EP0514337A1 - Process for dyeing hydrophobic textile material with disperse dyestuffs in supercritical CO2 - Google Patents

Process for dyeing hydrophobic textile material with disperse dyestuffs in supercritical CO2 Download PDF

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Publication number
EP0514337A1
EP0514337A1 EP92810343A EP92810343A EP0514337A1 EP 0514337 A1 EP0514337 A1 EP 0514337A1 EP 92810343 A EP92810343 A EP 92810343A EP 92810343 A EP92810343 A EP 92810343A EP 0514337 A1 EP0514337 A1 EP 0514337A1
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EP
European Patent Office
Prior art keywords
pressure
bar
dyeing
supercritical
textile material
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Granted
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EP92810343A
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German (de)
French (fr)
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EP0514337B1 (en
Inventor
Wolfgang Saus
Dierk Dr. Knittel
Eckhard Prof. Dr. Schollmeyer
Hans-Jürgen Dr. Buschmann
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Novartis AG
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Ciba Geigy AG
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Publication of EP0514337A1 publication Critical patent/EP0514337A1/en
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Classifications

    • 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
    • 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
    • D06P1/0004—General aspects of dyeing
    • 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
    • D06P1/928—Solvents other than hydrocarbons
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to a method for dyeing from supercritical CO2.
  • the object of the present invention was to improve this known method. This object is achieved by the method according to the invention.
  • the present invention thus relates to a process for dyeing hydrophobic textile material with disperse dyes by heating the textile material and the disperse dye in supercritical carbon dioxide at a pressure of 73 to 400 bar to a temperature of 80 to 300 ° C and then the pressure and the temperature lowered to below the critical pressure and the critical temperature, characterized in that the pressure reduction is carried out in several stages.
  • the process according to the invention has a number of advantages over dyeing processes from an aqueous liquor. Due to the fact that the CO2 used does not get into the wastewater, but is used again after dyeing, no wastewater pollution occurs in the process according to the invention. Furthermore, in the method according to the invention, the mass transfer processes required for the dyeing of the textile substrate run much faster in comparison to aqueous systems.
  • the textile substrate to be dyed can be flowed through particularly well and quickly.
  • there are no irregularities with regard to the flow through the winding body during the coloring of winding bodies which are to be regarded as causes for edge sequences or length sequences, for example in the conventional method for tree coloring of flat structures.
  • no dispersion dyes can undesirably agglomerate in the process according to the invention, as is sometimes the case with conventional dispersion dyeings, so that the use of the process according to the invention avoids the brightening of dispersion dyes known in conventional dyeing processes in aqueous systems and thus corresponding staining.
  • reductive post-cleaning can be dispensed with, even in the case of medium and dark shades, without the color fastness, in particular the rubbing and washing fastness, being impaired.
  • Another advantage of the process according to the invention is that disperse dyes can be used which consist exclusively of the actual dye and do not contain the usual dispersants and adjusting agents. For many dyes, there is also no need to grind the dyes.
  • supercritical CO2 means CO2 in which the pressure and the temperature of the CO2 are above the critical pressure and the critical temperature.
  • the supercritical CO2 approximately has the viscosity of the corresponding gas and a density which is approximately comparable with the density of the correspondingly liquefied gas.
  • the dyeing process according to the invention is carried out, for example, in such a way that the textile material to be dyed is placed together with the disperse dye in a pressure-resistant dyeing apparatus and heated to the dyeing temperature under CO2 pressure or by heating and then adjusting the desired CO2 pressure.
  • the dyeing temperature used in the process according to the invention depends essentially on the substrate to be colored. Usually it is between about 70 and 300 ° C, preferably between about 100 and 150 ° C.
  • the pressure to be applied must be at least so high that the CO2 is in a supercritical state. The higher the pressure, the greater the solubility of the dyes in CO2 in general, but the greater the expenditure on equipment.
  • the pressure is preferably between about 73 and 400 bar, in particular between about 150 and 250 bar. At the preferred dyeing temperature for polyester material of approximately 130 ° C., the pressure is approximately 200 bar.
  • the liquor ratio (mass ratio of textile material: CO2) when dyeing according to the inventive method depends on the goods to be treated and their presentation.
  • polyester yarns which are wound onto corresponding packages are to be dyed using the process according to the invention, this is preferably done with relatively short liquor ratios, i.e. Fleet ratios between 1: 2 to 1: 5.
  • Such short moth ratios generally cause difficulties in the conventional dyeing process in the aqueous system, since there is often the risk that the finely dispersed systems agglomerate due to the high dye concentration. However, this does not occur in the method according to the invention.
  • the desired pressure is set, if this has not already been reached due to the temperature increase.
  • the temperature and pressure are then for some time, e.g. Kept constant for 1 to 60 minutes, taking suitable measures, e.g. Stirring or shaking, or above all by circulation of the "dye liquor" ensures intensive mixing of the textile material and "dye liquor".
  • the length of time is generally not critical, but it has been shown that times of more than 10 minutes usually do not improve the dyeing yield.
  • the pressure is then reduced in several stages, preferably in 2 to 100 stages, which is done most simply by opening a valve and releasing a portion of CO2.
  • the rapid expansion results in cooling, that is, it is quasi-adiabatically expanded.
  • the density of the CO2 is changed by lowering the pressure. After closing the valve, heating to the Ambient temperature instead, so the pressure rises isochorically again. After approx. 30 seconds to a few minutes, when the pressure and temperature no longer rise practically, the pressure is reduced again and the process described above is repeated.
  • This mode of operation is preferably controlled automatically by a pressure and / or density and / or temperature program.
  • the pressure in each stage is preferably reduced by 0.1 to 20 bar, in particular 1 to 10 bar and above all by 2 to 5 bar.
  • the pressure in stages from a pressure between 200 and 300 bar to 100 to 130 bar.
  • the residual pressure can then be released in one step. Since the density of the supercritical CO2 decreases more at lower temperatures when the pressure is reduced, it has proven to be advantageous to take this into account by reducing the pressure levels.
  • the textile material is then removed from the dyeing machine and can often be used without further cleaning. In particular, it should be noted that no drying is required.
  • the method according to the invention is suitable for dyeing semi-synthetic and in particular synthetic hydrophobic fiber materials, especially textile materials.
  • Textile materials from blended fabrics which contain such semi-synthetic or synthetic hydrophobic textile materials can also be dyed by the process according to the invention.
  • Cellulose-21 ⁇ 2-acetate and cellulose triacetate are particularly suitable as semi-synthetic textile materials.
  • Synthetic hydrophobic textile materials consist primarily of linear, aromatic polyesters, for example those made of terephthalic acid and glycols, especially ethylene glycol or condensation products made of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane; from polycarbonates, e.g. from ⁇ , ⁇ -dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinyl chloride, polypropylene or polyamide, e.g. Polyamide 6.6, polamide 6.10, polyamide 6, polyamide 11 or poly (1,4-phenylene terephthalamide).
  • Microfilament fibers made of polyester e.g. Color polyethylene terephthalate, with very good levelness. It is also possible to color foils or wires from this material.
  • Suitable dyes for the process according to the invention are, above all, dispersion dyes, i.e. dyes which are sparingly soluble or almost insoluble in water.
  • dyes from the following classes are possible: Nitro dyes, for example nitrodiphenylamine dyes, methine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes, tricyanovinyl dyes and azo dyes such as monoazo and disazo dyes.
  • Nitro dyes for example nitrodiphenylamine dyes, methine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes, tricyanovinyl dyes and azo dyes such as monoazo and disazo dyes.
  • a strip of polyester fabric and 1.5% by weight, based on the polyester fabric, of the dye of the formula are placed in an autoclave
  • the autoclave is flushed with CO2 gas and heated to 130 ° C under 10 bar CO2 pressure at a heating rate of 2 ° C per minute, the stirrer running at approx. 100 revolutions per minute. Then the pressure is increased to 250 bar within 1.5 to 2.5 minutes and the stirrer speed is increased to about 700 revolutions per minute.
  • the pressure is reduced by 5 bar within 5 to 15 seconds by releasing CO2, the temperature in the autoclave falling by about 2 ° C. After closing the valve, the pressure increases again by about 2 bar within the next minute and the temperature returns to the original value.
  • the pressure is again reduced by 7 bar within 5 to 15 seconds by releasing CO2, the valve is closed and the system waits for 1 minute to set a constant temperature and a constant pressure. This process is repeated until the pressure has dropped to 180 bar. (approx. 15 minutes) The residual pressure in the autoclave is then released and the polyester fabric is removed from the hot autoclave.
  • a red-dyed polyester fabric of similar quality to that obtained by dyeing by customary methods from an aqueous liquor is obtained.
  • Example 1 If one works as described in Example 1, but after reaching 130 ° C. and a pressure of 250 bar and a stirrer speed of 700 revolutions per minute, these conditions are kept constant for 25 minutes, then the pressure in the autoclave is released within 30 seconds. cools and removes the dyed polyester fabric, the color depth is only approx. 1 10th the color depth obtained in Example 1.

Abstract

When dyeing polyester textile materials with disperse dyestuffs from supercritical CO2, deeper dyeings are obtained if the subsequent pressure reduction is carried out in several steps.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Färben aus überkritischem CO₂.The present invention relates to a method for dyeing from supercritical CO₂.

Aus der DE-A-3 906 724 ist bereits bekannt, dass man textile Substrate aus überkritischem CO₂ mit Dispersionsfarbstoffen färben kann, indem man das Textilmaterial und den Dispersionsfarbstoff unter einem CO₂-Druck von etwa 190 bar während etwa 10 Minuten auf etwa 130°C erhitzt und anschliessend das Volumen vergrössert, wodurch das CO₂ expandiert. Dieses Verfahren liefert jedoch nicht immer vollständig befriedigende Ergebnisse, da die Farbausbeute, vor allem bei höheren Farbstoffkonzentrationen, zum Teil zu wünschen übrig lässt.From DE-A-3 906 724 it is already known that you can dye textile substrates from supercritical CO₂ with disperse dyes by the textile material and the disperse dye under a CO₂ pressure of about 190 bar for about 10 minutes to about 130 ° C. heated and then increased in volume, causing the CO₂ to expand. However, this method does not always give completely satisfactory results, since the color yield, especially at higher dye concentrations, leaves something to be desired.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, dieses bekannte Verfahren zu verbessern. Diese Aufgabe wird durch das erfindungsgemässe Verfahren gelöst.The object of the present invention was to improve this known method. This object is achieved by the method according to the invention.

Die vorliegende Erfindung betrifft somit ein Verfahren zum Färben von hydrophobem Textilmaterial mit Dispersionsfarbstoffen, indem man das Textilmaterial und den Dispersionsfarbstoff in überkritischem kohlendioxid bei einem Druck von 73 bis 400 bar auf eine Temperatur von 80 bis 300°C erhitzt und anschiiessend den Druck und die Temperatur bis unterhalb des kritischen Druckes und der kritischen Temperatur erniedrigt, dadurch gekennzeichnet, dass man die Druckerniedrigung in mehreren Stufen durchführt.The present invention thus relates to a process for dyeing hydrophobic textile material with disperse dyes by heating the textile material and the disperse dye in supercritical carbon dioxide at a pressure of 73 to 400 bar to a temperature of 80 to 300 ° C and then the pressure and the temperature lowered to below the critical pressure and the critical temperature, characterized in that the pressure reduction is carried out in several stages.

Überraschenderweise erhält man bei dieser Arbeitsweise erheblich tiefere Färbungen als in dem bekannten Verfahren, bei dem die Druckerniedrigung in 1 Stufe durchgeführt wird.Surprisingly, this procedure gives considerably deeper colors than in the known process, in which the pressure is reduced in one step.

Das erfindungsgemässe Verfahren weist eine Reihe von Vorteilen gegenüber Färbeverfahren aus wässriger Flotte auf. Bedingt dadurch, dass das eingesetzte CO₂ nicht ins Abwasser gelangt, sondern nach der Färbung erneut eingesetzt wird, treten bei dem erfindungsgemässen Verfahren keine Abwasserbelastungen auf. Ferner laufen bei dem erfindungsgemässen Verfahren die für die Färbung des textilen Substrates erforderlichen Stoffaustauschvorgänge im Vergleich zu wässrigen Systemen wesentlich schneller ab.The process according to the invention has a number of advantages over dyeing processes from an aqueous liquor. Due to the fact that the CO₂ used does not get into the wastewater, but is used again after dyeing, no wastewater pollution occurs in the process according to the invention. Furthermore, in the method according to the invention, the mass transfer processes required for the dyeing of the textile substrate run much faster in comparison to aqueous systems.

Dies wiederum führt dazu, dass das zu färbende textile Substrat besonders gut und schnell durchströmt werden kann. Bei Anwendung des erfindungsgemässen Verfahrens treten bei der Färbung von Wickelkörpern keine Ungleichmässigkeiten bezüglich der Durchströmung des Wickelkörpers auf, welche beispielsweise bei dem herkömmlichen Verfahren bei der Baumfärbung von Flächengebilden als Ursachen für kantenabläufe bzw. Längen abläufe anzusehen sind. Ebenfalls können bei dem erfindungsgemässen Verfahren keine Dispersionsfärbstoffe unerwünscht agglomerieren, wie dies bei den herkömmlichen Dispersionsfärbungen bisweilen der Fall ist, so dass somit durch Anwendung des erfindungsgemässen Verfahrens die bei herkömmlichen Färbeverfahren in wässrigen Systemen bekannten Aufhellungen von Dispersionsfärbstoffen und damit entsprechende Fleckenbildungen vermieden werden.This in turn means that the textile substrate to be dyed can be flowed through particularly well and quickly. When using the method according to the invention, there are no irregularities with regard to the flow through the winding body during the coloring of winding bodies, which are to be regarded as causes for edge sequences or length sequences, for example in the conventional method for tree coloring of flat structures. Likewise, no dispersion dyes can undesirably agglomerate in the process according to the invention, as is sometimes the case with conventional dispersion dyeings, so that the use of the process according to the invention avoids the brightening of dispersion dyes known in conventional dyeing processes in aqueous systems and thus corresponding staining.

Darüber hinaus kann bei Färbungen mit Dispersionsfärbstoffen durch Anwendung des erfindungsgemässen Verfahrens auch bei mittleren und dunklen Farbtönen auf eine reduktive Nachreinigung verzichtet werden, ohne dass hierdurch die Farbechtheiten, insbesondere die Reib- und Waschechtheiten, verschlechtert werden.In addition, in the case of dyeings with disperse dyes, reductive post-cleaning can be dispensed with, even in the case of medium and dark shades, without the color fastness, in particular the rubbing and washing fastness, being impaired.

Ein weiterer Vorteil des erfindungsgemässen Verfahrens besteht darin, dass man Dispersionsfarbstoffe einsetzen kann, die ausschliesslich aus dem eigentlichen Farbstoff bestehen und nicht die üblichen Dispergatoren und Stellmittel enthalten. Bei vielen Farbstoffen kann zudem auf eine Mahlung der Farbstoffe verzichtet werden.Another advantage of the process according to the invention is that disperse dyes can be used which consist exclusively of the actual dye and do not contain the usual dispersants and adjusting agents. For many dyes, there is also no need to grind the dyes.

Unter dem Begriff überkritisches CO₂ versteht man CO₂, bei dem der Druck und die Temperatur des CO₂ oberhalb des kritischen Druckes und der kritischen Temperatur liegen. Hierbei weist das überkritische CO₂ annähernd die Viskosität des entsprechenden Gases und eine Dichte auf, die näherungsweise mit der Dichte des entsprechend verflüssigten Gases vergleichbar ist.The term supercritical CO₂ means CO₂ in which the pressure and the temperature of the CO₂ are above the critical pressure and the critical temperature. Here, the supercritical CO₂ approximately has the viscosity of the corresponding gas and a density which is approximately comparable with the density of the correspondingly liquefied gas.

Das erfindungsgemässe Färbeverfahren wird beispielsweise in der Art durchgeführt, dass man das zu färbende Textilmaterial zusammen mit dem Dispersionsfarbstoff in eine druckfeste Färbeapparatur gibt und unter CO₂-Druck auf die Färbetemperatur aufheizt oder indem man aufheizt und dann den gewünschten CO₂-Druck einstellt.The dyeing process according to the invention is carried out, for example, in such a way that the textile material to be dyed is placed together with the disperse dye in a pressure-resistant dyeing apparatus and heated to the dyeing temperature under CO₂ pressure or by heating and then adjusting the desired CO₂ pressure.

Die bei dem erfindungsgemässen Verfahren angewendete Färbetemperatur richtet sich im wesentlichen nach dem zu färbenden Substrat. Normalerweise liegt sie etwa zwischen 70 und 300°C, vorzugsweise zwischen etwa 100 und 150°C.The dyeing temperature used in the process according to the invention depends essentially on the substrate to be colored. Usually it is between about 70 and 300 ° C, preferably between about 100 and 150 ° C.

Der anzuwendende Druck muss mindestens so gross sein, dass das CO₂ in überkritischem Zustand vorliegt. Je höher der Druck, desto grösser ist im allgemeinen die Löslichkeit der Farbstoffe im CO₂, desto grösser ist jedoch auch der apparative Aufwand. Vorzugsweise liegt der Druck zwischen etwa 73 und 400 bar, insbesondere zwischen etwa 150 und 250 bar. Bei der bevorzugten Färbetemperatur für Polyestermaterial von ca. 130°C beträgt der Druck etwa 200 bar.The pressure to be applied must be at least so high that the CO₂ is in a supercritical state. The higher the pressure, the greater the solubility of the dyes in CO₂ in general, but the greater the expenditure on equipment. The pressure is preferably between about 73 and 400 bar, in particular between about 150 and 250 bar. At the preferred dyeing temperature for polyester material of approximately 130 ° C., the pressure is approximately 200 bar.

Das Flottenverhältnis (Massenverhältnis Textilmaterial: CO₂) beim Färben nach dem erfindungsgemässen Verfahren richtet sich nach der zu behandelnden Ware und deren Aufmachung.The liquor ratio (mass ratio of textile material: CO₂) when dyeing according to the inventive method depends on the goods to be treated and their presentation.

Üblicherweise variiert es zwischen einem Wert von 1:2 bis 1:100, vorzugsweise etwa 1:5 bis 1:75. Sollen beispielsweise Polyestergarne, die auf entsprechende kreuzspulen aufgewickelt sind, nach dem erfindungsgemässen Verfahren gefärbt werden, so geschieht dies vorzugsweise bei relativ kurzen Flottenverhältnissen, d.h. Flottenverhältnissen zwischen 1:2 bis 1:5. Derartige kurze Mottenverhältnisse bereiten in der Regel bei dem herkömmlichen Färbeverfahren im wässrigen System Schwierigkeiten, da hierbei bedingt durch die hohe Farbstoffkonzentration häufig die Gefahr besteht, dass die feindispersen Systeme agglomerieren. Dies tritt jedoch bei dem erfindungsgemässen Verfahren nicht auf.Usually it varies between a value of 1: 2 to 1: 100, preferably about 1: 5 to 1:75. If, for example, polyester yarns which are wound onto corresponding packages, are to be dyed using the process according to the invention, this is preferably done with relatively short liquor ratios, i.e. Fleet ratios between 1: 2 to 1: 5. Such short moth ratios generally cause difficulties in the conventional dyeing process in the aqueous system, since there is often the risk that the finely dispersed systems agglomerate due to the high dye concentration. However, this does not occur in the method according to the invention.

Nach Erreichen der Färbetemperatur wird der gewünschte Druck eingestellt, falls dieser nicht schon infolge der Temperaturerhöhung erreicht wurde. Die Temperatur und der Druck werden dann für einige Zeit, z.B. 1 bis 60 Minuten konstant gehalten, wobei man durch geeignete Massnahmen, z.B. Rühren oder Schütteln, oder vor allem durch Zirkulation der "Färbeflotte" für eine intensive Durchmischung von Textilmaterial und "Färbeflotte" sorgt. Die Zeitdauer ist im allgemeinen nicht kritisch, doch hat sich gezeigt, dass Zeiten von mehr als 10 Minuten meist keine Verbesserung der färberischen Ausbeute bringen.After reaching the dyeing temperature, the desired pressure is set, if this has not already been reached due to the temperature increase. The temperature and pressure are then for some time, e.g. Kept constant for 1 to 60 minutes, taking suitable measures, e.g. Stirring or shaking, or above all by circulation of the "dye liquor" ensures intensive mixing of the textile material and "dye liquor". The length of time is generally not critical, but it has been shown that times of more than 10 minutes usually do not improve the dyeing yield.

Anschliessend wird der Druck in mehreren Stufen, vorzugsweise in 2 bis 100 Stufen, erniedrigt, was am einfachsten durch Öffnen eines Ventils und Ablassen eines CO₂-Anteils geschieht. Durch die schnelle Expansion erfolgt eine Abkühlung, d.h., es wird quasi adiabatisch expandiert. Ausserdem wird durch die Druckerniedrigung die Dichte des CO₂ verändert. Nach Schliessen des Ventils findet wieder Erwärmung auf die Umgebungstemperatur statt, der Druck steigt also isochor wieder an. Nach ca. 30 Sekunden bis wenigen Minuten, wenn Druck und Temperatur pracktisch nicht mehr steigen, wird der Druck erneut erniedrigt und der oben beschriebene Vorgang wiederholt. Vorzugsweise steuert man diese Arbeitsweise automatisch durch ein Druck- und/oder Dichte- und/oder Temperaturprogramm.The pressure is then reduced in several stages, preferably in 2 to 100 stages, which is done most simply by opening a valve and releasing a portion of CO₂. The rapid expansion results in cooling, that is, it is quasi-adiabatically expanded. In addition, the density of the CO₂ is changed by lowering the pressure. After closing the valve, heating to the Ambient temperature instead, so the pressure rises isochorically again. After approx. 30 seconds to a few minutes, when the pressure and temperature no longer rise practically, the pressure is reduced again and the process described above is repeated. This mode of operation is preferably controlled automatically by a pressure and / or density and / or temperature program.

Vorzugsweise wird der Druck in jeder Stufe um 0,1 bis 20 bar, insbesondere 1 bis 10 bar und vor allem um 2 bis 5 bar erniedrigt.The pressure in each stage is preferably reduced by 0.1 to 20 bar, in particular 1 to 10 bar and above all by 2 to 5 bar.

Ausserdem ist es bevorzugt, den Druck in Stufen von einem Druck zwischen 200 und 300 bar auf 100 bis 130 bar zu erniedrigen. Anschliessend kann man den Restdruck in einer Stufe entspannen. Da bei tieferen Temperaturen bei Verminderung des Druckes die Dichte des überkritischen CO₂ stärker abnimmt, hat es sich als günstig erwiesen, diesen Umstand durch Verkleinern der Druckstufen zu berücksichtigen.In addition, it is preferred to reduce the pressure in stages from a pressure between 200 and 300 bar to 100 to 130 bar. The residual pressure can then be released in one step. Since the density of the supercritical CO₂ decreases more at lower temperatures when the pressure is reduced, it has proven to be advantageous to take this into account by reducing the pressure levels.

Das Textilmaterial wird danach dem Färbeapparat entnommen und ist häufig ohne weitere Reinigung gebrauchsfähig. Insbesondere ist zu beachten, dass keine Trocknung erforderlich ist.The textile material is then removed from the dyeing machine and can often be used without further cleaning. In particular, it should be noted that no drying is required.

Zur Reinigung des überkritischen CO₂ nach der Färbung bestehen mehrere Möglichkeiten. Man kann z.B. den in dem überkritischen CO₂ verbleibenden Farbstoffrest über entsprechende Filter ad- bzw. absorbieren. Hierfür eignen sich insbesondere die an sich bekannten kieselgel-, kieselgur-, kohle-, Zeolith- und Aluminiumoxidfilter.There are several options for cleaning the supercritical CO₂ after dyeing. You can e.g. ad or absorb the remaining dye in the supercritical CO₂ through appropriate filters. The known silica gel, kieselguhr, carbon, zeolite and aluminum oxide filters are particularly suitable for this.

Darüber hinaus besteht die Möglichkeit, die nach der Färbung in dem überkritischen CO₂ verbleibenden Farbstoffe durch eine Temperaturerhöhung und/oder Druckerniedrigung und/oder eine Volumenvergrösserung zu entfernen. Hierbei erfolgt eine Dichteerniedrigung, wobei die erniedrigte Dichte noch im überkritischen Bereich liegen kann. Man kann aber auch dies so weit fortsetzen, bis sich das überkritische CO₂ in das entsprechende Gas umwandelt, das dann aufgefangen wird und erneut nach Überführung in den überkritischen Zustand zur Färbung von weiteren Substraten verwendet wird. Hierbei scheiden sich die Farbstoffe als flüssige oder feste Farbstoffe ab, die entsprechend gesammelt und für weitere Färbungen weiterverwendet werden können.In addition, there is the possibility of removing the dyes remaining in the supercritical CO₂ by coloring by increasing the temperature and / or reducing the pressure and / or increasing the volume. In this case, the density is reduced, although the reduced density can still be in the supercritical range. But you can also continue this until the supercritical CO₂ converts to the corresponding gas, which is then collected and used again after transferring to the supercritical state for coloring other substrates. The dyes separate out as liquid or solid dyes, which can be collected accordingly and used for further dyeings.

Das erfindungsgemässe Verfahren eignet sich zum Färben von halbsynthetischen und insbesondere synthetischen hydrophoben Fasermaterialien, vor allem Textilmaterialien.The method according to the invention is suitable for dyeing semi-synthetic and in particular synthetic hydrophobic fiber materials, especially textile materials.

Textilmaterialien aus Mischgeweben, die derartige halbsynthetische bzw. synthetische hydrophobe Textilmaterialien enthalten, können ebenfalls nach dem erfindungsgemässen Verfahren gefärbt werden.Textile materials from blended fabrics which contain such semi-synthetic or synthetic hydrophobic textile materials can also be dyed by the process according to the invention.

Als halbsyntetische Textilmaterialien kommen vor allem Cellulose-2½-Acetat und Cellulosetriacetat in Frage.Cellulose-2½-acetate and cellulose triacetate are particularly suitable as semi-synthetic textile materials.

Synthetische hydrophobe Textilmaterialien bestehen vor allem aus linearen, aromatischen Polyestern, beispielsweise solchen aus Terephthalsäure und Glykolen, besonders Ethylenglykol oder kondensationsprodukten aus Terephthalsäure und 1,4-Bis-(hydroxymethyl)-cyclohexan; aus Polycarbonaten, z.B. aus α,α-Dimethyl-4,4′-dihydroxy-diphenylmethan und Phosgen, aus Fasern auf Polyvinylchlorid-, Polypropylen- oder Polyamid-Basis, z.B. Polyamid 6.6, Polamid 6.10, Polyamid 6, Polyamid 11 oder Poly(1,4-phenylenterephthalamid).Synthetic hydrophobic textile materials consist primarily of linear, aromatic polyesters, for example those made of terephthalic acid and glycols, especially ethylene glycol or condensation products made of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane; from polycarbonates, e.g. from α, α-dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinyl chloride, polypropylene or polyamide, e.g. Polyamide 6.6, polamide 6.10, polyamide 6, polyamide 11 or poly (1,4-phenylene terephthalamide).

Nach dem erfindungsgemässen Verfahren lassen sich auch Mikrofilament-Fasern aus Polyester, z.B. Polyethylenterephthalat, mit sehr guter Egealität färben. Ausserdem ist es auch möglich, Folien oder Drähte aus diesem Material zu färben.Microfilament fibers made of polyester, e.g. Color polyethylene terephthalate, with very good levelness. It is also possible to color foils or wires from this material.

Als Farbstoffe kommen für das erfindungsgemässe Verfahren vor allem Dispersionsfarbstoffe, d.h., in Wasser schwerlösliche oder nahezu unlösliche Farbstoffe in Betracht.Suitable dyes for the process according to the invention are, above all, dispersion dyes, i.e. dyes which are sparingly soluble or almost insoluble in water.

Es kommen z.B. Farbstoffe aus folgenden klassen in Frage:
   Nitrofarbstoffe, z.B. Nitrodiphenylaminfarbstoffe, Methinfarbstoffe, Chinolinfarbstoffe, Aminonaphthochinonfarbstoffe, Cumarinfarbstoffe und insbesondere Anthrachinonfarbstoffe, Tricyanvinylfarbstoffe und Azofarbstoffe, wie Monoazo und Disazofarbstoffe.For example, dyes from the following classes are possible:
Nitro dyes, for example nitrodiphenylamine dyes, methine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes, tricyanovinyl dyes and azo dyes such as monoazo and disazo dyes.

Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken.The following examples illustrate the invention without restricting it.

Beispiel 1example 1

In einen Autoklaven gibt man einen Streifen Polyestergewebe sowie 1,5 Gew.%, bezogen auf das Polyestergewebe, des Farbstoffs der Formel

Figure imgb0001
A strip of polyester fabric and 1.5% by weight, based on the polyester fabric, of the dye of the formula are placed in an autoclave
Figure imgb0001

Der Autoklav wird mit CO₂-Gas gespült und unter 10 bar CO₂-Druck mit einer Aufheizgeschwindigkeit von 2°C pro Minute auf 130°C aufgeheizt, wobei der Rührer mit ca. 100 Umdrehungen pro Minute läuft. Dann erhöht man den Druck innerhalb von 1,5 bis 2,5 Minuten auf 250 bar und steigert die Rührergeschwindigkeit auf ca. 700 Umdrehungen pro Minute.The autoclave is flushed with CO₂ gas and heated to 130 ° C under 10 bar CO₂ pressure at a heating rate of 2 ° C per minute, the stirrer running at approx. 100 revolutions per minute. Then the pressure is increased to 250 bar within 1.5 to 2.5 minutes and the stirrer speed is increased to about 700 revolutions per minute.

Nach 1 Minute wird der Druck innerhalb von 5 bis 15 Sekunden durch Ablassen von CO₂ um 5 bar erniedrigt, wobei die Temperatur im Autoklaven um etwa 2°C sinkt. Nach Schliessen des Ventils steigt der Druck innerhalb der nächsten Minute wieder um etwa 2 bar an und die Temperatur erreicht wieder den ursprünglichen Wert.After 1 minute, the pressure is reduced by 5 bar within 5 to 15 seconds by releasing CO₂, the temperature in the autoclave falling by about 2 ° C. After closing the valve, the pressure increases again by about 2 bar within the next minute and the temperature returns to the original value.

Jetzt wird erneut der Druck innerhalb von 5 bis 15 Sekunden durch Ablassen von CO₂ um 7 bar erniedrigt, das Ventil geschlossen und 1 Minute zur Einstellung einer konstanten Temperatur und eines konstanten Druckes gewartet. Dieser Vorgang wird so oft wiederholt, bis der Druck auf 180 bar abgesunken ist. (ca. 15 Minuten) Danach wird der Restdruck im Autoklaven abgelassen und das Polyestergewebe aus dem heissen Autoklaven entnommen.Now the pressure is again reduced by 7 bar within 5 to 15 seconds by releasing CO₂, the valve is closed and the system waits for 1 minute to set a constant temperature and a constant pressure. This process is repeated until the pressure has dropped to 180 bar. (approx. 15 minutes) The residual pressure in the autoclave is then released and the polyester fabric is removed from the hot autoclave.

Man erhält ein rot gefärbtes Polyestergewebe in ähnlicher Qualität wie beim Färben nach üblichen Methoden aus wässriger Flotte.A red-dyed polyester fabric of similar quality to that obtained by dyeing by customary methods from an aqueous liquor is obtained.

Beispiel 2Example 2

Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle des dort eingesetzten Farbstoffes eine äquivalente Menge des Farbstoffes der Formel

Figure imgb0002

so erhählt man gelb gefärbtes Polyestergewebe in ähnlicher Qualität wie beim Färben nach üblichen Methoden aus wässriger Flotte.If the procedure is as described in Example 1, but instead of the dye used there, an equivalent amount of the dye of the formula is used
Figure imgb0002
thus one selects yellow-dyed polyester fabric of a quality similar to that obtained by dyeing by conventional methods from an aqueous liquor.

Beispiel 3 (Vergleichsbeispiel) Example 3 (comparative example )

Arbeitet man wie im Beispiel 1 beschrieben, hält man jedoch nach Erreichen von 130°C und einem Druck von 250 bar und einer Rührergeschwindigkeit von 700 Umdrehungen pro Minute diese Bedingungen während 25 Minuten konstant, lässt dann den Druck im Autoklaven innerhalb von 30 Sekunden ab, kühlt ab und entnimmt das gefärbte Polyestergewebe, so beträgt die Farbtiefe nur ca. 1 10

Figure imgb0003
der im Beispiel 1 erhaltenen Farbtiefe.If one works as described in Example 1, but after reaching 130 ° C. and a pressure of 250 bar and a stirrer speed of 700 revolutions per minute, these conditions are kept constant for 25 minutes, then the pressure in the autoclave is released within 30 seconds. cools and removes the dyed polyester fabric, the color depth is only approx. 1 10th
Figure imgb0003
 the color depth obtained in Example 1.

Claims (17)

Verfahren zum Färben von hydrophobem Textilmaterial mit Dispersionsfarbstoffen, indem man das Textilmaterial und den Dispersionsfarbstoff in überkritischem Kohlendioxid bei einem Druck von 73 bis 400 bar auf eine Temperatur von 80 bis 300°C erhitzt und anschliessend den Druck und die Temperatur bis unterhalb des kritischen Druckes und der kritischen Temperatur erniedrigt, dadurch gekennzeichnet, dass man die Druckerniedrigung in mehreren Stufen durchführt.Process for dyeing hydrophobic textile material with disperse dyes by heating the textile material and the disperse dye in supercritical carbon dioxide at a pressure of 73 to 400 bar to a temperature of 80 to 300 ° C and then the pressure and the temperature to below the critical pressure and of the critical temperature, characterized in that the pressure reduction is carried out in several stages. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man die Druckerniedrigung in 2 bis 100 Stufen durchführt.A method according to claim 1, characterized in that one carries out the pressure reduction in 2 to 100 stages. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass man den Druck in jeder Stufe um 0,1 bis 20 bar erniedrigt und nach jeder Stufe abwartet, bis sich wieder ein praktisch konstanter Druck eingestellt hat.Method according to one of claims 1 or 2, characterized in that the pressure is reduced by 0.1 to 20 bar in each stage and after each stage is waited until a practically constant pressure has returned. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man den Druck in jeder Stufe um 1 bis 10 bar, vorzugsweise 2 bis 5 bar erniedrigt.Process according to one of claims 1 to 3, characterized in that the pressure is reduced in each stage by 1 to 10 bar, preferably 2 to 5 bar. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man den Druck in Stufen von einem Druck zwischen 200 und 300 bar auf 100 bis 130 bar erniedrigt.Method according to one of claims 1 to 4, characterized in that the pressure is reduced in stages from a pressure between 200 and 300 bar to 100 to 130 bar. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Druckerniedrigung durch ein Druck- und/oder Dichte- und/oder Temperaturprogramm steuert.Method according to one of claims 1 to 5, characterized in that the pressure reduction is controlled by a pressure and / or density and / or temperature program. Verfahren gemäss Anspruch 6, dadurch gekennzeichnet, dass man die Druckerniedrigung so steuert, dass die Abnahme der Dichte in konstanten Stufen erfolgt.A method according to claim 6, characterized in that the pressure reduction is controlled so that the decrease in density takes place in constant steps. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass man einen Dispersionsfarbstoff einsetzt, der frei von Zusätzen, insbesondere frei von Stellmitteln und Dispergiermitteln, ist.Method according to one of claims 1 to 7, characterized in that one uses a disperse dye which is free of additives, in particular free of adjusting agents and dispersing agents. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man das Textilmaterial auf Temperaturen zwischen etwa 70°C und etwa 300°C, vorzugsweise zwischen etwa 100°C und etwa 150°C, erhitzt.Method according to one of claims 1 to 8, characterized in that the textile material at temperatures between about 70 ° C and about 300 ° C, preferably heated between about 100 ° C and about 150 ° C. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man bei einem Druck zwischen etwa 73 bar und etwa 400 bar, vorzugsweise zwischen etwa 150 bar und etwa 250 bar, arbeitet.Method according to one of claims 1 to 9, characterized in that one works at a pressure between about 73 bar and about 400 bar, preferably between about 150 bar and about 250 bar. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man das Substrat zu Beginn in einem Flottenverhältnis zwischen etwa 1:2 bis etwa 1:100, vorzugsweise zwischen etwa 1:5 und etwa 1:75, färbt.Method according to one of claims 1 to 10, characterized in that the substrate is initially dyed in a liquor ratio between about 1: 2 to about 1: 100, preferably between about 1: 5 and about 1:75. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man nach der Färbung das verwendete überkritische CO₂ reinigt und erneut zum Färben verwendet.Method according to one of claims 1 to 10, characterized in that after the dyeing the supercritical CO₂ used is cleaned and used again for dyeing. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass man das überkritische CO₂ mittels eines Filters reinigt.A method according to claim 12, characterized in that the supercritical CO₂ is cleaned by means of a filter. Verfahren nach einem der Ansprüche 12 oder 13, dadurch gekennzeichnet, dass man das überkritische CO₂ durch eine Temperaturerhöhung und/oder Druckerniedrigung und/oder Volumenvergrösserung reinigt.Method according to one of claims 12 or 13, characterized in that the supercritical CO₂ is cleaned by increasing the temperature and / or lowering the pressure and / or increasing the volume. Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass man nach der Färbung den nicht verbrauchten Farbstoff erneut zum Färben verwendet.Method according to one of claims 1 to 14, characterized in that after dyeing the unused dye is used again for dyeing. Anwendung des Verfahrens gemäss einem der Ansprüche 1 bis 15 zum Färben von Textilmaterial aus Polyester.Application of the method according to one of claims 1 to 15 for dyeing textile material made of polyester. Das nach dem Verfahren gemäss einem der Ansprüche 1 bis 16 gefärbte Textilmaterial.The textile material dyed by the process according to one of claims 1 to 16.
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US6615620B2 (en) 2000-01-13 2003-09-09 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
CN103339316A (en) * 2011-02-02 2013-10-02 Ykk株式会社 Cleaning method and cleaning device
CN103339316B (en) * 2011-02-02 2015-11-25 Ykk株式会社 Cleaning method and cleaning device

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JPH05132880A (en) 1993-05-28
EP0514337B1 (en) 1995-11-22
US5250078A (en) 1993-10-05
DE59204395D1 (en) 1996-01-04

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