EP0474598B1 - Procédé de teinture de matériau textile hydrophobe avec des colorants de dispersion dans du CO2 surcritique - Google Patents

Procédé de teinture de matériau textile hydrophobe avec des colorants de dispersion dans du CO2 surcritique Download PDF

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Publication number
EP0474598B1
EP0474598B1 EP91810686A EP91810686A EP0474598B1 EP 0474598 B1 EP0474598 B1 EP 0474598B1 EP 91810686 A EP91810686 A EP 91810686A EP 91810686 A EP91810686 A EP 91810686A EP 0474598 B1 EP0474598 B1 EP 0474598B1
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Prior art keywords
process according
formula
hydrogen
dye
c4alkyl
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German (de)
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EP0474598A1 (fr
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Wolfgang Dr. Schlenker
Dieter Dr. Werthemann
Peter Dr. Liechti
Angelo Della Casa
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Novartis AG
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Ciba Geigy AG
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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
    • 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 in each case. 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. Therefore, relatively large amounts of colored waste water accumulate during dyeing, which have to be cleaned in a complex manner.
  • 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 process according to the invention provides that, instead of the aqueous liquors described above, color 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 has approximately the viscosity of the corresponding gas and a density that 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 end up in 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 dyeing the textile substrate run much faster in comparison to aqueous systems. This in turn leads to that 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 the causes of 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 the formation of corresponding stains.
  • 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.
  • 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 with 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 may 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 dihydrooxazine 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 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, 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 dyed. 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 by the process according to the invention 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 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 liquor 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 supercritical CO2 converts to 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. Afterwards, the heating is switched off with compressed air. Pressure and temperature decrease exponentially. After two hours, about 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 rub, 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:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)

Claims (17)

  1. Procédé de teinture de matériaux textiles hydrophobes par des colorants de dispersion, caractérisé en ce que l'on traite le matériau textile dans du CO₂ supercritique avec un colorant de formule
    Figure imgb0027
    Figure imgb0028
    Figure imgb0029
     dans lesquelles
    R représente un atome d'hydrogène ou R et R₄ représentent, ensemble avec l'atome d'azote et les deux atomes de carbone les reliant, un cycle à 5 ou 6 chaînons,
    R₁ représente un groupe cyano ou un résidu de formule
    Figure imgb0030
     où X est un résidu -NH, -N-(alkyle en C₁₋₄), O ou S,
    R₂ représente un atome d'hydrogène ou un groupe cyano,
    R₃ représente un atome d'hydrogène ou un groupe alkyle en C₁₋₄,
    R₄ et R₅ représentent chacun indépendamment un groupe alkyle en C₁₋₆ pouvant être substitué, ou R₄ et R₅ représentent, ensemble avec l'atome d'azote auquel ils sont liés, un cycle à 5 ou 6 chaînons,
    R₆ et R₇ représentent indépendamment chacun un groupe alkyle en C₁₋₁₂,
    R₈ représente un atome d'hydrogène, un groupe alkyle en C₁₋₄ ou un groupe alcényle en C₂₋₄,
    R₉ représente un groupe alkyle en C₁₋₆,
    R₁₀ représente un groupe alkyle en C₁₋₆ ou phényl-(alkyle en C₁₋₆),
    R₁₁ et R₁₂ représentent indépendamment chacun un groupe alkyle en C₁₋₄,
    Y un résidu de formule (11) ou de formule
    Figure imgb0031
     n vaut 0 ou 1,
    R₁₃ représente un groupe alcoxy en C₁₋₆, alcoxy en C₁₋₆-alcoxy en C₂₋₄, (alcoxy en C₁₋₄)-carbonyle-alcoxy en C₂₋₄, ou alcoxy en C₁₋₄-alcoxy(en C₁₋₄)-carbonyl -alcoxy en C₂₋₄ et
    R₁₄ représente un atome d'hydrogène, un groupe phénoxy ou phénylthio.
  2. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (1) dans laquelle R₁ représente un groupe cyano ou un résidu de formule (11) où X est un groupe -NH,
    R₂ représente un atome d'hydrogène ou un groupe cyano,
    R₃ représente un atome d'hydrogène ou un groupe méthyle ou éthyle,
    R₄ représente un groupe alkyle en C₁₋₄,
    R₅ représente un groupe alkyle en C₁₋₄ pouvant être substitué par un résidu cyano, phényle, phénoxy, phénylthio, phénylcarbonyloxy, phénylaminocarbonyloxy ou par un résidu de formule
    Figure imgb0032
     ou R₄ et R₅ forment, ensemble avec l'atome d'azote et les deux atomes de carbone les reliant, un cycle tétrahydropyridine comportant de 0 à 4 groupes méthyle.
  3. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (2), dans lequel
    R₃ représente un atome d'hydrogène, un groupe méthyle ou éthyle et R₆ et R₇ représentent indépendamment un groupe alkyle en C₄₋₈.
  4. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (3) dans laquelle R₈ représente un atome d'hydrogène ou un groupe allyle, R₉ représente un groupe alkyle en C₁₋₄ et R₁₀ représente un groupe alkyle en C₁₋₄ ou phényl-(alkyle en C₁₋₄).
  5. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (4), dans laquelle R₁₁ et R₁₂ représentent un groupe méthyle ou éthyle, R₂ représente un atome d'hydrogène ou un groupe cyano et Y un résidu de formule (11) ou de formule
    Figure imgb0033
     dont le noyau phényle peut être substitué par un groupe alkyle en C₁₋₄ ou par un atome de chlore.
  6. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (5) dans laquelle n vaut 1.
  7. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (6) dans laquelle R₁₃ représente un groupe alcoxy en C₁₋₄ ou alcoxy en C₁₋₄ -(alcoxy en C₂₋₄)-carbonyl-alcoxy en C₂₋₄.
  8. Procédé conforme à la revendication 1, caractérisé en ce que l'on utilise un colorant de formule (7) dans laquelle R₁₄ représente un atome d'hydrogène, un groupe phénylthio.
  9. Procédé conforme à la revendication 1 , caractérisé en ce que l'on utilise un colorant de formule (8), (9) ou (10).
  10. Procédé conforme à une des revendications 1 à 9, caractérisé en ce que l'on utilise un colorant exempt d'adjuvants, en particulier exempt d'agents d'ajustement et d'agents de dispersion.
  11. Procédé conforme à une des revendication 1 à 10, caractérisé en ce que l'on teint à des températures comprises entre environ 90 °C et environ 200 °C, de préférence entre environ 100 °C et environ 150 °C.
  12. Procédé conforme à une des revendications 1 à 11, caractérisé en ce que l'on teint à une pression comprise entre environ 73 bar et environ 400 bar, de préférence entre environ 150 bar et environ 250 bar.
  13. Procédé conforme à une des revendications 1 à 12, caractérisé en ce que le substrat est teint avec un rapport de bain compris entre environ 1/2 et environ 1/100, de préférence entre environ 1/5 et environ 1/75.
  14. Procédé conforme à une des revendications 1 à 13, caractérisé en ce que l'on épure le CO₂ supercritique utilisé apre's la teinture et que l'on l'utilise de nouveau pour une teinture ultérieure.
  15. Procédé conforme à la revendication 14, caractérisé en ce que l'on épure le CO₂ supercritique à l'aide d'un filtre.
  16. Procédé conforme à la revendication 14 ou 15, caractérisé en ce que l'on épure le CO₂ supercritique par abaissement de la température et/ou de la pression et/ou par augmentation du volume.
  17. Utilisation du procédé conforme à une des revendications 1 à 16 pour la teinture de matériaux textiles en polyester.
EP91810686A 1990-09-03 1991-08-27 Procédé de teinture de matériau textile hydrophobe avec des colorants de dispersion dans du CO2 surcritique Expired - Lifetime EP0474598B1 (fr)

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CH2838/90 1990-09-03
CH283890 1990-09-03

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EP0474598B1 true EP0474598B1 (fr) 1994-12-21

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514337B1 (fr) * 1991-05-17 1995-11-22 Ciba-Geigy Ag Procédé de teinture de matériaux textile avec des colorants dispersés dans du CO2 supercritique
EP0543779A1 (fr) * 1991-11-20 1993-05-26 Ciba-Geigy Ag Procédé d'azurage optique de matériau textile hydrophobe avec des azurants optiques dispersés dans du CO2 supercritique
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 (zh) * 2021-10-27 2021-12-24 天津工业大学 一种基于超临界二氧化碳的染整方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3906724C2 (de) * 1989-03-03 1998-03-12 Deutsches Textilforschzentrum Verfahren zum Färben von textilen Substraten

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DE59103971D1 (de) 1995-02-02
EP0474598A1 (fr) 1992-03-11

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