EP0080642B1 - Dyeing process - Google Patents

Dyeing process Download PDF

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Publication number
EP0080642B1
EP0080642B1 EP82110546A EP82110546A EP0080642B1 EP 0080642 B1 EP0080642 B1 EP 0080642B1 EP 82110546 A EP82110546 A EP 82110546A EP 82110546 A EP82110546 A EP 82110546A EP 0080642 B1 EP0080642 B1 EP 0080642B1
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Prior art keywords
denotes
parts
radical
formula
liquor
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German (de)
French (fr)
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EP0080642A1 (en
Inventor
Dietrich Dr. Hildebrand
Udo Winfried Dr. Hendricks
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Bayer AG
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Bayer 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
    • 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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
    • D06P3/8238—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye
    • D06P3/8252—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye using dispersed and 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
    • D06P1/0056—Dyeing with polymeric dyes involving building the polymeric dyes on the fibres
    • D06P1/0064—Dyeing with polymeric dyes involving building the polymeric dyes on the fibres by using reactive polyfunctional compounds, e.g. crosslinkers
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/10—Material containing basic nitrogen containing amide groups 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/924—Polyamide fiber

Definitions

  • the present invention relates to a new process for dyeing cellulose-containing fiber materials with reactive dyes according to the pull-out principle.
  • level dyeings can be achieved even without such an outlay on equipment if, instead of alkali, the dye bath containing salt and possibly other auxiliaries is added a glycidyl compound which causes the pH to rise continuously as the temperature rises.
  • Q is only zero if m and n are zero and the glycidyl radical is bound to a heteroatom of Z.
  • the bridge member Y is preferably bonded to a nitrogen atom of Z.
  • the aliphatic and cycloaliphatic hydrocarbon radicals are, in particular, optionally branched radicals having up to 8 carbon atoms.
  • Preferred aliphatic radicals Z and preferred alkyl radicals R and R are those with 1-5 carbon atoms.
  • Preferred cycloaliphatic radicals Z and cycloalkyl radicals R are the cyclopentyl and the cyclohexyl radical.
  • Aryl or aralkyl are especially phenyl or benzyl.
  • A stands for example for a C 2 -C 6 alkylene or a phenylene radical.
  • an initial pH of the dye liquor which is between pH 5 and pH 8 (in particular between pH 6.5 and 7.5).
  • the final pH of the aforementioned dye liquors is then from pH 8 to pH 11.5, preferably from pH 9.5 to 10.5.
  • glycidyl compounds are added to the dye liquors used, which, when cleaved, first release alkali and then acid (e.g. esters of phosphoric acid and glycidyl groups contain alcohols, in which case the pH of the dye liquor initially rises slowly and so favors a dyeing of the cellulose or polyamide portion of the fiber, in which case the slowly released phosphoric acid finally causes the pH to drop again and favors dyeing of the other portion of the fiber (eg polyester) in the acidic range).
  • the pH range therefore rises from pH 5 to 8 to values around pH 8-10 and then falls towards the end of the dyeing process without addition of acid at temperatures from 80 to 130 ° C. to values from pH 5 to pH 7.
  • the process according to the invention is generally carried out in such a way that Starting temperatures are between 20 and 40 ° C and the end temperatures between 45 and 125 ° C.
  • the process can advantageously also be carried out at a constant temperature, for example at 65 °.
  • 100 parts of a mercerized cotton yarn are placed in the form of cross-wound bobbins on the yarn dyeing machine in 1000 parts of a liquor consisting of 90 parts of common salt, 8 parts of the compound of the formula There are 2 parts of dye 11 and 900 parts of water.
  • the initial pH of the liquor is 6.9.
  • the liquor is heated at a rate of 12 ° / min. heated to 95 ° C and held at this temperature for 15 min.
  • the final pH of the liquor is 9.2.
  • the exhausted remaining liquor is then drained off and the dyeing obtained is rinsed cold and warm and, as usual, for 10 minutes. cooked with fresh water. A clear blue color is obtained.
  • the initial pH of the liquor is 7.5. It is heated to 95 ° C. in 60 min and dyed at this temperature for 1 hour. The pH of the liquor slowly rises to pH 9.2 and then gradually drops to 6.5.
  • the initial pH of the liquor is 8.2. It is dyed at 60 ° C for 2 hours. During this time, the pH slowly increases to 11.3. after the usual rinsing and boiling soaps, a level, deep green color with good fastness properties is obtained.

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

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zum Färben von Cellulose enthaltenden Fasermaterialien mit Reaktivfarbstoffen nach dem Ausziehprinzip.The present invention relates to a new process for dyeing cellulose-containing fiber materials with reactive dyes according to the pull-out principle.

Es ist allgemein bekannt, daß für die Fixierung der Reaktivfarbstoffe auf der Faser ein Alkalizusatz erforderlich ist.It is generally known that an alkali additive is required to fix the reactive dyes on the fiber.

Diese Arbeitsweise zeigt jedoch verschiedene Nachteile, von denen die insbesondere bei höheren Temperaturen auftretende Spaltung der Farbstoff-Faser-Bindung der gravierendste ist.However, this procedure shows various disadvantages, the most serious of which is the cleavage of the dye-fiber bond which occurs particularly at higher temperatures.

Es wurde deshalb bereits vorgeschlagen (vgl. DE-A-1619464), den alkalischen Färbebädern bestimmte halogenhaltige Säurespender zuzusetzen, u.a. 3-Chlorpropylenoxyd, wodurch sich der pH-Wert während des Fixiervorganges erniedrigt.It has therefore already been proposed (cf. DE-A-1619464) to add certain halogen-containing acid donors to the alkaline dye baths, including 3-chloropropylene oxide, which lowers the pH during the fixing process.

Aber auch diese Färbemethode konnte nicht voll befriedrigen, da sie zu unegalen Färbungen führt - sofern man nicht eine aufwendige pH-Steuerung betreibt.However, this dyeing method could not be fully satisfactory either, since it leads to uneven dyeing - unless one operates a complex pH control.

Überraschenderweise wurde nun gefunden, daß man auch ohne einen solchen apparativen Aufwand zu egalen Färbungen gelangt, wenn man anstelle von Alkali dem Salz und ggf. andere Hilfsstoffe enthaltenden Färbebad eine Glycidylverbindung zusetzt, die mit steigender Temperatur einen kontinuierlichen pH-Wert-Anstieg bewirkt.Surprisingly, it has now been found that level dyeings can be achieved even without such an outlay on equipment if, instead of alkali, the dye bath containing salt and possibly other auxiliaries is added a glycidyl compound which causes the pH to rise continuously as the temperature rises.

Der Einsatz von Glycidylverbindungen in der Textilfärberei ist zwar an sich nichts völlig Neues, jedoch diente er bislang ausschließlich zur Echtheitsverbesserung von vorzugsweise nicht-reaktive Farbstoffen (vgl. z.B. DE-B 12 39 266 und GB-A 1 236 882).The use of glycidyl compounds in textile dyeing is in itself nothing completely new, but so far it has only been used to improve the authenticity of preferably non-reactive dyes (see e.g. DE-B 12 39 266 and GB-A 1 236 882).

Als für das erfindungsgemäße Verfahren besonders geeignete Glycidylreste enthaltenden Verbindungen kommen in Frage: Glycidylgruppen enthaltende Verbindungen der Formel

Figure imgb0001
worin

  • Q einen Rest der Formel
    Figure imgb0002
  • Z einen 1-4-wertigen aliphatischen Kohlenwasserstoffrest, der durch S-Atome unterbrochen sein kann, einen cycloaliphatischen Kohlenwasserstoffrest, einen gesättigten heterocyclischen Rest oder die Gruppen
    Figure imgb0003
    Figure imgb0004
  • R Wasserstoff oder Alkyl,
  • R, Alkyl, Cycloalkyl, Aryl oder Aralkyl,
  • Y einen Rest der Formel
    Figure imgb0005
  • A Alkylen oder Arylen,
  • m 0 oder 1,
  • n 0-10
  • q 0 oder 1 und
  • p 1-4 bedeuten.
Suitable compounds containing glycidyl groups that are particularly suitable for the process according to the invention are: compounds of the formula containing glycidyl groups
Figure imgb0001
 wherein
  • Q is a residue of the formula
    Figure imgb0002
  • Z is a 1-4-valent aliphatic hydrocarbon radical which can be interrupted by S atoms, a cycloaliphatic hydrocarbon radical, a saturated heterocyclic radical or the groups
    Figure imgb0003
    Figure imgb0004
  • R is hydrogen or alkyl,
  • R, alkyl, cycloalkyl, aryl or aralkyl,
  • Y is a residue of the formula
    Figure imgb0005
  • A alkylene or arylene,
  • m 0 or 1,
  • n 0-10
  • q 0 or 1 and
  • p mean 1-4.

Dabei steht q nur dann für null, wenn m und n für null stehen und der Glycidylrest an ein Heteroatom von Z gebunden ist.Q is only zero if m and n are zero and the glycidyl radical is bound to a heteroatom of Z.

Wenn p für 2-4 steht, sind die Substituenten Q mit verschiedenen Atomen von Z verbunden.If p stands for 2-4, the substituents Q are connected to different atoms of Z.

Das Brückenglied Y ist vorzugsweise an ein Stickstoffatom von Z gebunden.The bridge member Y is preferably bonded to a nitrogen atom of Z.

Bei den aliphatischen und cycloaliphatischen Kohlenwasserstoffresten handelt es sich insbesondere um gegebenenfalls verzweigte Reste mit bis zu 8 C-Atomen.The aliphatic and cycloaliphatic hydrocarbon radicals are, in particular, optionally branched radicals having up to 8 carbon atoms.

Bevorzugte aliphatische Reste Z und bevorzugte Alkylreste R und R, sind solche mit 1-5 Kohlenstoffatomen.Preferred aliphatic radicals Z and preferred alkyl radicals R and R are those with 1-5 carbon atoms.

Bevorzugte cycloaliphatische Reste Z und Cycloalkylreste R, sind der Cyclopentyl- und der Cyclohexylrest.Preferred cycloaliphatic radicals Z and cycloalkyl radicals R are the cyclopentyl and the cyclohexyl radical.

Aryl bzw. Aralkyl stehen insbesondere für Phenyl bzw. Benzyl.Aryl or aralkyl are especially phenyl or benzyl.

A steht z.B. für einen C2-C6-Alkylen oder einen Phenylenrest.A stands for example for a C 2 -C 6 alkylene or a phenylene radical.

Als Beispiele für heterocyclische Reste Z seien der 1,3,5-Hexahydrotriazin-Rest oder Reste der Formel

Figure imgb0006
genannt, worin

  • R2 für Wasserstoff oder gemeinsam für Sauerstoff,
  • R3 für Wasserstoff oder Methyl und
    Figure imgb0007
  • oder -CH2- stehen, oder die Gruppierung
    Figure imgb0008
  • für einen o-Phenylenrest steht.
  • Von den Verbindungen der Formel I sind die der Formeln
    Figure imgb0009
    worin
  • Z, einen 1-4-wertigen aliphatischen Kohlenwasserstoffrest mit 1-5 Kohlenstoffatomen bedeutet, und n und p die vorstehend genannte Bedeutung haben,
    Figure imgb0010
    worin
  • n die vorstehend genannte Bedeutung hat, und
    Figure imgb0011
    worin
  • Z2 den 1,3,5-Hexahydrotriazinrest oder einen Rest der Formel II,
  • Y, ―CO―CH2―CH2― oder ―SO2―CH2―CH2― und
  • p, 1-3 bedeuten,
  • n die vorstehend genannte Bedeutung hat, und der in eckigen Klammern stehende Rest an ein Stickstoffatom von Z2 gebunden ist, bevorzugt.
Examples of heterocyclic radicals Z are the 1,3,5-hexahydrotriazine radical or radicals of the formula
Figure imgb0006
 called, in which
  • R 2 for hydrogen or together for oxygen,
  • R 3 is hydrogen or methyl and
    Figure imgb0007
  • or -CH 2 - stand, or the grouping
    Figure imgb0008
  • represents an o-phenylene radical.
  • Of the compounds of formula I are those of the formulas
    Figure imgb0009
     wherein
  • Z represents a 1-4-valent aliphatic hydrocarbon radical having 1-5 carbon atoms, and n and p have the meaning given above,
    Figure imgb0010
     wherein
  • n has the meaning given above, and
    Figure imgb0011
     wherein
  • Z 2 is the 1,3,5-hexahydrotriazine radical or a radical of the formula II,
  • Y, ―CO ― CH 2 ―CH 2 - or ―SO 2 ―CH 2 ―CH 2 - and
  • p, 1-3 mean
  • n has the meaning given above, and the residue in square brackets is bonded to a nitrogen atom of Z 2 , is preferred.

Als Beispiele für die Verbindungen 1 seien genannt:

Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
n = 0 - 8, insbesondere 1 - 6
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Weiterhin kommen in Betracht:
Figure imgb0027
sowie, falls es sich bei den Glycicylgruppen aufweisen den Verbindungen um Alkohole handelt, deren Ester mit Säuren, z.B. mit Phosphorsäure.
Figure imgb0028
zw. Monokaliumsulfat.Examples of compounds 1 are:
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
 n = 0-8, especially 1-6
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
 The following can also be considered:
Figure imgb0027
 and, if the compounds have glycicyl groups, are alcohols, their esters with acids, for example with phosphoric acid.
Figure imgb0028
between monopotassium sulfate.

Als geeignete schwach alkalisch reagierende Salze seien beispielsweise genannt:

  • Natrium- bzw. Kaliumbicarbonat, Natriumacetat, Dinatrium-bzw. Dikaliumphosphat, Tetranatriumpyrophosphat.
  • Die einzusetzenden Mengen an Salz richten sich nach der Farbtiefe und der gewünschten Färbetemperatur bzw. dem Flottenverhältnis, sie können in einfacher Weise durch Vorversuch ermittelt werden.
  • Die beim erfindungsgemäßen Verfahren eingesetzten Salze können ferner allein und/oder in Mischung verwendet werden. Als vorteilhaft haben sich Mischungen von 30 bis 120 gll, bevorzugt 50-80 g/l eines Neutralsalzes wie Natriumchlorid oder Natriumsulfat mit 0,2 bis 4 g/1 eines schwach alkalisch reagierende oder schwach sauer reagierenden Salzes erwiesen.
  • Der Anfangs-pH-Wert des Färbebades richtet sich nach dem zu färbenden Gewebe. Zur Einstellung des gewünschten Anfangs-pH-Wertes eignen sich außer Mischungen von schwach sauer und schwach alkalisch reagierenden Salzen, Zusätze von schwachen Säuren wie Essigsäure.
Examples of suitable weakly alkaline salts are:
  • Sodium or potassium bicarbonate, sodium acetate, disodium or. Dipotassium phosphate, tetrasodium pyrophosphate.
  • The amounts of salt to be used depend on the color depth and the desired dyeing temperature or the liquor ratio; they can be determined in a simple manner by means of a preliminary test.
  • The salts used in the process according to the invention can also be used alone and / or in a mixture. Mixtures of 30 to 120 gll, preferably 50-80 g / l of a neutral salt such as sodium chloride or sodium sulfate with 0.2 to 4 g / 1 of a weakly alkaline or weakly acidic salt have proven to be advantageous.
  • The initial pH of the dye bath depends on the tissue to be dyed. In addition to mixtures of weakly acidic and weakly alkaline salts, additions of weak acids such as acetic acid are suitable for setting the desired initial pH.

Beim Färben von Cellulosefasern oder Cellulose/Polyamidmischfasern wählt man vorzugssweise einen Ausgangs-pH-Wert der Färbeflotte, der zwischen pH 5 und pH 8 liegt (insbesondere zwischen pH 6,5 bis 7,5). Der End-pH-Wert der vorgenannten Färbeflotten liegt dann bei pH 8 bis pH 11,5, vorzugsweise bei pH 9,5 bis 10,5.When dyeing cellulose fibers or cellulose / polyamide mixed fibers, it is preferred to choose an initial pH of the dye liquor which is between pH 5 and pH 8 (in particular between pH 6.5 and 7.5). The final pH of the aforementioned dye liquors is then from pH 8 to pH 11.5, preferably from pH 9.5 to 10.5.

Bei einer bestimmten insbesondere für Mischfasern geeigneten Variante des Verfahrens werden den verwendeten Färbeflotten Glycidylverbindungen beigegeben, die bei ihrer Spaltung zunächst Alkali und dann Säure freisetzen (z.B. Ester aus Phosphorsäure und Glycidylgruppen enthalten Alkoholen, wobei in diesem Falle der pH-Wert der Färbeflotte zunächst langsam ansteigt und so ein Färben des Cellulose oder Polyamidanteils der Faser begünstigt wobei dann durch die langsam freigesetzte Phosphorsäure der pH-Wert schlißlich wieder fällt und ein Anfärben des anderen Anteils der Faser (z.B. Polyester) im sauren Bereich begünstigt). Bei dieser letztgenannten Variante steigt daher der pH-Bereich von pH 5 bis 8 auf Werte um pH 8-10 an und fällt dann gegen Ende des Färbevorgangs ohne Säurezusatz bei Temperaturen von 80 bis 130°C auf Werte von pH 5 bis pH 7.In a particular variant of the process which is particularly suitable for mixed fibers, glycidyl compounds are added to the dye liquors used, which, when cleaved, first release alkali and then acid (e.g. esters of phosphoric acid and glycidyl groups contain alcohols, in which case the pH of the dye liquor initially rises slowly and so favors a dyeing of the cellulose or polyamide portion of the fiber, in which case the slowly released phosphoric acid finally causes the pH to drop again and favors dyeing of the other portion of the fiber (eg polyester) in the acidic range). In this latter variant, the pH range therefore rises from pH 5 to 8 to values around pH 8-10 and then falls towards the end of the dyeing process without addition of acid at temperatures from 80 to 130 ° C. to values from pH 5 to pH 7.

Das erfindungsgemäße Verfahren wird im allgemeinen so durchgeführt, daß .die Anfangstemperaturen zwischen 20 und 40°C und die Endtemperaturn zwischen 45 und 125°C liegen. Das Verfahren kann vorteilhafterweise auch bei konstanter Temperatur, z.B. bei 65°, durchgeführt werden.The process according to the invention is generally carried out in such a way that Starting temperatures are between 20 and 40 ° C and the end temperatures between 45 and 125 ° C. The process can advantageously also be carried out at a constant temperature, for example at 65 °.

Beispiel 1example 1

100 Teile einer Baumwollwirkware werden in eine handelsüliche Jetfärbeanlage eingezogen und diese mit 700 Teilen Wasser zu 25°C und 70 Teilen Kochsalz beschickt. Anschließend werden 10 Teile der Verbindung der Formel

Figure imgb0029
wobei sich ein pH von 6 bis 7 ergab, sowie 2 Teile des Farbstoffs 1 zugesetzt und die Flotte bei guter Waren-und Flottenzirkulation auf 80°C erwärmt. Es wird 1 Stunde bei dieser Temperatur gefärbt. Der End-pH-Wert liegt bei 10,3. Anschließend wird nach Ablassen der Restflotte in der üblichen Weise kalt und warm gespült und kochend geseift.100 parts of a knitted cotton fabric are drawn into a commercially available jet dyeing machine and this is charged with 700 parts of water at 25 ° C. and 70 parts of table salt. Then 10 parts of the compound of formula
Figure imgb0029
 a pH of 6 to 7 resulted, and 2 parts of dye 1 were added and the liquor was heated to 80 ° C. with good circulation of goods and liquor. It is dyed at this temperature for 1 hour. The final pH is 10.3. Then, after draining off the remaining liquor, it is rinsed cold and warm in the usual manner and soaped at the boil.

Man erhält eine egale Rotfärbung.A level red coloration is obtained.

Beispiel 2Example 2

100 Teile eines mercerisierten Baumwollgarns werden in Form von Kreuzspulen auf dem Garnfärbeapparat in 1000 Teile einer Flotte gebracht, die aus 90 Teilen Kochsalz, 8 Teilen der Verbindung der Formel

Figure imgb0030
2 Teilen des Farbstoffs 11 sowie 900 Teilen Wasser besteht. Der Anfangs-pH-Wert der Flotte beträgt 6,9. Die Flotte wird mit einer Aufheizgeschwindigkeit von 12 °/min. auf 95°C erwärmt und 15 min bei dieser Temperatur gehalten. Der End-pH der Flotte beträgt 9,2. Anschließend wird die erschöpfte Restflotte abgelassen und die erhaltene Färbung kalt und warm gespült und wie üblich 10 min. mit frischem Wasser gekocht. Man erhält eine klare Blaufärbung.100 parts of a mercerized cotton yarn are placed in the form of cross-wound bobbins on the yarn dyeing machine in 1000 parts of a liquor consisting of 90 parts of common salt, 8 parts of the compound of the formula
Figure imgb0030
 There are 2 parts of dye 11 and 900 parts of water. The initial pH of the liquor is 6.9. The liquor is heated at a rate of 12 ° / min. heated to 95 ° C and held at this temperature for 15 min. The final pH of the liquor is 9.2. The exhausted remaining liquor is then drained off and the dyeing obtained is rinsed cold and warm and, as usual, for 10 minutes. cooked with fresh water. A clear blue color is obtained.

Beispiel 3Example 3

100 Teile eines Rayonspinnkuchens werden in Form von Zwirnwickeln auf dem Garnfärbeapparat in 1000 Teile einer auf 80°C erwärmten Flotte gebracht, welche 80,00 Teile Natriumsulfat

  • 0,25 Teile Monoatriumphosphat
  • 8,00 Teile der Verbindung der Formel
    Figure imgb0031
    909.75 Teile Wasser sowie 2 Teile des Farbstoffs 111 enthält. Der Anfangs-pH der Flotte beträgt 5,5. Es wird im geschlossenen Apparat in 1 h auf 110°C gebracht und 1 h bei dieser Temperatur gehalten. Der End-pH beträgt 8. Man erhält eine egale gute durchgefärbte Gelbfärbung, welche nach dem üblichen Spülen und kochenden Seifen ein hervorragendes Echtheitsniveau aufweist.
100 parts of a rayon spider cake are placed in the form of twine wraps on the yarn dyeing machine in 1000 parts of a liquor heated to 80 ° C., which contains 80.00 parts of sodium sulfate
  • 0.25 parts mono sodium phosphate
  • 8.00 parts of the compound of the formula
    Figure imgb0031
     Contains 909.75 parts of water and 2 parts of dye 111. The initial pH of the liquor is 5.5. It is brought to 110 ° C. in the closed apparatus in 1 h and kept at this temperature for 1 h. The final pH is 8. A completely solid yellow color is obtained which, after the usual rinsing and boiling soaps, has an excellent level of authenticity.

Beispiel 4Example 4

100 Teile eines Textilmaterials bestehend aus 50 Teilen Zellwolle und 50 Teilen Polyester, werden auf einer Haspelkufe mit einer 65°C warmen Flotte behandelt, bestehend aus 80 Teilen Kochsalz100 parts of a textile material consisting of 50 parts of cellulose and 50 parts of polyester are treated on a reel runner with a 65 ° C warm liquor consisting of 80 parts of table salt

3 Teilen der Verbindung der Formel

Figure imgb0032

  • 1 Teil des Farbstoffs IV
  • 1 Teil des Farbstoffs VI
  • 1 Teil dinaphthylmethandisulfonsaures Natrium (Dispergiermittel)
  • 1 Teil Natriummetanitrobenzolsulfonat (Antioxydans)
  • 2 Teilen Trichlorbenzol (Carrier) und
  • 1200 Teilen Wasser.
3 parts of the compound of formula
Figure imgb0032
  • 1 part of dye IV
  • 1 part of dye VI
  • 1 part of sodium dinaphthylmethane disulfonic acid (dispersant)
  • 1 part sodium metanitrobenzenesulfonate (antioxidant)
  • 2 parts of trichlorobenzene (carrier) and
  • 1200 parts of water.

Der Anfangs-pH der Flotte beträgt 7,5. Es wird in 60 min auf 95°C erwärmt und 1 Stunde bei dieser Temperatur gefärbt. Der pH-Wert der Flotte steigt langsam auf pH 9,2 und fällt dann allmählich auf den Wert 6,5 ab.The initial pH of the liquor is 7.5. It is heated to 95 ° C. in 60 min and dyed at this temperature for 1 hour. The pH of the liquor slowly rises to pH 9.2 and then gradually drops to 6.5.

Nach dem üblichen Spülen und kochendem Seifen erhält man eine Rotfärbung mit guten Echtheitseigenschaften.After the usual rinsing and boiling soaping, a red color is obtained with good fastness properties.

Beispiel 5Example 5

100 Teile einer mercerisierten Baumwollwirkware werden auf eine Düsenfärbemaschine mit einer 60-C warmen Flotte behandelt, bestehend aus 80 Teilen Kochsalz

  • 0,5 Teilen Natriumbicarbonat
  • 6 Teilen der Verbindung der Formel
    Figure imgb0033
  • 2 Teilen des Farbstoffs V und
  • 800 Teilen Wasser.
100 parts of a mercerized cotton knitwear are treated on a jet dyeing machine with a 60 ° C warm liquor consisting of 80 parts of table salt
  • 0.5 parts sodium bicarbonate
  • 6 parts of the compound of formula
    Figure imgb0033
  • 2 parts of dye V and
  • 800 parts of water.

Der Anfangs-pH-Wert der Flotte beträgt 8,2. Es wird 2 Stunden bei 60°C gefärbt. In dieser Zeit steigt der pH-Wert Lngsam auf 11,3. nach dem üblichen Spülen und kochenden Seifen erhält man eine egale, tiefe Grünfärbung mit guten Echtheitseigenschaften.

Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
 The initial pH of the liquor is 8.2. It is dyed at 60 ° C for 2 hours. During this time, the pH slowly increases to 11.3. after the usual rinsing and boiling soaps, a level, deep green color with good fastness properties is obtained.
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039

Claims (2)

1. Process for evenly dyeing cellulose-containing fibre materials with reactive dyestuffs by the exhaustion method in the presence of salts and optionally further auxiliaries, characterised in that a glycidyl compound which causes a continuous increase in the ph value as the temperature rises, is added to the dye bath. -
2. Process according to Claim, characterised in that exhaustion liquors are used which contain a compound of the general formula
Figure imgb0047
wherein
Q denotes a radical of the formula
Figure imgb0048
Z denotes a 1-4-valent aliphatic hydrocarbon radical which can be interrupted by S-atoms, a cycloaliphatic hydrocarbon radical, a saturated heterocyclic radical or the groups
Figure imgb0049
Figure imgb0050
R denotes hydrogen or alkyl,
R, denotes alkyl, cycloalkyl, aryl or aralkyl,
Y denotes a radical of the formula
Figure imgb0051
A denotes alkylene or arylene,
m denotes 0 or 1,
n denotes 0-10,
q denotes 0 or 1, and
p denotes 1-4.
EP82110546A 1981-11-27 1982-11-16 Dyeing process Expired EP0080642B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3147153 1981-11-27
DE19813147153 DE3147153A1 (en) 1981-11-27 1981-11-27 COLORING PROCEDURE

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EP0080642B1 true EP0080642B1 (en) 1986-10-15

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Families Citing this family (15)

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Publication number Priority date Publication date Assignee Title
JPS59116482A (en) * 1982-12-23 1984-07-05 住友化学工業株式会社 Dyeing of blended fiber material
JPS63315680A (en) * 1987-06-17 1988-12-23 日本サ−ファクタント工業株式会社 Leveling agent for reactive dye and dyeing method
JPH0720987B2 (en) * 1987-10-21 1995-03-08 花王株式会社 Methods for modifying peptides and proteins
EP0620311B1 (en) * 1993-04-15 1998-02-11 Nippon Sanmo Sensyoku Co.,Ltd. Modified wool and process of imparting shrink-proofing property to wool
US5655936A (en) * 1995-12-18 1997-08-12 Yazaki Corporation Self locking, constant pressure electrical terminal for threaded studs
US6066183A (en) * 1998-04-13 2000-05-23 I-Hwa Industrial Co., Ltd. Liquid dispersed dye of the azo or anthraquinone type
US6520384B2 (en) * 2001-04-30 2003-02-18 Ketan C. Mehta Apparatus and method for nasal rinse
USD629884S1 (en) 2009-12-16 2010-12-28 Water Pik, Inc. Powered irrigator for sinus cavity rinse
US8888752B2 (en) * 2009-12-16 2014-11-18 Water Pik, Inc. Bottle for sinus cavity rinse
US8991660B2 (en) * 2009-12-16 2015-03-31 Water Pik, Inc. Squeeze bottle for sinus cavity rinse
US9061096B2 (en) 2009-12-16 2015-06-23 Water Pik, Inc. Powered irrigator for sinus cavity rinse
US8486029B2 (en) * 2009-12-16 2013-07-16 Water Pik, Inc. Pot for sinus cavity rinse
EP2534206B1 (en) * 2010-02-09 2014-04-02 Unilever PLC Dye polymers
US8409152B2 (en) 2010-06-25 2013-04-02 Water Pik, Inc. Faceted nasal seal
USD670373S1 (en) 2010-12-16 2012-11-06 Water Pik, Inc. Powered irrigator for sinus cavity rinse

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE503812C (en) * 1925-12-10 1930-08-08 I G Farbenindustrie Akt Ges Process for the preparation of colored condensation products of Kuepen dyes
FR1216308A (en) * 1957-09-25 1960-04-25 Ciba Geigy Process for dyeing polyhydroxy materials
GB922403A (en) * 1958-10-28 1963-04-03 American Cyanamid Co Triazine dyes and process of producing same
DE1239266B (en) * 1962-04-28 1967-04-27 Basf Ag Process for dyeing and / or printing textile goods
DE1619464A1 (en) * 1966-02-23 1970-10-29 Hoechst Ag Process for dyeing cellulose fibers with reactive dyes or mixtures of cellulose and polyester fibers with reactive and disperse dyes
BE737603A (en) * 1968-09-25 1970-02-02
CH509369A (en) * 1969-05-07 1971-06-30 Ciba Geigy Ag Process for the production of stable preparations of reaction products from epoxies and amines
US3673558A (en) * 1970-05-04 1972-06-27 Ciba Ltd Polyaddition products and process for their manufacture
DE2914142A1 (en) * 1979-04-07 1980-11-13 Bayer Ag METHOD FOR ONE-BATHING, ONE-STEP DYEING OR PRINTING OF CELLULOSE FIBERS WITH FIBER REACTIVE DISPERSION DYES
GB2028876B (en) * 1978-09-01 1982-10-13 Bayer Ag Process for dyeing and printing cellulose fibres with reactive dyestuffs
DE2838274A1 (en) * 1978-09-01 1980-03-13 Bayer Ag METHOD FOR COLORING AND PRINTING CELLULOSE FIBERS WITH REACTIVE DYES
DE2922484A1 (en) * 1979-06-01 1980-12-04 Bayer Ag COLORING PROCEDURE

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EP0080642A1 (en) 1983-06-08
US4439206A (en) 1984-03-27
JPS5891876A (en) 1983-05-31
DE3147153A1 (en) 1983-06-01
DE3273813D1 (en) 1986-11-20

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