EP0474598A1 - Process for dyeing of hydrophobic textile material with disperse dyestuff in supercritical CO2 - Google Patents
Process for dyeing of hydrophobic textile material with disperse dyestuff in supercritical CO2 Download PDFInfo
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- EP0474598A1 EP0474598A1 EP91810686A EP91810686A EP0474598A1 EP 0474598 A1 EP0474598 A1 EP 0474598A1 EP 91810686 A EP91810686 A EP 91810686A EP 91810686 A EP91810686 A EP 91810686A EP 0474598 A1 EP0474598 A1 EP 0474598A1
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- alkyl
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- dye
- alkoxy
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Classifications
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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
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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
- D06P1/0004—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
- 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
Definitions
- the present invention relates to a method for dyeing hydrophobic textile material with disperse dyes.
- Hydrophobic textile materials are usually dyed from aqueous dyeing liquors. Complete bath exhaustion never occurs, i.e. the dyes do not draw quantitatively onto the substrate to be colored. This in turn means that the dye liquor remaining after the dyeing process still contains, depending on the respective dyes and substrates, more or less large amounts of dye. For this reason, relatively large amounts of colored waste water accumulate during dyeing, which have to be laboriously cleaned.
- the present invention has for its object to provide a method for dyeing textile material in which no or no significant amounts of colored waste water are obtained.
- the present invention thus relates to a process for dyeing hydrophobic textile material with disperse dyes, which is characterized in that the textile material in supercritical carbon dioxide with a dye of the formula or treated in what R is hydrogen or R and R4 together with the N atom and the two C atoms connecting them form a 5- or 6-membered ring, R1 cyan or a radical of the formula is where X is -NH, -N-C1-C4-alkyl, O or S, R2 is hydrogen or cyan, R3 is hydrogen or C1-C4 alkyl, R4 and R5 independently of one another each optionally substituted C1-C6-alkyl or R4 and R5 together with the nitrogen atom to which they are attached, a 5- or 6-membered ring, R6 and R7 are each independently C1-C12 alkyl, R8 is hydrogen, C1-C4-alkyl or C2-C4-alkenyl, R9 C1-C6 alkyl, R10 C1
- the method according to the invention provides that instead of the aqueous liquors described above, such liquors are used in which the water is replaced by supercritical carbon dioxide.
- 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 method according to the invention has a number of advantages. Due to the fact that the supercritical 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. This in turn leads to that too dyeing textile substrate 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 runs or length runs, for example, in the conventional method for tree coloring of flat structures.
- no disperse 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 disperse dyes known in conventional dyeing processes in aqueous systems and thus corresponding staining.
- 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.
- a preferred embodiment of the process according to the invention consists in using a dye of the formula (1) in which R1 is cyan or a radical of the formula (11) in which X is -NH, R2 is hydrogen or cyan, R3 is hydrogen, methyl or ethyl, R4 C1-C4 alkyl, R5 C1-C4 alkyl, which by cyan, phenyl, phenoxy, phenylthio, phenylcarbonyloxy, phenylaminocarbonyloxy or a radical of the formula may be substituted, means or wherein R and R4 together with the N atom and the two C atoms connecting them forms a tetrahydropyridine ring with 0 to 4 methyl groups.
- a dye of the formula (2) in which R3 is hydrogen, methyl or ethyl and R6 and R7 each represent C4-C8-alkyl, or a dye of the formula (3), in which R8 is hydrogen or allyl, R9 C1-C4 alkyl and R10 C1-C4-alkyl or phenyl-C1-C4-alkyl, or used a dye of formula (4), wherein R11 and R12 each methyl or ethyl, R2 is hydrogen or cyan and Y is a residue of the formula which can be substituted in the phenyl ring by C1-C4-alkyl or chlorine, or a dye of the formula (5), in which n is 1, or a dye of the formula (6) in which R13 is C1-C4-alkoxy or C1-C4 -Alkoxy-C2-C4-alkoxycarbonyl-C2-C4-alkoxy means
- alkyl radicals are generally understood to mean straight-chain, branched or cyclic alkyl groups. It is e.g. around methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1- Methylpentyl, neopentyl, 1-, 2- or 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, dodecyl, cyclopentyl, cyclohexyl, methylcyclohexyl and the associated isomers.
- the alkyl radicals preferably contain 1 to 6 carbon atoms,
- alkyl radicals can be substituted, e.g. by halogen, hydroxy, alkoxy, cyan or phenyl.
- substituted alkyl radicals are hydroxyethyl, methoxymethyl, ethoxyethyl, cyanoethyl, propoxypropyl, benzyl, chloroethyl or cyanoethyl.
- Suitable alkoxy radicals are preferably soclhe having 1 to 4 carbon atoms, for example methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy or tert-butoxy.
- phenyl radicals can also be substituted, e.g. by chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyan.
- R and R4 together with the nitrogen atom and the two carbon atoms connecting them can form a 5- or 6-membered ring which has another heteroatom, e.g. May contain oxygen or sulfur.
- the ring can also be substituted, e.g. by hydroxy, alkoxy, alkyl, halogen, CN or phenyl, or another fused benzene ring.
- Preferred rings, which are formed by R, R4 and the connecting carbon atoms and the nitrogen atom, are di-hydrooxazine and di- or tetrahydropyridine rings which carry 0 to 4 methyl groups.
- R4 and R5 can also form a piperidine, morpholine or piperazine residue together with the N atom connecting them.
- the piperazine radical can be substituted on the N atom not connected to the phenyl ring by C1-C4-alkyl or hydroxy-C1-C4-alkyl or amino-C1-C4-alkyl.
- the preferred substituent is hydroxyethyl.
- the dyes listed in the examples are very particularly preferred.
- the dyes of the formulas (1) to (10) are known or can be prepared in a manner known per se.
- 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 mainly 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, for example from ⁇ , ⁇ -dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinyl chloride, polypropylene or polyamide, for example polyamide 6.6, polyamide 6.10, polyamide 6, polyamide 11 or poly (1,4-phenylene terephthalamide).
- the dyeing temperature used in the process according to the invention depends essentially on the substrate to be colored. Usually it is between about 90 and 200 ° 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 pressure is preferably between about 73 and 400 bar, in particular between 150 and 250 bar.
- 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. 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 on corresponding packages are to be dyed using the process according to the invention, this is preferably done for relatively short ones Fleet ratios, ie Fleet ratios between 1: 2 to 1: 5.
- Such short liquor ratios generally cause difficulties in the conventional dyeing process in the aqueous system, since due to the high dye concentration there is often the risk that the finely dispersed systems agglomerate. However, this does not occur in the method according to the invention.
- the supercritical CO2 is converted into the corresponding gas, which is then collected and used again after transferring to the supercritical state for coloring further substrates.
- the dyes separate out as liquid or solid dyes, which accordingly can be collected and used for further staining.
- the internal temperature quickly drops to approx. -10 ° C.
- the contents of the autoclave are heated to 130 ° C at about 3 ° C / min.
- the internal pressure rises to approx. 200 bar. These conditions are kept constant for 30 minutes. Thereafter, the heating is switched off with compressed air when the heating is switched off. Pressure and temperature decrease exponentially. After two hours, approx. 70 bar are reached, after which the pressure is released by opening a valve.
- Yellow-dyed polyester fabric of a quality similar to that obtained by dyeing by conventional methods from an aqueous liquor is obtained.
- the rubbing, light and wash fastness of the coloring are equally good.
- Example 1 The method described in Example 1 can also be used to produce dyeings on polyester fabric using the following dyes:
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Färben von hydrophobem Textilmaterial mit Dispersionsfarbstoffen.The present invention relates to a method for dyeing hydrophobic textile material with disperse dyes.
Hydrophobe Textilmaterialien werden üblicherweise aus wässrigen Färbeflotten gefärbt. Dabei tritt niemals eine vollständige Baderschöpfung auf, d.h. die Farbstoffe ziehen nicht quantitativ auf das jeweils zu färbende Substrat. Dies wiederum führt dazu, dass die nach dem Färbevorgang verbleibende Farbstoffflotte noch, abhängig von den jeweiligen Farbstoffen und Substraten, mehr oder weniger grosse Mengen Farbstoff enthält. Daher fallen beim Färben relativ grosse Mengen an farbigen Abwässern an, die aufwendig gereinigt werden müssen.Hydrophobic textile materials are usually dyed from aqueous dyeing liquors. Complete bath exhaustion never occurs, i.e. the dyes do not draw quantitatively onto the substrate to be colored. This in turn means that the dye liquor remaining after the dyeing process still contains, depending on the respective dyes and substrates, more or less large amounts of dye. For this reason, relatively large amounts of colored waste water accumulate during dyeing, which have to be laboriously cleaned.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Färben von Textilmaterial zur Verfügung zu stellen, bei dem keine oder keine nennenswerten Mengen an farbigen Abwässern anfallen.The present invention has for its object to provide a method for dyeing textile material in which no or no significant amounts of colored waste water are obtained.
Diese Aufgabe wird durch das erfindungsgemässe Verfahren gelöst.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, das dadurch gekennzeichnet ist, dass man das Textilmaterial in überkritischem Kohlendioxid mit einem Farbstoff der Formel
oder
behandelt, worin
R Wasserstoff oder R und R₄ zusammen mit dem N-Atom und den beiden sie verbindenden C-Atomen einen 5- oder 6-gliedrigen Ring,
R₁ Cyan oder ein Rest der Formel
ist, wobei X -NH, -N-C₁-C₄-Alkyl, O oder S bedeutet,
R₂ Wasserstoff oder Cyan,
R₃ Wasserstoff oder C₁-C₄-Alkyl,
R₄ und R₅ unabhängig voneinander je gegebenenfalls substituiertes C₁-C₆-Alkyl oder R₄ und R₅ zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5-oder 6-gliedrigen Ring,
R₆ und R₇ unabhängig voneinander je C₁-C₁₂-Alkyl,
R₈ Wasserstoff, C₁-C₄-Alkyl oder C₂-C₄-Alkenyl,
R₉ C₁-C₆-Alkyl,
R₁₀ C₁-C₆-Alkyl oder Phenyl-C₁-C₆-alkyl,
R₁₁ und R₁₂ unabhängig voneinander je C₁-C₄-Alkyl,
Y einen Rest der Formel (11) oder der Formel
R₁₃ C₁-C₆-Alkoxy, C₁-C₆-Alkoxy-C₂-C₄-alkoxy, C₁-C₄-Alkoxycarbonyl-C₂-C₄-alkoxy oder C₁-C₄-Alkoxy-C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy und
R₁₄ Wasserstoff, Phenoxy oder Phenylthio bedeuten.The present invention thus relates to a process for dyeing hydrophobic textile material with disperse dyes, which is characterized in that the textile material in supercritical carbon dioxide with a dye of the formula
or
treated in what
R is hydrogen or R and R₄ together with the N atom and the two C atoms connecting them form a 5- or 6-membered ring,
R₁ cyan or a radical of the formula
is where X is -NH, -N-C₁-C₄-alkyl, O or S,
R₂ is hydrogen or cyan,
R₃ is hydrogen or C₁-C₄ alkyl,
R₄ and R₅ independently of one another each optionally substituted C₁-C₆-alkyl or R₄ and R₅ together with the nitrogen atom to which they are attached, a 5- or 6-membered ring,
R₆ and R₇ are each independently C₁-C₁₂ alkyl,
R₈ is hydrogen, C₁-C₄-alkyl or C₂-C₄-alkenyl,
R₉ C₁-C₆ alkyl,
R₁₀ C₁-C₆-alkyl or phenyl-C₁-C₆-alkyl,
R₁₁ and R₁₂ independently of one another each C₁-C₄-alkyl,
Y is a radical of the formula (11) or of the formula
R₁₃ C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₂-C₄-alkoxy, C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy or C₁-C₄-alkoxy-C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy and
R₁₄ represent hydrogen, phenoxy or phenylthio.
Das erfindungsgemässe Verfahren sieht vor, anstelle der vorstehend beschriebenen wässrigen Flotten solche Farbflotten zu verwenden, bei denen das Wasser durch überkritisches Kohlendioxid ersetzt ist. 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 method according to the invention provides that instead of the aqueous liquors described above, such liquors are used in which the water is replaced by supercritical carbon dioxide. 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 Verfahren weist eine Reihe von Vorteilen auf. Bedingt dadurch, dass das hierbei eingesetzte überkritische 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. 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 beziehungsweise Längenabläufe anzusehen sind. Ebenfalls können bei dem erfindungsgemässen Verfahren keine Dispersionsfarbstoffe 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 Aufhellungn von Dispersionsfarbstoffen und damit entsprechende Fleckenbildungen vermieden werden.The method according to the invention has a number of advantages. Due to the fact that the supercritical 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. This in turn leads to that too dyeing textile substrate 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 runs or length runs, for example, in the conventional method for tree coloring of flat structures. Likewise, no disperse 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 disperse dyes known in conventional dyeing processes in aqueous systems and thus corresponding staining.
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.
Eine bevorzugte Ausführungsform des erfindungsgemässen Verfahren besteht darin, dass man einen Farbstoff der Formel (1) verwendet, worin
R₁ Cyan oder ein Rest der Formel (11) ist, worin X -NH bedeutet,
R₂ Wasserstoff oder Cyan,
R₃ Wasserstoff, Methyl oder Ethyl,
R₄ C₁-C₄-Alkyl,
R₅ C₁-C₄-Alkyl, welches durch Cyan, Phenyl, Phenoxy, Phenylthio, Phenylcarbonyloxy, Phenylaminocarbonyloxy oder einen Rest der Formel
substituiert sein kann, bedeutet oder worin R und R₄ zusammen mit dem N-Atom und den beiden sie verbindenden C-Atomen einen Tetrahydropyridinring mit 0 bis 4 Methylgruppen bildet.A preferred embodiment of the process according to the invention consists in using a dye of the formula (1) in which
R₁ is cyan or a radical of the formula (11) in which X is -NH,
R₂ is hydrogen or cyan,
R₃ is hydrogen, methyl or ethyl,
R₄ C₁-C₄ alkyl,
R₅ C₁-C₄ alkyl, which by cyan, phenyl, phenoxy, phenylthio, phenylcarbonyloxy, phenylaminocarbonyloxy or a radical of the formula
may be substituted, means or wherein R and R₄ together with the N atom and the two C atoms connecting them forms a tetrahydropyridine ring with 0 to 4 methyl groups.
Weitere bevorzugte Ausführungsformen des erfindungsgemässen Verfahrens bestehen darin, dass man einen Farbstoff der Formel (2) verwendet, worin
R₃ Wasserstoff, Methyl oder Ethyl und
R₆ und R₇ je C₄-C₈-Alkyl bedeuten, oder einen Farbstoff der Formel (3), worin
R₈ Wasserstoff oder Allyl,
R₉ C₁-C₄-Alkyl und
R₁₀ C₁-C₄-Alkyl oder Phenyl-C₁-C₄-alkyl bedeutet, oder einen Farbstoff der Formel (4) verwendet, worin
R₁₁ und R₁₂ je Methyl oder Ethyl,
R₂ Wasserstoff oder Cyan und
Y einen Rest der Formel
der im Phenylring durch C₁-C₄-Alkyl oder Chlor substituiert sein kann, bedeutet, oder einen Farbstoff der Formel (5), worin n 1 bedeutet, oder einen Farbstoff der Formel (6) worin R₁₃ C₁-C₄-Alkoxy oder C₁-C₄-Alkoxy-C₂-C₄-alkoxycarbonyl-C₂-C₄-alkoxy bedeutet, oder einen Farbstoff der Formel (7), worin R₁₄ Wasserstoff oder Phenylthio bedeutet.Further preferred embodiments of the process according to the invention consist in using a dye of the formula (2) in which
R₃ is hydrogen, methyl or ethyl and
R₆ and R₇ each represent C₄-C₈-alkyl, or a dye of the formula (3), in which
R₈ is hydrogen or allyl,
R₉ C₁-C₄ alkyl and
R₁₀ C₁-C₄-alkyl or phenyl-C₁-C₄-alkyl, or used a dye of formula (4), wherein
R₁₁ and R₁₂ each methyl or ethyl,
R₂ is hydrogen or cyan and
Y is a residue of the formula
which can be substituted in the phenyl ring by C₁-C₄-alkyl or chlorine, or a dye of the formula (5), in which n is 1, or a dye of the formula (6) in which R₁₃ is C₁-C₄-alkoxy or C₁-C₄ -Alkoxy-C₂-C₄-alkoxycarbonyl-C₂-C₄-alkoxy means, or a dye of formula (7), wherein R₁₄ is hydrogen or phenylthio.
Unter Alkylresten sind erfindungsgemäss generell geradkettige, verzweigte oder cyclische Alkylgruppen zu verstehen. Es handelt sich z.B. um Methyl, Ethyl, Propyl, i-Propyl, Butyl, i-Butyl, tert.-Butyl, Amyl, tert.-Amyl(1,1-Dimethylpropyl), 1,1,3,3-Tetramethylbutyl, Hexyl, 1-Methylpentyl, Neopentyl, 1-, 2- oder 3- Methylhexyl, Heptyl, n-Octyl, tert.-Octyl, 2-Ethylhexyl, n-Nonyl, Isononyl, Decyl, Dodecyl, Cyclopentyl, Cyclohexyl, Methylcyclohexyl sowie die dazugehörenden Isomeren. Die Alkylreste enthalten vorzugsweise 1 bis 6 C-Atome, vor allem 1 bis 4 C-Atome.According to the invention, alkyl radicals are generally understood to mean straight-chain, branched or cyclic alkyl groups. It is e.g. around methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1- Methylpentyl, neopentyl, 1-, 2- or 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, dodecyl, cyclopentyl, cyclohexyl, methylcyclohexyl and the associated isomers. The alkyl radicals preferably contain 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
Diese Alkylreste können substituiert sein, z.B. durch Halogen, Hydroxy, Alkoxy, Cyan oder Phenyl. Beispiele für solche substituierten Alkylreste sind Hydroxyethyl, Methoxymethyl, Ethoxyethyl, Cyanethyl, Propoxypropyl, Benzyl, Chlorethyl oder Cyanoethyl.These alkyl radicals can be substituted, e.g. by halogen, hydroxy, alkoxy, cyan or phenyl. Examples of such substituted alkyl radicals are hydroxyethyl, methoxymethyl, ethoxyethyl, cyanoethyl, propoxypropyl, benzyl, chloroethyl or cyanoethyl.
Geeignete Alkoxyreste sind vorzugsweise soclhe mit 1 bis 4 C-Atomen z.B. Methoxy, Ethoxy, Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy oder tert.-Butoxy.Suitable alkoxy radicals are preferably soclhe having 1 to 4 carbon atoms, for example methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy or tert-butoxy.
Auch die Phenylreste können substituiert sein, z.B. durch Chlor, Brom, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Nitro oder Cyan.The phenyl radicals can also be substituted, e.g. by chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, nitro or cyan.
R und R₄ können zusammen mit dem Stickstoffatom und den beiden sie verbindenden Kohlenstoffatomen einen 5- oder 6-gliedrigen Ring bilden, welcher ein weiteres Heteroatom, z.B. Sauerstoff oder Schwefel, enthalten kann. Ausserdem kann der Ring substituiert sein, z.B. durch Hydroxy, Alkoxy, Alkyl, Halogen, CN oder Phenyl, oder einen weiteren ankondensierten Benzolring tragen. Bevorzugte Ringe, welche durch R, R₄ und die verbindenden Kohlenstoffatome und das Stickstoffatom gebildet werden, sind Di-hydrooxazin- und Di- oder Tetrahydropyridinringe, welche 0 bis 4 Methylgruppen tragen.R and R₄ together with the nitrogen atom and the two carbon atoms connecting them can form a 5- or 6-membered ring which has another heteroatom, e.g. May contain oxygen or sulfur. The ring can also be substituted, e.g. by hydroxy, alkoxy, alkyl, halogen, CN or phenyl, or another fused benzene ring. Preferred rings, which are formed by R, R₄ and the connecting carbon atoms and the nitrogen atom, are di-hydrooxazine and di- or tetrahydropyridine rings which carry 0 to 4 methyl groups.
R₄ und R₅ können auch zusammen mit dem sie verbindenden N-Atom einen Piperidin-, Morpholin- oder Piperazinrest bilden. Der Piperazinrest kann am nicht mit dem Phenylring verbundenen N-Atom durch C₁-C₄-Alkyl oder Hydroxy-C₁-C₄-alkyl oder Amino-C₁-C₄-alkyl substituiert sein. Der bevorzugte Substituent ist Hydroxyethyl.R₄ and R₅ can also form a piperidine, morpholine or piperazine residue together with the N atom connecting them. The piperazine radical can be substituted on the N atom not connected to the phenyl ring by C₁-C₄-alkyl or hydroxy-C₁-C₄-alkyl or amino-C₁-C₄-alkyl. The preferred substituent is hydroxyethyl.
Wegen ihrer guten färberischen Eigenschaften im erfindungsgemässen Verfahren sind die in den Beispielen aufgeführten Farbstoffe ganz besonders bevorzugt.Because of their good coloring properties in the process according to the invention, the dyes listed in the examples are very particularly preferred.
Die Farbstoffe der Formeln (1) bis (10) sind bekannt oder können auf an sich bekannte Art hergestellt werden.The dyes of the formulas (1) to (10) are known or can be prepared in a manner known per se.
Das erfindungsgemässe Verfahren eignet sich zum Färben von halbsynthetischen und insbesondere synthetischen hydrophoben Fasermaterialien, vor allem Textilmaterialien. Textilmaterialien aus Mischgeweben, die derartige halbsynthetische beziehungsweise synthetische hydrophobe Textilmaterialien enthalten, können ebenfalls nach dem erfindungsgemässen Verfahren gefärbt werden.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.
Als halbsynthetische 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, Polyamid 6.10, Polyamid 6, Polyamid 11 oder Poly(1,4-phenylentere-phthalamid).Synthetic hydrophobic textile materials consist mainly 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, for example from α, α-dimethyl-4,4'-dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinyl chloride, polypropylene or polyamide, for example polyamide 6.6, polyamide 6.10, polyamide 6, polyamide 11 or poly (1,4-phenylene terephthalamide).
Die bei dem erfindungsgemässen Verfahren angewendete Färbetemperatur richtet sich im wesentlichen nach dem zu färbenden Substrat. Normalerweise liegt sie etwa zwischen 90 und 200°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 90 and 200 ° C, preferably between about 100 and 150 ° C.
Der anzuwendende Druck muss mindestens so gross sein, dass das CO₂ in überkritischem Zustand vorliegt. Vorzugsweise liegt der Druck zwischen etwa 73 und 400 bar, insbesondere zwischen 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 pressure is preferably between about 73 and 400 bar, in particular between 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. Ueblicherweise 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 Flottenverhältnisse 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.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. 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 on corresponding packages are to be dyed using the process according to the invention, this is preferably done for relatively short ones Fleet ratios, ie Fleet ratios between 1: 2 to 1: 5. Such short liquor ratios generally cause difficulties in the conventional dyeing process in the aqueous system, since due to the high dye concentration there is often the risk that the finely dispersed systems agglomerate. However, this does not occur in the method according to the invention.
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- beziehungsweise 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 dye residue remaining in the supercritical CO₂ via appropriate filters. The known silica gel, diatomaceous earth, carbon, zeolite and aluminum oxide filters are particularly suitable for this.
Darüberhinaus besteht die Möglichkeit, die nach der Färbung in dem überkritischen CO₂ verbleibenden Farbstoffe durch eine Temperatur- und/oder Druckerniedrigung und/oder eine Volumenvergrösserung zu entfernen. Hierbei wandelt sich das überkritische CO₂ in das entsprechende Gas um, das dann aufgefangen wird und erneut nach Ueberführung 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 after the dyeing by reducing the temperature and / or pressure and / or increasing the volume. Here, the supercritical CO₂ is converted into the corresponding gas, which is then collected and used again after transferring to the supercritical state for coloring further substrates. Here, the dyes separate out as liquid or solid dyes, which accordingly can be collected and used for further staining.
Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie darauf zu beschränken.The following examples illustrate the invention without restricting it.
24,5 µmol des Farbstoffes der Formel
werden auf dem Boden eines Autoklaven mit einem Innenvolumen von 500 ml vorgelegt. 330 g CO₂ werden in fester Form (Trockenreis) eingewogen. Ein Streifen Polyestergewebe von 5 g wird um die im Deckel des Autoklaven eingebauten Sensoren für Druck und Temperatur gewickelt und mit einem Faden zusammengeheftet.24.5 µmol of the dye of the formula
are placed on the bottom of an autoclave with an internal volume of 500 ml. 330 g of CO₂ are weighed in solid form (dry rice). A 5 g strip of polyester fabric is wrapped around the pressure and temperature sensors built into the lid of the autoclave and sewn together with a thread.
Nach dem Verschliessen des Autoklaven geht die Innentemperatur sehr schnell auf ca. -10°C zurück. Nachdem die Innentemperatur 0°C erreicht hat, wird der Inhalt des Autoklaven mit etwa 3°C/min auf 130°C aufgeheizt. Der Innendruck steigt dabei auf ca. 200 bar an. Diese Bedingungen werden 30 Minuten lang konstant gehalten. Danach wird bei ausgeschalteter Heizung mit Druckluft gekühlt. Druck und Temperatur nehmen dabei exponentiell ab. Nach zwei Stunden werden ca. 70 bar erreicht, danach wird durch Oeffnen eines Ventils entspannt.After the autoclave has been closed, the internal temperature quickly drops to approx. -10 ° C. After the internal temperature has reached 0 ° C, the contents of the autoclave are heated to 130 ° C at about 3 ° C / min. The internal pressure rises to approx. 200 bar. These conditions are kept constant for 30 minutes. Thereafter, the heating is switched off with compressed air when the heating is switched off. Pressure and temperature decrease exponentially. After two hours, approx. 70 bar are reached, after which the pressure is released by opening a valve.
Man erhält gelb gefärbtes Polyestergewebe in ähnlicher Qualität wie beim Färben nach üblichen Methoden aus wässriger Flotte. Insbesondere die Reib-, Licht- und Waschechtheit der Färbung sind gleich gut.Yellow-dyed polyester fabric of a quality similar to that obtained by dyeing by conventional methods from an aqueous liquor is obtained. In particular, the rubbing, light and wash fastness of the coloring are equally good.
Nach der im Beispiel 1 beschriebenen Methode lassen sich Färbungen auf Polyestergewebe auch mit den folgenden Farbstoffen herstellen:
Claims (18)
R Wasserstoff oder R und R₄ zusammen mit dem N-Atom und den beiden sie verbindenden C-Atomen einen 5- oder 6-gliedrigen Ring,
R₁ Cyan oder ein Rest der Formel
R₂ Wasserstoff oder Cyan,
R₃ Wasserstoff oder C₁-C₄-Alkyl,
R₄ und R₅ unabhängig voneinander je gegebenenfalls substituiertes C₁-C₆-Alkyl oder R₄ und R₅ zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5-oder 6-gliedrigen Ring,
R₆ und R₇ unabhängig voneinander je C₁-C₁₂-Alkyl,
R₈ Wasserstoff, C₁-C₄-Alkyl oder C₂-C₄-Alkenyl,
R₉ C₁-C₆-Alkyl,
R₁₀ C₁-C₆-Alkyl oder Phenyl-C₁-C₆-alkyl,
R₁₁ und R₁₂ unabhängig voneinander je C₁-C₄-Alkyl,
Y einen Rest der Formel (11) oder der Formel
R₁₃ C₁-C₆-Alkoxy, C₁-C₆-Alkoxy-C₂-C₄-alkoxy, C₁-C₄-Alkoxycarbonyl-C₂-C₄-alkoxy oder C₁-C₄-Alkoxy-C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy und
R₁₄ Wasserstoff, Phenoxy oder Phenylthio bedeuten.Process for dyeing hydrophobic textile material with disperse dyes, characterized in that the textile material in supercritical carbon dioxide with a dye of the formula
R is hydrogen or R and R₄ together with the N atom and the two C atoms connecting them form a 5- or 6-membered ring,
R₁ cyan or a radical of the formula
R₂ is hydrogen or cyan,
R₃ is hydrogen or C₁-C₄ alkyl,
R₄ and R₅ independently of one another each optionally substituted C₁-C₆-alkyl or R₄ and R₅ together with the nitrogen atom to which they are attached, a 5- or 6-membered ring,
R₆ and R₇ are each independently C₁-C₁₂ alkyl,
R₈ is hydrogen, C₁-C₄-alkyl or C₂-C₄-alkenyl,
R₉ C₁-C₆ alkyl,
R₁₀ C₁-C₆-alkyl or phenyl-C₁-C₆-alkyl,
R₁₁ and R₁₂ independently of one another each C₁-C₄-alkyl,
Y is a radical of the formula (11) or of the formula
R₁₃ C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₂-C₄-alkoxy, C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy or C₁-C₄-alkoxy-C₁-C₄-alkoxycarbonyl-C₂-C₄-alkoxy and
R₁₄ represent hydrogen, phenoxy or phenylthio.
R₁ Cyan oder ein Rest der Formel (11) ist, worin X -NH bedeutet,
R₂ Wasserstoff oder Cyan,
R₃ Wasserstoff, Methyl oder Ethyl,
R₄ C₁-C₄-Alkyl,
R₅ C₁-C₄-Alkyl, welches durch Cyan, Phenyl, Phenoxy, Phenylthio, Phenylcarbonyloxy, Phenylaminocarbonyloxy oder einen Rest der Formel
R₁ is cyan or a radical of the formula (11) in which X is -NH,
R₂ is hydrogen or cyan,
R₃ is hydrogen, methyl or ethyl,
R₄ C₁-C₄ alkyl,
R₅ C₁-C₄ alkyl, which by cyan, phenyl, phenoxy, phenylthio, phenylcarbonyloxy, phenylaminocarbonyloxy or a radical of the formula
R₃ Wasserstoff, Methyl oder Ethyl und
R₆ und R₇ je C₄-C₈-Alkyl bedeuten.A method according to claim 1, characterized in that one uses a dye of formula (2), wherein
R₃ is hydrogen, methyl or ethyl and
R₆ and R₇ each represent C₄-C₈-alkyl.
R₈ Wasserstoff oder Allyl,
R₉ C₁-C₄-Alkyl und
R₁₀ C₁-C₄-Alkyl oder Phenyl-C₁-C₄-alkyl bedeutet.A method according to claim 1, characterized in that one uses a dye of formula (3), wherein
R₈ is hydrogen or allyl,
R₉ C₁-C₄ alkyl and
R₁₀ C₁-C₄-alkyl or phenyl-C₁-C₄-alkyl means.
R₁₁ und R₁₂je Methyl oder Ethyl,
R₂ Wasserstoff oder Cyan und
Y einen Rest der Formel
R₁₁ and R₁₂ each methyl or ethyl,
R₂ is hydrogen or cyan and
Y is a residue of the formula
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH283890 | 1990-09-03 | ||
| CH2838/90 | 1990-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0474598A1 true EP0474598A1 (en) | 1992-03-11 |
| EP0474598B1 EP0474598B1 (en) | 1994-12-21 |
Family
ID=4242736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91810686A Expired - Lifetime EP0474598B1 (en) | 1990-09-03 | 1991-08-27 | Process for dyeing of hydrophobic textile material with disperse dyestuff in supercritical CO2 |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0474598B1 (en) |
| AT (1) | ATE116018T1 (en) |
| DE (1) | DE59103971D1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250078A (en) * | 1991-05-17 | 1993-10-05 | Ciba-Geigy Corporation | Process for dyeing hydrophobic textile material with disperse dyes from supercritical CO2 : reducing the pressure in stages |
| US5269815A (en) * | 1991-11-20 | 1993-12-14 | Ciba-Geigy Corporation | Process for the fluorescent whitening of hydrophobic textile material with disperse fluorescent whitening agents from super-critical carbon dioxide |
| 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 |
| CN113832752A (en) * | 2021-10-27 | 2021-12-24 | 天津工业大学 | Dyeing and finishing method based on supercritical carbon dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3906724A1 (en) * | 1989-03-03 | 1990-09-13 | Deutsches Textilforschzentrum | Dyeing process |
-
1991
- 1991-08-27 EP EP91810686A patent/EP0474598B1/en not_active Expired - Lifetime
- 1991-08-27 AT AT91810686T patent/ATE116018T1/en not_active IP Right Cessation
- 1991-08-27 DE DE59103971T patent/DE59103971D1/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3906724A1 (en) * | 1989-03-03 | 1990-09-13 | Deutsches Textilforschzentrum | Dyeing process |
Non-Patent Citations (1)
| Title |
|---|
| JOURNAL OF ORGANIC CHEMISTRY. Bd. 49, Nr. 26, 1984, EASTON US Seiten 5097 - 5101; JOHN A. HYATT: 'Liquid and supercritical carbon dioxide as organic solvents' * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250078A (en) * | 1991-05-17 | 1993-10-05 | Ciba-Geigy Corporation | Process for dyeing hydrophobic textile material with disperse dyes from supercritical CO2 : reducing the pressure in stages |
| US5269815A (en) * | 1991-11-20 | 1993-12-14 | Ciba-Geigy Corporation | Process for the fluorescent whitening of hydrophobic textile material with disperse fluorescent whitening agents from super-critical carbon dioxide |
| 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 |
| 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 |
| CN113832752A (en) * | 2021-10-27 | 2021-12-24 | 天津工业大学 | Dyeing and finishing method based on supercritical carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59103971D1 (en) | 1995-02-02 |
| EP0474598B1 (en) | 1994-12-21 |
| ATE116018T1 (en) | 1995-01-15 |
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