycol ethers, polyglycol, polyglycol ethers, alcohols such as isoamyl alcohol, isobutanol or isopropanol.
  • the baths may have wiper lips.
  • the invention relates to a molded article available or prepared by one of the methods of the invention.
  • an effective solidification and coagulation system for the dry-jet wet Spinning process can be constructed as follows and used for the molding of cellulosic materials and additives.
  • a molding composition a composition of cellulose 12.9%, amine oxide (NMMO - N-methyl-morpholine-N-oxide) 76.3%, water 10.8% was used and fed to the spinning apparatus.
  • the spinning mass flow is divided into individual spinning positions or spinning groups and fed to the individual spinning positions.
  • the mass is pressed under pressure and formed into the shaped bodies, which are additionally stretched in an air gap between the extrusion openings and the coagulation bath.
  • a stretching of the moldings is not always desirable and does not always have to be done on the extrudates.
  • the shaped body is introduced into a coagulation bath.
  • a pre-, partial or complete solidification of the shaped body is carried out, wherein for pre-, partial or complete solidification different compositions of the coagulation bath can be used.
  • the pre-stretched, partially or fully solidified stretched shaped body obtains its desired product properties in the first coagulation bath and is brought from the first bath via a further deflection device into an underlying second bath for further treatment of the shaped body via a deflection and transport device located in the first bath.
  • the treatment in the first bath can be that coagulation, washing, damping, solvent exchange, impregnation, crosslinking of the molding with different chemicals and reagents can be carried out.
  • a further treatment in the second bath may consist in that a coagulation, washing, damping, solvent exchange, impregnation, crosslinking of the molding with different chemicals and reagents can be carried out.
  • the coagulation liquid is supplied to the molded body close to the body and the surface.
  • the first bath is characterized in that only as much precipitation or treatment or coagulation bath is supplied, as is carried out with the precipitate from the first bath.
  • the precipitation or treatment or coagulation bath may be passed over squeezing devices or wiper lips after the first bath, thereby causing excess liquid to be returned to the first bath (dripping). before the precipitate is fed to the second bath for continuous further treatment.
  • the second bath is used for washing, from which the washed, treated manufactured precipitate is discharged via a deflection device mounted therein. The process can be extended by several washing or treatment stages at will.
  • All deflection rollers in the baths and the Koagulations practickeitseinmünditch can be configured independently of each other movable or fixed, in particular movable to adjust the treatment times in the first and / or second bath flexible.
  • the inlet to the first coagulation bath can have an opening for controlling the inflow of coagulating liquid into the coagulation bath, wherein a control-related overflow is fed to the second coagulation bath.
  • This overflow can be adjusted on the one hand via a free overflow edge or by means of control flap.
  • a spinning solution with a NMMO to cellulose ratio of 9.83 (“specific NMMO INPUT") was fed to a spinneret.
  • the filament curtain was bundled by means of a ceramic bundling roll onto a compact filament bundle.
  • the amount of fresh fluid to the coagulation bath and the amount of overflow from the coagulation bath were measured and compared with the cellulosic effluent exiting the coagulation bath.
  • the “total fleet” was calculated from the summation of the sub-fleets mentioned above:
  • the overflow stream was subjected to a weight-analytical measurement to determine the NMMO content [% by weight].
  • the amount of NMMO overflow (calculated from the amount of overflow [kg / h] and NMMO content [% by weight]) was subtracted from the amount of NMMO fed to the system by means of the fresh bath and spinning jet.
  • the quantity of NMMO removed by the pulping stream and the bundle of fibers was related to the quantity of cellulose removed in order to obtain the "specific NMMO-OUTPUT".
  • a spinning solution with a NMMO to cellulose ratio of 6.12 (“specific NMMO-INPUT") was fed to a spinneret.
  • the flat filament curtain extruded as in Example 1 was passed through the coagulation bath at a draw-off speed of 32 m / min.
  • the flat filament curtain was not bundled, but passed as a flat curtain over guide elements and thus supplied to the next treatment steps.
  • the amount of fresh fluid supplied and the quantity of coagulation fluid dragged out could be determined by the experimental setup as in Fig. 3 to be kept in balance, no overflow from the coagulation bath had occurred.
  • the amount of fresh fluid was measured and compared with the cellulosic stream leaving the coagulation bath.
  • the quantity of NMMO removed by the pulping stream and the bundle of fibers was related to the quantity of cellulose removed in order to obtain the "specific NMMO-OUTPUT".
  • a spinning solution with a NMMO to cellulose ratio of 5.02 (“special NMMO-INPUT") was fed to a spinneret.
  • the flat filament curtain extruded as in Example 1 was passed through the coagulation bath at a draw-off speed of 37 m / min.
  • Coagulation liquid could be removed from the coagulation bath in sufficient quantities and the same amount of fresh liquid supplied in order to achieve the desired NMMO concentration in the coagulation bath of about 35% (measured: 34.9%).
  • the quantity of fresh liquid supplied and the quantity of coagulation liquid dragged out could be determined by the test arrangement as described in US Pat Fig. 3 in combination with Fig. 7 to be kept in balance, no overflow from the coagulation bath had occurred.
  • the amount of fresh fluid was measured and compared with the cellulosic stream leaving the coagulation bath.
  • the total fleet thus corresponded to the liquor ratio Ausschleppstrom to cellulose stream.
  • the amount of NMMO discharged by the pullout stream and the bundle of fibers corresponded to the amount of NMMO supplied to the system by means of the fresh bath and the spinning stream.
  • the quantity of NMMO removed by the pulping stream and the bundle of fibers was related to the quantity of cellulose removed in order to obtain the "specific NMMO-OUTPUT".
  • a spinning solution with a NMMO to cellulose ratio of 5.87 (“specific NMMO INPUT”) was fed to a spinneret.
  • the experiment was carried out as in Example 3, however, the flat filament curtain was at the end of the exchange path according to Fig. 8 via 2 stripping devices (top and bottom), which return a part of the dragged coagulation back into the coagulation tub, withdrawn from the coagulation. Pure water was added to the coagulation bath at a temperature of 20 ° C.
  • Coagulation fluid could be withdrawn from the coagulation bath in sufficient quantities and the same amount of fresh fluid supplied to the desired NMMO concentration in the coagulation bath of about 40% (measured: 40.5%).
  • the quantity of fresh liquid supplied and the amount of coagulation liquid dragged out could be determined by the test arrangement as described in US Pat Fig. 3 in combination with Fig. 8 to be kept in balance, no overflow from the coagulation bath had occurred.
  • the amount of fresh fluid was measured and compared with the cellulosic stream leaving the coagulation bath.
  • the amount of NMMO discharged by the pullout stream and the bundle of fibers corresponded to the amount of NMMO supplied to the system by means of the fresh bath and the spinning stream.
  • the quantity of NMMO removed by the pulping stream and the bundle of fibers was related to the quantity of cellulose removed in order to obtain the "specific NMMO-OUTPUT".
EP12187870.6A 2012-10-10 2012-10-10 Bain de filage et procédé de renforcement d'un corps de formage Withdrawn EP2719801A1 (fr)

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EP12187870.6A EP2719801A1 (fr) 2012-10-10 2012-10-10 Bain de filage et procédé de renforcement d'un corps de formage
TW102136592A TWI609899B (zh) 2012-10-10 2013-10-09 將定型物體固化的紡織浴和紡織方法
RU2015116641A RU2649270C2 (ru) 2012-10-10 2013-10-10 Коагуляционная ванна (варианты) и способ упрочнения формованного изделия (варианты)
US14/434,625 US10208402B2 (en) 2012-10-10 2013-10-10 Spin bath and method for consolidation of a shaped article
KR1020157012140A KR102105865B1 (ko) 2012-10-10 2013-10-10 방적 배스 및 성형체의 강화 방법
CN201380062926.7A CN104838048B (zh) 2012-10-10 2013-10-10 用于成形制品的凝固的纺织浴和方法
EP13776771.1A EP2906742B1 (fr) 2012-10-10 2013-10-10 Bain de filage et procédé de renforcement d'un corps de formage
PCT/EP2013/071135 WO2014057022A1 (fr) 2012-10-10 2013-10-10 Bain de filage et procédé de préparation d'un corps moulé
ZA2015/02381A ZA201502381B (en) 2012-10-10 2015-04-09 Spin bath and method for consolidation of a shaped article

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CN106222771B (zh) * 2016-07-22 2019-02-22 中国纺织科学研究院有限公司 一种纤维素纤维的制备方法
EP3470557A1 (fr) * 2017-10-12 2019-04-17 Lenzing Aktiengesellschaft Dispositif de filage et procédé destiné à rattacher le fil à un dispositif de filage
EP3505659A1 (fr) 2018-08-30 2019-07-03 Aurotec GmbH Procédé et dispositif de filage des filaments à déviation
CN110057644B (zh) * 2019-05-13 2020-08-04 中国科学院山西煤炭化学研究所 纺丝液的极限氧指数的测定方法
CN115537956A (zh) * 2022-09-28 2022-12-30 百事基材料（青岛）股份有限公司 一种含生物活性成分的lyocell大生物纤维及其制备方法

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CN104838048B (zh) 2017-10-13
KR102105865B1 (ko) 2020-05-04
EP2906742A1 (fr) 2015-08-19
CN104838048A (zh) 2015-08-12
TW201418334A (zh) 2014-05-16
ZA201502381B (en) 2016-01-27
WO2014057022A1 (fr) 2014-04-17
US10208402B2 (en) 2019-02-19
KR20150068982A (ko) 2015-06-22
EP2906742B1 (fr) 2017-03-22
RU2649270C2 (ru) 2018-03-30
RU2015116641A (ru) 2016-12-10
US20150247261A1 (en) 2015-09-03

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