EP0305858A2 - Process for dyeing polyamide fibres - Google Patents

Process for dyeing polyamide fibres Download PDF

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Publication number
EP0305858A2
EP0305858A2 EP88113674A EP88113674A EP0305858A2 EP 0305858 A2 EP0305858 A2 EP 0305858A2 EP 88113674 A EP88113674 A EP 88113674A EP 88113674 A EP88113674 A EP 88113674A EP 0305858 A2 EP0305858 A2 EP 0305858A2
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Prior art keywords
liquor
group
methyl
alkyl
hydrogen
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German (de)
French (fr)
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EP0305858A3 (en
EP0305858B1 (en
Inventor
Norbert Hucke
Ergun Tamer
Wilfrid Jans
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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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/06—Material containing basic nitrogen containing amide groups using acid 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
    • D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes

Definitions

  • the polyamide materials are brought into contact with an aqueous liquor at 40-90 ° C. which, in addition to the auxiliary mixture mentioned, contains one or more dyes and, if appropriate, other customary coloring auxiliaries with the exception of the acid required for fixation and exhaustion of the bath.
  • the acid is added at a constant temperature between 40 and 90 ° C.
  • the auxiliary mixture preferably contains components A and B in a weight ratio of 1: 1 to 1: 0.5.
  • the radicals R include, for example, the dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eikosyl, behenyl, octadecenyl and abietyl radicals.
  • R3 be as optionally substituted C1-C4-alkyl groups, the methyl, ethyl, n-propyl, i-propyl, n or sec-butyl group, further by a hydroxy, carboxyl, lower carbalkoxy or carbonamide group substituted C2-C4-alkyl radicals, such as the 2-hydroxyethyl, carbonamidomethyl radical.
  • the optionally substituted aralkyl radicals are especially the benzyl and phenylethyl radical, which can be substituted by OH, Cl or CH3.
  • Preferred arylene is phenylene
  • the anionic group A ⁇ are in particular the SO3 ⁇ - and SO4 ⁇ group.
  • M ⁇ preferably represents an alkali ion such as sodium and potassium ion, an alkaline earth metal ion such as calcium and magnesium ion and an ammonium ion such as ammonium ion or the ammonium ions derived from mono-, di- or triethanolamine.
  • Suitable anions X ⁇ are conventional inorganic or organic anions, for example Chloride, bromide, iodide, methosulfate, sulfate, phosphate or acetate.
  • Preferred compounds of the formulas (I) and (II) are compounds of the formulas wherein R ′ for C12-C22 alkyl, R1 'for methyl or a group of the formulas R2 ′ for hydrogen or methyl, R3 'for hydrogen, methyl, which may be substituted by CONH2 or COOMe, ethyl, which may be substituted by OH, or benzyl and A ′ ⁇ stand for SO4 ⁇ or SO3 ⁇ , and Me, m and n have the meaning given above.
  • the sum of m + n is preferably 18-40.
  • Preferred compounds of the formula (III) are compounds of the formula wherein R4 'represents hydrogen, methyl, benzyl or the group R5 ′ for the group R6 'represent -CHR2'- or phenylene and R ', R2', X ⁇ , x, y and z have the meaning given above.
  • the compounds (I), (II) and (III) are prepared by known processes.
  • the compounds (I) and (II) are known for example from DE-A-1 940 178.
  • the compounds (III) are prepared by the action of ethylene oxide or mixtures of ethylene oxide and up to 20% propylene oxide, butylene oxide or styrene oxide on primary or secondary amines or those tertiary amines which contain a hydroxyl group.
  • amines include: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, arachylamine, oleylamine, abietylamine, hexadecylmethylamine, octadecylmethylamine, N- ( ⁇ -hydroxyethyl) methylhexadecylamine, N- ( ⁇ -hydroxyethyl) methyl-octadecylamine ( ⁇ -hydroxypropyl) methyl octadecylamine and N- (2-hydroxy-2-phenyl-ethyl) methyl octadecenylamine.
  • the compounds of Tables 1 and 2 may be mentioned as representatives of the compounds (I), (II) and (III).
  • the dyeing material containing polyamide groups e.g. as a yarn, for example on large-capacity bobbins, as a woven fabric, flake, sliver or knitted fabric, brought into contact with the liquor preheated to 40 to 90 ° C.
  • the liquor and the material to be dyed can also be heated together to a higher temperature within this temperature range if the temperature of the merging was in the lower part of this range.
  • the acid required for fixation and bath exhaustion is added to the liquor at a constant temperature between 40 and 90 ° C., preferably in the course of 20 to 60 minutes.
  • the acid can be introduced into the circulating dyeing liquor in the required amount using a commercially available, controllable metering device according to a linear, degressive or preferably progressive metering curve.
  • the desired pH value which is in particular 4.5 to 5
  • the dyeing process can already be completed. However, it can also be completed by further dyeing in the temperature range mentioned, for example for 5 to 30 minutes.
  • the optimal treatment temperature depends on the material to be stained. It is 40 to 70 ° C for synthetic polyamides, 70 to 80 ° C for silk and 75 to 90 ° C for wool.
  • the preferred concentration of the mixture A / B is 0.1 to 2.0 g, in particular 0.3 to 0.8 g, per liter of dye liquor.
  • the preferred liquor ratio is 1: 5-25, especially 1: 6-20.
  • Acid dyes in particular 1: 2 metal complex dyes, with one or more acid groups, as are described, for example, in the Color Index Vol. 1, 3rd ed., Pp. 1001-1561, are suitable for the process according to the invention.
  • the polyamide materials can be dyed using the pull-out method in a shortened procedure while maintaining the best possible quality in excellent levelness. Flawless dyeings are achieved even with dyes that are difficult to level, such as whale dyes.
  • the procedure is shortened in that the dyeing liquor can be heated up in a shorter time than by conventional methods in which the dyeing material is already in the liquor and the liquor has the required pH.
  • Wool yarn skeins are introduced at 85 ° C in a 1:20 liquor ratio in a dyeing liquor, which is in liters 2 g sodium sulfate (calcined) 0.65 g 1: 2 chromium complex of the azo dye CI acid brown 415 0.4 g of the auxiliary mixture consisting of 50 parts of the product of the formula and 50 parts of the reaction product of 1 mole of stearylamine and 10 moles of ethylene oxide.
  • Wool yarn wound on large-capacity bobbins is placed in a dyeing machine.
  • the dye liquor heated to 85 ° C., is then pumped in from the liquor preparation tank, which is in liters 2 g sodium sulfate (calcined) 0.3 g of the auxiliary mixture consisting of 50 parts of the product of the formula C18H37- CH2-CH2-O) 34-CH2-CH2-SO3 ⁇ Na ⁇ and 50 parts of the reaction product from 1 mol of N-methyl-stearylamine and 15 mol of ethylene oxide, such as 0.2 g of a defoamer, 0.47 g of the dye CI acid yellow 232, 0.48 g of the dye CI acid red 414, 0.36 g of the dye CI acid blue 351 contains.
  • the fleet ratio is 1:10.
  • There will be 45 liters per liter of liquor 3.6 g of glacial acetic acid added to the dye liquor circulating at a constant temperature of 85 ° C via an automatic dosing
  • Woolen fabric is wound on a dyeing tree and loaded in the tree dyeing machine with a dye liquor preheated to 85 ° C, which contains the following additives in liters: 2 g sodium sulfate (calcined) 0.4 g of the auxiliary mixture consisting of 60 parts of the product of the formula and 40 parts of the reaction product of 1 mole of N-stearyl-oxibenzylamine and 18 moles of ethylene oxide 0.2 g defoamer 2.5 g of dye CI acid blue 92 (CI 13 390) 0.6 g of dye CI acid yellow 49 (CI 18 640) 0.6 g of dye CI acid red 42 (CI 17 070) The fleet ratio is 1:10.
  • Debossed silk fabric is placed at 70 ° C in a prepared dyeing liquor, which contains the following additives per liter: 1 g metal complex dye CI acid yellow 232 0.8 g metal complex dye CI acid red 414 1.1 g metal complex dye CI acid black 220 0.8 g of the auxiliary mixture consisting of 60 parts of the product of the formula and 40 parts of the reaction product from 1 mole of tallow fatty amine and 12 moles of ethylene oxide 1 g sodium sulfate (calcined) The fleet ratio is 1:10. After the dye liquor has been uniformly distributed on the substrate to be colored, a metering device is used within 45 minutes at a constant temperature of 70 ° C.
  • Yarn strands of polyamide 6 are placed in a dyeing liquor containing the following additives at 60 ° C. 0.75 g of the acid dye CI acid orange 156 0.45 g of the acid dye CI acid red 425 0.5 g of the acid dye CI acid blue 324 1 g of an auxiliary mixture as described in Example 1, and 1 g sodium sulfate (calcined)
  • the liquor ratio is 1:20, the initial pH 9.0, the weight percentages refer to 1 liter.

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

Abstract

An isothermal dyeing process for dyeing natural and synthetic polyamide materials is carried out in the presence of a mixture of assistants consisting of A. compounds of the formula <IMAGE> or quaternisation products thereof of the formula <IMAGE> and B. compounds of the formula <IMAGE> wherein the symbols have the meanings stated in the description.

Description

Gegenstand der Erfindung ist ein Isotherm-Färbeverfahren zum Färben von natürlichen und synthetischen Polyamid­materialien in Gegenwart eines Hilfsmittelgemisches aus

  • A. Polyalkylenglykoletherketten aufweisenden Verbin­dungen der Formel
    Figure imgb0001
     oder deren Quaternierungsprodukte der Formel
    Figure imgb0002
     worin
    R für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl,
    R₁ für C₁-C₄-Alkyl oder eine Gruppe der Formeln
    Figure imgb0003
     R₂ für Wasserstoff oder Methyl,
    R₃ für Wasserstoff, gegebenenfalls substituiertes C₁-C₄-Alkyl oder Aralkyl,
    A⊖ für eine anionische Gruppe,
    M⊕ für ein Kation und
    m und n unabhängig voneinander für eine ganze Zahl von 1 bis 40 stehen und die Summe von m und n 5 bis 70 ist mit der Maßgabe, daß mindestens 80 % der im Molekül enthaltenen Alkylenoxid-Einheiten Ethylen­oxid-Einheiten sind,
    und
  • B. Polyalkylenglykoletherketten aufweisenden Verbin­dungen der Formel
    Figure imgb0004
     worin
    R und R₂ die vorstehend genannte Bedeutung haben, und
    R₄ für Wasserstoff, gegebenenfalls substituiertes C₁-C₄-Alkyl oder Aralkyl oder die Gruppe
    Figure imgb0005
     R₅ für die Gruppe
    Figure imgb0006
     R₆ für -CHR₂- oder Arylen,
    X⊖ für ein Anion und
    x, y und z unabhängig voneinander für eine ganze Zahl von 1 - 20 stehen und die Summe von x, y und z 10 - 20 ist mit der Maßgabe, daß mindestens 80 % der im Molekül enthaltenen Alkylenoxid-Einheiten Ethylenoxid-Einheiten sind.
The invention relates to an isothermal dyeing process for dyeing natural and synthetic polyamide materials in the presence of an auxiliary mixture
  • A. Compounds of the formula containing polyalkylene glycol ether chains
    Figure imgb0001
     or their quaternization products of the formula
    Figure imgb0002
     wherein
    R for C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,
    R₁ for C₁-C₄ alkyl or a group of the formulas
    Figure imgb0003
     R₂ is hydrogen or methyl,
    R₃ is hydrogen, optionally substituted C₁-C₄ alkyl or aralkyl,
    A ⊖ for an anionic group,
    M ⊕ for a cation and
    m and n independently of one another represent an integer from 1 to 40 and the sum of m and n is 5 to 70 with the proviso that at least 80% of the alkylene oxide units contained in the molecule are ethylene oxide units,
    and
  • B. Polyalkylene glycol ether chains having compounds of the formula
    Figure imgb0004
     wherein
    R and R₂ have the meaning given above, and
    R₄ for hydrogen, optionally substituted C₁-C₄ alkyl or aralkyl or the group
    Figure imgb0005
     R₅ for the group
    Figure imgb0006
     R₆ for -CHR₂- or arylene,
    X ⊖ for an anion and
    x, y and z independently of one another represent an integer from 1 to 20 and the sum of x, y and z is 10 to 20 with the proviso that at least 80% of the alkylene oxide units contained in the molecule are ethylene oxide units.

Die Polyamidmaterialien werden mit einer wäßrigen Flotte von 40 - 90°C in Berührung gebracht, die außer dem ge­nannten Hilfsmittelgemisch einen oder mehrere Farbstoffe und gegebenenfalls weitere übliche Färbehilfsmittel mit Ausnahme der zur Fixierung und Baderschöpfung erforder­lichen Säure enthält. Die Säure wird bei konstanter Tem­peratur zwischen 40 und 90°C hinzugefügt.The polyamide materials are brought into contact with an aqueous liquor at 40-90 ° C. which, in addition to the auxiliary mixture mentioned, contains one or more dyes and, if appropriate, other customary coloring auxiliaries with the exception of the acid required for fixation and exhaustion of the bath. The acid is added at a constant temperature between 40 and 90 ° C.

Das Hilfsmittelgemisch enthält vorzugsweise die Kompo­nenten A und B im Gewichtsverhältnis 1:1 bis 1:0,5.The auxiliary mixture preferably contains components A and B in a weight ratio of 1: 1 to 1: 0.5.

Als Reste R seien beispielsweise der Dodecyl-, Tetrade­cyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Eikosyl-, Behenyl-, Octadecenyl- und Abietylrest ge­nannt.The radicals R include, for example, the dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eikosyl, behenyl, octadecenyl and abietyl radicals.

Für R₃ seien als gegebenenfalls substituierte C₁-C₄-Al­kylgruppen die Methyl-, Ethyl-, n-Propyl-, i-Propyl-, n- oder sec.-Butylgruppe, ferner durch eine Hydroxy-, Carboxyl-, niedere Carbalkoxy- oder Carbonamidgruppe substituierte C₂-C₄-Alkylreste, wie der 2-Hydroxyethyl-, Carbonamidomethylrest, genannt. Als gegebenenfalls sub­stituierte Aralkylreste kommen vor allem der Benzyl- und Phenylethyl-Rest in Betracht, die durch OH, Cl oder CH₃ substituiert sein können.For R₃ be as optionally substituted C₁-C₄-alkyl groups, the methyl, ethyl, n-propyl, i-propyl, n or sec-butyl group, further by a hydroxy, carboxyl, lower carbalkoxy or carbonamide group substituted C₂-C₄-alkyl radicals, such as the 2-hydroxyethyl, carbonamidomethyl radical. The optionally substituted aralkyl radicals are especially the benzyl and phenylethyl radical, which can be substituted by OH, Cl or CH₃.

Bevorzugtes Arylen ist Phenylen.Preferred arylene is phenylene.

Als anionische Gruppe A⊖ kommen insbesondere die SO₃⊖- und SO₄⊖-Gruppe in Betracht.The anionic group A ⊖ are in particular the SO₃ ⊖ - and SO₄ ⊖ group.

M⊕ steht vorzugsweise für ein Alkaliion wie das Natrium- und Kaliumion, ein Erdalkaliion wie das Calcium- und Magnesiumion und ein Ammoniumion wie das Ammoniumion oder die sich vom Mono-, Di- oder Triethanolamin ablei­tende Ammoniumionen.M ⊕ preferably represents an alkali ion such as sodium and potassium ion, an alkaline earth metal ion such as calcium and magnesium ion and an ammonium ion such as ammonium ion or the ammonium ions derived from mono-, di- or triethanolamine.

Als geeignete Anionen X⊖ kommen übliche anorganische oder organische Anionen in Betracht, beispielsweise Chlorid, Bromid, Iodid, Methosulfat, Sulfat, Phosphat oder Acetat.Suitable anions X ⊖ are conventional inorganic or organic anions, for example Chloride, bromide, iodide, methosulfate, sulfate, phosphate or acetate.

Bevorzugte Verbindungen der Formeln (I) und (II) sind Verbindungen der Formeln

Figure imgb0007
worin
R′ für C₁₂-C₂₂-Alkyl,
R₁′ für Methyl oder eine Gruppe der Formeln
Figure imgb0008
 R₂′ für Wasserstoff oder Methyl,
R₃′ für Wasserstoff, Methyl, das durch CONH₂ oder COOMe substituiert sein kann, Ethyl, das durch OH substi­tuiert sein kann, oder Benzyl und
A′⊖ für SO₄⊖ oder SO₃⊖ stehen, und
Me, m und n die vorstehend angegebene Bedeutung haben.Preferred compounds of the formulas (I) and (II) are compounds of the formulas
Figure imgb0007
 wherein
R ′ for C₁₂-C₂₂ alkyl,
R₁ 'for methyl or a group of the formulas
Figure imgb0008
 R₂ ′ for hydrogen or methyl,
R₃ 'for hydrogen, methyl, which may be substituted by CONH₂ or COOMe, ethyl, which may be substituted by OH, or benzyl and
A ′ ⊖ stand for SO₄ ⊖ or SO₃ ⊖ , and
Me, m and n have the meaning given above.

Die Summe von m + n liegt vorzugsweise bei 18 - 40.The sum of m + n is preferably 18-40.

Bevorzugte Verbindungen der Formel (III) sind Verbin­dungen der Formel

Figure imgb0009
worin
R₄′ für Wasserstoff, Methyl, Benzyl oder die Gruppe
Figure imgb0010
 R₅′ für die Gruppe
Figure imgb0011
 R₆′ für -CHR₂′- oder Phenylen stehen und
R′, R₂′, X⊖, x, y und z die vorstehend angegebene Bedeu­tung haben.Preferred compounds of the formula (III) are compounds of the formula
Figure imgb0009
 wherein
R₄ 'represents hydrogen, methyl, benzyl or the group
Figure imgb0010
 R₅ ′ for the group
Figure imgb0011
 R₆ 'represent -CHR₂'- or phenylene and
R ', R₂', X ⊖ , x, y and z have the meaning given above.

Die Verbindungen (I), (II) und (III) werden nach bekann­ten Verfahren hergestellt. Die Verbindungen (I) und (II) sind beispielsweise aus der DE-A-1 940 178 bekannt. Die Verbindungen (III) werden hergestellt durch Einwirkung von Ethylenoxid oder Mischungen aus Ethylenoxid und bis zu 20 % Propylenoxid, Butylenoxid oder Styroloxid auf primäre oder sekundäre Amine oder solche tertiären Amine, die eine Hydroxylgruppe enthalten. Als Amine seien beispielsweise genannt: Dodecylamin, Tetradecyl­amin, Hexadecylamin, Octadecylamin, Arachylamin, Oleyl­amin, Abietylamin, Hexadecylmethylamin, Octadecylmethyl­amin, N-(β-Hydroxyethyl)-methyl-hexadecylamin, N-(β-­Hydroxyethyl)-methyl-octadecylamin, N-(β-Hydroxypropyl)-­methyl-octadecylamin und N-(2-Hydroxy-2-phenyl-ethyl)-­methyl-octadecenylamin.The compounds (I), (II) and (III) are prepared by known processes. The compounds (I) and (II) are known for example from DE-A-1 940 178. The compounds (III) are prepared by the action of ethylene oxide or mixtures of ethylene oxide and up to 20% propylene oxide, butylene oxide or styrene oxide on primary or secondary amines or those tertiary amines which contain a hydroxyl group. Examples of amines include: dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, arachylamine, oleylamine, abietylamine, hexadecylmethylamine, octadecylmethylamine, N- (β-hydroxyethyl) methylhexadecylamine, N- (β-hydroxyethyl) methyl-octadecylamine (β-hydroxypropyl) methyl octadecylamine and N- (2-hydroxy-2-phenyl-ethyl) methyl octadecenylamine.

Als Vertreter der Verbindungen (I), (II) und (III) seien die Verbindungen der Tabellen 1 und 2 genannt.

Figure imgb0012
Figure imgb0013
 The compounds of Tables 1 and 2 may be mentioned as representatives of the compounds (I), (II) and (III).
Figure imgb0012
Figure imgb0013

Bei dem erfindungsgemäßen Verfahren wird das Polyamid­gruppen enthaltende Färbegut, das z.B. als Garn, bei­spielsweise auf Großraumspulen, als Gewebe, Flocke, Kammzug oder Wirkware vorliegen kann, mit der auf 40 bis 90°C vorgeheizten Flotte in Berührung gebracht. Flotte und Färbegut können auch innerhalb dieses Temperaturbe­reichs gemeinsam auf eine höhere Temperatur erhitzt wer­den, wenn die Temperatur der Zusammenführung im unteren Teil dieses Bereiches lag.In the process according to the invention, the dyeing material containing polyamide groups, e.g. as a yarn, for example on large-capacity bobbins, as a woven fabric, flake, sliver or knitted fabric, brought into contact with the liquor preheated to 40 to 90 ° C. The liquor and the material to be dyed can also be heated together to a higher temperature within this temperature range if the temperature of the merging was in the lower part of this range.

Die zur Fixierung und Baderschöpfung erforderliche Säure wird bei gleichbleibender Temperatur zwischen 40 und 90°C, vorzugsweise im Laufe von 20 bis 60 Minuten, der Flotte zugefügt. Die Säure kann über eine handelsüb­liche, regelbare Dosiervorrichtung nach einer linearen, degressiven oder vorzugsweise progressiven Dosierkurve in der erforderlichen Menge in die zirkulierende Färbe­flotte eingebracht werden. Nach Einreichen des gewünsch­ten pH-Wertes, der insbesonders bei 4,5 bis 5 liegt, kann der Färbeprozeß bereits abgeschlossen sein. Er kann aber auch durch weiteres Färben im genannten Tempera­turbereich, beispielsweise während 5 bis 30 Minuten, vollendet werden.The acid required for fixation and bath exhaustion is added to the liquor at a constant temperature between 40 and 90 ° C., preferably in the course of 20 to 60 minutes. The acid can be introduced into the circulating dyeing liquor in the required amount using a commercially available, controllable metering device according to a linear, degressive or preferably progressive metering curve. After the desired pH value has been submitted, which is in particular 4.5 to 5, the dyeing process can already be completed. However, it can also be completed by further dyeing in the temperature range mentioned, for example for 5 to 30 minutes.

Die optimale Behandlungstemperatur hängt vom Färbegut ab. Sie liegt für synthetische Polyamide bei 40 bis 70°C, für Seide bei 70 bis 80°C und für Wolle bei 75 bis 90°C.The optimal treatment temperature depends on the material to be stained. It is 40 to 70 ° C for synthetic polyamides, 70 to 80 ° C for silk and 75 to 90 ° C for wool.

Die bevorzugte Konzentration des Gemisches A/B liegt bei 0,1 bis 2,0 g, insbesondere 0,3 bis 0,8 g, pro Liter Färbeflotte.The preferred concentration of the mixture A / B is 0.1 to 2.0 g, in particular 0.3 to 0.8 g, per liter of dye liquor.

Das bevorzugte Flottenverhältnis liegt bei 1:5-25, ins­besondere bei 1:6-20.The preferred liquor ratio is 1: 5-25, especially 1: 6-20.

Für das erfindungsgemäße Verfahren eignen sich Säure­farbstoffe, insbesondere 1:2-Metallkomplexfarbstoffe, mit einer oder mehreren Säuregruppen, wie sie beispiels­weise im Colour Index Vol. 1, 3. Ed., S. 1001-1561, be­schrieben werden.Acid dyes, in particular 1: 2 metal complex dyes, with one or more acid groups, as are described, for example, in the Color Index Vol. 1, 3rd ed., Pp. 1001-1561, are suitable for the process according to the invention.

Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, die Polyamidmaterialien nach dem Ausziehverfahren in verkürzter Arbeitsweise unter bestmöglicher Qualitäts­erhaltung in einer hervorragenden Egalität zu färben. Selbst mit schwer egalisierbaren Farbstoffen wie Walk­farbstoffen werden einwandfreie Färbungen erzielt. Die Arbeitsweise wird dadurch verkürzt, daß die Färbeflotte in kürzerer Zeit aufgeheizt werden kann als nach konven­tionellen Verfahren, bei denen sich das Färbegut bereits in der Flotte befindet und diese den erforderlichen pH-­Wert hat.With the aid of the method according to the invention, the polyamide materials can be dyed using the pull-out method in a shortened procedure while maintaining the best possible quality in excellent levelness. Flawless dyeings are achieved even with dyes that are difficult to level, such as whale dyes. The procedure is shortened in that the dyeing liquor can be heated up in a shorter time than by conventional methods in which the dyeing material is already in the liquor and the liquor has the required pH.

Die in den folgenden Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the following examples are parts by weight.

Beispiel 1example 1

Wollgarnstränge werden bei 85°C im Flottenverhältnis 1:20 in einer Färbeflotte eingebracht, welche im Liter

2 g      Natriumsulfat (kalziniert)
0,65 g      1:2-Chromkomplex des Azofarbstoffes C.I. acid brown 415
0,4 g      des Hilfsmittelgemisches bestehend aus 50 Teilen des Produktes der Formel

Figure imgb0014

und 50 Teilen des Umsetzungsproduktes aus 1 Mol Stearylamin und 10 Mol Ethylenoxid enthält.Wool yarn skeins are introduced at 85 ° C in a 1:20 liquor ratio in a dyeing liquor, which is in liters

2 g sodium sulfate (calcined)
0.65 g 1: 2 chromium complex of the azo dye CI acid brown 415
0.4 g of the auxiliary mixture consisting of 50 parts of the product of the formula
Figure imgb0014
and 50 parts of the reaction product of 1 mole of stearylamine and 10 moles of ethylene oxide.

Nach gleichmäßigem Benetzen des Materials werden 1,5 g Eisessig im Liter innerhalb 45 Minuten bei 85°C zudo­siert. Die Dosierung erfolgt dabei progressiv mit Hilfe eines kommerziellen Dosiergerätes. Nach dieser Zeit er­hält man eine ausgezeichnet gleichmäßige Färbung bei guter Baderschöpfung.After uniformly wetting the material, 1.5 g of glacial acetic acid are added per liter at 85 ° C within 45 minutes. The dosing is done progressively with the help of a commercial dosing device. After this time you get an exceptionally uniform color with good bath exhaustion.

Beispiel 2Example 2

Auf Großraumspulen aufgewickeltes Wollgarn wird in einen Färbeapparat gegeben. Aus dem Flottenansatzbehälter wird sodann die auf 85°C erhitzte Färbeflotte hineingepumpt, welche im Liter

2 g      Natriumsulfat (kalziniert)
0,3 g      des Hilfsmittelgemisches bestehend aus 50 Teilen des Produktes der Formel


C₁₈H₃₇-

Figure imgb0015
CH₂-CH₂-O)₃₄-CH₂-CH₂-SO₃⊖ Na⊕

und 50 Teilen des Umsetzungsproduktes aus 1 Mol N-­Methyl-Stearylamin und 15 Mol Ethylenoxid,
sowie

0,2 g      eines Entschäumers,
0,47 g      des Farbstoffes C.I. acid yellow 232,
0,48 g      des Farbstoffes C.I. acid red 414,
0,36 g      des Farbstoffes C.I. acid blue 351

enthält. Das Flottenverhältnis beträgt 1:10. Es werden während 45 Minuten pro Liter Flotte

3,6 g      Eisessig

über eine automatische Dosiervorrichtung in die bei konstanter Temperatur von 85°C zirkulierende Färbeflotte gegeben.Wool yarn wound on large-capacity bobbins is placed in a dyeing machine. The dye liquor, heated to 85 ° C., is then pumped in from the liquor preparation tank, which is in liters

2 g sodium sulfate (calcined)
0.3 g of the auxiliary mixture consisting of 50 parts of the product of the formula


C₁₈H₃₇-
Figure imgb0015
CH₂-CH₂-O) ₃₄-CH₂-CH₂-SO₃ ⊖ Na ⊕

and 50 parts of the reaction product from 1 mol of N-methyl-stearylamine and 15 mol of ethylene oxide,
such as

0.2 g of a defoamer,
0.47 g of the dye CI acid yellow 232,
0.48 g of the dye CI acid red 414,
0.36 g of the dye CI acid blue 351

contains. The fleet ratio is 1:10. There will be 45 liters per liter of liquor

3.6 g of glacial acetic acid

added to the dye liquor circulating at a constant temperature of 85 ° C via an automatic dosing device.

Nach weiteren 15 Minuten Behandlungszeit bei dieser Tem­peratur ist das Färbebad erschöpft. Man erhält eine aus­gezeichnet gleichmäßige Braun-Färbung mit guter Fixie­rung, obwohl die nur mäßig egalisierende Metallkomplex­farbstoff-Kombination nahe Kochtemperatur auf das Färbe­gut gebracht wurde.After a further 15 minutes of treatment at this temperature, the dye bath is exhausted. An exceptionally uniform brown coloration with good fixation is obtained, although the only moderately leveling metal complex dye combination was brought to the material to be stained close to the cooking temperature.

Beispiel 3Example 3

Wollgewebe wird auf einem Färbebaum gewickelt und im Baumfärbeapparat mit einer auf 85°C vorgeheizten Färbe­flotte beschickt, welche die folgenden Zusätze im Liter enthält:

2 g      Natriumsulfat (kalziniert)
0,4 g      des Hilfsmittelgemisches bestehend aus 60 Teilen des Produktes der Formel

Figure imgb0016

und 40 Teilen des Umsetzungsproduktes aus 1 Mol N-­Stearyl-Oxibenzylamin und 18 Mol Ethylenoxid

0,2 g      Entschäumer
2,5 g      Farbstoff C.I. acid blue 92 (C.I. 13 390)
0,6 g      Farbstoff C.I. acid yellow 49 (C.I. 18 640)
0,6 g      Farbstoff C.I. acid red 42 (C.I. 17 070)

Das Flottenverhältnis beträgt 1:10.Woolen fabric is wound on a dyeing tree and loaded in the tree dyeing machine with a dye liquor preheated to 85 ° C, which contains the following additives in liters:

2 g sodium sulfate (calcined)
0.4 g of the auxiliary mixture consisting of 60 parts of the product of the formula
Figure imgb0016
and 40 parts of the reaction product of 1 mole of N-stearyl-oxibenzylamine and 18 moles of ethylene oxide

0.2 g defoamer
2.5 g of dye CI acid blue 92 (CI 13 390)
0.6 g of dye CI acid yellow 49 (CI 18 640)
0.6 g of dye CI acid red 42 (CI 17 070)

The fleet ratio is 1:10.

Nach ausreichendem Benetzen werden über eine Dosiervor­richtung progressiv

3 g      Ameisensäure 85 %ig pro Liter

der zirkulierenden Flotte während 60 Minuten zugegeben. Nach einer weiteren Behandlung von 30 Minuten bei 85°C erhält man eine hervorragend gleichmäßige Färbung in einem Marineblau-Farbton.After sufficient wetting, they are progressive via a dosing device

3 g of 85% formic acid per liter

added to the circulating liquor over 60 minutes. After a further treatment of 30 minutes at 85 ° C you get an excellent uniform color in a navy blue color.

Beispiel 4Example 4

Entbastetes Seidengewebe gibt man bei 70°C in eine vor­bereitete Färbeflotte, welche die folgenden Zusätze pro Liter enthält:

1 g      Metallkomplexfarbstoff C.I. acid yellow 232
0,8 g      Metallkomplexfarbstoff C.I. acid red 414
1,1 g      Metallkomplexfarbstoff C.I. acid black 220
0,8 g      des Hilfsmittelgemisches, bestehend aus 60 Teilen des Produktes der Formel

Figure imgb0017
und 40 Teilen des Umsetzungsproduktes aus 1 Mol Talgfettamin und 12 Mol Ethylenoxid

1 g      Natriumsulfat (kalziniert)

Das Flottenverhältnis beträgt 1:10.
Nach gleichmäßiger Verteilung der Färbeflotte auf dem zu färbenden Substrat werden mittels einer Dosiervor­richtung innerhalb 45 Minuten bei einer konstant gehal­tenen Temperatur von 70°C

1,5 g      Essigsäure 100 % pro Liter als verdünnte

Lösung in die Färbeflotte gegeben. Nach weiteren 15 Minuten Verweilen in bewegter Flotte bei 70°C erhält man eine hervorragend egale Färbung in einem vollen Braunton, welche die gleichen Echtheiten wie eine nach konventioneller Färbeweise erstellte Färbung ergibt.Debossed silk fabric is placed at 70 ° C in a prepared dyeing liquor, which contains the following additives per liter:

1 g metal complex dye CI acid yellow 232
0.8 g metal complex dye CI acid red 414
1.1 g metal complex dye CI acid black 220
0.8 g of the auxiliary mixture consisting of 60 parts of the product of the formula
Figure imgb0017
 and 40 parts of the reaction product from 1 mole of tallow fatty amine and 12 moles of ethylene oxide

1 g sodium sulfate (calcined)

The fleet ratio is 1:10.
After the dye liquor has been uniformly distributed on the substrate to be colored, a metering device is used within 45 minutes at a constant temperature of 70 ° C.

1.5 g acetic acid 100% per liter as diluted

Solution added to the dye liquor. After a further 15 minutes in a moving liquor at 70 ° C., an excellently level dyeing in a full brown tone is obtained, which gives the same fastness properties as a dyeing prepared using conventional dyeing methods.

Beispiel 5Example 5

In eine die nachfolgenden Zusätze enthaltende Färbe­flotte werden bei 60°C Garnstränge aus Polyamid 6 gege­ben.

0,75 g      des Säurefarbstoffes C.I. acid orange 156
0,45 g      des Säurefarbstoffes C.I. acid red 425
0,5 g      des Säurefarbstoffes C.I. acid blue 324
1 g      eines Hilfsmittelgemisches, wie im Beispiel 1 beschrieben, und
1 g      Natriumsulfat (kalziniert)

Das Flottenverhältnis beträgt 1:20, der Anfangs-pH-Wert 9,0, die angegebenen Gewichtsanteile beziehen sich auf 1 Liter.Yarn strands of polyamide 6 are placed in a dyeing liquor containing the following additives at 60 ° C.

0.75 g of the acid dye CI acid orange 156
0.45 g of the acid dye CI acid red 425
0.5 g of the acid dye CI acid blue 324
1 g of an auxiliary mixture as described in Example 1, and
1 g sodium sulfate (calcined)

The liquor ratio is 1:20, the initial pH 9.0, the weight percentages refer to 1 liter.

Nach 10 Minuten bei 60°C werden innerhalb 45 Minuten

0,2 g      Essigsäure 60 %ig pro Liter als verdünnte

Lösung über eine Dosiervorrichtung mit progressiver Steigerung zugegeben.After 10 minutes at 60 ° C within 45 minutes

0.2 g 60% acetic acid per liter as diluted

Solution added via a metering device with progressive increase.

Danach erreicht man einen pH-Wert von 5,5 und beläßt das zu färbende Material noch weitere 20 Minuten in der be­wegten Flotte. Es wird eine satte Braunfärbung erhalten, welche eine sehr gute Egalität aufweist. Die erreichten Echtheiten entsprechen einer üblichen Färbung nach einem konventionellen Verfahren.Then a pH of 5.5 is reached and the material to be dyed is left in the agitated liquor for a further 20 minutes. A rich brown color is obtained, which has very good levelness. The fastness properties achieved correspond to a conventional dyeing using a conventional process.

Claims (9)

1. Verfahren zum Färben von natürlichen und synthe­tischen Polyamidmaterialien, dadurch gekennzeich­net, daß man die Polyamidmaterialien mit einer Flotte von 40 bis 90°C in Berührung bringt, die einen oder mehrere Farbstoffe und ein Gemisch aus A. Polyalkylenglykoletherketten aufweisenden Verbindungen der Formel
Figure imgb0018
 oder deren Quaternierungsprodukte der Formel
Figure imgb0019
 worin
R für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl,
R₁ für C₁-C₄-Alkyl oder eine Gruppe der Formeln
Figure imgb0020
 R₂ für Wasserstoff oder Methyl,
R₃ für Wasserstoff, gegebenenfalls substi­tuiertes C₁-C₄-Alkyl oder Aralkyl,
A⊖ für eine anionische Gruppe,
M⊕ für ein Kation und
m und n unabhängig voneinander für eine ganze Zahl von 1 bis 40 stehen und die Summe von m und n 5 bis 70 ist mit der Maßgabe, daß min­destens 80 % der im Molekül enthaltenen Alky­lenoxid-Einheiten Ethylenoxid-Einheiten sind,
und B. Polyalkylenglykoletherketten aufweisenden Ver­bindungen der Formel
Figure imgb0021
 worin
R und R₂ die vorstehend genannte Bedeutung haben, und
R₄ für Wasserstoff, gegebenenfalls substi­tuiertes C₁-C₄-Alkyl oder Aralkyl oder die Gruppe
Figure imgb0022
 R₅ für die Gruppe
Figure imgb0023
 R₆ für -CHR₂- oder Arylen,
X⊖ für ein Anion und
x, y und z unabhängig voneinander für eine ganze Zahl von 1 - 20 stehen und die Summe von x, y und z 10 - 20 ist mit der Maßgabe, daß mindestens 80 % der im Molekül enthaltenen Alkylenoxid-Einheiten Ethylenoxid-Einheiten sind, enthält, und bei einer konstanten Tempe­ratur zwischen 40 - 90°C Säure zufügt. 1. A process for dyeing natural and synthetic polyamide materials, characterized in that the polyamide materials are brought into contact with a liquor of 40 to 90 ° C which comprises one or more dyes and a mixture A. Compounds of the formula containing polyalkylene glycol ether chains
Figure imgb0018
 or their quaternization products of the formula
Figure imgb0019
 wherein
R for C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,
R₁ for C₁-C₄ alkyl or a group of the formulas
Figure imgb0020
 R₂ is hydrogen or methyl,
R₃ is hydrogen, optionally substituted C₁-C₄ alkyl or aralkyl,
A ⊖ for an anionic group,
M ⊕ for a cation and
m and n independently of one another represent an integer from 1 to 40 and the sum of m and n is 5 to 70 with the proviso that at least 80% of the alkylene oxide units contained in the molecule are ethylene oxide units,
and B. Polyalkylene glycol ether chains having compounds of the formula
Figure imgb0021
 wherein
R and R₂ have the meaning given above, and
R₄ for hydrogen, optionally substituted C₁-C₄ alkyl or aralkyl or the group
Figure imgb0022
 R₅ for the group
Figure imgb0023
 R₆ for -CHR₂- or arylene,
X ⊖ for an anion and
x, y and z independently of one another represent an integer from 1 to 20 and the sum of x, y and z is 10 to 20 with the proviso that at least 80% of the alkylene oxide units contained in the molecule are ethylene oxide units , and add acid at a constant temperature between 40 - 90 ° C. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Gemisch aus A und B in einem Gewichts­verhältnis von 1:1 bis 1:0,5 verwendet.2. The method according to claim 1, characterized in that the mixture of A and B is used in a weight ratio of 1: 1 to 1: 0.5. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Komponente A Verbindungen der Formeln
Figure imgb0024
 worin
R′ für C₁₂-C₂₂-Alkyl,
R₁′ für Methyl oder eine Gruppe der Formeln
Figure imgb0025
 R²′ für Wasserstoff oder Methyl,
R₃′ für Wasserstoff, Methyl, das durch CONH₂ oder COOMe substituiert sein kann, Ethyl, das durch OH substituiert sein kann, oder Benzyl und
A′⊖ für SO₄⊖ oder SO₃⊖ stehen, und
Me, m und n die in Anspruch 1 angegebene Bedeutung haben,
und als Komponente B Verbindungen der Formel
Figure imgb0026
 worin
R₄′ für Wasserstoff, Methyl, Benzyl oder die Gruppe
Figure imgb0027
 R₅′ für die Gruppe
Figure imgb0028
 R₆′ für -CHR₂′- oder Phenylen stehen und
X⊖, x, y und z die in Anspruch 1 angegebene Bedeu­tung haben,
verwendet.3. The method according to claim 1, characterized in that as component A compounds of the formulas
Figure imgb0024
 wherein
R ′ for C₁₂-C₂₂ alkyl,
R₁ 'for methyl or a group of the formulas
Figure imgb0025
 R² ′ for hydrogen or methyl,
R₃ 'for hydrogen, methyl, which may be substituted by CONH₂ or COOMe, ethyl, which may be substituted by OH, or benzyl and
A ′ ⊖ stand for SO₄ ⊖ or SO₃ ⊖ , and
Me, m and n have the meaning given in claim 1,
and as component B compounds of the formula
Figure imgb0026
 wherein
R₄ 'represents hydrogen, methyl, benzyl or the group
Figure imgb0027
 R₅ ′ for the group
Figure imgb0028
 R₆ 'represent -CHR₂'- or phenylene and
X ⊖ , x, y and z have the meaning given in claim 1,
used. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man der Flotte 0,1 bis 2,0 g/l des Gemisches A/B zusetzt.4. The method according to claim 1, characterized in that 0.1 to 2.0 g / l of the mixture A / B is added to the liquor. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man mit einem Flottenverhältnis von 1:5-25 ar­beitet.5. The method according to claim 1, characterized in that one works with a liquor ratio of 1: 5-25. 6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Säure während 20 bis 60 Minuten zu­setzt.6. The method according to claim 1, characterized in that the acid is added for 20 to 60 minutes. 7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Säure bis zu einem pH-Wert von 4,5-5 zusetzt.7. The method according to claim 1, characterized in that the acid is added up to a pH of 4.5-5. 8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man synthetische Polyamidmaterialien mit einer Flotte von 40 bis 70°C, Seide mit einer Flotte von 70 bis 80°C und Wolle mit einer Flotte von 75 bis 90°C in Berührung bringt.8. The method according to claim 1, characterized in that synthetic polyamide materials with a liquor of 40 to 70 ° C, silk with a liquor of 70 to 80 ° C and wool with a liquor of 75 to 90 ° C in contact. 9. Polyamidmaterialien, die nach dem Verfahren des Anspruchs 1 gefärbt werden.9. polyamide materials which are dyed by the process of claim 1.
EP88113674A 1987-09-03 1988-08-23 Process for dyeing polyamide fibres Expired - Lifetime EP0305858B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3729460 1987-09-03
DE19873729460 DE3729460A1 (en) 1987-09-03 1987-09-03 METHOD FOR DYING POLYAMIDE FIBERS

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164975B (en) * 1961-03-22 1964-03-12 Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius &. Brüning, Frankfurt/M Use of water-soluble condensation products as leveling agents.
CH388903A (en) * 1963-01-05 1964-11-30 Sandoz Ag Process for producing level dyeings with anionic dyes on textiles or for peeling off such dyeings
AT270570B (en) * 1965-09-09 1969-05-12 Ciba Geigy Process for dyeing nitrogen-containing textile fibers
DE1940178A1 (en) * 1969-08-07 1971-03-04 Bayer Ag AEthanesulfonic acid derivatives
DE2802304A1 (en) * 1977-01-24 1978-07-27 Ciba Geigy Ag METHOD OF COLORING WOOL FIBER MATERIAL

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164975B (en) * 1961-03-22 1964-03-12 Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius &. Brüning, Frankfurt/M Use of water-soluble condensation products as leveling agents.
CH388903A (en) * 1963-01-05 1964-11-30 Sandoz Ag Process for producing level dyeings with anionic dyes on textiles or for peeling off such dyeings
AT270570B (en) * 1965-09-09 1969-05-12 Ciba Geigy Process for dyeing nitrogen-containing textile fibers
DE1940178A1 (en) * 1969-08-07 1971-03-04 Bayer Ag AEthanesulfonic acid derivatives
DE2802304A1 (en) * 1977-01-24 1978-07-27 Ciba Geigy Ag METHOD OF COLORING WOOL FIBER MATERIAL

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EP0305858B1 (en) 1992-12-16
DE3729460A1 (en) 1989-03-16

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