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EP0080642A1 - Dyeing process - Google Patents

Dyeing process Download PDF

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Publication number
EP0080642A1
EP0080642A1 EP82110546A EP82110546A EP0080642A1 EP 0080642 A1 EP0080642 A1 EP 0080642A1 EP 82110546 A EP82110546 A EP 82110546A EP 82110546 A EP82110546 A EP 82110546A EP 0080642 A1 EP0080642 A1 EP 0080642A1
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EP
European Patent Office
Prior art keywords
dye
liquors
parts
radical
dyeing
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.)
Granted
Application number
EP82110546A
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German (de)
French (fr)
Other versions
EP0080642B1 (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 dyeing process based on the pull-out principle.
  • the process according to the invention is characterized in that dye liquors are used which, in addition to the dye or a dye mixture, contain one or more salts, at least one compound containing a glycidyl radical and, if appropriate, further auxiliaries.
  • the process of the invention is particularly suitable for dyeing cellulose fiber materials and / or polyamide materials and cellulose fiber materials and / or fiber mixtures containing reactive dyes using the pull-out principle.
  • Suitable salts in the process according to the invention are primarily neutral reacting salts, optionally in a mixture with weakly acidic or weakly alkaline reacting salts.
  • 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 1 are those having 1-5 carbon atoms.
  • Preferred cycloaliphatic radicals Z and cycloalkyl radicals R 1 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.
  • heterocyclic radicals Z are the 1,3,5-hexahydrotriazine radical or radicals of the formula called, wherein R 2 for hydrogen or together for oxygen, R 3 for hydrogen or methyl and B for or -CH 2 - stand, or the grouping represents an o-phenylene radical.
  • the compounds containing glycidyl groups are alcohols, their esters with acids, e.g. with phosphoric acid.
  • the amounts of compounds containing glycidyl radical to be used by the process according to the invention depend on the depth of color to be achieved and the liquor ratio.
  • the following reactive dye classes are preferably suitable as dyes suitable for the process according to the invention for dyeing cellulose: organic dyes from the series of the anthraquinone, azo, azo metal complex series, formazane, oxazine and phthalocyanine series, the at least one fiber-reactive group such as the sulfatoethylsulfonyl , Monochlorotriazinyl, dichlorotriazinyl, dichloroquinoxalinyl, trichloropyrimidinyl, monofluorotriazinyl, 2,4-difluoro-5-chloropyrimidinyl, 2-fluoro-5-chloro-6-methylpyrimidinyl, 4-fluoro-5-chloropyrimidinyl group .
  • Fibers are used to dye the non-cellulose portion of the respective mixed fiber using the dyes customary for the corresponding fiber, such as, for example, dispersion dyes, in the usual concentration ratios.
  • the dyes customary for the corresponding fiber such as, for example, dispersion dyes, in the usual concentration ratios.
  • the process according to the invention is particularly suitable for dyeing cellulose fibers and fibers containing cellulose.
  • cellulose fibers cotton, rayon, rayon.
  • polyester fibers The following fibers are listed as a mixture with cellulose: polyester fibers, polyamide fibers.
  • the method according to the invention is also suitable for dyeing wool or wool in a mixture with other fibers such as e.g. Acrylate, polyester, polyamide fibers.
  • the starting pH value and the amount and type of auxiliary substances which may have been added should be selected.
  • auxiliaries are: leveling agents, dispersants, antioxidants, carrier substances, etc.
  • the amounts of salt to be used depend on the color depth and the desired dyeing temperature or the liquor ratio, and can be determined in a simple manner by preliminary use.
  • the saise used in the process according to the invention can also be used alone and / or in a mixture.
  • Mixtures of 30 to 120 g / l, 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 reaction have proven to be advantageous.
  • the initial pH of the dye bath depends on the tissue to be dyed.
  • suitable for setting the desired initial pH value suitable for setting the desired initial pH value. Addition of weak acids like acetic acid.
  • 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 above-mentioned dye liquors is then from pH 8 to pH 11.5, preferably from pH 9.5 to 10.5.
  • dyeing wool one selects an initial pH value between pH 2 and pH 5, the final pH value then being between pH 5 and pH 7.
  • the added glycidyl compound leads to a continuous increase in pH with increasing temperature, the increase profile of which depends on various factors, e.g. also depends on the reaction of the reactive dye with the cellulose fiber and on the type of glycidyl compound used.
  • glycidyl compounds are added to the dye liquors used which, when they are cleaved, first release alkali and then acid (e.g. esters from alcohols containing phosphoric acid and glycidyl groups, in which case the pH of the dye liquor initially rises slowly and thus favors a dyeing of the cellulose or polyamide portion of the fiber, the pH then finally falling again due to the slowly released phosphoric acid and fostering 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 the initial temperatures are between 20 and 40 ° C. and the final 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 2 parts of dye II and 900 parts of water.
  • the initial pH of the liquor is 6.9.
  • the liquor is heated at a rate of 1/2 ° / min. heated to 95 ° C and 15 min. kept at this temperature.
  • 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 will be in 60 min. warmed to 95 ° C 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 you get a level, deep green color with good fastness properties.

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

Abstract

Die vorliegende Erfindung betrifft ein neues Färbeverfahren nach dem Ausziehprinzip. Es ist dadurch gekennzeichnet, daß Färbeflotten verwendet werden, welche neben dem Farbstoff oder Farbstoffgemisch ein oder mehrere Salze, mindestens eine einen Glycidylrest aufweisende Verbindung sowie gegebenenfalls weitere Hilfsstoffe enthalten.The present invention relates to a new dyeing process based on the pull-out principle. It is characterized in that dye liquors are used which, in addition to the dye or dye mixture, contain one or more salts, at least one compound containing a glycidyl radical and, if appropriate, further auxiliaries.

Description

Die vorliegende Erfindung betrifft ein neues Färbeverfahren nach dem Ausziehprinzip.The present invention relates to a new dyeing process based on the pull-out principle.

Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß Färbeflotten verwendet werden, welche neben dem Farbstoff oder einem Farbstoffgemisch ein oder mehrere Salze, mindestens eine einen Glycidylrest aufweisende Verbindung sowie gegebenenfalls weitere Hilfsstoffe enthalten.The process according to the invention is characterized in that dye liquors are used which, in addition to the dye or a dye mixture, contain one or more salts, at least one compound containing a glycidyl radical and, if appropriate, further auxiliaries.

Das erfindungsgemäße Verfahren eignet sich im besonderen Maße zum Färben von Cellulosefasermaterialien und/oder Polyamidmaterialien und Cellulosefasermaterialien und/ oder Polyamidmaterialien enthaltenden Fasermischungen mit Reaktivfarbstoffen nach dem Ausziehprinzip.The process of the invention is particularly suitable for dyeing cellulose fiber materials and / or polyamide materials and cellulose fiber materials and / or fiber mixtures containing reactive dyes using the pull-out principle.

Als Salze kommen beim erfindungsgemäßen Verfahren in erster Linie neutral reagierende Salze, gegebenenfalls im Gemisch mit schwach sauer oder schwach alkalisch reagierenden Salzen in Frage.Suitable salts in the process according to the invention are primarily neutral reacting salts, optionally in a mixture with weakly acidic or weakly alkaline reacting salts.

Als für das erfindungsgemäße Verfahren besonders geeignete Glycidylreste enthaltende 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
    R1-NH-CO-, -OC-NH-A-NH-CO-
  • R Wasserstoff oder Alkyl,
  • R1 Alkyl, Cycloalkyl, Aryl oder Aralkyl,
  • Y einen Rest der Formel -CO-CH2-CH2-, -SO2-CH2-CH2- oder -CH2-CH2-A Alkylen oder Arylen,
  • m 0 oder 1,
  • n 0 - 10,
  • q 0 oder 1 und
  • p 1-4 bedeuten.
Suitable compounds containing glycidyl radicals which 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 1 -NH-CO-, -OC-NH-A-NH-CO-
  • R is hydrogen or alkyl,
  • R 1 is alkyl, cycloalkyl, aryl or aralkyl,
  • Y is a residue of the formula -CO-CH2 - CH 2 -, -SO 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -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 R1 sind solche mit 1-5 Kohlenstoffatomen. Bevorzugte cycloaliphatische Reste Z und Cycloalkylreste R1 sind der Cyclopentyl- und der Cyclohexylrest.Preferred aliphatic radicals Z and preferred alkyl radicals R and R 1 are those having 1-5 carbon atoms. Preferred cycloaliphatic radicals Z and cycloalkyl radicals R 1 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 imgb0005
genannt, worin R2 für Wasserstoff oder gemeinsam für Sauerstoff, R3 für Wasserstoff oder Methyl und B für
Figure imgb0006
oder -CH2- stehen, oder die Gruppierung
Figure imgb0007
für einen o-Phenylenrest steht.Examples of heterocyclic radicals Z are the 1,3,5-hexahydrotriazine radical or radicals of the formula
Figure imgb0005
 called, wherein R 2 for hydrogen or together for oxygen, R 3 for hydrogen or methyl and B for
Figure imgb0006
 or -CH 2 - stand, or the grouping
Figure imgb0007
 represents an o-phenylene radical.

Von den Verbindungen der Formel I sind die der Formeln

Figure imgb0008
worin Z1 einen 1-4-wertigen aliphatischen Kohlenwasserstoffrest mit 1-5 Kohlenstoffatomen bedeutet, und n und p die vorstehend genannte Bedeutung haben,
Figure imgb0009
worin n die vorstehend genannte Bedeutung hat, und
Figure imgb0010
worin

  • Z2 den 1,3,5-Hexahydrotriazinrest oder einen Rest der Formel II,
  • Y1 -CO-CH2-CH2- oder -SO2-CH2-CH2- und
  • P1 1-3 bedeuten,
  • n die vorstehend genannte Bedeutung hat, und der in eckigen Klammern stehende Rest an ein Stickstoffatom von Z2 gebunden ist, bevorzugt.
Of the compounds of formula I are those of the formulas
Figure imgb0008
 in which Z 1 denotes a 1-4-valent aliphatic hydrocarbon radical having 1-5 carbon atoms, and n and p have the meaning given above,
Figure imgb0009
 wherein n has the meaning given above, and
Figure imgb0010
 wherein
  • Z 2 is the 1,3,5-hexahydrotriazine radical or a radical of the formula II,
  • Y 1 -CO-CH 2 -CH 2 - or -SO 2 -CH 2 -CH 2 - and
  • P 1 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 I seien genannt:

Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
n = 0 - 8, insbesondere 1 - 6
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Weiterhin kommen in Betracht:
Figure imgb0028
Figure imgb0029
Figure imgb0030
 The following may be mentioned as examples of the compounds I:
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
 n = 0-8, especially 1-6
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
 The following can also be considered:
Figure imgb0028
Figure imgb0029
Figure imgb0030

sowie, falls es sich bei den Glycidylgruppen aufweisenden Verbindungen um Alkohole handelt, deren Ester mit Säuren, z.B. mit Phosphorsäure.and, if the compounds containing glycidyl groups are alcohols, their esters with acids, e.g. with phosphoric acid.

Die nach dem erfindungsgemäßen Verfahren einzusetzenden Mengen an Glycidylrest aufweisenden Verbindungen richten sich nach der zu erreichenden Farbtiefe und dem Flottenverhältnis.The amounts of compounds containing glycidyl radical to be used by the process according to the invention depend on the depth of color to be achieved and the liquor ratio.

Im allgemeinen setzt man 1 bis 20 g Glycidyl-Verbindung pro Liter Färbeflotte und bevorzugt 3 bis 6 g Glycidyl- Verbindung pro Liter Färbeflotte ein.In general, 1 to 20 g of glycidyl compound per liter of dye liquor and preferably 3 to 6 g of glycidyl compound per liter of dye liquor are used.

Als für das erfindungsgemäße Verfahren zum Färben der Cellulose geeignete Farbstoffe kommen folgende Reaktivfarbstoffklassen vorzugsweise in Frage: organische Farbstoffe aus der Reihe der Anthrachinon-, Azo-, Azometallkomplex-, Formazan-, Oxazin- und Phthalocyaninreihe, die mindestens eine faserreaktive Gruppe wie die Sulfatoethylsulfonyl-, Monochlortriazinyl-, Dichlortriazinyl-, Dichlorchinoxalinyl-, Trichlorpyrimidinyl-, Monofluortriazinyl-, 2,4-Difluor-5-chlorpyrimidinyl-, 2-Fluor-5-chlor-6-methylpyrimidinyl-, 4-Fluor-5-chlor- pyrimidinylgruppe aufweisen. Reaktivfarbstoffe der vorgenannten Struktur sind in der Literatur in großer Zahl beschrieben worden (vgl. dazu beispielsweise DE-OS 1,186,160, DE-OS 1,544,499, DE-OS 1,228,013, DE-OS 1,644,171, DE-OS 2,556,640, DE-OS 1,644,208, DE-OS 1,644,617, DE-OS 1,644,616, Venkataraman, The Chemistry of Synthetic Dyes, Volume VI, Reactive Dyes; Academic Press, New York, London 1972). Insbesondere bevorzugt werden die in den Beispielen spezifizierten sowie mit ihnen strukturell verwandte Reaktivfarbstoffe beim erfindungsgemäßen Verfahren eingesetzt. Bei den in den Beispielen angegebenen Teilen handelt es sich in allen Fällen um Gewichtsteile.The following reactive dye classes are preferably suitable as dyes suitable for the process according to the invention for dyeing cellulose: organic dyes from the series of the anthraquinone, azo, azo metal complex series, formazane, oxazine and phthalocyanine series, the at least one fiber-reactive group such as the sulfatoethylsulfonyl , Monochlorotriazinyl, dichlorotriazinyl, dichloroquinoxalinyl, trichloropyrimidinyl, monofluorotriazinyl, 2,4-difluoro-5-chloropyrimidinyl, 2-fluoro-5-chloro-6-methylpyrimidinyl, 4-fluoro-5-chloropyrimidinyl group . A large number of reactive dyes of the aforementioned structure have been described in the literature (cf. for example DE-OS 1,186,160, DE-OS 1,544,499, DE-OS 1,228,013, DE-OS 1,644,171, DE-OS 2,556,640, DE-OS 1,644,208, DE- OS 1,644,617, DE-OS 1,644,616, Venkataraman, The Chemistry of Synthetic Dyes, Volume VI, Reactive Dyes; Academic Press, New York, London 1972). The reactive dyes specified in the examples and structurally related to them are particularly preferably used in the process according to the invention. In all cases, the parts given in the examples are parts by weight.

Beim Färben von Mischgewebe aus Cellulose und anderen Fasern werden zur Färbung des Nichtcellulose-Anteils der jeweiligen Mischfaser die für die entsprechende Faser üblichen Farbstoffe wie z.B. Dispersionsfarbstoffe in üblichen Konzentrationsverhältnissen eingesetzt. Im übrigen sei auch hier auf die Ausführungsbeispiele verwiesen.When dyeing blended fabrics made of cellulose and others Fibers are used to dye the non-cellulose portion of the respective mixed fiber using the dyes customary for the corresponding fiber, such as, for example, dispersion dyes, in the usual concentration ratios. For the rest, reference is also made here to the exemplary embodiments.

Das erfindungsgemäße Verfahren ist wie eingangs erwähnt bestens für das Färben von Cellulosefasern sowie von Cellulose enthaltenden Fasern geeignet. Als Cellulosefasern seien genannt: Baumwolle, Rayon, Zellwolle.As mentioned at the outset, the process according to the invention is particularly suitable for dyeing cellulose fibers and fibers containing cellulose. The following may be mentioned as cellulose fibers: cotton, rayon, rayon.

Als im Gemisch mit Cellulose vorliegenden Fasern seien aufgeführt: Polyesterfasern, Polyamidfasern.The following fibers are listed as a mixture with cellulose: polyester fibers, polyamide fibers.

Das erfindungsgemäße Verfahren ist außerdem geeignet für das Färben von Wolle oder von Wolle im Gemisch mit anderen Fasern wie.z.B. Acrylat-, Polyester-, Polyamidfasern.The method according to the invention is also suitable for dyeing wool or wool in a mixture with other fibers such as e.g. Acrylate, polyester, polyamide fibers.

Im Hinblick auf die obengenannten zu färbenden Materialien ist der Ausgangs-pH-Wert sowie Menge und Art der gegebenenfalls zugesetzten Hilfsstoffe zu wählen. Als solche Hilfsstoffe kommen beispielsweise in Frage: Egalisiermittel, Dispergiermittel, Antioxydantien, Carrier-Substanzen usw..With regard to the above-mentioned materials to be colored, the starting pH value and the amount and type of auxiliary substances which may have been added should be selected. Examples of such auxiliaries are: leveling agents, dispersants, antioxidants, carrier substances, etc.

Beim erfindungsgemäßen Verfahren kommen als neutral reagierende Salze vor allen NaCl und Na2S04 in Betracht. Als beim erfindungsgemäßen Verfahren besonders geeignete schwach sauer reagierende Salze können beispielsweise genannt werden: Mononatrium- bzw. Monokaliumphosphat und Mononatrium- bzw. Monokaliumsulfat.In the process according to the invention come into consideration as neutral reacting salts before all NaCl and Na 2 S0 4 . Weakly acidic salts which are particularly suitable in the process according to the invention can be mentioned, for example: monosodium or monopotassium phosphate and monosodium or monopotassium sulfate.

Als geeignete schwach alkalisch reagierende Salze seien beispielsweise genannt:

  • Natrium- bzw. Kaliumbicarbonat, Natriumacstat, Dinatrium- bzw. Dikaliumphosphat, Tetranatriuapyrophosphat.
Examples of suitable weakly alkaline salts are:
  • Sodium or potassium bicarbonate, Natriumacstat, disodium or D ikaliumphosphat, Tetranatriuapyrophosphat.

Die einzusetzenden Mengen an Salz richten sich nach der Farbtiefe und der gewünschten Färbetemperatur bzw. dem Flottenverhältnis, sie können in einfacher Weise durch Vorverauche ermittelt werden.The amounts of salt to be used depend on the color depth and the desired dyeing temperature or the liquor ratio, and can be determined in a simple manner by preliminary use.

Die beim erfindungwgemäBen Verfahre eingesetzten Saise köanen ferner allein und/oder in Mischung verwendet verden. Als vorteilhaft haben sich Mischungen von 30 bis 120 g/l, bevorzugt 50-80 g/l eiaes Meutualsalzes vie Natriumchlorid oder Natriumsulfat mit 0,2 bis 4 g/1 eines schwach alkalisch reagierenden oder schwach sauer reagierenden Sales erwiesen.The saise used in the process according to the invention can also be used alone and / or in a mixture. Mixtures of 30 to 120 g / l, 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 reaction have proven to be advantageous.

Der Anfanga-pH-Wert des Färbebades richtet sich nach dem zu färbenden Gewebe. Zur Einwtellung des gewünschten Anfanqä-pH-Wentes eignsn sich außer Mischungen von schwach sauer und schwach allcalisch reagierenden Salzen. Zusätze von schwachen Säuren wie Essigsäure.The initial pH of the dye bath depends on the tissue to be dyed. In addition to mixtures of weakly acidic and weakly allcalic salts, suitable for setting the desired initial pH value. Addition of weak acids like acetic acid.

Beim Färben von Cellulosefasern und/oder Polyamidfasern wählt man vorzugsweise 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. Beim Färben von Wolle wählt man einen Ausgangs-pH-Wert der zwischen pH 2 und pH 5 liegt, wobei dann der End-pH-Wert zwischen pH 5 und pH 7 liegt. Durch die zugesetzte Glycidylverbindung erreicht man mit steigender Temperatur einen kontinuierlichen pH-Wert-Anstieg, dessen Anstiegsprofil von unterschiedlichen Faktoren z.B. auch von der stattfindenden Umsetzung des Reaktivfarbstoffs mit der Cellulosefaser und von der Art der eingesetzten Glycidylverbindung abhängt.When dyeing cellulose fibers and / or polyamide 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 above-mentioned dye liquors is then from pH 8 to pH 11.5, preferably from pH 9.5 to 10.5. When dyeing wool, one selects an initial pH value between pH 2 and pH 5, the final pH value then being between pH 5 and pH 7. The added glycidyl compound leads to a continuous increase in pH with increasing temperature, the increase profile of which depends on various factors, e.g. also depends on the reaction of the reactive dye with the cellulose fiber and on the type of glycidyl compound used.

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 enthaltenden 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 schließlich 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 they are cleaved, first release alkali and then acid (e.g. esters from alcohols containing phosphoric acid and glycidyl groups, in which case the pH of the dye liquor initially rises slowly and thus favors a dyeing of the cellulose or polyamide portion of the fiber, the pH then finally falling again due to the slowly released phosphoric acid and fostering 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 Endtemperaturen 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 the initial temperatures are between 20 and 40 ° C. and the final 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 handelsübliche 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 imgb0031
wobei sich ein pH von 6 bis 7 ergab, sowie 2 Teile des Farbstoffs I 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 imgb0031
 a pH of 6 to 7 resulted, and 2 parts of dye I 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 imgb0032
2 Teilen des Farbstoffs II sowie 900 Teilen Wasser besteht. Der Anfangs-pH-Wert der Flotte beträgt 6,9. Die Flotte wird mit einer Aufheizgeschwindigkeit von 1/2 °/ 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 imgb0032
 2 parts of dye II and 900 parts of water. The initial pH of the liquor is 6.9. The liquor is heated at a rate of 1/2 ° / min. heated to 95 ° C and 15 min. kept at this temperature. 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 Mononatriumphosphat
  • 8,00 Teile der Verbindung der Formel
  • Figure imgb0033
    909,75 Teile Wasser
  • sowie 2 Teile des Farbstoffs III 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
  • 80.00 parts of sodium sulfate
  • 0.25 parts of monosodium phosphate
  • 8.00 parts of the compound of the formula
  • Figure imgb0033
     909.75 parts water
  • and 2 parts of dye III. 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 Kochsalz
3 Teilen der Verbindung der Formel

Figure imgb0034

  • 1 Teil des Farbstoffs IV
  • 1 Teil den Farbstoffs VI
  • 1 Teil dinaphthylmethandisulfonsaures Natrium (Dispergiermittel)
  • 1 Teil Natriummetanitrobenzolsulfonat (Antioxydans)
  • 2 Teilen Trichlorbenzol (Carrier) und 1200 Teilen Wasser.
100 parts of a textile material consisting of 50 parts and 50 parts of rayon polyesters, on a H aspelkufe with a 65 ° C warm treated liquor consisting of 80 parts of sodium chloride
3 parts of the compound of formula
Figure imgb0034
  • 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 will be in 60 min. warmed to 95 ° C 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 imgb0035
  • 2 Teilen des Farbstoffs V und
  • 800 Teilen Wasser.
10 0 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 imgb0035
  • 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 langsam auf 11,3. Nach dem üblichen Spülen und kochenden Seifen erhält man eine egale, tiefe Grünfärbung mit guten Echtheitseigenschaften.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 you get a level, deep green color with good fastness properties.

Beispiel 6Example 6

100 Teile eines chlorierten Wollstrickgarns werden auf einen Strangfärbeapparat in 2000 Teile einer auf 40°C erwärmten Flotte gebracht, bestehend'aus

  • (a) 1 Teil des Farbstoffs II
  • (b) 1 Teil des Farbstoffs III
  • (c) 10 Teilen Natriumsulfat
  • (d) 4 Teilen der Verbindung der Formel
    Figure imgb0036
  • (e) 2 Teilen der Verbindung der Formel
    Figure imgb0037
    (Egalisiermittel für Reaktivfarbstoff)
  • (f) 2 Teilen 30 %ige Essigsäure und 1980 Teilen Wasser.
100 parts of a chlorinated wool knitting yarn are placed on a skein dyeing machine in 2000 parts of a liquor heated to 40 ° C consisting of
  • (a) 1 part of dye II
  • (b) 1 part of dye III
  • (c) 10 parts of sodium sulfate
  • (d) 4 parts of the compound of the formula
    Figure imgb0036
  • (e) 2 parts of the compound of the formula
    Figure imgb0037
     (Leveling agent for reactive dye)
  • (f) 2 parts of 30% acetic acid and 1980 parts of water.

Es wird in 1 Stunde auf Kochtemperatur gebracht und 1 Stunde kochend gefärbt. Nach dem kalten Spülen und 15 Minuten Nachbehandeln mit frischem Wasser bei 80° wird mit 1/2 Teil Essigsäure 60 %ig in 2000 Teilen Flotte abgesäuert. Man erhält eine egale Grünfärbung mit guten Echtheitseigenschaften.It is brought to boiling temperature in 1 hour and stained boiling for 1 hour. After cold rinsing and aftertreatment with fresh water at 80 ° for 15 minutes, the mixture is acidified with 1/2 part 60% acetic acid in 2000 parts liquor. A level green color with good fastness properties is obtained.

Führt man die Färbung in der gleichen Weise wie beschrieben aus, verwendet aber anstelle von 4'Teilen der Verbindung (d) und 2 Teilen der Verbindung (e) 3 Teile der Verbindung der Formel

Figure imgb0038
so erhält man ebenfalls eine egale Färbung mit guten Echtheitseigenschaften.If the dyeing is carried out in the same manner as described, but instead of 4 parts of compound (d) and 2 parts of compound (e), 3 parts of the compound of the formula are used
Figure imgb0038
 this also gives a level dyeing with good fastness properties.

Claims (9)

1. Verfahren zum Färben von Fasern nach dem Ausziehprinzip, dadurch gekennzeichnet, daß eine Färbeflotte verwendet wird, welche neben dem Farbstoff oder dem Farbstoffgemisch, ein oder mehrere Salze sowie mindestens eine einen Glycidylrest aufweisende Verbindung sowie gegebenenfalls weitere Hilfsstoffe enthält.1. A process for dyeing fibers according to the pull-out principle, characterized in that a dyeing liquor is used which, in addition to the dye or the dye mixture, contains one or more salts and at least one compound containing a glycidyl radical and optionally further auxiliaries. 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Cellulosefaser- und/oder Polyamidfaser- und Cellulosefaser und/oder Polyamidfaser enthaltendes Material mit Reaktivfarbstoffen gefärbt wird.2. The method according to claim 1, characterized in that cellulose fiber and / or polyamide fiber and cellulose fiber and / or polyamide fiber-containing material is dyed with reactive dyes. 3. Verfahren gemäß Anspruch 1 bis 2, dadurch gekennzeichnet, daß man Ausziehflotten verwendet, die eine Verbindung der allgemeinen Formel
Figure imgb0039
enthalten, worin Q einen Rest der Formel
Figure imgb0040
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 imgb0041
Figure imgb0042
, R -NH-CO-, -OCNH-A-NH-CO-, R Wasserstoff oder Alkyl, R1 Alkyl, Cycloalkyl, Aryl oder Aralkyl, Y einen Rest der Formel -CO-CH2-CH2-, -SO2-CH2-CH2- oder -CH2-CH 2- A Alkylen oder Arylen, m 0 oder 1, n 0 - 10, q 0 oder 1 und p 1-4 bedeuten. 3. The method according to claim 1 to 2, characterized in that one uses pull-out liquors containing a compound of the general formula
Figure imgb0039
 contain, wherein Q is a radical of the formula
Figure imgb0040
 Z is a 1-4-valent aliphatic hydrocarbon residue which can be interrupted by S atoms, a cycloaliphatic hydrocarbon residue, a saturated heterocyclic residue or the groups
Figure imgb0041
Figure imgb0042
 , R -NH-CO-, -OCNH-A-NH-CO-, R is hydrogen or alkyl, R 1 is alkyl, cycloalkyl, aryl or aralkyl, Y is a radical of the formula -CO-CH 2 -CH 2 -, -SO 2 -CH 2 -CH 2 - or - C H 2 -C H 2 - A alkylene or arylene, m 0 or 1, n 0-10, q 0 or 1 and p mean 1-4. 4. Verfahren gemäß Anspruch 1 bis 3, dadurch gekennzeichnet, daß man Ausziehflotten verwendet, die eine Verbindung der allgemeinen Formel
Figure imgb0043
enthalten, worin Z1 einen 1-4-wertigen aliphatischen Kohlenwasserstoffrest mit 1-5 Kohlenstoffatomen bedeutet, und n und p die Bedeutung des Anspruchs 3 haben. 4. The method according to claim 1 to 3, characterized records that one uses pull-out liquors which a compound of the general formula
Figure imgb0043
 included in what Z 1 represents a 1-4-valent aliphatic hydrocarbon radical having 1-5 carbon atoms, and n and p have the meaning of claim 3. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß Färbeflotten verwendet werden, welche NaCl oder Na2S04 enthalten.5. The method according to claim 1 to 4, characterized in that dye liquors are used which contain NaCl or Na 2 S0 4 . 6. Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß Färbeflotten verwendet werden, die neben NaCl oder Na2SO4 ein Salz- oder Salzgemisch der Reihe Mono- oder Dinatriumphosphat, Mono- oder Dikaliumphosphat, Natrium- oder Kaliumacetat, Natrium- oder Kaliumhydrogensulfat oder Natriumborat aufweisen.6. The method according to claim 1 to 5, characterized in that dye liquors are used which, in addition to NaCl or Na 2 SO 4, a salt or salt mixture of the series mono- or disodium phosphate, mono- or dipotassium phosphate, sodium or potassium acetate, sodium or Potassium bisulfate or sodium borate. 7. Verfahren nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die verwendeten Färbeflotten einen Anfangs-pH-Wert von 5 bis 8 und einen End-pH-Wert von 8 bis 11,5 aufweisen.7. The method according to claim 1 to 6, characterized in that the dyeing liquors used have an initial pH of 5 to 8 and an end pH of 8 to 11.5. 8. Verfahren nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß die verwendeten Färbeflotten eine Anfangstemperatur von 20 bis 40°C und eine Endtemperatur von 45 bis 120°C aufweisen.8. The method according to claim 1 to 7, characterized in that the dye liquors used have an initial temperature of 20 to 40 ° C and an end temperature of 45 to 120 ° C. 9) Verfahren nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die verwendeten Färbeflotten einen Anfangs-pH-Wert von 5 bis 8, anschließend mit zunehmender Temperatur einen höheren pH-Wert von 8 bis 10 durchlaufen und anschließend ohne Zusatz von Säure bei einem längeren Verweilen bei Temperaturen von 80 bis 130°C einen End-pH-Wert von 5 bis 8 einnehmen.
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049
 9 ) Method according to claim 1 to 6, characterized in that the dye liquors used have an initial pH of 5 to 8, then pass through a higher pH of 8 to 10 with increasing temperature and then without the addition of acid for a longer period Linger at a temperature of 80 to 130 ° C, take a final pH of 5 to 8.
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049
EP82110546A 1981-11-27 1982-11-16 Dyeing process Expired EP0080642B1 (en)

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