EP0569793A1 - Process for dyeing of polyamides in the presence of manganese (II) salts - Google Patents

Abstract

The novel process for dyeing polyamide fibres with acid dyes by adding small amounts of metal salts to the dyebath yields dyeings having a better lightfastness by up to three points.

Description

The present invention relates to a new process for dyeing polyamide fibers with acid dyes, which provides dyeings with improved light fastness.

For most textile uses, polyamide fibers must be matted, which is technically achieved by adding titanium dioxide pigments.

However, it is generally known that the presence of titanium dioxide in the polyamide fiber adversely affects its photo stability. The more pigmented a fiber is, the less lightfast it is. Efforts are known from the literature to improve the light resistance of undyed polyamide fibers either by adding spinning mass to metal ions such as Mn²⁺, Cu⁺, Cu²⁺ or Co²⁺ or by surface treatment of the polyamide fiber (Textile Finishing 20 , No. 11 (1985), 346 and JP 57 089 664).

Attempts have also been made to improve the lightfastness of dyeings on polyamide by adding copper (II) salts to the dyebath (textile finishing 20 , loc.cit.). Due to the lack of fiber affinity of the copper ions, a large excess of copper (II) salt is required. Organic copper complex compounds have a better fiber affinity. It is known to add such copper complex compounds, in particular those of diazometin derivatives, to the dyebath to improve the light fastness of the dyeing (Textilveredelung 24 , No. 5 (1989), 182).

However, the methods known from the prior art are not satisfactory in all requirements. In particular when dyeing polyamide microfibers that have a high degree of matting, it has hitherto been possible to obtain only dyeings of inadequate lightfastness with acid dyes at the acidic pH values required for these dyes.

The organic copper complexes known from the prior art show little or no improvement in the light fastness of the dyeing obtained when dyeing with acid dyes.

Since particularly deep shades can be achieved with acid dyes on polyamide, there was therefore a need for a dyeing process for acid dyes which gives dyeings of improved lightfastness.

The present invention relates to a process for dyeing polyamide fibers with acid dyes, characterized in that small amounts of nickel, zinc, cobalt, zirconium or manganese salts are added to the dye bath. Surprisingly, the dyeings obtained with the process according to the invention show improved lightfastness.

The method according to the invention is suitable for dyeing polyamide fibers with a fiber strength of 0.6 to 3 dtex, in particular ultra-deep-matt microfibers with a fiber strength of 0.6 to 1.2 dtex. Ultra-deep matt polyamide fibers generally contain up to 2% titanium dioxide pigments. The particle size of the pigments used is generally 0.1 to 1 μm.

In principle, all inorganic and organic salts such as chlorides, nitrates, sulfates, acetates, phosphates, formates, oxalates or lactates of the metals mentioned are suitable for carrying out the process according to the invention. Organic manganese (II) salts such as in particular manganese acetate are preferably used. The metal salts mentioned are preferably used during the dyeing process in the dye bath in amounts of 0.1 to 1 g / l, preferably 0.1 to 0.5 g / l, added.

The metal salts mentioned can also be used in any mixture with one another and in a mixture with Cu (I) and Cu (II) salts.

Acid dyes suitable for carrying out the process according to the invention are azo, anthraquinone and metal complex dyes or combinations thereof, which have to be dyed in the acidic pH range for bath exhaustion below pH 6.

Examples include: Cr complex of

The dyeing according to the process according to the invention is generally carried out under the conditions customary for dyeings on polyamide with acid dyes, i.e. at a temperature of 85 to 110 ° C and a pH below 6, preferably between 4.0 and 6.

In a preferred embodiment of the process according to the invention, a complexing agent is added to the dyebath which is capable of forming a complex with the metal ions mentioned. Examples of possible complexing agents are:
Gluconic acid; Polyaminopolycarboxylic acids; Phosphorus compounds such as tripolyphosphates, orthophosphates, phosphonic acid, phosphonoalkane polycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid; Polycarboxylic acids such as citric acid, ethylenediaminetetraacetic acid and polyacrylic acids and their derivatives.

• verschiedenen Alkylarylsulfonsäuren mit Halogenarylsulfonsäuren
• sulfonierten Phenolen, β-Naphtholen etc. mit Formaldehyd und verschiedenen Stickstoff-Verbindungen
• reaktionsfähigen AIkylarylverbindungen mit aromatischen Sulfonsäuren, wie z.B. Benzylchlorid mit Naphthalinsulfonsäure
• Diphenyletherderivaten u.ä. mit Arylsulfonaten und Formaldehyd
• Kresolsulfonsäuren mit Formaldehyd
• Harnstoff-Formaldehyd mit Phenolsulfonsäure
• Phenol und Formaldehyd, die sulfomethyliert werden,

sowie der Reihe der Ligninsulfonate, wie sie z.B. in Chwala/Anger, Handbuch der Textilhilfsmittel, 2. Auflage, Verlag Chemie, Weinheim 1977, Seite 506 ff, beschrieben sind, zugesetzt.In a likewise preferred embodiment of the process according to the invention, the dyebath is a dispersant, preferably an anionic dispersant, for example from the series of polycondensates from:

• various alkylarylsulfonic acids with haloarylsulfonic acids
• sulfonated phenols, β-naphthols etc. with formaldehyde and various nitrogen compounds
• reactive alkyl aryl compounds with aromatic sulfonic acids, such as benzyl chloride with naphthalenesulfonic acid
• Diphenyl ether derivatives and the like with aryl sulfonates and formaldehyde
• Cresol sulfonic acids with formaldehyde
• Urea formaldehyde with phenol sulfonic acid
• Phenol and formaldehyde, which are sulfomethylated,

as well as the series of lignosulfonates, as described, for example, in Chwala / Anger, Handbuch der Textilhilhilmittel, 2nd edition, Verlag Chemie, Weinheim 1977, page 506 ff.

• 1.
  • a) basische Stickstoffatome enthaltende wasserlösliche Polyalkylenglykolether, wie sie z.B. in der DAS 1 619 652 beschrieben sind,
  • b) alkoxylierte Fettamine der allgemeinen Formel
    
    worin

    R

    für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkenyl steht,

    x und y

    unabhängig voneinander für eine Zähl von 5 - 70, vorzugsweise 15 - 50, stehen und

    R₁

    für Wasserstoff, Methyl, Ethyl oder Phenyl steht,

  • c) Umsetzungsprodukte von Alkylaminen mit 12 bis 22 C-Atomen mit Formaldehyd, Phenolen und 15 - 50 Äquivalenten Ethylenoxid, wobei die Komponenten a), b) und c) als Einzelverbindungen oder als Gemische untereinander eingesetzt werden können.
• 2. Verbindungen der Formel (vgl. DAS 1 940 178 und EP 305 858)
  
  worin

  R

  für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl steht,

  R₁

  für C₁-C₄-Alkyl oder eine Gruppe der Formel
  
  
  
          -(CH₂-CHR₂-O)_y-H
  
  oder
  
          -(CH₂-CHR₂-O)_y-CH₂-CH₂-A^⊖M^⊕
  
  steht,

  R₂

  für H, Methyl, Ethyl oder Phenyl steht,

  M^⊕

  für ein Kation, insbesondere ein Alkali-, Erdalkali- oder Ammoniumion oder ein Mono-, Di- oder Triethanolammoniumion steht,

  A^⊖

  für eine anionische Gruppe, inbesondere SO₄^⊖ oder SO₃^⊖ steht, und

  x und y

  unabhängig voneinander für eine Zahl von 5 bis 70, vorzugsweise 15 bis 50 stehen,

  bzw. deren Quaternisierungsprodukte der Formel
  
  worin

  R, R₁, R₂, M^⊕, A^⊖, x und y

  die oben angegebene Bedeutung haben und

  R₃

  für gegebenenfalls durch Hydroxy, Carboxyl, niederes Carbalkoxy oder Carbonamid substituiertes C₁-C₈-Alkyl steht

  (vgl. DAS 1 940 178; EP 305 858).
• 3.
  • a) Alkoxylierte Fettalkohole (vgl. EP 312 493) der Formel
    
    
    
            RO(CH₂CHR₁O)_x-H
    
    
    
    worin

    R

    für C₁₂-C₂₂-Alkyl, C₁₂-C₂₂-Alkenyl oder C₁₂-C₂₂-Cycloalkyl steht,

    R₁

    für H, Methyl, Ethyl oder Phenyl steht, und

    x

    für 12 - 60 steht,

    und/oder
  • b) quaternierte Ammoniumverbindungen von Polyglykolverbindungen der Formel
    
    worin

    R₁

    für Alkyl oder Alkenyl mit jeweils 12 bis 22 Kohlenstoffatomen steht,

    R₂

    für gegebenenfalls durch Hydroxy, Carboxyl, niederes Carbalkoxy oder Carbonamid substituiertes C₁-C₈-Alkyl steht,

    R₃

    für H, Methyl, Ethyl oder Phenyl steht,

    x und y

    unabhängig voneinander für eine Zahl von 5 - 70, vorzugsweise 15-50, stehen, und

    A^⊖

    für ein Anion, vorzugsweise für Cl^⊖ oder das Methosulfatanion, steht.

• 4. Oberflächenaktive Schwefelsäureester- oder Sulfonsäuregruppen enthaltende Verbindungen wie (siehe auch DAS 1 920 357)
  • a) Alkylarylsulfonsäuren,
  • b) Alkansulfonsäuren,
  • c) Amide aus höhermolekularen Fettsäuren und Aminoalkylsulfonsäuren,
  • d) sulfatierte, höhermolekulare Fettsäuren bzw. deren Ester
  • e) Alkylsulfate wie Natriumdodecylsulfat, Alkylethersulfate (z.B. wie 3a), Alkylpolyethersulfate.
  Als sulfatierte höhermolekulare Fettsäuren bzw. deren Ester kommen in Frage:
  • Sulfatierungsprodukte der Öl- bzw. Elaidinsäure oder der Ricinolsäure und deren Alkylester, z.B. der Methyl-, Ethyl-, Propyl- oder Butylester, oder des Glycerinesters dieser Fettsäuren, z.B. des Ricinusöles.
• 5. Sulfonierte, aromatische Kondensationsprodukte beispielsweise aus Naphthalin, Formaldehyd und Schwefelsäure.
• 6. Verbindungen der Formel (vgl. DAS 2 945 102)
  
  worin

  R

  für C₄-C₁₂-Alkyl, C₁-C₁₂-Alkoxy, Phenyl, Cyclohexyl oder C₂-C₈-Hydroxyalkoxy steht,

  R₁

  für H oder C₁-C₄-Alkyl steht,

  x

  für eine ganze Zahl von 1 bis 10 steht und

  y

  für Zahlen von 1 bis $\text{x+1}$

  

  steht.

• 7.
  • a) Verbindungen mit der Formel (vgl. DAS 1 444 267)
    
    ${\text{R(A)}}_{\text{x}}\text{R₁,}$
    
    
    
    worin

    R

    für sulfonierte Benzol- oder Naphthalinringe,

    R₁

    für sulfonierte Benzol- oder Naphthalinringe,

    A

    für CH₂, SO₂ oder NH, und

    x

    für 0 bis 4 steht,

  • b) ein schwach kationisches komplexbildendes Mittel wie beispielsweise Polyvinylpyrrolidon oder ein Kondensationsprodukt von Ethylenoxid mit einem Fettamin mit langer Kette.
• 8. Polyglykolether sulfogruppenhaltiger durch Kohlenwasserstoffe substituierter Phenole oder Naphthole (vgl. DAS 1 288 066)
  
  worin

  Ar

  für einen Benzol- oder Naphthalinrest,

  R

  für einen Kohlenwasserstoffrest, insbesondere Cycloalkyl, Aralkylrest oder Alkylrest mit mindestens 7 Kohlenstoffatomen steht,

  R₁

  für H oder Methyl,

  x

  für 1 bis 8

  X

  für OH, Cl, CN, O-Alkyl oder OOC-Alkyl bzw. eine anionische Atomgruppierung wie OSO₃H, OPO₃H₂ oder OCH₂CO₂H steht; ferner die Alkali- oder Ammoniumsalze dieser Verbindungen sowie ihre Salze mit Aminen, z.B. Ethanolamin, Diethanolamin, Triethanolamin und Cyclohexylamin.

In a further preferred embodiment of the process according to the invention, a surface-active auxiliary is added to the dyebath. The following are preferably suitable as surface-active aids:

• 1.
  • a) water-soluble polyalkylene glycol ethers containing basic nitrogen atoms, as described, for example, in DAS 1 619 652,
  • b) alkoxylated fatty amines of the general formula
    
    wherein

    R

    represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkenyl,

    x and y

    independently stand for a count of 5 - 70, preferably 15 - 50, and

    R₁

    represents hydrogen, methyl, ethyl or phenyl,

  • c) reaction products of alkylamines having 12 to 22 carbon atoms with formaldehyde, phenols and 15-50 equivalents of ethylene oxide, components a), b) and c) being able to be used as individual compounds or as mixtures with one another.
• 2. Compounds of the formula (cf. DAS 1 940 178 and EP 305 858)
  
  wherein

  R

  represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,

  R₁

  for C₁-C₄ alkyl or a group of the formula
  
  
  
  - (CH₂-CHR₂-O) _y -H
  
  or
  
  - (CH₂-CHR₂-O) _y -CH₂-CH₂-A ^⊖ M ^⊕
  
  stands,

  R₂

  represents H, methyl, ethyl or phenyl,

  M ^⊕

  represents a cation, in particular an alkali metal, alkaline earth metal or ammonium ion or a mono-, di- or triethanolammonium ion,

  A ^⊖

  represents an anionic group, in ^particular SO₄ ^⊖ or SO₃ ^⊖ , and

  x and y

  independently of one another represent a number from 5 to 70, preferably 15 to 50,

  or their quaternization products of the formula
  
  wherein

  R, R₁, R₂, M ^⊕ , A ^⊖ , x and y

  have the meaning given above and

  R₃

  represents C₁-C₈-alkyl optionally substituted by hydroxy, carboxyl, lower carbalkoxy or carbonamide

  (see DAS 1 940 178; EP 305 858).
• 3rd
  • a) Alkoxylated fatty alcohols (cf. EP 312 493) of the formula
    
    
    
    RO (CH₂CHR₁O) _x -H
    
    
    
    wherein

    R

    represents C₁₂-C₂₂-alkyl, C₁₂-C₂₂-alkenyl or C₁₂-C₂₂-cycloalkyl,

    R₁

    represents H, methyl, ethyl or phenyl, and

    x

    stands for 12 - 60,

    and or
  • b) quaternized ammonium compounds of polyglycol compounds of the formula
    
    wherein

    R₁

    represents alkyl or alkenyl each having 12 to 22 carbon atoms,

    R₂

    represents C₁-C₈-alkyl optionally substituted by hydroxy, carboxyl, lower carbalkoxy or carbonamide,

    R₃

    represents H, methyl, ethyl or phenyl,

    x and y

    independently represent a number from 5 to 70, preferably 15 to 50, and

    A ^⊖

    is an anion, preferably represents Cl ^⊖ or methosulfate anion, is.

• 4. Compounds containing surface-active sulfuric acid ester or sulfonic acid groups such as (see also DAS 1 920 357)
  • a) alkylarylsulfonic acids,
  • b) alkanesulfonic acids,
  • c) amides from higher molecular weight fatty acids and aminoalkylsulfonic acids,
  • d) sulfated, higher molecular weight fatty acids or their esters
  • e) alkyl sulfates such as sodium dodecyl sulfate, alkyl ether sulfates (eg as 3a), alkyl polyether sulfates.
  The following can be considered as sulfated higher molecular fatty acids or their esters:
  • Sulphation products of oleic or elaidic acid or ricinoleic acid and their alkyl esters, for example the methyl, ethyl, propyl or butyl ester, or of the glycerol ester of these fatty acids, for example of castor oil.
• 5. Sulfonated, aromatic condensation products, for example from naphthalene, formaldehyde and sulfuric acid.
• 6. Compounds of the formula (cf. DAS 2 945 102)
  
  wherein

  R

  represents C₄-C₁₂-alkyl, C₁-C₁₂-alkoxy, phenyl, cyclohexyl or C₂-C₈-hydroxyalkoxy,

  R₁

  represents H or C₁-C₄-alkyl,

  x

  represents an integer from 1 to 10 and

  y

  for numbers from 1 to $\text{x + 1}$

  

  stands.

• 7.
  • a) Compounds with the formula (cf. DAS 1 444 267)
    
    ${\text{R (A)}}_{\text{x}}\text{R₁,}$
    
    
    
    wherein

    R

    for sulfonated benzene or naphthalene rings,

    R₁

    for sulfonated benzene or naphthalene rings,

    A

    for CH₂, SO₂ or NH, and

    x

    represents 0 to 4,

  • b) a weakly cationic complexing agent such as polyvinyl pyrrolidone or a condensation product of ethylene oxide with a long chain fatty amine.
• 8. Polyglycol ethers of sulfo-containing phenols or naphthols substituted by hydrocarbons (cf. DAS 1 288 066)
  
  wherein

  Ar

  for a benzene or naphthalene residue,

  R

  represents a hydrocarbon radical, in particular cycloalkyl, aralkyl radical or alkyl radical with at least 7 carbon atoms,

  R₁

  for H or methyl,

  x

  for 1 to 8

  X

  represents OH, Cl, CN, O-alkyl or OOC-alkyl or an anionic atomic grouping such as OSO₃H, OPO₃H₂ or OCH₂CO₂H; furthermore the alkali or ammonium salts of these compounds and their salts with amines, for example ethanolamine, diethanolamine, triethanolamine and cyclohexylamine.

In principle, the complexing agents, dispersants and surface-active agents mentioned can be added to the dyebath to carry out the process according to the invention both individually and in any mixture with one another.

The complexing agents mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.

The dispersants mentioned are added to the dyebath in general amounts of 0.1 to 5 g / l, preferably 0.5 to 2 g / l.

The surface-active agents mentioned are generally added to the dyebath in quantities of 0.5 to 4%, preferably 1 to 2%, based on the weight of the polyamide fiber to be dyed.

Of the complexing agents mentioned, phosphonoalkane polycarboxylic acids, such as 2-phosphonobutane-1,2,4-tricarboxylic acid, are preferred.

Of the dispersants mentioned, condensation products of naphthalenesulfonic acid and formaldehyde are preferably used.

Of the surface-active agents mentioned, alkoxylated fatty alcohols and the compounds mentioned under 1 are of particular importance.

In a very particularly preferred embodiment of the process according to the invention, the combination of the following surface-active agents is added to the dyebath:
0.05-2.5 g / l of a mixture (M) consisting of 25-35 parts by weight of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, 4-6 parts by weight of an alkoxylated fatty amine, 1-3 parts by weight of one Implementation product from alkylamines with formaldehyde, phenol and ethylene oxide and 30-56 parts by weight of water, the parts by weight being based on the total mixture (M), and 0.05-2.5 g / l of an alkoxylated fatty alcohol.

example 1

A polyamide microfiber (deep matt woven 1.15 dtex) that was washed, desized and fixed was mixed with a mixture of 1% C.I. Acid Yellow 242.2% C.I. Acid Blue 264 and 1% C.I. Acid Blue 290 by the HT process (liquor ratio 1:20) at 110 ° C. and a pH of 5 in the presence of 0.1 g / l manganese (II) acetate, 1.0 g / l of a commercially available surface-active agent Agent consisting of polyalkylene glycol ether (LEVEGAL LPA®) and 1.0 g / l of a surface-active agent consisting of the reaction product of oleyl alcohol colored with 50 equivalents of ethylene oxide for 60 minutes.

Claims (8)

Process for dyeing polyamide fibers with acid dyes, characterized in that small amounts of nickel, zinc, cobalt, zirconium or manganese salts are added to the dye bath. Process according to claim 1, characterized in that the polyamide fibers are microfibers with a fiber thickness of 0.6 to 1.2 dtex and a content of titanium dioxide pigments of up to 2%. Process according to claim 1, characterized in that small amounts of manganese (II) salts in the form of the chlorides, nitrates, sulfates, acetates, phosphates, formates, oxalates or lactates are added to the dyebath. Process according to claim 1, characterized in that the salts are added to the dyebath in quantities of 0.1 to 1 g / l, preferably 0.1 to 0.5 g / l. Process according to claim 1, characterized in that the acid dyes are azo dyes, antrachinone dyes and metal complex dyes or mixtures thereof. Process according to claim 1, characterized in that a complexing agent and / or an anionic dispersing agent and / or a surface-active agent is added to the dyebath. Process according to claim 1, characterized in that one or more surface-active agents are added to the dyebath. A method according to claim 1, characterized in that the dye bath as a surface-active agent is a combination of a water-soluble polyalkylene glycol ether containing basic nitrogen atoms, a alkoxylated fatty amine and a reaction product of alkylamines with formaldehyde, phenols and ethylene oxide is added.