EP0141078B1 - Process for dyeing cellulosic fibres - Google Patents

Process for dyeing cellulosic fibres Download PDF

Info

Publication number
EP0141078B1
EP0141078B1 EP84109394A EP84109394A EP0141078B1 EP 0141078 B1 EP0141078 B1 EP 0141078B1 EP 84109394 A EP84109394 A EP 84109394A EP 84109394 A EP84109394 A EP 84109394A EP 0141078 B1 EP0141078 B1 EP 0141078B1
Authority
EP
European Patent Office
Prior art keywords
radical
alkyl
levelling agent
dyeing
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84109394A
Other languages
German (de)
French (fr)
Other versions
EP0141078A2 (en
EP0141078A3 (en
Inventor
Fredgar Dr. Hoffmann
Klaus Dr. Walz
Marga Haene
Gunther Dr. Hoffarth
Hans Dr. Schulze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0141078A2 publication Critical patent/EP0141078A2/en
Publication of EP0141078A3 publication Critical patent/EP0141078A3/en
Application granted granted Critical
Publication of EP0141078B1 publication Critical patent/EP0141078B1/en
Expired legal-status Critical Current

Links

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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/62—Natural or regenerated cellulose using direct dyes

Definitions

  • the invention relates to a process for the discontinuous dyeing of cellulose fibers in the presence of a leveling agent of the formula
  • a hydrophobic hydrocarbon radical is preferably understood to mean an optionally unsaturated aliphatic radical with more than 8 carbon atoms or a cycloaliphatic or aromatic radical with more than 10 carbon atoms.
  • Cycloalkyl stands in particular for cyclopentyl, cyclohexyl, tetra- and decahydronaphthyl and their derivatives substituted by C 1 -C 12 -alkyl or the abietyl radical.
  • Suitable aryl radicals are, for example, the phenyl and naphthyl radicals and their derivatives substituted by C 1 -C 12 alkyl, cyclohexyl or phenyl-C 1 -C 3 alkyl.
  • Aralkyl preferably represents benzyl or phenylethyl substituted by C 1 -C 12 alkyl.
  • R may be mentioned as examples of the radicals R in formula (I): the octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eikosyl, behenyl, Undecenyl, dodecenyl, heptadecenyl, octadecenyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, cyclohexylphenyl, p-tert.-butylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, phenylethylphenyl or phenylethylphenyl or phenylethylphenyl or.
  • Suitable anions X (-) are customary inorganic or organic anions, for example chloride, bromide, iodide, methosulfate, ethosulfate, sulfate, phosphate, phosphite, methanesulfonate, acetate or toluenesulfonate.
  • the compounds (I) are prepared by known processes.
  • cellulose can in particular be mixed with direct dyes, e.g. are described in "Color Index” 3rd edition (1971), Vol. 2, pp. 2007-2477, and with reactive dyes which, for. B. are described in "The Chemistry of Synthetic Dyes” (K. Venkataraman), Vol. VI (1972).
  • leveling agents mentioned is particularly advantageous when dyeing with direct dyes and especially when salt is added before the dye is added ("all-in" process).
  • Salt is to be understood here as the electrolyte, the addition of which is customary in order to achieve a high dye yield, preferably sodium sulfate or sodium chloride.
  • Direct dyes absorb very quickly with exhaust dyeing processes, even at low temperatures. This creates irregularities that must be compensated for in the course of dyeing. Salt accelerates the uptake, but is necessary to achieve the desired yield. In order to avoid excessive initial irregularities, the salt is therefore generally added only after the end temperature has been reached, usually in portions. This is a complex way of working.
  • Salt can only do so under very favorable conditions (well migrating dyes, high liquor circulation rate or goods circulation speed). Beginning to be added ("all-in" method). With this simpler procedure, the unevenness that initially arises must be compensated for by migration, which requires longer dyeing times or more leveling aids (and therefore a lower dye yield) than in the case of batch additions.
  • the leveling agents slow down the absorption of the dyes in the initial phase of dyeing at a low temperature, especially below 50 ° C. This prevents inadmissible irregularities.
  • the effect of the auxiliaries wears off, and the absorption of the dyes can be controlled via the temperature control.
  • the auxiliaries to be used according to the invention hardly retain any dye in most cases. If in special cases, e.g. B. with a large amount of auxiliary or dyes with strong interaction with the auxiliary required, the restrained effect of the auxiliary can be further reduced by dyeing at alkaline pH (above pH 8) compared to weakly acidic or neutral staining.
  • the order of the additions is either (a) salt, leveling agent, dyes or (b) salt, leveling agent + dyes or (c) salt + leveling agent, dyes.
  • the amount of leveling agent is generally between 0.1 and 2%, based on the weight of the textile to be dyed.
  • the permissible initial rate of bath depletion depends on the demands on the level, the goods of the dyeing system, the color depth and nuance and the dyes (pull-up behavior, combinability, migrability). It is generally between 20 and 60% bath exhaustion in the first 10 minutes; preferably between 20 and 40% / 10min.
  • the leveling agents (I) are furthermore preferably suitable for dyeing with reactive dyes; especially if leveling agents, salt or salt and alkali are added before the dyes.
  • salt and alkali are usually added after the reactive dyes, in portions, in order to avoid the dyes being drawn in or fixed too quickly and thus resulting in irregularities.
  • particularly favorable dyeing conditions good leveling dyes, high liquor flow or running speed of the goods, temperature / pH control
  • salt or salt and alkali be added to the dye liquor at the beginning without dyeing unevenly.
  • leveling agent (I) in the presence of the leveling agent (I) can be dyed under the usual practical conditions using an "all-in" method.
  • salt and alkali are added to the dye liquor, then the leveling agent, either before or together with the reactive dye.
  • the leveling agent amount and process control temperature and / or pH value are selected according to the same criteria as described above for direct dyes.
  • a 600 g chalk spool made of bleached cotton is dyed in a laboratory cross-winder.
  • 121 liquors are heated to 50 ° C. with 60 g of Nacl, pumped into the dyeing vessel and then pumped from the inside to the outside at 2 circulations / min through the cheese.
  • 1.2 g of the auxiliary from Table 3 After 5 minutes of circulation, 1.2 g of the auxiliary from Table 3 and, after a further 5 minutes, 0.4 g of Direct Orange 39 (CI 40 215), 0.95 g of Direct Red 76 (CI 40 270) and 0.54 g Direct Blue 71 (CI 34 140) dissolved in approx. 150 ml water, added.
  • the mixture is heated to 90 ° C at 2 ° C / min, dyed at 90 ° C for 60 min, cooled to 70 ° C in 10 min, rinsed 3 x 10 min and 20 min at 18 g of a cationic aftertreatment agent. A level coloring is obtained.
  • a 600 g cheese bobbin made from bleached cotton yarn is dyed in a laboratory cheese bobbin winder as follows: 11 l of a liquor at 25 ° C., the 550 g of Na 2 SO 4 , 22 g of Na 2 CO 3 and 3 g of the leveling agent are pumped into the dyeing vessel and further from the inside and outside through the coil at 1.5 circulations / min. After 5 minutes of circulation, 0.6 g each of the golden yellow dye of DE-AS 1 191 059, table in columns 19/20, lines 3 and 4 from below, and the blue dye of DE-AS 1 264 647, example 2 , added. After a further 10 minutes, the mixture is heated to 50 ° C. in the course of 20 minutes, stained for 60 minutes at 50 ° C., rinsed 2 ⁇ 5 minutes cold, 2 ⁇ 10 minutes at 98 ° C. and rinsed cold 1 ⁇ 5 minutes . A level coloring is obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Description

Gegenstand der Erfindung ist ein Verfahren zum diskontinuierlichen Färben von Cellulosefasern in Gegenwart eines Egalisiermittels der FormelThe invention relates to a process for the discontinuous dyeing of cellulose fibers in the presence of a leveling agent of the formula

Figure imgb0001
in der

  • A für einen Rest -CO-O-R1-, -(OR1)x-OCO-CH2-, -CO-NH-R2-, -NH-CO-O-R1-, -(OR1)x-OCH2CO-OR1-oder -(OR1)X oder für eine Einfachbindung,
  • B für einen Rest -CO-NH-, -CO- oder -R2-NH-CO-oder für eine Einfachbindung,
  • R für einen Alkyl- oder Alkenylrest mit je 8-22 C-Atomen oder einen Cycloalkyl-, Aryl- oder Aralkylrest mit je 10-22 C-Atomen,
  • R1 und R2 für C2- oder C3-Alkylen,
  • R3 für C1-C20-Alkyl, das durch -0-, -NH-, -N(R4)-, -NH-CO-NH- oder Phenylen unterbrochen sein kann, für C2-C2p-Alkenyl, Cycloalkyl, Aryl oder Aralkyl mit je 6-22 C-Atomen und
  • R4 für Wasserstoff oder C1-C4-Alkyl stehen,
Figure imgb0001
 in the
  • A for a radical -CO-OR 1 -, - (OR 1 ) x- OCO-CH 2 -, -CO-NH-R 2 -, -NH-CO-OR 1 -, - (OR 1 ) x -OCH 2 CO-OR 1 -or - (OR 1 ) X or for a single bond,
  • B for a radical -CO-NH-, -CO- or -R 2 -NH-CO- or for a single bond,
  • R represents an alkyl or alkenyl radical each having 8-22 carbon atoms or a cycloalkyl, aryl or aralkyl radical each having 10-22 carbon atoms,
  • R 1 and R 2 are C 2 or C 3 alkylene,
  • R 3 for C 1 -C 20 alkyl, which can be interrupted by -0-, -NH-, -N (R 4 ) -, -NH-CO-NH- or phenylene, for C 2 -C 2 p- Alkenyl, cycloalkyl, aryl or aralkyl, each with 6-22 carbon atoms and
  • R 4 represents hydrogen or C 1 -C 4 alkyl,

wobei die genannten Substituenten ihrerseits durch Hydroxy oder Halogen, die cyclischen Substituenten außerdem durch C1-C12-Alkyl und der Rest R3 außerdem durch einen Rest der Formel

Figure imgb0002
substituiert sein können,

  • x und y für Null oder eine ganze Zahl von 1-40 stehen, wobei die Summe x + y 10-40 betragen soll,
  • n für 0 oder 1 und
  • X(-) für ein Anion stehen,
the substituents mentioned in turn by hydroxy or halogen, the cyclic substituents also by C 1 -C 12 alkyl and the radical R 3 also by a radical of the formula
Figure imgb0002
 can be substituted,
  • x and y stand for zero or an integer from 1-40, where the sum x + y should be 10-40,
  • n for 0 or 1 and
  • X (-) stand for an anion,

mit der Maßgabe, daß mindestens eine Estergruppe enthalten ist und mindestens 80 Gew.-% der Alkylenoxyeinheiten aus Ethylenoxyeinheiten besteht.with the proviso that at least one ester group is contained and at least 80% by weight of the alkyleneoxy units consists of ethyleneoxy units.

Unter einem hydrophoben Kohlenwasserstoffrest wird vorzugsweise ein gegebenenfalls ungesättigter aliphatischer Rest mit über 8 Kohlenstoffatomen oder ein cycloaliphatischer oder aromatischer Rest mit über 10 Kohlenstoffatomen verstanden.A hydrophobic hydrocarbon radical is preferably understood to mean an optionally unsaturated aliphatic radical with more than 8 carbon atoms or a cycloaliphatic or aromatic radical with more than 10 carbon atoms.

Cycloalkyl steht insbesondere für Cyclopentyl, Cyclohexyl, Tetra- und Decahydronaphthyl und ihre durch C1-C12-Alkyl substituierten Derivate oder den Abietylrest.Cycloalkyl stands in particular for cyclopentyl, cyclohexyl, tetra- and decahydronaphthyl and their derivatives substituted by C 1 -C 12 -alkyl or the abietyl radical.

Geeignete Arylreste sind beispielsweise der Phenyl- und der Naphthylrest und ihre durch C1-C12-Alkyl, Cyclohexyl oder Phenyl-C1-C3-Alkyl substituierten Derivate.Suitable aryl radicals are, for example, the phenyl and naphthyl radicals and their derivatives substituted by C 1 -C 12 alkyl, cyclohexyl or phenyl-C 1 -C 3 alkyl.

Aralkyl steht vorzugsweise für durch C1-C12-Alkyl substituiertes Benzyl oder Phenylethyl.Aralkyl preferably represents benzyl or phenylethyl substituted by C 1 -C 12 alkyl.

Als Reste R in der Formel (I) seien beispielsweise die 20 folgenden genannt: der Octyl-, Decyl-, Undecyl-, Dodecyl-, Tetradecyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Eikosyl-, Behenyl-, Undecenyl-, Dodecenyl, Heptadecenyl-, Octadecenyl-, Tetrahydronaphthyl-, Decahydronaphthyl-, Abietyl-, Cyclohexylphenyl-, p-tert.-Butylphenyl-, Octylphenyl-, Nonylphenyl-, Dodecylphenyl-, Phenylethylphenyl- oder Phenylpropylphenylrest.The following R may be mentioned as examples of the radicals R in formula (I): the octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eikosyl, behenyl, Undecenyl, dodecenyl, heptadecenyl, octadecenyl, tetrahydronaphthyl, decahydronaphthyl, abietyl, cyclohexylphenyl, p-tert.-butylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, phenylethylphenyl or phenylethylphenyl or phenylethylphenyl or.

Als geeignete Anionen X(-) kommen übliche anorganische oder organische Anionen in Frage, beispielsweise Chlorid, Bromid, Jodid, Methosulfat, Ethosulfat, Sulfat, Phosphat, Phosphit, Methansulfonat, Acetat oder Toluolsulfonat.Suitable anions X (-) are customary inorganic or organic anions, for example chloride, bromide, iodide, methosulfate, ethosulfate, sulfate, phosphate, phosphite, methanesulfonate, acetate or toluenesulfonate.

Bevorzugte Verbindungen der Formel (I) sind solche der Formeln

Figure imgb0003
und
Figure imgb0004
in denen

  • R, R1, R3 und X (-) die in Formel (I) angegebene Bedeutung haben, und
  • m für 0 oder 1 und
  • p für 10-40 stehen.
  • Besonders bevorzugt sind solche Verbindungen der Formeln (11) und (III), in denen R für einen C8-C22-Alkyl-oder -Alkenylrest und
  • R3 in Formel (11) für den Rest
    Figure imgb0005
    bzw.
  • in Formel (111) für den Rest
    Figure imgb0006
    und p für 10 - 30 stehen.
Preferred compounds of the formula (I) are those of the formulas
Figure imgb0003
 and
Figure imgb0004
 in which
  • R, R 1 , R 3 and X (-) have the meaning given in formula (I), and
  • m for 0 or 1 and
  • p stands for 10-40.
  • Those compounds of the formulas (11) and (III) in which R is a C 8 -C 22 alkyl or alkenyl radical and
  • R 3 in formula (11) for the rest
    Figure imgb0005
     respectively.
  • in formula (111) for the rest
    Figure imgb0006
     and p stand for 10-30.

Die Verbindungen (I) werden nach bekannten Verfahren hergestellt.The compounds (I) are prepared by known processes.

Nach dem erfindungsgemäßen Verfahren kann Cellulose insbesondere mit Direktfarbstoffen, die z.B. beschrieben werden in "Colour Index" 3. Auflage (1971), Bd. 2, S. 2007-2477, und mit Reaktivfarbstoffen, die z. B. beschrieben werden in "The Chemistry of Synthetic Dyes" (K. Venkataraman), Vol. VI (1972) gefärbt werden.In the process according to the invention, cellulose can in particular be mixed with direct dyes, e.g. are described in "Color Index" 3rd edition (1971), Vol. 2, pp. 2007-2477, and with reactive dyes which, for. B. are described in "The Chemistry of Synthetic Dyes" (K. Venkataraman), Vol. VI (1972).

Besonders vorteilhaft ist der Einsatz der genannten Egalisiermittel beim Färben mit Direktfarbstoffen und insbesondere, wenn Salz vor der Farbstoffzugabe zugesetzt wird ("all-in"-Verfahren). Unter Salz ist hierbei der Elektrolyt zu verstehen, dessen Zusatz üblich ist, um eine hohe Farbstoffausbeute zu erreichen, vorzugsweise Natriumsulfat oder Natriumchlorid.The use of the leveling agents mentioned is particularly advantageous when dyeing with direct dyes and especially when salt is added before the dye is added ("all-in" process). Salt is to be understood here as the electrolyte, the addition of which is customary in order to achieve a high dye yield, preferably sodium sulfate or sodium chloride.

Direktfarbstoffe ziehen bei Auszieh-Färbeverfahren selbst bei niedriger Temperatur sehr schnell auf. Dadurch entstehen Unegalitäten, die im Laufe des Färbens wieder ausgeglichen werden müssen. Salz beschleunigt das Aufziehen noch, ist aber nötig, um die gewünschte Ausbeute zu erreichen. Um zu große anfängliche Unegalitäten zu vermeiden, wird daher im allgemeinen das Salz erst nach Erreichen der Endtemperatur zugesetzt, und zwar meist portionsweise. Dies ist eine aufwendige Arbeitsweise.Direct dyes absorb very quickly with exhaust dyeing processes, even at low temperatures. This creates irregularities that must be compensated for in the course of dyeing. Salt accelerates the uptake, but is necessary to achieve the desired yield. In order to avoid excessive initial irregularities, the salt is therefore generally added only after the end temperature has been reached, usually in portions. This is a complex way of working.

Nur unter sehr günstigen Bedingungen (gut migrierende Farbstoffe, hohe Flottenumwälzrate oder Warenumlaufgeschwindigkeit) kann Salz auch zu. Beginn zugesetzt werden ("all-in"-Verfahren). Bei dieser einfacheren Arbeitsweise muß die zunächst entstehende Unegalität durch Migration ausgeglichen werden, was längere Färbezeiten oder mehr Egalisierhilfsmittel (und dadurch eine niedrigere Farbstoff-Ausbeute) bedingt als bei Satznachsatz.Salt can only do so under very favorable conditions (well migrating dyes, high liquor circulation rate or goods circulation speed). Beginning to be added ("all-in" method). With this simpler procedure, the unevenness that initially arises must be compensated for by migration, which requires longer dyeing times or more leveling aids (and therefore a lower dye yield) than in the case of batch additions.

Mit den üblichen Egalisierhilfsmitteln läßt sich das Aufziehen der Farbstoffe nicht in dem gewünschten Maß bremsen: Entweder ist die bremsende Wirkung des Egalisierhilfsmittels zu gering oder die Ausbeute wird zu stark beeinträchtigt. Zudem ist die Wirkung sehr vom Farbstofftyp abhängig.With conventional leveling aids, the absorption of the dyes cannot be slowed down to the desired extent: either the leveling agent's braking effect is too low or the yield increases severely impaired. In addition, the effect is very dependent on the type of dye.

Es wurde gefunden, daß ein "all-in-Verfahren" für Direktfarbstoffe ohne zusätzliche Migrierzeit und ohne Beeinträchtigung der Farbstoffausbeute in Gegenwart der Egalisiermittel (1) möglich ist. Die Egalisiermittel bremsen das Aufziehen der Farbstoffe in der Anfangsphase des Färbens bei niedriger Temperatur, insbesondere unterhalb 50° C. Dadurch werden unzulässige Unegalitäten vermieden. Beim Aufheizen läßt die Wirkung der Hilfsmittel nach, und das Aufziehen der Farbstoffe kann über die Temperaturführung gesteuert werden. Bei der üblichen Endtemperatur - insbesondere oberhalb 80°C, vorzugsweise 90 - 100°C halten die erfindungdsgemäß zu verwendenden Hilfsmittel in den meisten Fällen kaum Farbstoff zurück. Falls in Sonderfällen, z. B. bei hoher Hilfsmittelmenge oder Farbstoffen mit starker Wechselwirkung mit dem Hilfsmittel, erforderlich, kann die rückhaltende Wirkung des Hilfsmittels durch Färben bei alkalischem pH-Wert (über pH 8) gegenüber schwach saurer oder neutraler Färbeweise weiter gesenkt werden.It has been found that an "all-in process" for direct dyes is possible in the presence of the leveling agents (1) without additional migration time and without impairing the dye yield. The leveling agents slow down the absorption of the dyes in the initial phase of dyeing at a low temperature, especially below 50 ° C. This prevents inadmissible irregularities. When heating, the effect of the auxiliaries wears off, and the absorption of the dyes can be controlled via the temperature control. At the usual final temperature - in particular above 80 ° C., preferably 90-100 ° C., the auxiliaries to be used according to the invention hardly retain any dye in most cases. If in special cases, e.g. B. with a large amount of auxiliary or dyes with strong interaction with the auxiliary required, the restrained effect of the auxiliary can be further reduced by dyeing at alkaline pH (above pH 8) compared to weakly acidic or neutral staining.

Bei dem bevorzugten "all-in"-Verfahren ist die Reihenfolge der Zusätze entweder (a) Salz, Egalisiermittel, Farbstoffe oder (b) Salz, Egalisiermittel + Farbstoffe oder (c) Salz + Egalisiermittel, Farbstoffe.In the preferred "all-in" process, the order of the additions is either (a) salt, leveling agent, dyes or (b) salt, leveling agent + dyes or (c) salt + leveling agent, dyes.

Die Egalisiermittelmenge liegt in der Regel zwischen 0,1 und 2 %, bezogen auf das Gewicht des zu färbenden Textils. Die zulässige anfängliche Baderschöpfungsgeschwindigkeit, nach der die Egalisiermittelmenge festgelegt wird, hängt von den Ansprüchen an die Egalität, der ware der Färbeanlage, der Farbtiefe und Nuance und den Farbstoffen (Aufziehverhalten, Kombinierbarkeit, Migriervermögen) ab. Sie liegt im allgemeinen zwischen 20 und 60 % Baderschöpfung in den ersten 10 Minuten; vorzugsweise zwischen 20 und 40 % /10min.The amount of leveling agent is generally between 0.1 and 2%, based on the weight of the textile to be dyed. The permissible initial rate of bath depletion, according to which the amount of leveling agent is determined, depends on the demands on the level, the goods of the dyeing system, the color depth and nuance and the dyes (pull-up behavior, combinability, migrability). It is generally between 20 and 60% bath exhaustion in the first 10 minutes; preferably between 20 and 40% / 10min.

Die Vorteile des Verfahrens sind; einfaches "all-in"-Verfahren für alle Direktfarbstoffe und ohne zusätzliche Migrierzeit, hohes Egalitätsniveau durch kontrolliertes Anfärben bei kurzer Färbezeit, hohe Ausbeute und Reproduzierbarkeit, geringe Abwasserbelastung.The advantages of the procedure are; Simple "all-in" process for all direct dyes and without additional migration time, high level of uniformity through controlled dyeing with short dyeing times, high yield and reproducibility, low wastewater pollution.

Weiterhin sind die Egalisiermittel (I), bevorzugt geeignet für das Färben mit Reaktivfarbstoffen; insbesondere, wenn Egalisiermittel, Salz oder Salz und Alkali vor den Farbstoffen zugesetzt werden.The leveling agents (I) are furthermore preferably suitable for dyeing with reactive dyes; especially if leveling agents, salt or salt and alkali are added before the dyes.

Bei den bisher üblichen Verfahren werden Salz und Alkali meist nach den Reaktivfarbstoffen zugesetzt, und zwar portionsweise, um ein zu rasches Aufziehen bzw. Fixieren der Farbstoffe und dadurch entstehende Unegalitäten zu vermeiden. Nur unter besonders günstigen Färbebedingungen (gut egalisierende Farbstoffe, hohe Flottenströmung oder Laufgeschwindigkeit der Ware, Temperatur-/ pH-Steuerung) können bisher Salz oder Salz und Alkali der Färbeflotte zu Beginn zugegeben werden, ohne unegal zu färben.In the processes customary hitherto, salt and alkali are usually added after the reactive dyes, in portions, in order to avoid the dyes being drawn in or fixed too quickly and thus resulting in irregularities. Only under particularly favorable dyeing conditions (good leveling dyes, high liquor flow or running speed of the goods, temperature / pH control) can salt or salt and alkali be added to the dye liquor at the beginning without dyeing unevenly.

Demgegenüber kann in Gegenwart der Egalisiermittel (I) unter den üblichen Praxisbedingungen nach einem "all-in"-Verfahren gefärbt werden. Hierbei werden zunächst Salz und Alkali der Färbeflotte zugegeben, sodann das Egalisiermittel, entweder vor oder gemeinsam mit dem Reaktivfarbstoff. Egalisiermittelmenge und Verfahrensführung (Temperatur und/oder pH-Wert) werden nach den gleichen Kriterien gewählt, wie oben für Direktfarbstoffe beschrieben.In contrast, in the presence of the leveling agent (I) can be dyed under the usual practical conditions using an "all-in" method. First, salt and alkali are added to the dye liquor, then the leveling agent, either before or together with the reactive dye. The leveling agent amount and process control (temperature and / or pH value) are selected according to the same criteria as described above for direct dyes.

Beispiel 1example 1

1. 3 kg gebleichter und vorgewaschener Baumwoll-Wirkware werden als Strang in einer Haspelkufe ohne Flottenumwälzung in 60 I Färbeflotte bei 2 Warenumläufen/min wie folgt gefärbt:1. 3 kg of bleached and prewashed cotton knitwear are dyed as a strand in a reel runner without liquor circulation in 60 l dyeing liquor at 2 circulations / min as follows:

Bei einer Starttemperatur von 40°C werden 240 g NaCl dem Färbebad zugesetzt. Nach 10 min wird eine konzentrierte Färbeflotte, bestehend aus 1,2 g Direct Yellow 50 (C.I. 29 025), 1,2 g Direct Violet 47 (C.I. 25 410) und 0,85 g Direct Blue 71 (C.I. 34 140) sowie 8,5 g des Hilfsmittels der Formel

Figure imgb0007
in ca 1 1 Wasser gelöst, zugegeben. Nach 5 min bei 40° C wird mit 2°C/min auf 90° C aufgeheizt, 30 min bei 90° C gefärbt, mit 2°C/min auf 70°C abgekühlt, 3 x gespült und 20 min bei 30°C mit 30 g eines kationischen Nachbehandlungsmittels (Kondensationsprodukt eines Amins mit Formaldehyd) behandelt. Es resultiert eine egale Färbung.At a starting temperature of 40 ° C 240 g NaCl are added to the dyebath. After 10 minutes, a concentrated dyeing liquor consisting of 1.2 g Direct Yellow 50 (CI 29 025), 1.2 g Direct Violet 47 (CI 25 410) and 0.85 g Direct Blue 71 (CI 34 140) and 8 , 5 g of the auxiliary of the formula
Figure imgb0007
 dissolved in about 1 liter of water, added. After 5 minutes at 40 ° C., the mixture is heated to 90 ° C. at 2 ° C./min, dyed at 90 ° C. for 30 minutes, cooled to 70 ° C. at 2 ° C./min, rinsed 3 times and 20 minutes at 30 ° C. treated with 30 g of a cationic aftertreatment agent (condensation product of an amine with formaldehyde). The result is a level coloring.

Verwendet man in Beispiel 1 eines der in den Tabellen 1 und 2 aufgeführten Egalisiermittel, so erhält man ebenfalls egale Färbungen.

Figure imgb0008
Figure imgb0009
 If one of the leveling agents listed in Tables 1 and 2 is used in Example 1, level dyeings are also obtained.
Figure imgb0008
Figure imgb0009

Vergleichsfärbung:

  • Wie in Beispiel 1, jedoch ohne Hilfsmittel und 60 min bei 90°C gefärbt. Nan erhält eine unegale (steifige) Färbung.
Comparative staining:
  • As in Example 1, but without auxiliaries and colored at 90 ° C. for 60 min. Nan gets an uneven (stiff) color.

Beispiel 2Example 2

Eine 600 g-Kreizspule aus gebleichter Baumwolle wird in einem Labor-Kreuzspulapparat gefärbt. Hierbei werden 121 Flotte mit 60 g Nacl auf 50°C erwärmt, in das Färbegefäß gepumpt und im weiteren von innen nach außen mit 2 Umwälzungen / min durch die Kreuzspule gepumpt. Nach 5minütiger Zirkulation werden 1,2 g des Hilfsmittels aus der Tabelle Beispiel 3 und nach weiteren 5 min 0,4 g Direct Orange 39 (C.I. 40 215), 0,95 g Direct Red 76 (C.I. 40 270) und 0,54 g Direct Blue 71 (C.I. 34 140) in ca. 150 ml Wasser gelöst, zugesetzt. Nach weiteren 10 min Verweilzeit bei 50°C wird mit 2°C/min auf 90°C geheizt, 60 min bei 90°C gefärbt, in 10 min auf 70°C gekühlt, 3 x je 10 min gespült und 20 min mit 18 g eines kationischen Nachbehandlungsmittels behandelt. Man erhält eine egale Färbung.A 600 g chalk spool made of bleached cotton is dyed in a laboratory cross-winder. Here, 121 liquors are heated to 50 ° C. with 60 g of Nacl, pumped into the dyeing vessel and then pumped from the inside to the outside at 2 circulations / min through the cheese. After 5 minutes of circulation, 1.2 g of the auxiliary from Table 3 and, after a further 5 minutes, 0.4 g of Direct Orange 39 (CI 40 215), 0.95 g of Direct Red 76 (CI 40 270) and 0.54 g Direct Blue 71 (CI 34 140) dissolved in approx. 150 ml water, added. After a further 10 min dwell time at 50 ° C, the mixture is heated to 90 ° C at 2 ° C / min, dyed at 90 ° C for 60 min, cooled to 70 ° C in 10 min, rinsed 3 x 10 min and 20 min at 18 g of a cationic aftertreatment agent. A level coloring is obtained.

Beispiel 3Example 3

Eine 600 g Kreuzspule aus gebleichtem Baumwollgarn wird in einem Labor-Kreuzspulapparatur wie folgt gefärbt: 11 I einer 25° C warmen Flotte, die 550 g Na2SO4, 22 g Na2CO3 und 3 g des Egalisiermittels

Figure imgb0010
Figure imgb0011
erhält, werden in das Färbegefäß und im weiteren von innen nch außen mit 1,5 Umwälzungen/min durch die Spule gepumpt. Nach 5-minütiger Zirkulation werden je 0,6 g des goldgelben Farbstoffs der DE-AS 1 191 059, Tabelle in Spalten 19/20, Zeilen 3 und 4 von unten, und des blauen Farbstoffs der DE-AS 1 264 647, Beispiel 2, zugesetzt. Nach weiteren 10 Min. wird innerhalb von 20 Min. auf 50°C aufgeheizt, 60 Min. bei 50°C gefärbt, 2 x 5 Min. kalt, 2 x 10 Min. bei 98°C und 1 x 5 Min. kalt gespült. Man erhält eine egale Färbung.A 600 g cheese bobbin made from bleached cotton yarn is dyed in a laboratory cheese bobbin winder as follows: 11 l of a liquor at 25 ° C., the 550 g of Na 2 SO 4 , 22 g of Na 2 CO 3 and 3 g of the leveling agent
Figure imgb0010
Figure imgb0011
 are pumped into the dyeing vessel and further from the inside and outside through the coil at 1.5 circulations / min. After 5 minutes of circulation, 0.6 g each of the golden yellow dye of DE-AS 1 191 059, table in columns 19/20, lines 3 and 4 from below, and the blue dye of DE-AS 1 264 647, example 2 , added. After a further 10 minutes, the mixture is heated to 50 ° C. in the course of 20 minutes, stained for 60 minutes at 50 ° C., rinsed 2 × 5 minutes cold, 2 × 10 minutes at 98 ° C. and rinsed cold 1 × 5 minutes . A level coloring is obtained.

Claims (6)

1. Process of batch dyeing cellulose fibres in the presence of a levelling agent, characterized in that a levelling agent of the formula
Figure imgb0016
is used in which
A represents a -CO-0-R1-, -(OR1)x-OCO-CH2-' -CO-NH-R2-, -NH-CO-O-R1-, -(OR1)x-OCH2CO-OR1)x- or -(OR1)x- radical or a single bond,
B represents a -CO-NH-, -CO- or -R2-NH-CO- radical or a single bond,
R represents an alkyl or alkenyl radical in each case having 8-22 carbon atoms, or a cycloalkyl, aryl or aralkyl radical in each case having 10-22 carbon atoms,
R1 and R2 represent C2- or C3-alkylene,
R3 represents C1-C20alkyl which may be interrupted by -0-, -NH-, -N(R4)-, -NH-CO-NH- or phenyl, or represents C2-C20-alkyl, or cycloalkyl, aryl or aralkyl in each case having 6-22 carbon atoms and
R4 represents hydrogen or C1-C4-alkyl, it being possible for the substituents mentioned to be substituted themselves by hydroxyl or halogen, and for the cyclic substituents, in addition, to be substituted by C1-C12- alkyl, and for the R3 radical, in addition, to be substituted by a radical of the formula
Figure imgb0017
x and y represent zero or an integer from 1-40, with the sum x + y to be 10-40,
n represents 0 or 1, and
xl-) represents an anion,
with the proviso that at least one ester group is present and at least 80 % by weight of the alkylene oxide units comprise ethylene oxide units.
2. Process according to Claim 1, characterized in that the levelling agent used is one of the formula
Figure imgb0018
in which
R, R3 and X(-) have the meaning given in Claim 1,
m represents 0 or 1, and
p represents 10-40.
3. Process according to Claim 1, characterized in that the levelling agent used is one of the formula
Figure imgb0019
in which
R, R1, R3 and X(-) have the meaning given in Claim 1, and
p represents 10-40.
4. Process according to Claim 1, characterized in that salt is added to the dyeing bath before addition of the dye.
5. Process according to Claim 1, characterized in that the levelling agent is used in an amount of 0.1-2 % by weight, relative to the cellulose fibres.
6. Process according to Claim 5, characterized in that the dyeing is carried out using direct dyes, and the amount of levelling agent is selected so that the bath exhaustion in the first 10 minutes is between 20 and 60 %.
EP84109394A 1983-08-16 1984-08-08 Process for dyeing cellulosic fibres Expired EP0141078B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833329445 DE3329445A1 (en) 1983-08-16 1983-08-16 METHOD FOR COLORING CELLULOSE FIBERS
DE3329445 1983-08-16

Publications (3)

Publication Number Publication Date
EP0141078A2 EP0141078A2 (en) 1985-05-15
EP0141078A3 EP0141078A3 (en) 1986-12-10
EP0141078B1 true EP0141078B1 (en) 1988-06-29

Family

ID=6206585

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84109394A Expired EP0141078B1 (en) 1983-08-16 1984-08-08 Process for dyeing cellulosic fibres

Country Status (2)

Country Link
EP (1) EP0141078B1 (en)
DE (2) DE3329445A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3618517A1 (en) * 1985-06-04 1986-12-04 Lion Corp., Tokio/Tokyo Emulsifying agent for emulsion polymerisation
DE3729459A1 (en) * 1987-09-03 1989-03-16 Bayer Ag METHOD FOR COLORING CELLULOSE FIBERS
GB9120227D0 (en) * 1991-09-23 1991-11-06 Ici Plc Printing process and pretreatment composition
DE4135115A1 (en) * 1991-10-24 1993-04-29 Trigon Chemie Gmbh New cationic quat. ammonium chloride surfactants - used as brighteners, conditioners and disinfectants, e.g. for textiles
DE102004045861B4 (en) * 2004-09-20 2008-05-08 Dystar Textilfarben Gmbh & Co. Deutschland Kg A process for the ring dyeing of textile fabrics of cellulosic fibers and mixed materials containing cellulosic fibers and subsequently produced ring-dyed fabrics and mixed materials
FR2926979B1 (en) * 2008-02-04 2010-12-17 Oreal NOVEL CATIONIC COMPOUNDS, COMPOSITIONS COMPRISING SAME, USE AS CONDITIONER, AND COSMETIC PROCESSING METHOD.
CN114507961B (en) * 2022-01-06 2022-11-29 广州启文纺织科技有限公司 Dye sample control method, storage medium and readable program

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB466772A (en) * 1935-10-31 1937-05-31 Ig Farbenindustrie Ag Improvements in dyeings
GB474671A (en) * 1936-04-29 1937-10-29 Ig Farbenindustrie Ag Improvements in the manufacture and production of nitrogenous condensation products
ES367288A1 (en) * 1968-05-17 1971-04-01 Sandoz Ag Levelling agents for and process for colouring a fibrous natural polyamide with reactive dyes
GB1423047A (en) * 1973-05-14 1976-01-28 Ici Ltd Dyeing additives
CH638362GA3 (en) * 1977-06-10 1983-09-30
DE2805239A1 (en) * 1978-02-08 1979-08-09 Sandoz Ag Polyetherester(s) contg. quaternary amino gps. - for use as dyeing aids with cationic dyes

Also Published As

Publication number Publication date
EP0141078A2 (en) 1985-05-15
DE3472426D1 (en) 1988-08-04
DE3329445A1 (en) 1985-03-07
EP0141078A3 (en) 1986-12-10

Similar Documents

Publication Publication Date Title
EP0545207B1 (en) Reactive dye mixture with improved combination characteristics
EP0089004B1 (en) Process for dyeing fibrous material from natural polyamides
DE2633615C3 (en) Process for dyeing synthetic polyamide fiber materials
EP0141078B1 (en) Process for dyeing cellulosic fibres
DE2556376C2 (en) Process for dyeing polyacrylonitrile fiber material
EP0023341B1 (en) Padding aid, process for its preparation and process for dyeing cellulosic fibres or mixtures of cellulosic fibres together with synthetic fibres with sulphur, sulphur vat, vat and reactive dyestuffs
DE2812039C3 (en) Process for dyeing wool and synthetic polyamide fibers
EP0593392B1 (en) Process for dyeing of natural and synthetic polyamide fibers with dye mixtures
EP1772553A1 (en) Method of dyeing wool fibres
EP0305839B1 (en) Process for dyeing cellulosic fibres
DE68918639T2 (en) Dyeing aid composition and dyeing process.
EP0121887B1 (en) Process for level dyeing synthetic fibres
EP0105034A1 (en) Dyeing aid and process for dyeing of polyacrylonitrile fibre material
DE2512520C2 (en) PROCESS FOR DYING CELLULOSE FIBERS, NITROGEN FIBERS, SYNTHETIC FIBERS AND THEIR MIXTURES
DE2631265C3 (en) Process for level dyeing of slow, normal or fast drawing polyacrylonitrile materials
EP0305858B1 (en) Process for dyeing polyamide fibres
EP0278440A2 (en) Use of sulphurous acid cyclic esters in dyeing polyamide textile materials, and dyeing process
DE2409437A1 (en) PROCESS FOR SELECTIVE DYEING OF MIXED FIBERS OR MIXED FIBERS TEXTILES
DE2943750A1 (en) METHOD FOR COLORING POLYACRYLNITRILE FIBERS
EP0045458A1 (en) Continuous or semi-continuous process for dyeing a voluminous woven fabric containing cellulosic fibres with azoic developing dyes
DE1801715C3 (en) Process for the single bath dyeing of mixtures of cellulose, polyester and polyacrylonitrile fibers
DE1266271B (en) Dyeing of cellulose fibers and nitrogenous fibers
AT201026B (en) Use of substituted imidazoline compounds as leveling agents
DE2747699C3 (en) Rapid liquor dyeing process for piece goods made from cellulose fibers in strand form
DE1953068C3 (en) Auxiliaries for dyeing cellulose fibers, nitrogen-containing fibers, synthetic fibers and their fiber blends and their use

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19840808

AK Designated contracting states

Designated state(s): CH DE FR GB LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE FR GB LI

17Q First examination report despatched

Effective date: 19871022

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3472426

Country of ref document: DE

Date of ref document: 19880804

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940714

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940727

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19940812

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940826

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950808

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19950831

Ref country code: CH

Effective date: 19950831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950808

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST