EP0105034B1 - Dyeing aid and process for dyeing of polyacrylonitrile fibre material - Google Patents

Description

• (A) ein quaternäres Ammoniumsalz, welches mindestens ein basisches Stickstoffatom aufweist, an welches mindestens ein aliphatischer Rest mit 6 bis 22 Kohlenstoffatomen gebunden ist, und
• (B) ein Aminoxid der Formel
  
  worin
  • X_i Alkyl oder Alkenyl je mit 8 bis 18 Kohlenstoffatomen und
  • X₂ und X₃, unabhängig voneinander, Niederalkyl oder Hydroxy-Niederalkyl bedeuten, enthält.

The present invention relates to a new dyeing aid, which is characterized in that it is at least

• (A) a quaternary ammonium salt which has at least one basic nitrogen atom to which at least one aliphatic radical having 6 to 22 carbon atoms is bonded, and
• (B) an amine oxide of the formula
  
  wherein
  • X _i alkyl or alkenyl each with 8 to 18 carbon atoms and
  • X ₂ and X ₃ , independently of one another, denote lower alkyl or hydroxy lower alkyl.

Lower alkyl represents those groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms, such as e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl.

This dyeing aid is suitable as a wetting, venting, retarding and leveling agent for dyeing slow, normal or fast-drawing polyacrylonitrile fibers with migrating or non-migrating cationic dyes or their mixtures.

The quaternary ammonium salts which can be used as component (A) can have migrating or non-migrating properties. However, migrating quaternary ammonium salts are preferably used, which advantageously have only a low retarding effect at the end of the dyeing process.

Quaternary ammonium salts whose cation weight is less than 400, especially less than 250, whose parachor is less than 1200, in particular less than 800 and whose log P is less than 8, preferably less than 7.0, are particularly suitable. Among these, preference is given to those whose cation weight is less than 275, whose parachor is less than 700 and whose log P is less than 6.4.

worin

• R einen aliphatischen Kohlenwasserstoffrest mit 5 bis 21 Kohlenstoffatomen, vorzugsweise 7 bis 18 Kohlenstoffatomen,
• Q die direkte Bindung oder Sauerstoff,
• Y, und Y₂, unabhängig voneinander, Niederalkyl, Cycloalkyl oder Hydroxyniederalkyl, vorzugsweise Methyl, Ethyl oder 2-Hydroxyethyl oder
• Y, und Y₂ zusammen mit dem sie verbindenden Stickstoffatom einen fünf- oder sechsgliedrigen, gesättigten, heterocyclischen Rest, wie z.B. Pyrrolidino, Piperidino oder Morpholino,
• Y₃ Niederalkyl, Hydroxy-Niederalkyl, Epoxy-Niederalkyl, Cyano-Niederalkyl, Carbamoyl-Niederalkyl oder Aralkyl, wie z.B. Benzyl, Chlorbenzyl oder a-Methylbenzyl,
• Y₁, Y₂ und Y₃ zusammen mit dem sie verbindenden Stickstoffatom einen gegebenenfalls durch Niederalkyl substituierten Pyrdinring und
• An⁸ das Anion einer organischen oder anorganischen Säure, wie z.B. das Chlorid-, Bromid-, Sulfat-, Benzolsulfonat-, p-Toluolsulfonat-, Methosulfat-, Ethosulfat- oder Methophosphation,

bedeuten.Quaternary ammonium salts that can be used are, for example, quaternary ammonium compounds of the formula

wherein

• R is an aliphatic hydrocarbon radical having 5 to 21 carbon atoms, preferably 7 to 18 carbon atoms,
• Q the direct bond or oxygen,
• Y, and Y ₂ , independently of one another, lower alkyl, cycloalkyl or hydroxy-lower alkyl, preferably methyl, ethyl or 2-hydroxyethyl or
• Y and Y ₂ together with the nitrogen atom connecting them form a five- or six-membered, saturated, heterocyclic radical, such as, for example, pyrrolidino, piperidino or morpholino,
• Y ₃ lower alkyl, hydroxy lower alkyl, epoxy lower alkyl, cyano lower alkyl, carbamoyl lower alkyl or aralkyl, such as, for example, benzyl, chlorobenzyl or a-methylbenzyl,
• Y ₁ , Y ₂ and Y ₃ together with the nitrogen atom connecting them represent a pyridine ring which is optionally substituted by lower alkyl and
• An ^{8 is} the anion of an organic or inorganic acid, such as, for example, the chloride, bromide, sulfate, benzenesulfonate, p-toluenesulfonate, methosulfate, ethosulfate or methophosphate ion,

mean.

In the formula (1), R preferably denotes an alkyl radical or alkenyl radical each having 5 to 21 carbon atoms, especially 7 to 18 carbon atoms. Examples of such alkyl radicals are pentyl, hexyl, octyl, decyl, dodecyl, cocosyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl. R is preferably pentyl, hexyl, octyl, decyl, dodecyl, cocosyl or myristyl or a mixture of these alkyl radicals.

Q is preferably the direct bond between R and -CH ₂ -.

The Y radicals can be the same or different from one another.

As the cycloalkyl radical, Y and Y _{2 are,} for example, cyclopentyl or preferably cyclohexyl.

Y and Y ₂ are preferably methyl, ethyl or especially 2-hydroxyethyl.

If Y _{3 represents} a lower alkyl radical, it is in particular methyl or ethyl. If Y _{3 is} hydroxy-lower alkyl or cyano-lower alkyl, it is primarily 2-hydroxyethyl, 3-hydroxypropyl or 2-cyanoethyl. As epoxy lower alkyl, Y ₃ preferably denotes the epoxypropyl group. As carbamoyl lower alkyl, Y _{3 is} in particular the carbamoylmethyl group. Y ₃ is preferably methyl, ethyl or benzyl.

If Y and Y ₂ together with the nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, thiomorpholino or preferably morpholino.

Anions An ⁸ include both anions of inorganic acids, for example the chloride, bromide, fluoride, sulfate or phosphate ion, and also organic acids, for example aromatic or aliphatic sulfonic acids, such as, for example, benzenesulfonate, p-toluenesulfonate, chlorobenzenesulfonate, Methanesulfonate or ethanesulfonate ion and the anions of acidic alkyl esters of inorganic acids, such as, for example, the methosulfate, ethosulfate or methophosphate ion. At ⁸ is mainly the chloride or methosulfate ion.

worin

• R₁ Alkyl mit 5 bis 15 Kohlenstoffatomen,
• Q Sauerstoff oder vorzugsweise die direkte Bindung,
• Y₄ und Y₅ Niederalkyl oder Hydroxy-Niederalkyl,
• Y₆ Methyl, Ethyl oder Benzyl und
• (An)⊖₁ das Chlorid- oder Methosulfation
• bedeuten.

Quaternary ammonium salts of the formula are particularly suitable among the compounds of the formula (1)

wherein

• R ₁ alkyl having 5 to 15 carbon atoms,
• Q is oxygen or preferably the direct bond,
• Y ₄ and Y ₅ lower alkyl or hydroxy lower alkyl,
• Y _{6 is} methyl, ethyl or benzyl and
• (An) ⊖ ₁ the chloride or methosulfate ion
• mean.

Practically important representatives of quaternary ammonium compounds of the formula (2) are N-hexyl - N, N, N-trimethylammonium chloride, Nn-dodecyl - N, N, N-trimethylammonium chloride, Nn-dodecyl - N, N-di-2 -hydroxyethyl-N-benzylammonium chloride, Nn-dodecyl-N, N-di-2-hydroxymethyl-N-methylammonium methosulfate, Nn-dodecyloxymethyl-N, N, N - trimethylammonium chloride, N-cocosyl-N, N-di- 2 - hydroxyethyl-N-methyl-ammonium methosulfate, N - cetyl-N, N, N-trimethylammonium chloride, N-oleyl - N, N-dimethyl-N-benzylammonium chloride, N-stearyl-N, N-dimethyl-N -benzylammonium chloride, or especially N-cocosyl-N, N, N-trimethylammonium methosulfate, N-cocosyl-N, N-dimethyl-N-benzylammonium chloride or N-cocosyl-N, N-di-2-hydroxyethyl- -N-benzylammonium chloride.

worin V Wasserstoff, Methyl oder Ethyl bedeutet, R₂ einen Alkyl- oder Alkenylrestjeweils mit 6 bis 18 Kohlenstoffatomen bedeutet und An⁸ die oben angegebene Bedeutung hat, verwendet werden.Furthermore, quaternary ammonium salts of the formula

wherein V represents hydrogen, methyl or ethyl, R _{2 represents} an alkyl or alkenyl radical each having 6 to 18 carbon atoms and An ^{8 has} the meaning given above.

worin R₃ n-Octyl oder n-Dodecyl bedeutet, besonders geeignet.Of these, the compounds are of the formula

wherein R _{3 is} n-octyl or n-dodecyl, particularly suitable.

worin R₂, Y₃, Y₄, Y₅ und An⁸ die angegebene Bedeutung haben und n 2 oder 3 bedeutet.Quaternary ammonium salts of the formula are also suitable

wherein R ₂ , Y ₃ , Y ₄ , Y ₅ and An ^{8 have} the meaning given and n is 2 or 3.

Examples of these compounds of formula (5) are quaternary ammonium salts by definition, which e.g. by reaction of coconut oil fatty acid chloride with N, N-dimethylpropylenediamine and then by quaternization with methyl chloride, dimethyl sulfate, glycol chlorohydrin, epichlorohydrin or benzyl chloride.

worin

• V_i Alkyl mit 6 bis 18 Kohlenstoffatomen,
• V₂ Niederalkyl, Hydroxy-Niederalkyl oder Benzyl und
• R₄ Wasserstoff, Alkyl mit 1 bis 18, vorzugsweise 1 bis 4 Kohlenstoffatomen oder Phenyl bedeuten, und
• An⁸ die oben angegebene Bedeutung hat,

oder der Formel

worin R₅ Alkyl mit 8 bis 18 Kohlenstoffatomen, V₃ und V₄ unabhängig voneinander je Wasserstoff, Niederalkyl oder Hydroxy-Niederalkyl darstellen, wobei V₃ und V₄ zusammen mit der Gruppe

auch den Rest eines teilweise gesättigten Ringes, besonders eines Diazolin- oder Tetrahydrodiazinringes bilden können und An⊖ die angegebene Bedeutung hat.Other quaternary ammonium salts of which can be used as component (A) entspre, _- chen the formula

wherein

• V _i alkyl having 6 to 18 carbon atoms,
• V ₂ lower alkyl, hydroxy lower alkyl or benzyl and
• R _{4 is} hydrogen, alkyl having 1 to 18, preferably 1 to 4 carbon atoms or phenyl, and
• ^{8 has} the meaning given above,

or the formula

wherein R _{5 is} alkyl with 8 to 18 carbon atoms, V ₃ and V ₄ each independently represent hydrogen, lower alkyl or hydroxy-lower alkyl, V ₃ and V ₄ together with the group

can also form the rest of a partially saturated ring, especially a diazoline or tetrahydrodiazine ring and An⊖ has the meaning given.

Examples of compounds of the formula (6) are: 1-dodecyl-3-benzyl-imidazolium chloride and 1-hexadecyl-2-isopropyl-3-methylimidazolium methosulfate.

• N-Octadecyl-guanidiniumchlorid, N-Hexadecyl-N^L -methyl-N'^L2-hydroxyethylguanidiniumchlorid und 2-Octylaminoimidazoliumacetat.

Examples of suitable compounds of the formula (7) are:

• N-octadecyl-guanidinium chloride, N-hexadecyl-N ^L -methyl-N ' ^L 2-hydroxyethylguanidinium chloride and 2-octylaminoimidazolium acetate.

Mixtures according to the definition of quaternary ammonium salts can also be used as component (A) in the dyeing aid according to the invention.

Among the compounds of the formulas (1) to (7), those of the formula (2) in which Q denotes the direct bond are particularly preferred.

The quaternary ammonium salts by definition are used in amounts of 20 to 50 percent by weight, based on the total weight of the dyeing aid.

The amine oxides which are suitable as component (B) can also be present in the dyeing aid according to the invention as mixtures which contain two or more of the amine oxides of the formula (i).

• N-Dodecyl-N,N-dimethylaminoxid
• N-Myristyl-N,N-dimethylaminoxid
• N-Dodecyl-N,N-di-2-hydroxyethylaminoxid
• N-Hexadecyl-N,N-di-2-hydroxyethylaminoxid
• N-Hexadecyl-N,N-dimethylaminoxid
• N-Stearyl-N,N-dimethylaminoxid
• N-Oleyl-N,N-di-2-hydroxyethylaminoxid
• N-Stearyl-N,N-di-2-hydroxyethylaminoxid und
• N-Kokosyl-N,N-di-2-hydroxyethylaminoxid.

Practically important representatives of amine oxides of the formula (i) are:

• N-dodecyl-N, N-dimethylamine oxide
• N-myristyl-N, N-dimethylamine oxide
• N-dodecyl-N, N-di-2-hydroxyethylamine oxide
• N-hexadecyl-N, N-di-2-hydroxyethylamine oxide
• N-hexadecyl-N, N-dimethylamine oxide
• N-stearyl-N, N-dimethylamine oxide
• N-oleyl-N, N-di-2-hydroxyethylamine oxide
• N-stearyl-N, N-di-2-hydroxyethylamine oxide and
• N-Cocosyl-N, N-di-2-hydroxyethylamine oxide.

Mixtures of these amine oxides can also be used advantageously.

The amine oxides of the formula (i) are used in amounts of 10 to 25, preferably 12 to 20, percent by weight, based on the total weight of the aqueous dyeing aid.

• (Aa) ein quaternäres Ammoniumsalz der Formel
  
  worin
  • R₂ Alkyl oder Alkenyl jeweils mit 6 bis 18 Kohlenstoffatomen,
  • Y₄ und Y₅ Niederalkyl oder Hydroxy-Niederalkyl, insbesondere Methyl, Ethyl oder 2-Hydroxyethyl,
  • Y₆ Methyl, Ethyl oder Benzyl und (An)8 das Chlorid- oder Methosulfation und (Bb) ein Aminoxid der Formel (i) sind.

Preferred dyeing auxiliaries according to the invention contain at least the following components:

• (Aa) a quaternary ammonium salt of the formula
  
  wherein
  • R _{2 is} alkyl or alkenyl each having 6 to 18 carbon atoms,
  • Y ₄ and Y ₅ lower alkyl or hydroxy lower alkyl, in particular methyl, ethyl or 2-hydroxyethyl,
  • Y _{6 is} methyl, ethyl or benzyl and (An) 8 is the chloride or methosulfate ion and (Bb) is an amine oxide of the formula (i).

The dyeing auxiliaries according to the invention can preferably be prepared by simply stirring the components (A) and (B) mentioned in water. This gives homogeneous, preferably aqueous, clear mixtures which are very stable in storage at room temperature. Components (A) and (B) are generally present in a weight ratio of 9: 1 to 3: 7, preferably 6: 1 to 1: 1 and in particular 4: 1 to 2: 1.

These dyeing aids preferably contain, based on the total mixture, 25 to 45 percent by weight of component (A) 8 to 20 percent by weight of component (B) and 35 to 67 percent by weight of water.

The new dyeing auxiliaries are used in particular as wetting, venting and in particular leveling and retarding agents in the dyeing of polyacrylonitrile fiber materials. They therefore allow the leveled substrate to be perfectly level.

The present invention also relates to a process for dyeing polyacrylonitrile fiber material with cationic dyes. The process is characterized in that this material is dyed in the presence of the dyeing aid according to the invention. Components (A) and (B) can also be added separately to the dyebath.

The amounts used in which the dyeing aid according to the invention is added to the dyebath advantageously range between 0.1 to 5 percent by weight, preferably 0.5 to 3 percent by weight, based on the weight of the material to be dyed.

Both migrating and non-migrating dyes can be used as cationic dyes.

Suitable migrating cationic dyes are, in particular, those with a more or less delocalized positive charge, whose cation weight is less than 310, whose parachor is less than 750 and whose log P is less than 3.2. The Parachor is according to the article by O.R. Quayle [Chem. Rev. 53, 439 (1953)] and log P means the relative lipophilicity, the calculation of which by C. Hanach et al [J. Med. Chem. 16, 1207 (1973)]. The influence of the charge of the dye cations was not taken into account, which results in 6 log units higher log P values. Preferred migrating cationic dyes are those whose cation weight is less than 275, whose parachor is less than 680 and whose log P is less than 2.8.

Non-migrating cationic dyes are, in particular, those whose cation weight is greater than 310 and whose parachor is greater than 750.

The cationic, migrating and non-migrating dyes can belong to different classes of dyes. In particular, they are salts, for example chlorides, sulfates or metal halides, for example zinc chloride double salts of azo dyes, such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketonimine, cyanine, xanthene , Azine, oxazine or thiazine dyes.

Mixtures of the cationic dyes can also be used. Dye combinations of at least 2 or preferably 3 migrating or non-migrating cationic dyes are particularly preferred for the production of level dichromic or trichromatic dyeings, it also being possible to use mixtures of migrating and non-migrating cationic dyes.

The amount of dyes added to the liquor depends on the desired depth of color. In general, amounts of dye of 0.01 to 5, preferably 0.05 to 2 percent by weight, based on the weight of the material to be dyed, have proven to be advantageous.

The dye liquor can also electrolytes, especially inorganic, such as alkali metal salts, expediently sodium salts, such as e.g. Sodium chloride or sodium sulfate, potassium salts such as e.g. Potassium chloride or potassium sulfate, ammonium salts such as e.g. Contain ammonium chloride or ammonium sulfate. These electrolytes can be used in amounts of 1 to 20, preferably 5 to 10 percent by weight, based on the material to be colored.

In addition, the dye liquors can contain acids, for example mineral acids, such as sulfuric acid or phosphoric acid or organic acids, suitably lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. These acids primarily serve to adjust the pH of the liquors used according to the invention, which are generally 2 to 8 preferably 3 to 6. To stabilize a certain pH value, alkali metal acetate, for example sodium acetate or ammonium acetate, citrate or phosphate, can also be present in the dye liquor.

The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio depends on the equipment, the substrate and the packaging, and the packing density. However, it can be chosen within a wide range, e.g. 1: 4 to 1: 100, but is usually between 1: 5 to 1: 40.

The temperature at which dyeing is carried out is at least 70 ° C and generally it is not higher than 106 ° C. It is preferably in the range from 80 to 103 ° C.

The process can be carried out by either briefly treating the material to be dyed first with the dyeing aid according to the invention and then dyeing it, or preferably treating it simultaneously with the dyeing aid and the dye. The material to be dyed is preferably allowed to advance at 70-90 ° C. in the bath, which is adjusted to a pH of 3 to 5, then the dyeing aid and the dye are added and the temperature is raised to 98 ° within 15 to 45 minutes C and dyeing at this temperature for 30 to 60 minutes, or one goes into the dyeing liquor at boiling temperature and dyeing at this temperature for 30 to 60 minutes. However, it is also possible for the dyeing liquor to be heated to a temperature of 105 ° C. in the course of 15 to 30 minutes (high-temperature dyeing) and then to be left at this temperature for 15 to 45 minutes.

At the end of the dyeing, the dyeing liquor is slowly cooled and the dyeings are rinsed with water and dried.

The acrylic fibers which can be dyed by the process according to the invention include the commercially available types of polymeric or mixed-polymer acrylonitrile. In the case of the acrylonitrile copolymers, the proportion of acrylonitrile is expediently at least 80% by weight, based on the weight of the copolymer. As a rule, polyacrylonitrile fibers consist of approx. 85% by weight of acrylonitrile and approx. 15% of copolymer.

The polyacrylonitrile fibers can have different draw properties, i.e. the method according to the invention can be applied to all types of polyacrylonitrile fibers, namely so-called fast-pulling, normal-pulling and slow-pulling polyacrylonitrile fibers.

The fiber material to be dyed can be in various forms. Examples include: loose material, sliver, cable, yarn, cross-wound bobbins, warp beams, muffs, wound packages, knitted fabrics, fabrics, carpets. The fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / cotton, polyacrylonitrile / polyester or polyacrylonitrile / wool can be used.

As already mentioned, level individual and in particular mixed tone dyeings are achieved at the usual dyeing temperatures and when using non-migrating or migrating dyes. Irrespective of the type of polyacrylonitrile fiber to be dyed, areas of the substrate which have hydrophobic impurities and therefore undesirable air bubbles can also be dyed in any way, since the auxiliary mixture according to the invention acts simultaneously as a deaerating and retarding agent. In addition, the method according to the invention enables any over-dyeing of irregular dyeings in black. It also allows nuances at cooking temperature.

The dyeings obtained are distinguished by good fastness properties, in particular wet fastness properties such as fastness to washing, water, sweat and decorative. The other fastnesses of the dyeings, e.g. Lightfastness and fastness to rubbing are not affected by the use of the dyeing auxiliaries according to the invention.

In the following examples, the percentages are by weight unless otherwise specified. The amounts of the dyes relate to commercial, i.e. Coupé goods and with quaternary ammonium compounds and amine oxides on pure substance. For the dyes and the quaternary ammonium salts mean: K cation weight, Pa Parachor and log P relative lipophilicity.

example 1

• 45 g des Färbereihilfsmittels (1), bestehend aus
  • 35% einer quaternären Ammonium-Verbindung der Formel
    
  • 10% N-Myristyl-N,N-dimethylaminoxid und
  • 55% Wasser,
• 1,25 g des gelben Farbstoffes der Formel
  
  • Kationgewicht: 330 Parachor: 814 log P: 4,15 0,45 g des roten Farbstoffs der Formel
    
  • Kationgewicht: 321 Parachor: 764 log P: 3,22
• 1,20 g des blauen Farbstoffes der Formel
  
  • Kationgewicht: 371 Parachor: 817 log P: 3,84
  
  zugesetzt. Danach lässt man die Flotte weitere 5 Minuten bei 70 °C zirkutieren und erhöht die Temperatur im Verlaufe von 60 Minuten auf 98°C, worauf das Garn während 60 Minuten bei dieser Temperatur gefärbt wird.

2 kg of a pre-shrunk yarn made of fast-drawing polyacrylonitrile fibers are treated in a dyeing machine with 34 liters of an aqueous liquor which contains 200 g of calcined sodium sulfate and which is adjusted to a pH of 4 with 80% acetic acid for 5 minutes at 80 ° C. Then the fleet

• 45 g of dyeing aid (1) consisting of
  • 35% of a quaternary ammonium compound of the formula
    
  • 10% N-myristyl-N, N-dimethylamine oxide and
  • 55% water,
• 1.25 g of the yellow dye of the formula
  
  • Cation weight: 330 Parachor: 814 log P: 4.15 0.45 g of the red dye of the formula
    
  • Cation weight: 321 Parachor: 764 log P: 3.22
• 1.20 g of the blue dye of the formula
  
  • Cation weight: 371 Parachor: 817 log P: 3.84
  
  added. The liquor is then left to circulate at 70 ° C. for a further 5 minutes and the temperature is raised to 98 ° C. in the course of 60 minutes, after which the yarn is dyed at this temperature for 60 minutes.

The dyeing liquor is then slowly cooled to 60 ° C. and the yarn is rinsed and dried.

A well-dyed yarn with a level gray coloration of good wet, light and rub fastness properties is obtained. The color is much quieter than the color obtained when the quaternary ammonium compound is used without the amine oxide being used.

Example 2

Paraffin is partially applied by hand to a fabric made of normal-pulling polyacrylonitrile fibers and fixed at 60 ° C.

• 0,08 g des Färbereihilfsmittels (1) und eine Farbstoffmischung bestehend aus
• 0,04 g des gelben Farbstoffes der Formel (101)
• 0,01 g des roten Farbstoffes der Formel (102) und
• 0,03 g des blauen Farbstoffes der Formel (103)

zugesetzt. Hernach wird die Temperatur der Flotte im Verlaufe von 30 Minuten auf 98°C erhöht und dann das Gewebe während 30 Minuten bei dieser Temperatur gefärbt. Man kühlt anschliessend die Färbeflotte langsam auf 60°C ab und spült und trocknet das Gewebe.5 g of the tissue contaminated with paraffin are treated in a dyeing machine with 200 ml of an aqueous liquor containing 0.5 g of calcined sodium sulfate and adjusted to a pH of 4 with 80% acetic acid for 5 minutes at 70.degree. Then the fleet

• 0.08 g of dyeing aid (1) and a dye mixture consisting of
• 0.04 g of the yellow dye of the formula (101)
• 0.01 g of the red dye of the formula (102) and
• 0.03 g of the blue dye of the formula (103)

added. The temperature of the liquor is then raised to 98 ° C. in the course of 30 minutes and the fabric is then dyed at this temperature for 30 minutes. The dyeing liquor is then slowly cooled to 60 ° C. and the fabric is rinsed and dried.

A well-dyed fabric is obtained which shows no marking of the paraffin application.

Example 3

2000 g of fast-pulling polyacrylonitrile yarn (as muff) are treated in a circulator with 34 liters of an aqueous dyeing liquor containing 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70 ° C.

• 45 g des Färbereihilfsmittels (1)
• 4 g des gelben Farbstoffes der Formel
  

Then the dye liquor

• 45 g of dyeing aid (1)
• 4 g of the yellow dye of the formula
  

Cation weight: 317 Parachor: 734 log P: 6.5 added. The liquor is then allowed to circulate at 70 ° C. for a further 5 minutes, the temperature is then increased to 98 ° C. in the course of 30 minutes and dyeing is carried out at this temperature for 15 minutes.

To shade, 22.5 g of the dyeing agent (1) are added to the dyeing liquor without cooling. After a further 5 minutes, 0.4 of the blue dye of the formula (103) is added and the dyeing is continued at 98 ° C. for a further 40 minutes. The liquor is then slowly cooled to 60 ° C., the substrate is rinsed and dried.

In order to see any irregularities, the yarn is knitted so that the inner and outer part lie side by side. The knitted fabric is characterized by excellent levelness, while maintaining good wet, light and rub fastness.

Example 4

2 kg of a pre-shrunk yarn made of fast-drawing polyacrylonitrile fibers are treated in a circulation apparatus with 34 liters of an aqueous liquor which contains 200 g of calcined sodium sulfate and 40 ml of 80% acetic acid for 5 minutes at 70.degree.

• 45 g des Färbereihilfsmittels (1)
• 1 g des gelben Farbstoffes der Formel
  
  Kationgewicht: 226 Parachor: 558 log P: 2,49
• 1 g des roten Farbstoffes der Formel
  
  Kationgewicht: 230 Parachor: 574 log P: 0,92
• 2 g des blauen Farbstoffes der Formel
  
  Kationgewicht: 270 Parachor: 577 log P: 1,97 zugesetzt.

After that, the fleet

• 45 g of dyeing aid (1)
• 1 g of the yellow dye of the formula
  
  Cation weight: 226 Parachor: 558 log P: 2.49
• 1 g of the red dye of the formula
  
  Cation weight: 230 Parachor: 574 log P: 0.92
• 2 g of the blue dye of the formula
  
  Cation weight: 270 Parachor: 577 log P: 1.97 added.

The liquor is then left to circulate at 70 ° C. for a further 5 minutes, the temperature is raised to 98 ° C. in the course of 30 minutes and the fiber material is dyed at this temperature for 60 minutes.

The liquor is then slowly cooled to 60 ° C., the substrate is rinsed and dried.

This gives a level blue-gray color with good wet, light and rub fastness.

Example 5

• 2 g des Färbreihilfsmittels (2), bestehend aus
• 35% einer quaternären Ammoniumverbindung der
• Formel (22) [Kokosyl - N (CH₃)₃ ]⊕ CH₃S0₄⊖
• 10% N-Kokosyl-N,N-di-2-hydroxyethylaminoxid und
• 55% Wasser
• 0,42 g des gelben Farbstoffes der Formel (101) und 0,38 g des roten Farbstoffes der Formel (102)

gelöst zugesetzt. Danach wird das Substrat weitere 5 Minuten bei 70°C behandelt und anschliessend das Bad im Verlaufe von 30 Minuten auf 98°C erwärmt, worauf die Ware 30 Minuten bei dieser Temperatur gefärbt wird. Man kühlt dann die Färbeflotte langsam auf 60°C ab. Hierauf wird die Ware in ein zweites Färbebad eingebracht, welches 30 g kalziniertes Natriumsulfat in 4000 ml Wasser enthält. Danach werden der Flotte100 g of a furniture upholstery fabric consisting of polyacrylonitrile fibers and cotton (65:35) are mixed in a dyeing machine with 4000 ml of an aqueous liquor containing 5 g of calcined sodium sulfate and adjusted to a pH of 5 with 80% acetic acid for 5 minutes treated at 70 ° C. After that, the fleet

• 2 g of dyeing aid (2) consisting of
• 35% of a quaternary ammonium compound
• Formula (22) [Cocosyl - N (CH ₃ ) ₃ ] ⊕ CH ₃ S0 ₄ ⊖
• 10% N-cocosyl-N, N-di-2-hydroxyethylamine oxide and
• 55% water
• 0.42 g of the yellow dye of the formula (101) and 0.38 g of the red dye of the formula (102)

added dissolved. The substrate is then treated for a further 5 minutes at 70 ° C. and the bath is then heated to 98 ° C. in the course of 30 minutes, after which the goods are dyed at this temperature for 30 minutes. The dyeing liquor is then slowly cooled to 60 ° C. The goods are then placed in a second dyebath which contains 30 g of calcined sodium sulfate in 4000 ml of water. After that, the fleet

und 3 g m-Nitrobenzolsulfonsäure-Natriumsalz zugefügt.2 g of the dye of the formula

and 3 g of sodium m-nitrobenzenesulfonic acid added.

The dyeing is carried out at 40 ° C. for 45 minutes, then 1 g of sodium carbonate and after 5 minutes 2 ml of a 30% aqueous sodium hydroxide solution are added and the substrate is treated for a further 40 minutes. Finally, the substrate is rinsed, soaped and dried.

A brilliant red coloring of the upholstery fabric with good fastness properties is obtained.

Example 6

• 0,012 g des Farbstoffs der Formel
  
• 0,0025 g des Farbstoffes der Formel
  
• 0,001 g des Farbstoffes der Formel
  
  gelöst zugesetzt und das Substrat 5 Minuten bei 50°C behandelt.

10 g of a mixed fabric consisting of polyacrylonitrile fibers and wool (50:50) are mixed in a dyeing machine with an aqueous liquor containing 0.3 g of ammonium sulfate, 0.5 g of calcined sodium sulfate, 0.05 g of a mixture of a quaternized adduct of 30 Moles of ethylene oxide with 1 mole of C ₂₀ -C ₂₂ fatty amine and the acid ester of the adduct of 16 moles of ethylene oxide with 1 mole of tallow fatty acid amide (1: 2) and adjusted to pH 5 with 80% acetic acid for 5 minutes Treated at 50 ° C. After that

• 0.012 g of the dye of the formula
  
• 0.0025 g of the dye of the formula
  
• 0.001 g of the dye of the formula
  
  added dissolved and the substrate treated at 50 ° C for 5 minutes.

• Man fügt nun der Farbflotte
• 0,05 g des Färbereihilfsmittels (3) bestehend aus 35% einer quaternären Ammoniumverbindung der Formel (22), 10% N-Myristyl-N,N-dimethyl-aminoxid und 55% Wasser,
• 0,014 g des Farbstoffes der Formel (105),
• 0,004 g des Farbstoffes der Formel (106) und
• 0,0014 g des Farbstoffes der Formel (107)
• hinzu und färbt 45 Minuten bei 98°C. Hiernach wird die Färbeflotte in Verlauf von 10 Minuten abgekühlt, das Substrat gespült und getrocknet.

The dyeing liquor is heated to 98 ° C. in the course of 45 minutes and adjusted to a pH of 4.5 with acetic acid.

• Now add the paint fleet
• 0.05 g of the dyeing aid (3) consisting of 35% of a quaternary ammonium compound of the formula (22), 10% of N-myristyl-N, N-dimethylamine oxide and 55% of water,
• 0.014 g of the dye of the formula (105),
• 0.004 g of the dye of formula (106) and
• 0.0014 g of the dye of the formula (107)
• add and dye for 45 minutes at 98 ° C. The dye liquor is then cooled in the course of 10 minutes, the substrate is rinsed and dried.

This gives a level, light brown color with good fastness properties.

Claims (13)

1. A dyeing assistant composition which comprises at least

(A) a quaternary ammonium salt which contains at least one basic nitrogen atom to which is attached at least one aliphatic radical of 6 to 22 carbon atoms, and

(B) an amine oxide of the formula

wherein

X₁ is C₈-C₁₈alkyl or C₈-C₁₈alkenyl and

X₂ and X₃ are each independently lower alkyl or hydroxy-lower alkyl.

2. A dyeing assistant composition to claim 1, wherein component (A) is a quaternary ammonium compound of the formula

wherein

R is an aliphatic hydrocarbon radical of 5 to 21 carbon atoms, preferably 7 to 18 carbon atoms,

Q is the direct bond or oxygen,

Y₁ and Y₂ are each independently lower alkyl, cycloalkyl or hydroxy-lower alkyl or both together with the nitrogen atom to which they are attached are a 5- or 6-membered saturated heterocyclic radical,

Y₃ is lower alkyl, hydroxy-lower alkyl, epoxy-lower alkyl, cyano-lower alkyl, carbamoyl-lower alkyl or aralkyl, or

Yi, Y₂ and Y₃ together with the nitrogen atom to which they are attached are a pyridine ring which is unsubstituted or substituted by lower alkyl, and

An⁸ is the anion of an organic or inorganic acid.

3. A dyeing assistant composition according to claim 2, wherein component (A) is a quaternary ammonium compound of the formula (1), wherein Q is the direct bond.

4. A dyeing assistant composition according to either of claims 2 or 3, wherein component (A) is a quaternary ammonium compound of the formula (1), wherein Y, and Y₂ are methyl, ethyl or 2-hydroxyethyl, and Y₃ is methyl, ethyl or benzyl.

5. A dyeing assistant composition according to claim 1, wherein component (A) is a quaternary ammonium compound of the formula

wherein

Ri is C₅-C₁₅alkyl,

Q is oxygen or the direct bond,

Y₄ and Y₅ are lower alkyl or hydroxy-lower alkyl,

Y₆ is methyl, ethyl or benzyl and

(An)^p is the chloride or methosulfate ion.

6. A dyeing assistant composition according to claim 1, which comprises at least

(Aa) a quaternary ammonium of the formula

wherein

R₂ is C₆-C₁₈ alkyl or C₆-C₁₈ alkenyl, Y₄ and Y₅ are lower alkyl or hydroxy-lower alkyl, Y₆ is methyl, ethyl or benzyl, and

(An)⊖₁ is the chloride or methosulfate ion, and

(Bb) an amine oxide of the formula

wherein

X₁, X₂ and X₃ are as defined in claim 1.

7. A dyeing assistant composition according to any of claims 1 to 6, which contains components (A) and (B) in the weight ratio of 9 : 1 to 3: 7, preferably 6 : 1 to 1 : 1 and most preferably 4 : 1 to 2 : 1.

8. A dyeing assistant composition according to claim 1, which contains, based on the total composition

25 to 45% by weight of component (A),

8 to 20% by weight of component (B), and

35 to 67% by weight of water.

9. A process for dyeing polyacrylonitrile fibre material with cationic dyes, which comprises dyeing said material in the presence of a dyeing assistant composition comprising at least

(A) a quaternary ammonium salt which contains at least one basic nitrogen atom to which is attached at least one aliphatic radical of 6 to 22 carbon atoms, and

(B) an amine oxide of the formula

wherein

X, is C₈-C₁₈alkyl or C₈-C₁₈alkenyl and

X₂ and X₃ are each independently lower alkyl or hydroxy-lower alkyl.

10. A process according to claim 9, wherein component (A) of the dyeing assistant composition is a migrating quaternary ammonium compound.

11. A process according to either of claims 9 or 10, wherein the dyeing assistant composition is used in an amount of 0.1 to 5% by weight, preferably 0.5 to 3%, based on the weight of the goods to be dyed.

12. A process according to any one of claims 9 to 11, wherein dyeing is carried out with at least 2, or preferably 3, migrating or non-migrating cationic dyes or a mixture thereof.