EP0615561B1 - Process for dyeing a substrate in a supercritical fluid - Google Patents

Process for dyeing a substrate in a supercritical fluid Download PDF

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Publication number
EP0615561B1
EP0615561B1 EP93921794A EP93921794A EP0615561B1 EP 0615561 B1 EP0615561 B1 EP 0615561B1 EP 93921794 A EP93921794 A EP 93921794A EP 93921794 A EP93921794 A EP 93921794A EP 0615561 B1 EP0615561 B1 EP 0615561B1
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EP
European Patent Office
Prior art keywords
additives
dyestuff
fluid
extraction
dye
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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.)
Expired - Lifetime
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EP93921794A
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German (de)
French (fr)
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EP0615561A1 (en
Inventor
Kurt Truckenmüller
Gottlob Wörner
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Amann and Soehne GmbH and Co KG
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Amann and Soehne GmbH and Co KG
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Priority claimed from DE4237823A external-priority patent/DE4237823A1/en
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Publication of EP0615561A1 publication Critical patent/EP0615561A1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/94—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in solvents which are in the supercritical state
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B19/00—Treatment of textile materials by liquids, gases or vapours, not provided for in groups D06B1/00 - D06B17/00
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B5/00—Forcing liquids, gases or vapours through textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing impregnating
    • D06B5/12—Forcing liquids, gases or vapours through textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing impregnating through materials of definite length
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D06M23/105—Processes in which the solvent is in a supercritical state
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/922—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons

Definitions

  • the present invention relates to a method for dyeing a substrate in a supercritical fluid with the features of the preamble of patent claim 1.
  • a method with the features of the preamble of claim 1 is known from DE 39 06 724 A1.
  • textile substrates are dyed in a supercritical fluid, a preferred embodiment of this known method using dyes which consist exclusively of the actual color body and not the usual additives, such as Adjusting agents, dispersants and / or emulsifiers.
  • the known method has the disadvantage that those dyes which only contain the powdery coloring body and in which the abovementioned additives (e.g. adjusting agents, dispersants, emulsifiers) are absent can at most be handled on a laboratory scale.
  • the additives mentioned above prevent the dye powder from being electrostatically charged, for example, so that such an electrostatically charged dye powder adheres everywhere as soon as the corresponding container is opened and can thus lead to considerable malfunctions and incorrect production in the dyeing shop.
  • the present invention has for its object to provide a method of the type specified that is applicable on an industrial scale without the difficulties mentioned above.
  • the process according to the invention is based on the basic idea that a conventional dye, which is provided with additives and thus a commercially available dye, is first selected, but this conventional dye is subjected to a separation before the substrate is colored, such that the additives and the additive-free dye (color body) are obtained separately.
  • the dye thus freed from the additives, which is the pure dye body is either taken up directly in the supercritical fluid used for dyeing or in another liquid in the process according to the invention, so that the additive-free dye taken up in the other liquid can then be used later for coloring the substrate in the supercritical fluid.
  • the substrate to be colored is flowed through or flowed over with the supercritical fluid containing the pure color body.
  • the method according to the invention has a number of advantages.
  • any commercially available dye can be used in the process according to the invention, since the separation between the additives and the dye described above is brought about before the actual coloring, so that the process according to the invention is not limited to a few currently only available on a laboratory scale additive-free dyes is restricted. Due to the fact that the method according to the invention uses commercially available dyes, when using the method according to the invention the problems which are described at the beginning by way of example in connection with the powdery, additive-free dyes do not arise.
  • a first embodiment of the method according to the invention provides that the additive-free dye is isolated after the additives have been separated off and the isolated dye is taken up directly in the other liquid with the formation of a liquid-formed, additive-free dye, so that here too no additive-free dye powder is obtained as the end product and thus the problems mentioned at the outset (dusting, electrostatic charging) do not occur in this embodiment of the method according to the invention.
  • the process according to the invention is used to select the other liquid in which the additive-free dye is taken up, ie preferably dissolved or dispersed.
  • Other liquids for additive-free dyes are, for example, water, acetone, alcohols (C1 to C4 alcohols) and / or chlorinated hydrocarbons, either alone or in a mixture, with additive-free disperse dyes in particular acetone, acetone-water mixtures (mixing ratio V: V approximately 9: 1) or halogenated Hydrocarbons (chlorobenzene, methylene chloride) are used.
  • additive-free dye agglomerates are formed from the disperse dye, which are then separated off accordingly, for example by filtration and / or by centrifugation.
  • the additive-free dye isolated in this way is either taken up directly in the supercritical fluid used for the dyeing or the liquid-formed, additive-free dye is prepared by adding one of the aforementioned liquids, which is then storable and is used at a later time for dyeing.
  • the additives can just as well be removed from aqueous solutions of water-soluble dyes, such as reactive dyes, acid dyes or noun dyes, by salting out the additive-free dye (coloring matter) by adding salts and taking up the salted-out coloring matter directly in the liquids mentioned above, and so on then use a storable, liquid-formed dye later in the dyeing.
  • water-soluble dyes such as reactive dyes, acid dyes or noun dyes
  • a particularly suitable embodiment of the method according to the invention provides that the separation of the additives from the additive-free dye is carried out by extracting the conventional dye containing the additives becomes.
  • the selection of the fluid used for the extraction is based on this extraction.
  • the fluid can be selected in the extraction such that either the additives or the additive-free dye (coloring body) is dissolved out of the conventional dye, which then has the consequence that either the additives are in the extract and the coloring body remains as extraction residue or the color body is dissolved in the extract and the additives are in the extraction residue.
  • a first embodiment of the method according to the invention provides that such a fluid is selected during the extraction that it dissolves the additives from the conventional dye used.
  • the pure color body is obtained as an extraction residue, this procedure being particularly useful if the additive-free dye so separated is taken up immediately after the extraction for coloring the substrate in the supercritical fluid used for this purpose.
  • a preferred development of the previously described embodiment variant of the method according to the invention provides that the additives are extracted from the conventional dye with such a fluid that is subsequently used to dye the substrate.
  • This process variant of the process according to the invention then has the additional advantage that, due to the identity of the fluids, the storage of further fluids can be dispensed with. Residues of the fluid used in the extraction of the additives, which may remain in the extraction residue then obtained after the extraction of the conventional dye, that is to say in the additive-free dye, can then remain, the subsequent coloration do not bother. With this procedure of the method according to the invention, it is not absolutely necessary that the extraction with the fluid is carried out in the supercritical state, as will be required later for the coloring of the substrate.
  • the extraction of the additives can also be carried out with the fluid in the non-supercritical state, since a number of additives are readily soluble in a non-supercritical fluid, while the additive-free dye only becomes soluble in the same fluid in the supercritical state. This allows a particularly effective and rapid separation of the conventional dye into additives and additive-free dye, which then accumulates as a residue while the additives are in the fluid used.
  • a further development of the method according to the invention provides that the fluid loaded with the additives is passed over an adsorbent and / or absorption medium.
  • adsorbents or absorbents are used which remove the additives contained in the fluid, such as, for example, adjusting agents, oils, dispersants, emulsifiers or the like, simply and without problems, preferred adsorbents or absorbents silica gel, diatomaceous earth, aluminum oxide and / or activated carbon.
  • Another embodiment variant of the method according to the invention is based on the fact that a fluid is selected for the extraction which does not dissolve the additives from the conventional dye, as described above, but rather the additive-free dye.
  • the additive-free dye is obtained in the extract, so that such a dye can be isolated particularly easily and taken up in another liquid or is stored directly as a liquid-formed, additive-free dye, so that such a liquid and additive-free dye does not then occur during later dyeing Problems, for example no unwanted dusting, cause.
  • a particularly suitable development of the previously described embodiment variant of the method according to the invention, in which a fluid is selected for the extraction of the additive-free dye which dissolves the additive-free dye, provides that an organic solvent is used here as the fluid.
  • the additive-free dye contained in the organic solvent after the extraction can then be stored as a liquid-formed, additive-free dye or isolated by evaporating the organic solvent used, so that the pure color body is solid.
  • This pure, additive-free dye body is then either taken up directly in the supercritical fluid used for dyeing or dissolved and / or dispersed in another liquid for later use to form an additive-free liquid dye.
  • the additive-free dye is also extracted by an organic solvent that dissolves the additive-free dye.
  • the additive-free dye is isolated from the organic solvent in that the additive-free dye is absorbed and / or adsorbed on an absorber or adsorber. The pure color body absorbed or adsorbed in this way can then be added directly to the supercritical fluid used in the coloring or to the other liquid, the absorber or adsorber being recovered.
  • Another, particularly suitable embodiment variant of the method according to the invention provides that the extraction of the conventional dye is carried out with a fluid in the supercritical state.
  • this embodiment variant of the method according to the invention has the advantage that the extraction and thus the separation into additives and dye takes place within very short times, which is attributed to the fact that a supercritical fluid, due to its relatively low viscosity, which is comparable with corresponding gases Extracting conventional dye penetrates very well, which, depending on the fluid used, leads to an excellent and quick dissolution of the additives or the additive-free dye.
  • such a supercritical fluid has the advantage that it can be converted into the corresponding gas particularly easily and quickly by increasing the temperature, increasing the volume or lowering the pressure, so that, depending on the selection of the supercritical fluid used, the extracted, additive-free dye or additives solid or liquid, while the gaseous fluid can be collected and reused.
  • the selection of the supercritical fluid used for the extraction in the method according to the invention is directed depends on whether you want to extract the additives or the additive-free dye (color body). If, for example, polar additives, such as ionic dispersing or emulsifying agents, are to be extracted with the supercritical fluid, polar supercritical fluids such as ammonia, fluorine-chloroalkanes or mixtures of ammonia and / or fluorine-chlorine are preferably selected for this purpose. Alkanes with non-polar supercritical fluids, such as alkanes, carbon dioxide and / or carbon monoxide.
  • polar additives such as ionic dispersing or emulsifying agents
  • a non-polar, additive-free dye coloring body
  • alkanes in particular ethane, propane or pentane, carbon dioxide and / or carbon monoxide, are used alone or as a mixture as the supercritical extraction fluid.
  • a particularly advantageous development of the procedure described above, in which the conventional dye is extracted with a fluid and preferably a supercritical fluid, provides that a moderator is added to the fluid or the supercritical fluid during the extraction.
  • This moderator allows the dissolving behavior of the fluid or the supercritical fluid to be matched to the constituent to be extracted in each case (additives or dye free of additives) of the conventional dye, so that particularly fast extraction times result.
  • polar compounds such as preferably water, alcohols and / or salts, are suitable as moderators.
  • the concentration of these moderators varies between approximately 1% by volume and approximately 10% by volume, preferably between approximately 2% by volume and approximately 5% by volume, based on the volume of the fluid used or the supercritical fluid used or the fluid mixture or the supercritical fluid mixture.
  • the dye component (additives or dye free of additives) obtained in the extract can be special are simply insulated so that a temperature increase, pressure reduction and / or volume increase is brought about.
  • the liquid or solid constituents (additives or dye free of additives) contained in the extract then accumulate, while the supercritical fluid used escapes as a gas, which is collected accordingly and possibly reused.
  • the conventional dye is extracted with other, non-supercritical fluids in the method according to the invention, it is advisable to use a phase separation, liquid-liquid extraction, an ad to remove the dye components (additives or dye free from extraction) present in the extract after the extraction - And / or to remove absorption and / or filtration, so that the fluid free of additives or of additive-free dye can then be reused for further extraction.
  • the temperature which is used during the extraction in the method according to the invention depends on the fluid used in each case.
  • the extraction temperature usually varies between 10 ° C. and 240 ° C., preferably between 30 ° C. and 180 ° C.
  • the extraction temperature when using ethane as the extraction fluid is above 35 ° C., while the corresponding pressure is above 50 bar.
  • the extraction temperature is above 100 ° C and the pressure during the extraction is above 42 bar, while with supercritical pentane at a temperature above 197 ° C and a pressure above 34 bar, with supercritical trifluorochlorine Ethane at a temperature above 29 ° C and a pressure above 38 bar, with supercritical ethylene at a temperature above 9 ° C and a pressure above 50 bar, with supercritical ammonia at a temperature above 132 ° C and a pressure above 120 bar, with supercritical carbon dioxide at a temperature above 32 ° C and a pressure above 74 bar, the commercial dye is extracted.
  • the extraction time in the method according to the invention also depends on the conventional dye to be separated and the fluid used.
  • the extraction time usually varies between 2 minutes and 20 minutes, preferably between 5 minutes and 15 minutes.
  • any conventional dye can be used in the method according to the invention.
  • a disperse dye is selected as the conventional dye, since a particularly simple separation of the conventional dye into additives and additive-free dyes (color bodies) is possible in the case of dispersion dyes, in particular also by extraction. This is due to the fact that such disperse dyes are generally mixed with additives as ionic dispersants / emulsifiers, while the actual additive-free dye (color body) is non-polar.
  • the method according to the invention is also particularly suitable for dyeing textile substrates.
  • textile substrates can preferably be used here, which can be dyed with disperse dyes, such as in particular textiles, the polyester fibers (polyethylene terephthalate), aliphatic or aromatic polyamide fibers (Kevlar, Nomex, Polyamid6, Polyamid6.6), polyimide fibers, polyalkylene fibers, in particular polyethylene fibers or polypropylene fibers, contain or consist of these fibers.
  • textile substrates such as preferably yarns, embroidery threads, sewing threads, fabrics or made-up textile parts, can be dyed perfectly within a very short time using the process according to the invention.
  • additives in the sense of the present application is understood to mean all substances which are present in a conventional dye and whose chemical composition is different from the actual dye, i.e. the color body.
  • this term includes adjusting agents, oils, dispersants and emulsifiers.
  • dye in the present application includes not only a single dye but also a mixture of dyes, such a mixture of dyes, which usually consists of three to twelve dyes, is usually used in practice for dyeing.
  • the method according to the invention is explained in more detail below using an exemplary embodiment in conjunction with the drawing.
  • the single figure of the drawing shows a schematic view of an apparatus for performing the method according to the invention.
  • the apparatus shown schematically in the drawing has an autoclave 2 for receiving the textile substrate to be dyed, the autoclave 2 being connected via a ring line 6 to a circulation pump 4, so that the supercritical fluid used in the dyeing is conveyed via the pump 4 and the supercritical fluid flows against or flows through the textile substrate arranged in the autoclave.
  • a further autoclave 1 is provided in a bypass line 7 to the ring line 6, the further autoclave serving to hold the dye or dye mixture used in the dyeing.
  • An expansion autoclave 3 is located in a further bypass line 8 or 9 to the ring line 6. Furthermore, the apparatus has valves 11 to 18 which are arranged in the corresponding lines 5 to 10.
  • the valve 15 was opened, which caused the supercritical carbon dioxide to expand into the expansion vessel 3. After that, the valve 15 was closed. During the expansion, a milky liquid was obtained at the bottom of the expansion vessel 3 which, in addition to water, contained the additives extracted from the dye. This milky liquid was drained through the valve 18 designed as a lock. After the valve 18 was closed, further supercritical carbon dioxide was fed to the apparatus via the line 5 and the opened valve 17, this supercritical carbon dioxide being brought to a pressure of 190 bar and a temperature of 130.degree.
  • this supercritical carbon dioxide was first of all via the bypass line 7 and the opened valves 14 and 13 pumped through the further autoclave 1 so that the additive-free dye remaining in the autoclave could be taken up in this supercritical carbon dioxide.
  • the valves 14 and 13 were then closed, with the result that the supercritical carbon dioxide loaded with additive-free dyes was now pumped by means of the pump 4 via the ring line 6 and the opened valves 11 and 12 through the textile substrate arranged in the autoclave 2.
  • the carbon dioxide in the reservoir 3 was introduced into the stream of supercritical fluid via the opened valve 16 and the line 9.
  • the supercritical carbon dioxide was discharged through a filter (not shown) and a corresponding drain valve, so that the colored substrate arranged in the autoclave could be removed from the autoclave. It was found here that the textile substrate, which was a 1 kg spool of thread, was uniformly colored.
  • the fastness to rubbing, the fastness to dry heat fixation and the fastness to washing were determined from the coloring. It was found that the corresponding grades were one grade better than the corresponding specifications from the dye manufacturer for an aqueous dyeing with the identical dye.

Abstract

In a process for dyeing a substrate in a supercritical fluid, an additive-free dye is absorbed in the supercritical fluid and flows over and/or through the substrate to be dyed. A usual additive-containing dye is selected for dyeing and is separated into additives and additive-free dye before dyeing the substrate. The separated, additive-free dye is then directly absorbed in the supercritical fluid used for dyeing or in another liquid.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Färben eines Substrates in einem überkritischen Fluid mit den Merkmalen des Oberbegriffs des Patentanspruchs 1.The present invention relates to a method for dyeing a substrate in a supercritical fluid with the features of the preamble of patent claim 1.

Ein Verfahren mit den Merkmalen des Oberbegriffs des Patentanspruchs 1 ist aus der DE 39 06 724 A1 bekannt. Hierbei werden bei dem bekannten Verfahren textile Substrate in einem überkritischen Fluid gefärbt, wobei eine bevorzugte Ausführungsform dieses bekannten Verfahrens Farbstoffe einsetzt, die ausschließlich aus dem eigentlichen Farbkörper bestehen und nicht die üblichen Zusätze, wie z.B. Stellmittel, Dispergatoren und/oder Emulgatoren, enthalten.A method with the features of the preamble of claim 1 is known from DE 39 06 724 A1. Here, in the known method, textile substrates are dyed in a supercritical fluid, a preferred embodiment of this known method using dyes which consist exclusively of the actual color body and not the usual additives, such as Adjusting agents, dispersants and / or emulsifiers.

Das bekannte verfahren weist jedoch den Nachteil auf, daß solche Farbstoffe, die lediglich den pulverigen Farbkörper enthalten und bei denen die zuvor genannten Zusätze (z.B. Stellmittel, Dispergatoren, Emulgatoren) fehlen, allenfalls im Labormaßstab handhabbar sind. Dies hängt damit zusammen, daß die zuvor genannten Zusätze verhindern, daß sich das Farbstoffpulver beispielsweise elektrostatisch auflädt, so daß ein derartig elektrostatisch aufgeladenes Farbstoffpulver, sobald das entsprechende Gebinde geöffnet wird, überall anhaftet und somit zu erheblichen Störungen und Fehlproduktionen in der Färberei führen kann.However, the known method has the disadvantage that those dyes which only contain the powdery coloring body and in which the abovementioned additives (e.g. adjusting agents, dispersants, emulsifiers) are absent can at most be handled on a laboratory scale. This is due to the fact that the additives mentioned above prevent the dye powder from being electrostatically charged, for example, so that such an electrostatically charged dye powder adheres everywhere as soon as the corresponding container is opened and can thus lead to considerable malfunctions and incorrect production in the dyeing shop.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren der angegebenen Art zur Verfügung zu stellen, das großtechnisch ohne die zuvor genannten Schwierigkeiten anwendbar ist.The present invention has for its object to provide a method of the type specified that is applicable on an industrial scale without the difficulties mentioned above.

Diese Aufgabe wird erfindungsgemäß durch ein Verfahren mit den kennzeichnenden Merkmalen des Patentanspruchs 1 gelöst.According to the invention, this object is achieved by a method having the characterizing features of patent claim 1.

Das erfindungsgemäße Verfahren beruht auf dem Grundgedanken, daß hier zunächst ein herkömmlicher, mit Zusätzen versehener und somit ein handelsüblicher Farbstoff ausgewählt wird, wobei dieser herkömmliche Farbstoff vor dem Färben des Substrates jedoch einer Trennung unterworfen wird, derart, daß bei der Trennung die Zusätze und der zusatzfreie Farbstoff (Farbkörper) jeweils separat anfallen. Der so von den Zusätzen befreite Farbstoff, bei dem es sich um den reinen Farbkörper handelt, wird bei dem erfindungsgemäßen Verfahren entweder direkt in dem für das Färben eingesetzte überkritische Fluid oder in einer anderen Flüssigkeit aufgenommen, so daß der in der anderen Flüssigkeit aufgenommene zusatzfreie Farbstoff später dann zum Färben des Substrates in dem überkritischen Fluid eingesetzt werden kann. Dies führt dazu, daß bei der anschließenden Färbung das zu färbende Substrate mit dem den reinen Farbkörper enthaltenden überkritischen Fluid durchströmt bzw. angeströmt wird.The process according to the invention is based on the basic idea that a conventional dye, which is provided with additives and thus a commercially available dye, is first selected, but this conventional dye is subjected to a separation before the substrate is colored, such that the additives and the additive-free dye (color body) are obtained separately. The dye thus freed from the additives, which is the pure dye body, is either taken up directly in the supercritical fluid used for dyeing or in another liquid in the process according to the invention, so that the additive-free dye taken up in the other liquid can then be used later for coloring the substrate in the supercritical fluid. As a result, during the subsequent dyeing, the substrate to be colored is flowed through or flowed over with the supercritical fluid containing the pure color body.

Das erfindungsgemäße Verfahren weist eine Reihe von Vorteilen auf. So ist zunächst festzuhalten, daß man bei dem erfindungsgemäßen Verfahren jeden handelsüblichen Farbstoff einsetzen kann, da man vor der eigentlichen Färbung die zuvor beschriebene Auftrennung zwischen den Zusätzen und dem Farbstoff herbeiführt, so daß das erfindungsgemäße Verfahren nicht auf wenige, zur Zeit nur im Labormaßstab erhältliche zusatzfreie Farbstoffe eingeschränkt ist. Bedingt dadurch, daß das erfindungsgemäße Verfahren auf handelsübliche Farbstoffe zurückgreift, treten bei der Anwendung des erfindungsgemäßen Verfahrens nicht die Probleme auf, die eingangs beispielhaft in Verbindung mit den pulvrigen, zusatzfreien Farbstoffen beschrieben sind. Im einzelnen bedeutet dies, daß bei dem erfindungsgemäßen Verfahren keine statische Aufladung des eingesetzten Farbstoffes auftritt, da hier entweder der zusatzfreie Farbstoff direkt in dem für die Färbung eingesetzten überkritischen Fluid oder in der anderen Flüssigkeit aufgenommen wird, so daß bei dem erfindungsgemäßen Verfahren kein unerwünschtes Verstauben von zusatzfreiem Farbstoffpulver auftreten kann, da ein zusatzfreies Farbstoffpulver nicht für die Atmosphäre frei zugänglich in Erscheinung tritt. Dies wiederum führt dazu, daß bei Anwendung des erfindungsgemäßen Verfahrens der Produktionsablauf nicht gestört wird. Bedingt dadurch, daß für die Auftrennung des herkömmlichen Farbstoffes in Zusätze und zusatzfreiem Farbstoff (Farbkörper) ein relativ geringer apparativer Aufwand erforderlich ist, zeichnet sich das erfindungsgemäße Verfahren desweiteren durch eine hohe Wirtschaftlichkeit aus.The method according to the invention has a number of advantages. First of all, it should be noted that any commercially available dye can be used in the process according to the invention, since the separation between the additives and the dye described above is brought about before the actual coloring, so that the process according to the invention is not limited to a few currently only available on a laboratory scale additive-free dyes is restricted. Due to the fact that the method according to the invention uses commercially available dyes, when using the method according to the invention the problems which are described at the beginning by way of example in connection with the powdery, additive-free dyes do not arise. Specifically, this means that none in the process of the invention Static charging of the dye used occurs since either the additive-free dye is taken up directly in the supercritical fluid used for the dyeing or in the other liquid, so that no undesirable dusting of additive-free dye powder can occur in the process according to the invention, since an additive-free dye powder does not appears freely accessible to the atmosphere. This in turn means that the production process is not disturbed when the method according to the invention is used. Due to the fact that a relatively low outlay on equipment is required for the separation of the conventional dye into additives and additive-free dye (dye body), the process according to the invention is furthermore distinguished by a high degree of economy.

Eine erste Ausgestaltung des erfindungsgemäßen Verfahrens sieht vor, daß der zusatzfreie Farbstoff nach Abtrennung der Zusätze isoliert wird und der isolierte Farbstoff unmittelbar in der anderen Flüssigkeit unter Ausbildung eines flüssig formierten, zusatzfreien Farbstoffes aufgenommen wird, so daß auch hierbei kein zusatzfreies Farbstoffpulver als Endprodukt anfällt und somit nicht die eingangs genannten Probleme (Verstauben, elektrostatische Aufladung) bei dieser Ausführungsform des erfindungsgemäßen Verfahrens auftreten.A first embodiment of the method according to the invention provides that the additive-free dye is isolated after the additives have been separated off and the isolated dye is taken up directly in the other liquid with the formation of a liquid-formed, additive-free dye, so that here too no additive-free dye powder is obtained as the end product and thus the problems mentioned at the outset (dusting, electrostatic charging) do not occur in this embodiment of the method according to the invention.

Abhängig von dem jeweils eingesetzten handelsüblichen Farbstoff richtet sich bei dem erfindungsgemäßen Verfahren die Auswahl der anderen Flüssigkeit, in der der zusatzfreie Farbstoff aufgenommen, d.h. vorzugsweise gelöst oder dispergiert, wird. Als andere Flüssigkeiten für zusatzfreie Farbstoffe kommen beispielsweise Wasser, Aceton, Alkohole (C₁ bis C₄ Alkohole) und/oder chlorierte Kohlenwasserstoffe jeweils allein oder in Mischung in Frage, wobei für zusatzfreie Dispersionsfarbstoffe insbesondere Aceton, Aceton-Wasser-Gemische (Mischungsverhältnis V:V etwa 9:1) oder halogenierte Kohlenwasserstoffe (Chlorbenzol, Methylenchlorid) eingesetzt werden.Depending on the commercial dye used in each case, the process according to the invention is used to select the other liquid in which the additive-free dye is taken up, ie preferably dissolved or dispersed. Other liquids for additive-free dyes are, for example, water, acetone, alcohols (C₁ to C₄ alcohols) and / or chlorinated hydrocarbons, either alone or in a mixture, with additive-free disperse dyes in particular acetone, acetone-water mixtures (mixing ratio V: V approximately 9: 1) or halogenated Hydrocarbons (chlorobenzene, methylene chloride) are used.

Um die bei dem erfindungsgemäßen Verfahren erforderliche Trennung zwischen Zusätzen und Farbstoff durchzuführen, können grundsätzlich alle an sich bekannten Trennverfahren, wie beispielsweise Osmose, Membranfiltration, Chromatografie oder Ionenaustausch, angewendet werden.In order to carry out the separation between additives and dye required in the method according to the invention, basically all separation methods known per se, such as, for example, osmosis, membrane filtration, chromatography or ion exchange, can be used.

Für spezielle Farbstoffe, wie beispielsweise Dispersionsfarbstoffe, besteht darüber hinaus noch die Möglichkeit, hier eine Aufschlämmung in Wasser herzustellen, und anschließend die sich dabei bildende Dispersion, beispielsweise durch eine plötzliche Veränderung der Temperatur und/oder des pH-Wertes, zu brechen, so daß sich aus dem Dispersionsfarbstoff zusatzfreie Farbstoffagglomerate ausbilden, die dann entsprechend, beispielsweise durch Filtration und/oder durch Zentrifugieren, abgetrennt werden. Der so isolierte zusatzfreie Farbstoff wird entweder direkt in dem für das Färben eingesetzten überkritischen Fluid aufgenommen oder es wird durch Zusatz einer der zuvor genannten Flüssigkeiten der flüssig formierte, zusatzfreie Farbstoff hergestellt, der dann lagerfähig ist und zu einem späteren Zeitpunkt zum Färben verwendet wird.For special dyes, such as disperse dyes, there is also the possibility of producing a slurry in water and then breaking the dispersion that forms, for example by a sudden change in temperature and / or pH, so that additive-free dye agglomerates are formed from the disperse dye, which are then separated off accordingly, for example by filtration and / or by centrifugation. The additive-free dye isolated in this way is either taken up directly in the supercritical fluid used for the dyeing or the liquid-formed, additive-free dye is prepared by adding one of the aforementioned liquids, which is then storable and is used at a later time for dyeing.

Ebensogut können aus wäßrigen Lösungen von wasserlöslichen Farbstoffen, wie beispielsweise Reaktivfarbstoffen, Säurefarbstoffen oder Substantivfarbstoffen, die Zusätze dadurch entfernt werden, daß man den zusatzfreien Farbstoff (Farbkörper) durch Zusatz von Salzen aussalzt und den ausgesalzten Farbkörper direkt in den zuvor genannten Flüssigkeiten aufnimmt, um so dann einen lagerfähigen, flüssig formierten Farbstoff später bei der Färbung einzusetzen.The additives can just as well be removed from aqueous solutions of water-soluble dyes, such as reactive dyes, acid dyes or noun dyes, by salting out the additive-free dye (coloring matter) by adding salts and taking up the salted-out coloring matter directly in the liquids mentioned above, and so on then use a storable, liquid-formed dye later in the dyeing.

Eine besonders geeignete Ausführungsform des erfindungsgemäßen Verfahrens sieht vor, daß die Trennung der Zusätze von dem zusatzfreien Farbstoff dadurch erfolgt, daß der herkömmliche, die Zusätze enthaltene Farbstoff extrahiert wird. Abhängig von dem jeweils eingesetzten herkömmlichen Farbstoff, dem chemischen Aufbau der darin enthaltenen Zusätze und dem chemischen Aufbau des Farbkörpers richtet sich bei dieser Extraktion die Auswahl des für die Extraktion eingesetzten Fluids.A particularly suitable embodiment of the method according to the invention provides that the separation of the additives from the additive-free dye is carried out by extracting the conventional dye containing the additives becomes. Depending on the conventional dye used in each case, the chemical structure of the additives contained therein and the chemical structure of the color body, the selection of the fluid used for the extraction is based on this extraction.

Grundsätzlich kann bei der Extraktion das Fluid derart ausgewählt werden, daß aus dem herkömmlichen Farbstoff entweder die Zusätze oder der zusatzfreie Farbstoff (Farbkörper) herausgelöst wird, was dann zur Folge hat, daß sich entweder die Zusätze im Extrakt befinden und der Farbkörper als Extraktionsrückstand verbleibt oder der Farbkörper im Extrakt gelöst ist und sich die Zusätze im Extraktionsrückstand befinden.Basically, the fluid can be selected in the extraction such that either the additives or the additive-free dye (coloring body) is dissolved out of the conventional dye, which then has the consequence that either the additives are in the extract and the coloring body remains as extraction residue or the color body is dissolved in the extract and the additives are in the extraction residue.

Eine erste Ausführungsform des erfindungsgemäßen Verfahrens sieht vor, daß bei der Extraktion ein solches Fluid ausgewählt wird, das die Zusätze aus dem eingesetzten herkömmlichen Farbstoff löst. Hierbei fällt somit der reine Farbkörper als Extraktionsrückstand an, wobei sich diese Verfahrensweise insbesondere dann anbietet, wenn der so abgetrennte zusatzfreie Farbstoff unmittelbar im Anschluß an die Extraktion zum Färben des Substrates in dem hierfür eingesetzten überkritischen Fluid aufgenommen wird.A first embodiment of the method according to the invention provides that such a fluid is selected during the extraction that it dissolves the additives from the conventional dye used. In this case, the pure color body is obtained as an extraction residue, this procedure being particularly useful if the additive-free dye so separated is taken up immediately after the extraction for coloring the substrate in the supercritical fluid used for this purpose.

Eine bevorzugte Weiterbildung der zuvor beschriebenen Ausführungsvariante des erfindungsgemäßen Verfahrens sieht vor, daß die Zusätze aus dem herkömmlichen Farbstoff mit einem solchen Fluid extrahiert werden, das zum Färben des Substrates anschließend eingesetzt wird. Diese Verfahrensvariante des erfindungsgemäßen Verfahrens weist dann den zusätzlichen Vorteil auf, daß bedingt durch die Identität der Fluida auf die Bevorratung von weiteren Fluida verzichtet werden kann. Auch können Reste des bei der Extraktion der Zusätze eingesetzten Fluids, die ggf. nach der Extraktion des herkömmlichen Farbstoffes in dem dann anfallenden Extraktionsrückstand, d.h. somit in dem zusatzfreien Farbstoff, verbleiben, die sich hieran anschließende Färbung nicht stören. Bei dieser Verfahrensweise des erfindungsgemäßen Verfahrens ist es nicht unbedingt zwingend erforderlich, daß die Extraktion mit dem Fluid im überkritischen Zustand durchgeführt wird, wie dies später für das Färben des Substrates erforderlich ist. Hierbei kann ebenso die Extraktion der Zusätze mit dem Fluid im nicht überkritischen Zustand durchgeführt werden, da eine Reihe von Zusätzen in einem nicht überkritischen Fluid gut löslich sind, während der zusatzfreie Farbstoff hingegen erst in dem selben Fluid im überkritischem Zustand löslich wird. Dies erlaubt eine besonders wirksame und schnelle Auftrennung des herkömmlichen Farbstoffes in Zusätze und zusatzfreien Farbstoff, der dann als Rückstand anfällt, während sich die Zusätze in dem eingesetzten Fluid befinden.A preferred development of the previously described embodiment variant of the method according to the invention provides that the additives are extracted from the conventional dye with such a fluid that is subsequently used to dye the substrate. This process variant of the process according to the invention then has the additional advantage that, due to the identity of the fluids, the storage of further fluids can be dispensed with. Residues of the fluid used in the extraction of the additives, which may remain in the extraction residue then obtained after the extraction of the conventional dye, that is to say in the additive-free dye, can then remain, the subsequent coloration do not bother. With this procedure of the method according to the invention, it is not absolutely necessary that the extraction with the fluid is carried out in the supercritical state, as will be required later for the coloring of the substrate. Here, the extraction of the additives can also be carried out with the fluid in the non-supercritical state, since a number of additives are readily soluble in a non-supercritical fluid, while the additive-free dye only becomes soluble in the same fluid in the supercritical state. This allows a particularly effective and rapid separation of the conventional dye into additives and additive-free dye, which then accumulates as a residue while the additives are in the fluid used.

Um die bei der zuvor beschriebenen Ausführungsform des erfindungsgemäßen Verfahrens in dem Fluid befindliche Zusätze zu entfernen, sieht eine Weiterbildung des erfindungsgemäßen Verfahrens vor, daß das mit den Zusätzen beladene Fluid über einen Ad- und/oder Absorptionsmittel geführt wird. Hierfür werden dann solche Ad- bzw. Absorptionsmittel eingesetzt, die die in dem Fluid enthaltenen Zusätze, wie beispielsweise Stellmittel, Öle, Dispergiermittel, Emulgiermittel o. dgl., einfach und unproblematisch entfernen, wobei bevorzugte Ad- bzw. Absorptionsmittel Kieselgel, Kieselgur, Aluminiumoxid und/oder Aktivkohle sind.In order to remove the additives present in the fluid in the previously described embodiment of the method according to the invention, a further development of the method according to the invention provides that the fluid loaded with the additives is passed over an adsorbent and / or absorption medium. For this purpose, such adsorbents or absorbents are used which remove the additives contained in the fluid, such as, for example, adjusting agents, oils, dispersants, emulsifiers or the like, simply and without problems, preferred adsorbents or absorbents silica gel, diatomaceous earth, aluminum oxide and / or activated carbon.

Desweiteren besteht zur Entfernung der Zusätze aus dem Fluid die Möglichkeit, nach Durchführung der Extraktion der Zusätze die in dem Fluid befindlichen Zusätze durch eine Druck-, Temperatur- und/oder Volumenveränderung des Fluids das Lösevermögen des Fluids für die Zusätze derart zu verändern, daß die Zusätze aus dem Fluid ausfallen. Diese Variante des erfindungsgemäßen Verfahrens wird insbesondere immer dann angewendet, wenn für die Extraktion der Zusätze ein überkritisiches Fluid eingesetzt wird, da durch die zuvor beschriebenen Veränderungen dann das überkritische Fluid vorzugsweise in seinen nicht kritischen Zustand überführt wird und somit eine leichte Trennung zwischen Fluid und Zusätzen erfolgen kann, da durch eine Temperatur-und/oder Druckabsenkung und/oder eine Volumenvergrößerung in der Regel ein gasförmiges Fluid sowie die festen und/oder flüssigen, aus dem herkömmlichen Farbstoff extrahierten Zusätze anfallen.Furthermore, to remove the additives from the fluid there is the possibility, after carrying out the extraction of the additives, to change the additives in the fluid by changing the pressure, temperature and / or volume of the fluid to change the solvent capacity of the fluid in such a way that the Additives fail from the fluid. This variant of the method according to the invention is used in particular whenever a supercritical fluid is used for the extraction of the additives, since the changes described above then preferably bring the supercritical fluid into its non-critical state and thus a slight separation between fluid and additives can take place, since a temperature and / or pressure reduction and / or an increase in volume generally results in a gaseous fluid and the solid and / or liquid additives extracted from the conventional dye.

Eine andere Ausführungsvariante des erfindungsgemäßen Verfahrens beruht darauf, daß für die Extraktion ein solches Fluid ausgewählt wird, das aus dem herkömmlichen Farbstoff nicht, wie vorstehend beschrieben, die Zusätze sondern den zusatzfreien Farbstoff löst. Hierbei fällt somit der zusatzfreie Farbstoff im Extrakt an, so daß ein derartiger Farbstoff besonders leicht isoliert und in einer anderen Flüssigkeit aufgenommen werden kann oder direkt als flüssig formierter, zusatzfreier Farbstoff gelagert wird, so daß ein derartiger flüssiger und zusatzfreier Farbstoff dann beim späteren Färben keine Probleme, beispielsweise kein unerwünschtes Verstauben, bereitet.Another embodiment variant of the method according to the invention is based on the fact that a fluid is selected for the extraction which does not dissolve the additives from the conventional dye, as described above, but rather the additive-free dye. In this case, the additive-free dye is obtained in the extract, so that such a dye can be isolated particularly easily and taken up in another liquid or is stored directly as a liquid-formed, additive-free dye, so that such a liquid and additive-free dye does not then occur during later dyeing Problems, for example no unwanted dusting, cause.

Eine besonders geeignete Weiterbildung der zuvor beschriebenen Ausführungsvariante des erfindungsgemäßen Verfahrens, bei dem zur Extraktion des zusatzfreien Farbstoffes ein Fluid ausgewählt wird, das den zusatzfreien Farbstoff löst, sieht vor, daß hier als Fluid ein organisches Lösungsmittel verwendet wird. Der nach der Extraktion in dem organischen Lösungsmittel enthaltende zusatzfreie Farbstoff kann dann als flüssig formierter, zusatzfreier Farbstoff gelagert werden oder dadurch isoliert werden, daß das eingesetzte organische Lösungsmittel verdampft wird, so daß der reine Farbkörper fest anfällt. Dieser reine, zusatzfreie Farbkörper wird dann entweder direkt in dem für das Färben eingesetzten überkritischen Fluid aufgenommen oder zur späteren Verwendung in einer anderen Flüssigkeit unter Ausbildung eines zusatzfreien flüssigen Farbstoffes gelöst und/oder dispergiert.A particularly suitable development of the previously described embodiment variant of the method according to the invention, in which a fluid is selected for the extraction of the additive-free dye which dissolves the additive-free dye, provides that an organic solvent is used here as the fluid. The additive-free dye contained in the organic solvent after the extraction can then be stored as a liquid-formed, additive-free dye or isolated by evaporating the organic solvent used, so that the pure color body is solid. This pure, additive-free dye body is then either taken up directly in the supercritical fluid used for dyeing or dissolved and / or dispersed in another liquid for later use to form an additive-free liquid dye.

Bei einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens wird ebenfalls der zusatzfreie Farbstoff durch ein organisches Lösungsmittel, das den zusatzfreien Farbstoff löst, extrahiert. Abweichend zu der zuvor beschriebenen Ausführungsvariante wird dabei jedoch der zusatzfreie Farbstoff aus dem organischen Lösungsmittel dadurch isoliert, daß der zusatzfreie Farbstoff an einem Absorber bzw. Adsorber ab- und/oder adsorbiert wird. Der so ab- bzw. adsorbierte reine Farbkörper kann dann direkt dem bei der Färbung eingesetzten überkritischen Fluid oder der anderen Flüssigkeit zugesetzt werden, wobei der Absorber bzw. Adsorber wiedergewonnen wird.In a further embodiment of the method according to the invention, the additive-free dye is also extracted by an organic solvent that dissolves the additive-free dye. In contrast to the embodiment variant described above, the additive-free dye is isolated from the organic solvent in that the additive-free dye is absorbed and / or adsorbed on an absorber or adsorber. The pure color body absorbed or adsorbed in this way can then be added directly to the supercritical fluid used in the coloring or to the other liquid, the absorber or adsorber being recovered.

Eine andere, besonders geeignete Ausführungsvariante des erfindungsgemäßen Verfahrens sieht vor, daß die Extraktion des herkömmlichen Farbstoffes mit einem Fluid im überkritischen Zustand durchgeführt wird. Hierbei weist diese Ausführungsvariante des erfindungsgemäßen Verfahrens den Vorteil auf, daß die Extraktion und somit die Trennung in Zusätze und Farbstoff innerhalb von sehr kurzen Zeiten abläuft, was darauf zurückgeführt wird, daß ein überkritisches Fluid aufgrund seiner relativ niedrigen, mit entsprechenden Gasen vergleichbaren Viskosität den zu extrahierenden herkömmlichen Farbstoff sehr gut durchdringt, was abhängig von dem eingesetzten Fluid zu einem ausgezeichneten und schnellen Lösen der Zusätze oder des zusatzfreien Farbstoffes führt. Darüber hinaus weist ein derartiges überkritisches Fluid noch den Vorteil auf, daß es besonders einfach und schnell durch eine Temperaturerhöhung, Volumenvergrößerung oder Druckabsenkung in das entsprechende Gas überführbar ist, so daß dann je nach Auswahl des eingesetzten überkritischen Fluids der extrahierte, zusatzfreie Farbstoff oder die Zusätze fest bzw. flüssig anfallen, während das gasförmige Fluid aufgefangen und erneut verwendet werden kann.Another, particularly suitable embodiment variant of the method according to the invention provides that the extraction of the conventional dye is carried out with a fluid in the supercritical state. Here, this embodiment variant of the method according to the invention has the advantage that the extraction and thus the separation into additives and dye takes place within very short times, which is attributed to the fact that a supercritical fluid, due to its relatively low viscosity, which is comparable with corresponding gases Extracting conventional dye penetrates very well, which, depending on the fluid used, leads to an excellent and quick dissolution of the additives or the additive-free dye. In addition, such a supercritical fluid has the advantage that it can be converted into the corresponding gas particularly easily and quickly by increasing the temperature, increasing the volume or lowering the pressure, so that, depending on the selection of the supercritical fluid used, the extracted, additive-free dye or additives solid or liquid, while the gaseous fluid can be collected and reused.

Die Auswahl des bei dem erfindungsgemäßen Verfahren jeweils zur Extraktion eingesetzten überkritischen Fluids richtet sich danach, ob man die Zusätze oder den zusatzfreien Farbstoff (Farbkörper) extrahieren will. Sollen beispielsweise mit dem überkritischen Fluid polare Zusätze, wie z.B. ionische Dispergier- bzw. Emulgiermittel, extrahiert werden, so wählt man hierfür vorzugsweise polare überkritische Fluida, wie beispielsweise Ammoniak, Fluor-Chlor-Alkane oder Mischungen von Ammoniak und/oder Fluor-Chlor-Alkane mit nicht polaren überkritischen Fluida, wie beispielsweise Alkane, Kohlendioxid und/oder Kohlenmonoxid, aus. Soll hingegen ein unpolarer, zusatzfreier Farbstoff (Farbkörper) mit dem überkritischen Fluid extrahiert werden, so werden als überkritisches Extraktionsfluid Alkane, insbesondere Ethan, Propan oder Pentan, Kohlendioxid und/oder Kohlenmonoxid jeweils allein oder in Mischung eingesetzt.The selection of the supercritical fluid used for the extraction in the method according to the invention is directed depends on whether you want to extract the additives or the additive-free dye (color body). If, for example, polar additives, such as ionic dispersing or emulsifying agents, are to be extracted with the supercritical fluid, polar supercritical fluids such as ammonia, fluorine-chloroalkanes or mixtures of ammonia and / or fluorine-chlorine are preferably selected for this purpose. Alkanes with non-polar supercritical fluids, such as alkanes, carbon dioxide and / or carbon monoxide. If, on the other hand, a non-polar, additive-free dye (coloring body) is to be extracted with the supercritical fluid, alkanes, in particular ethane, propane or pentane, carbon dioxide and / or carbon monoxide, are used alone or as a mixture as the supercritical extraction fluid.

Eine besonders vorteilhafte Weiterbildung der zuvor beschriebenen Verfahrensweise, bei der man den herkömmlichen Farbstoff mit einem Fluid und vorzugsweise einem überkritischen Fluid extrahiert, sieht vor, daß man dem Fluid bzw. dem überkritischen Fluid bei der Extraktion einen Moderator zusetzt. Dieser Moderator gestattet es, das Löseverhalten des Fluids bzw. des überkritischen Fluids auf den jeweils zu extrahierenden Bestandteil (Zusätze oder zusatzfreier Farbstoff) des herkömmlichen Farbstoffes abzustimmen, so daß besonders schnelle Extraktionszeiten resultieren. Als Moderatoren kommen dabei insbesondere polare Verbindungen, wie vorzugsweise Wasser, Alkohole und/oder Salze, in Frage. Die Konzentration dieser Moderatoren variiert zwischen etwa 1 Vol.% und etwa 10 Vol.%, vorzugsweise zwischen etwa 2 Vol.% und etwa 5 Vol.%, bezogen auf das Volumen des jeweils verwendeten Fluids bzw. des eingesetzten überkritischen Fluids oder des Fluidgemisches bzw. des überkritischen Fluidgemisches.A particularly advantageous development of the procedure described above, in which the conventional dye is extracted with a fluid and preferably a supercritical fluid, provides that a moderator is added to the fluid or the supercritical fluid during the extraction. This moderator allows the dissolving behavior of the fluid or the supercritical fluid to be matched to the constituent to be extracted in each case (additives or dye free of additives) of the conventional dye, so that particularly fast extraction times result. In particular, polar compounds, such as preferably water, alcohols and / or salts, are suitable as moderators. The concentration of these moderators varies between approximately 1% by volume and approximately 10% by volume, preferably between approximately 2% by volume and approximately 5% by volume, based on the volume of the fluid used or the supercritical fluid used or the fluid mixture or the supercritical fluid mixture.

Wie bereits vorstehend erwähnt ist, kann bei Verwendung von überkritischen Fluida zur Extraktion von herkömmlichen Farbstoffen der im Extrakt anfallenden Farbstoffbestandteil (Zusätze oder zusatzfreier Farbstoff) dadurch besonders einfach isoliert werden, daß eine Temperaturerhöhung, Druckverminderung und/oder Volumenvergrößerung herbeigeführt wird. Hierbei fallen dann die im Extrakt enthaltenden flüssigen oder festen Bestandteile (Zusätze oder zusatzfreier Farbstoff) an, während das eingesetzte überkritische Fluid als Gas entweicht, das entsprechend aufgefangen und ggf. wiederverwendet wird. Wird hingegen bei dem erfindungsgemäßen Verfahren der herkömmliche Farbstoff mit anderen, nicht überkritischen Fluida extrahiert, so bietet es sich an, hier die im Extrakt nach der Extraktion vorhandenen Farbstoffbestandteile (Zusätze oder zusatzfreier Farbstoff) durch eine Phasentrennung, flüssig-flüssig-Extraktion, eine Ad- und/oder Absorption und/oder Filtration zu entfernen, so daß man das an Zusätzen bzw. an zusatzfreiem Farbstoff freie Fluid dann zur weiteren Extraktion wiederverwenden kann.As already mentioned above, when using supercritical fluids for the extraction of conventional dyes, the dye component (additives or dye free of additives) obtained in the extract can be special are simply insulated so that a temperature increase, pressure reduction and / or volume increase is brought about. The liquid or solid constituents (additives or dye free of additives) contained in the extract then accumulate, while the supercritical fluid used escapes as a gas, which is collected accordingly and possibly reused. If, on the other hand, the conventional dye is extracted with other, non-supercritical fluids in the method according to the invention, it is advisable to use a phase separation, liquid-liquid extraction, an ad to remove the dye components (additives or dye free from extraction) present in the extract after the extraction - And / or to remove absorption and / or filtration, so that the fluid free of additives or of additive-free dye can then be reused for further extraction.

Die Temperatur, die bei dem erfindungsgemäßen Verfahren während der Extraktion angewendet wird, richtet sich allgemein gesprochen nach dem jeweils eingesetzten Fluid. Üblicherweise variiert die Extraktionstemperatur zwischen 10 °C und 240 °C, vorzugsweise zwischen 30 °C und 180 °C.Generally speaking, the temperature which is used during the extraction in the method according to the invention depends on the fluid used in each case. The extraction temperature usually varies between 10 ° C. and 240 ° C., preferably between 30 ° C. and 180 ° C.

Wird beispielsweise bei dem erfindungsgemäßen Verfahren zur Auftrennung des herkömmlichen Farbstoffes bei der Extraktion mit einem überkritischen Fluid gearbeitet, liegt die Extraktionstemperatur bei der Verwendung von Ethan als Extraktionsfluid oberhalb von 35 °C, während der entsprechende Druck über 50 bar liegt. Bei Einsatz des überkritischen Fluids Propan liegt die Extraktionstemperatur oberhalb von 100 °C und der Druck bei der Extraktion über 42 bar, während mit überkritischem Pentan bei einer Temperatur oberhalb von 197 °C und einem Druck oberhalb von 34 bar, mit überkritischem Trifluor-Chlor-Ethan bei einer Temperatur oberhalb von 29 °C und einem Druck oberhalb von 38 bar, mit überkritischem Ethylen bei einer Temperatur oberhalb von 9 °C und einem Druck oberhalb von 50 bar, mit überkritischem Ammoniak bei einer Temperatur oberhalb von 132 °C und einem Druck oberhalb von 120 bar, mit überkritischem Kohlendioxid bei einer Temperatur oberhalb von 32 °C und einem Druck oberhalb von 74 bar der handelsübliche Farbstoff extrahiert wird.If, for example, in the process according to the invention for the separation of the conventional dye during extraction with a supercritical fluid, the extraction temperature when using ethane as the extraction fluid is above 35 ° C., while the corresponding pressure is above 50 bar. When using the supercritical fluid propane, the extraction temperature is above 100 ° C and the pressure during the extraction is above 42 bar, while with supercritical pentane at a temperature above 197 ° C and a pressure above 34 bar, with supercritical trifluorochlorine Ethane at a temperature above 29 ° C and a pressure above 38 bar, with supercritical ethylene at a temperature above 9 ° C and a pressure above 50 bar, with supercritical ammonia at a temperature above 132 ° C and a pressure above 120 bar, with supercritical carbon dioxide at a temperature above 32 ° C and a pressure above 74 bar, the commercial dye is extracted.

Auch die Extraktionszeit richtet sich bei dem erfindungsgemäßen Verfahren nach dem jeweils aufzutrennenden herkömmlichen Farbstoff sowie dem eingesetzte Fluid. Üblicherweise variiert die Extraktionszeit zwischen 2 Minuten und 20 Minuten, vorzugsweise zwischen 5 Minuten und 15 Minuten.The extraction time in the method according to the invention also depends on the conventional dye to be separated and the fluid used. The extraction time usually varies between 2 minutes and 20 minutes, preferably between 5 minutes and 15 minutes.

Wie bereits vorstehend erwähnt ist, kann bei dem erfindungsgemäßen Verfahren jeder herkömmliche Farbstoff eingesetzt werden. Besonders geeignet ist es jedoch, wenn man als herkömmlichen Farbstoff einen Dispersionsfarbstoff auswählt, da bei Dispersionsfarbstoffen eine besonders einfache Auftrennung des herkömmlichen Farbstoffes in Zusätze und zusatzfreie Farbstoffe (Farbkörper), insbesondere auch durch Extraktion, möglich ist. Dies hängt damit zusammen, daß derartige Dispersionsfarbstoffe in der Regel mit ionischen Dispergatoren/Emulgatoren als Zusätze versetzt sind, während der eigentliche zusatzfreie Farbstoff (Farbkörper) unpolar ist.As already mentioned above, any conventional dye can be used in the method according to the invention. However, it is particularly suitable if a disperse dye is selected as the conventional dye, since a particularly simple separation of the conventional dye into additives and additive-free dyes (color bodies) is possible in the case of dispersion dyes, in particular also by extraction. This is due to the fact that such disperse dyes are generally mixed with additives as ionic dispersants / emulsifiers, while the actual additive-free dye (color body) is non-polar.

Bezüglich der Substrate, die nach dem erfindungsgemäßen Verfahren gefärbt werden, ist festzuhalten, daß das erfindungsgemäße Verfahren insbesondere auch zum Färben von textilen Substraten geeignet ist. Hierbei können solche textilen Substrate vorzugsweise eingesetzt werden, die mit Dispersionsfarbstoffen färbbar sind, wie insbesondere Textilien, die Polyesterfasern (Polyethylenterephthalat), aliphatische oder aromatische Polyamidfasern (Kevlar, Nomex, Polyamid6, Polyamid6.6) Polyimid-fasern, Polyalkylenfasern, insbesondere Polyethylen-Fasern oder Polypropylen-Fasern, enthalten oder aus diesen Fasern bestehen.With regard to the substrates which are dyed by the method according to the invention, it should be noted that the method according to the invention is also particularly suitable for dyeing textile substrates. Such textile substrates can preferably be used here, which can be dyed with disperse dyes, such as in particular textiles, the polyester fibers (polyethylene terephthalate), aliphatic or aromatic polyamide fibers (Kevlar, Nomex, Polyamid6, Polyamid6.6), polyimide fibers, polyalkylene fibers, in particular polyethylene fibers or polypropylene fibers, contain or consist of these fibers.

Überraschend konnte festgestellt werden, daß nach dem erfindungsgemäßen Verfahren insbesondere textile Substrate, wie vorzugsweise Garne, Stickgarne, Nähgarne, Flächengebilde oder konfektionierte textile Teile, einwandfrei innerhalb von kürzester Zeit gefärbt werden können.Surprisingly, it was found that, in particular, textile substrates, such as preferably yarns, embroidery threads, sewing threads, fabrics or made-up textile parts, can be dyed perfectly within a very short time using the process according to the invention.

Unter den Begriff Zusätze im Sinne der vorliegenden Anmeldung werden alle Stoffe verstanden, die in einem herkömmlichen Farbstoff vorhanden sind und die in ihrer chemischen Zusammensetzung von dem eigentlichen Farbstoff, d.h. dem Farbkörper, abweichen. Insbesondere fallen unter diesen Begriff Stellmittel, Öle, Dispergatoren und Emulgatoren.The term additives in the sense of the present application is understood to mean all substances which are present in a conventional dye and whose chemical composition is different from the actual dye, i.e. the color body. In particular, this term includes adjusting agents, oils, dispersants and emulsifiers.

Der Begriff Farbstoff umfaßt in der vorliegenden Anmeldung nicht nur einen einzelnen Farbstoff sondern auch eine Mischung von Farbstoffen, wobei eine derartige Mischung von Farbstoffen, die in der Regel aus drei bis zwölf Farbstoffen besteht, üblicherweise in der Praxis zum Färben eingesetzt wird.The term dye in the present application includes not only a single dye but also a mixture of dyes, such a mixture of dyes, which usually consists of three to twelve dyes, is usually used in practice for dyeing.

Vorteilhafte Weiterbildungen des erfindungsgemäßen Verfahrens sind in den Unteransprüchen angegeben.Advantageous developments of the method according to the invention are specified in the subclaims.

Das erfindungsgemäße Verfahren wird nachfolgend anhand eines Ausführungsbeispiels in Verbindung mit der Zeichnung näher erläutert. Hierbei zeigt die einzige Figur der Zeichnung eine schematische Ansicht einer Apparatur zur Durchführung des erfindungsgemäßen Verfahrens.The method according to the invention is explained in more detail below using an exemplary embodiment in conjunction with the drawing. The single figure of the drawing shows a schematic view of an apparatus for performing the method according to the invention.

Die in der Zeichnung schematisch abgebildete Apparatur weist einen Autoklaven 2 zur Aufnahme des zu färbenden textilen Substrates auf, wobei der Autoklave 2 über eine Ringleitung 6 mit einer Zirkulationspumpe 4 verbunden ist, so daß über die Pumpe 4 das beim Färben eingesetzte überkritische Fluid gefördert wird und somit das in dem Autoklaven angeordnete textile Substrat von dem überkritischen Fluid angeströmt bzw. durchströmt wird.The apparatus shown schematically in the drawing has an autoclave 2 for receiving the textile substrate to be dyed, the autoclave 2 being connected via a ring line 6 to a circulation pump 4, so that the supercritical fluid used in the dyeing is conveyed via the pump 4 and the supercritical fluid flows against or flows through the textile substrate arranged in the autoclave.

In einer Bypassleitung 7 zur Ringleitung 6 ist ein weiterer Autoklave 1 vorgesehen, wobei der weitere Autoklave zur Aufnahme des beim Färben verwendeten Farbstoffes bzw. Farbstoffgemisches dient. In einer weiteren Bypassleitung 8 bzw. 9 zur Ringleitung 6 befindet sich ein Expansionsautoklave 3. Desweiteren weist die Apparatur Ventile 11 bis 18 auf, die in den entsprechenden Leitungen 5 bis 10 angeordnet sind.A further autoclave 1 is provided in a bypass line 7 to the ring line 6, the further autoclave serving to hold the dye or dye mixture used in the dyeing. An expansion autoclave 3 is located in a further bypass line 8 or 9 to the ring line 6. Furthermore, the apparatus has valves 11 to 18 which are arranged in the corresponding lines 5 to 10.

30 g eines herkömmlichen Dispersionsfarbstoffes, der mit Zusätzen versehen war, wurde in dem weiteren Autoklaven 1 angeordnet. Über die Leitung 5 und das geöffnete Ventil 17 wurde aus einem nicht gezeigten Reservoir Kohlendioxid bei einer Temperatur von 45 °C und einem Druck von 90 bar eingespeist, wobei das überkritische Kohlendioxid mit 2 Vol.% Wasser versetzt war. Dieses überkritische Kohlendioxid wurde zunächst für 5 Minuten über die geöffneten Ventile 14 und 13 und die Leitungen 7 und 6 derart zirkulieren gelassen, daß das überkritische und mit Wasser versetzte Kohlendioxid den in dem weiteren Autoklaven 1 angeordneten Farbstoff extrahierte. Zu diesem Zeitpunkt waren die Ventile 11, 12, 15, 16, 17 und 18 geschlossen.30 g of a conventional disperse dye, which was provided with additives, was placed in the further autoclave 1. Via line 5 and the opened valve 17, carbon dioxide was fed in from a reservoir (not shown) at a temperature of 45 ° C. and a pressure of 90 bar, 2% by volume of water being added to the supercritical carbon dioxide. This supercritical carbon dioxide was first circulated for 5 minutes via the opened valves 14 and 13 and the lines 7 and 6 in such a way that the supercritical and water-added carbon dioxide extracted the dye arranged in the further autoclave 1. At this point, valves 11, 12, 15, 16, 17 and 18 were closed.

Nach Ablauf der Extraktionszeit von fünf Minuten wurde das Ventil 15 geöffnet, was dazu führte, daß das überkritische Kohlendioxid in das Expansionsgefäß 3 expandierte. Hiernach wurde das Ventil 15 geschlossen. Bei der Expansion fiel am Boden des Expansionsgefäßes 3 eine milchige Flüssigkeit an, die neben Wasser die aus dem Farbstoff extrahierten Zusätze enthielt. Diese milchige Flüssigkeit wurde über das als Schleuse ausgebildete Ventil 18 abgelassen. Nachdem das Ventil 18 geschlossen wurde, wurde über die Leitung 5 und das geöffnete Ventil 17 weiteres überkritisches Kohlendioxid der Apparatur zugeführt, wobei dieses überkritische Kohlendioxid auf einen Druck von 190 bar und eine Temperatur von 130 °C gebracht wurde. Nach Schließen des Ventiles 17 wurde dieses überkritische Kohlendioxid zunächst über die Bypassleitung 7 und die geöffneten Ventile 14 und 13 durch den weiteren Autoklaven 1 gepumpt, so daß in diesem überkritischen Kohlendioxid der in dem Autoklaven verbliebene zusatzfreie Farbstoff aufgenommen werden konnte. Anschließend wurden die Ventile 14 und 13 geschlossen, was zur Folge hatte, daß das mit zusatzfreiem Farbstoffe beladene überkritische Kohlendioxid nunmehr mittels der Pumpe 4 über die Ringleitung 6 und die geöffneten Ventile 11 und 12 durch das im Autoklaven 2 angeordnete textile Substrat gepumpt wurde. Das in dem Reservoir 3 befindliche Kohlendioxid wurde dabei über das geöffnete Ventil 16 und die Leitung 9 in den Strom des überkritischen Fluid eingeführt.After the extraction time of five minutes, the valve 15 was opened, which caused the supercritical carbon dioxide to expand into the expansion vessel 3. After that, the valve 15 was closed. During the expansion, a milky liquid was obtained at the bottom of the expansion vessel 3 which, in addition to water, contained the additives extracted from the dye. This milky liquid was drained through the valve 18 designed as a lock. After the valve 18 was closed, further supercritical carbon dioxide was fed to the apparatus via the line 5 and the opened valve 17, this supercritical carbon dioxide being brought to a pressure of 190 bar and a temperature of 130.degree. After closing the valve 17, this supercritical carbon dioxide was first of all via the bypass line 7 and the opened valves 14 and 13 pumped through the further autoclave 1 so that the additive-free dye remaining in the autoclave could be taken up in this supercritical carbon dioxide. The valves 14 and 13 were then closed, with the result that the supercritical carbon dioxide loaded with additive-free dyes was now pumped by means of the pump 4 via the ring line 6 and the opened valves 11 and 12 through the textile substrate arranged in the autoclave 2. The carbon dioxide in the reservoir 3 was introduced into the stream of supercritical fluid via the opened valve 16 and the line 9.

Nach einer Gesamtfärbezeit von 7 Minuten wurde das überkritische Kohlendioxid über einen nicht gezeigten Filter und ein entsprechendes Ablaßventil abgelassen, so daß das in dem Autoklaven angeordnete gefärbte Substrat dem Autoklaven entnommen werden konnte. Hier zeigte sich, daß das textile Substrat, bei dem es sich um eine 1-kg-Garnspule handelte, gleichmäßig gefärbt war.After a total dyeing time of 7 minutes, the supercritical carbon dioxide was discharged through a filter (not shown) and a corresponding drain valve, so that the colored substrate arranged in the autoclave could be removed from the autoclave. It was found here that the textile substrate, which was a 1 kg spool of thread, was uniformly colored.

Von der Färbung wurden jeweils die Reibechtheit, die Trockenhitze-Fixierechtheit und die Waschechtheit bestimmt. Hierbei konnte festgestellt werden, daß die entsprechende Benotungen um eine Note besser war im Vergleich zu den entsprechenden Angaben des Farbstoffherstellers für eine wäßrige Färbung mit dem identischen Farbstoff.The fastness to rubbing, the fastness to dry heat fixation and the fastness to washing were determined from the coloring. It was found that the corresponding grades were one grade better than the corresponding specifications from the dye manufacturer for an aqueous dyeing with the identical dye.

Claims (22)

  1. A method for the dyeing of a substrate in a supercritical fluid, whereby a dyestuff without additives is taken up in a supercritical fluid, and therewith the substrate to be dyed is flowed against and/or cross-flowed, characterized in that a conventional dyestuff containing additives is chosen, that before dyeing of the substrate the additives and the dyestuff without additives are separated and that the separated dyestuff without additives is taken up directly in the supercritical fluid used for the dyeing or in another liquid.
  2. The method according to claim 1, characterized in that the dyestuff without additives is isolated after the separation of the additives and that then the isolated dyestuff is taken up in another liquid creating a dyestuff without additives formulated as a liquid.
  3. The method according to claim 2, characterized in that the dyestuff without additives is taken up in water, acetone, alcohol and/or in a chlorinated hydrocarbon creating thereby a liquid formulated dyestuff.
  4. The method according to one of the preceding claims, characterized in that the conventional dyestuff is extracted to separate the additives from the dyestuff without additives.
  5. The method according to claim 4, characterized in that for the extraction such a liquid is chosen which solves the additives out of the conventional dyestuff.
  6. The method according to claim 5, characterized in that the additives are extracted out of said conventional dyestuff with a fluid being used for the dyeing of the substrate.
  7. The method according to claim 6, characterized in that the conventional dyestuff is extracted with such a fluid being used for the dyeing, that the additives in the fluid are removed out of the fluid, and that thereafter the dyeing with the dyestuff without additives is directly carried out.
  8. The method according to claim 7, characterized in that for the removal of the additives out of the fluid the fluid is led over an ad- and/or absorber.
  9. The method according to claim 7 or 8, characterized in that for the separation of the additives out of the fluid a variation of the temperature, the pressure and/or the volume is carried out.
  10. The method according to one of the claims 1 to 4, characterized in that a fluid is chosen for the extraction solving the dyestuff without additives out of the conventional dyestuff.
  11. The method according to claim 10, characterized in that an organic solvent is used for the extraction of the conventional dyestuff, and that the organic solvent is evaporated after the extraction isolating thereby the dyestuff without additives extracted by the organic solvent.
  12. The method according to claim 10, characterized in that the conventional dyestuff is extracted with an organic solvent, and that after the extraction the dyestuff without additives solved in the organic solvent is ad- and/or absorbed on a ad- and/or absorber.
  13. The method according to one of the claims 1 to 9, characterized in that the conventional dyestuff is extracted with a supercritical fluid.
  14. The method according to claim 13, characterized in that alkane, preferably ethane, propane or pentane, ammonia, fluorine-chlorine-alkane, carbon dioxide and/or carbon monooxide each separately or in a mixture are chosen as supercritical fluid.
  15. The method according to one of the claims 4 to 14, characterized in that a moderator is added to said fluid used for the extraction.
  16. The method according to claim 15, characterized in that polar compounds , particularly water, alcohols and/or salts are used as moderator.
  17. The method according to one of the claims 4 to 16, characterized in that the extraction is carried out at a temperature between 10 °C and 240 °C, preferably between 30 °C and 180 °C.
  18. The method according to one of the claims 4 to 17, characterized in that the conventional dyestuff is extracted with the fluid between 2 and 20 minutes, preferably between 5 and 15 minutes.
  19. The method according to one of the claims 4 to 18, characterized in that after the extraction of the conventional dyestuff the additives containing in the extract or the dyestuff without additives containing in the extract are or is removed out of the extract by a phase separation, a liquid-liquid-extraction, an ad- and/or absorption and/or a filtration, and that then the fluid free of additives or free of dyestuff without additives is used again for the further extraction.
  20. The method according to one of the preceding claims, characterized in that a disperse dyestuff is chosen as conventional dyestuff.
  21. The method according to one of the preceding claims, characterized in that a textile substrate, preferably a yarn, an embroidery yarn, a sewing thread, a textile fabric or a made-up piece of fabric, is dyed as a substrate .
  22. The method according to one of the preceding claims, characterized in that the textile substrate contains or consists of polyester, polyamide, polyalkylene.
EP93921794A 1992-10-08 1993-10-05 Process for dyeing a substrate in a supercritical fluid Expired - Lifetime EP0615561B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4233659 1992-10-08
DE4233659 1992-10-08
DE4237823 1992-11-10
DE4237823A DE4237823A1 (en) 1992-10-08 1992-11-10 Process for coloring a substrate in a supercritical fluid
PCT/DE1993/000943 WO1994009201A1 (en) 1992-10-08 1993-10-05 Process for dyeing a substrate in a supercritical fluid

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EP0615561A1 EP0615561A1 (en) 1994-09-21
EP0615561B1 true EP0615561B1 (en) 1996-05-08

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DE59710165D1 (en) * 1996-12-04 2003-07-03 Amann & Soehne Process for dyeing textile substrates
US5938794A (en) * 1996-12-04 1999-08-17 Amann & Sohne Gmbh & Co. Method for the dyeing of yarn from a supercritical fluid
US6048369A (en) * 1998-06-03 2000-04-11 North Carolina State University Method of dyeing hydrophobic textile fibers with colorant materials in supercritical fluid carbon dioxide
US6261326B1 (en) 2000-01-13 2001-07-17 North Carolina State University Method for introducing dyes and other chemicals into a textile treatment system
US6676710B2 (en) 2000-10-18 2004-01-13 North Carolina State University Process for treating textile substrates
MX2019015500A (en) 2017-06-22 2020-12-03 Hbi Branded Apparel Entpr Llc Fabric treatment compositions and methods.

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DE3906724C2 (en) * 1989-03-03 1998-03-12 Deutsches Textilforschzentrum Process for dyeing textile substrates
DE4200352A1 (en) * 1992-01-09 1993-08-19 Deutsches Textilforschzentrum METHOD FOR APPLYING SUBSTANCES TO FIBER MATERIALS AND TEXTILE SUBSTRATES
WO1993018221A2 (en) * 1992-03-05 1993-09-16 Jasper Gmbh Process and device for treating textile substrates in supercritical fluids

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WO1994009201A1 (en) 1994-04-28

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