EP0414631A1 - Auxiliary agent mixture and its use in dyeing polyester fibre materials - Google Patents

Abstract

Dyeing auxiliary mixture comprising (A) a dicarboxyimidoester of the formula <IMAGE> where W is a dicarboxylic acid radical of at least 2 carbon atoms, R is an aliphatic, araliphatic or cycloaliphatic radical of not more than 24 carbon atoms and n is from 2 to 5, (B) an acid ester or salt thereof of an alkylene oxide adduct of the formula <IMAGE> where V is hydrogen or methyl, X is the acid radical of an inorganic oxygen atom containing acid or the radical of an organic acid, Y is an alpha -methylaralkyl radical, "Alkylen" is ethylene or propylene, m is from 1 to 3, m1 is 1 or 2 and n1 is from 4 to 50, and (C) a nonionic surfactant. The auxiliary mixture is suitable in particular for a rapid dyeing process for polyester fibre textile material, producing a rapid increase in the rate of migration of the disperse dyes.

Description

The present invention relates to a new auxiliary mixture and its use in dyeing polyester fiber materials.

• (A) einen Dicarboxyimidoester der Formel
  
  worin W einen mindestens 2 Kohlenstoffatome aufweisenden Rest einer Dicarbonsäure,
  R einen aliphatischen, araliphatischen oder cycloaliphatischen Rest mit höchstens 24 Kohlenstoffatomen, vorzugsweise höchstens 12 Kohlen­stoffatomen und
  n 2 bis 5 bedeuten,
• (B) einen sauren Ester oder dessen Salze eines Alkylenoxidadduktes der Formel
  
  worin
  V Wasserstoff oder Methyl,
  X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, wie z.B. Schwefelsäure oder Phosphorsäure, oder den Rest einer organischen Säure und
  Y einen α-Methylaralkylrest
  bedeuten,
  "Alkylen" für den Ethylenrest oder Propylenrest steht und
  m 1 bis 3, m₁ 1 oder 2 und n₁ 4 bis 50 sind und
• (C) ein nichtionogenes, zweckmässigerweise Polyethylenglykolethergruppen aufweisendes Tensid

enthält.The mixture of auxiliaries is characterized in that it is at least

• (A) a dicarboxyimido ester of the formula
  
  in which W is a radical of a dicarboxylic acid which has at least 2 carbon atoms,
  R is an aliphatic, araliphatic or cycloaliphatic radical having at most 24 carbon atoms, preferably at most 12 carbon atoms and
  n is 2 to 5,
• (B) an acidic ester or its salts of an alkylene oxide adduct of the formula
  
  wherein
  V is hydrogen or methyl,
  X is the acid residue of an inorganic, oxygen-containing acid, such as sulfuric acid or phosphoric acid, or the rest of an organic acid and
  Y is an α-methylaralkyl radical
  mean,
  "Alkylene" stands for the ethylene radical or propylene radical and
  m are 1 to 3, m₁ 1 or 2 and n₁ 4 to 50 and
• (C) a nonionic surfactant, suitably containing polyethylene glycol ether groups

contains.

The auxiliary mixture according to the invention advantageously contains
20 to 70 percent by weight of component (A)
15 to 40 percent by weight of component (B)
and 15 to 40 weight percent of component (C).

Components (A), (B) and (C) can be present as individual compounds or in the form of a mixture of two or more compounds.

Mixtures of components (B) and (C) are preferably used together.

In formula (1), W means, for example, a divalent aliphatic, cycloaliphatic or aromatic radical which is linked to the carboxyl groups of the imide group.

In the meaning of a divalent aliphatic radical, W advantageously represents a halogen-substituted, straight-chain or branched hydrocarbon radical of a saturated or ethylenically unsaturated dicarboxylic acid having 4 to 10 carbon atoms. Examples of such aliphatic saturated dicarboxylic acids are Succinic and glutaric acid. Ethylenically unsaturated dicarboxylic acids are preferably maleic, dimethyl maleic, dichloromaleic, citraconic, glutaconic or itaconic acid.

In the meaning of a divalent cycloaliphatic radical, W represents in particular the radical of a tetrahydro- or hexahydrophthalic acid.

W preferably represents the divalent radical of an aromatic dicarboxylic acid, such as, for example, a naphthalenedicarboxylic acid or phthalic acid.

W is preferably a phenylene radical which is substituted with halogen, e.g. Chlorine or bromine, C₁-C₄-alkyl such as methyl, tert-butyl or C₁-C₄-alkoxy such as methoxy can be substituted. W in particular denotes an unsubstituted phenylene radical.

As an aliphatic radical, R can be saturated or unsaturated, straight-chain or branched. R is advantageously an alkyl radical having 1 to 24, preferably 1 to 12, carbon atoms. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, pentyl, n-hexyl, 2-ethyl-hexyl, 1,1,3,3-tetramethylbutyl, n-octyl, n-dodecyl, myristyl, octadecyl, arachidyl or behenyl. As a cycloaliphatic radical, R is in particular a cyclopentyl or, above all, a cyclohexyl radical. The benzyl radical as R is particularly suitable as an araliphatic radical. n is preferably 5.

worin W₁ Alkylen oder Alkenylen mit 2 bis 4 Kohlenstoffatomen, Cyclohexylen oder Phenylen, das unsubstituiert oder durch Halogen, wie z.B. Chlor oder Brom, Methyl oder Methoxy substituiert ist, und
R₁ Alkyl mit 1 bis 12 Kohlenstofftomen, vorzugsweise 3 bis 8 Kohlenstoffatomen, Cyclohexyl oder Benzyl
bedeuten.Practically important dicarboxyimido esters of the formula (1) correspond to the formula

wherein W₁ alkylene or alkenylene having 2 to 4 carbon atoms, cyclohexylene or phenylene, which is unsubstituted or substituted by halogen, such as chlorine or bromine, methyl or methoxy, and
R₁ alkyl having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms, cyclohexyl or benzyl
mean.

Typical representatives of the dicarboxyimido esters used according to the invention are
Phthalimido-hexanoic acid methyl ester,
Phthalimido-hexanoic acid ethyl ester,
Phthalimido-hexanoic acid propyl ester,
N-butyl phthalimido-hexanoate,
2-ethylhexyl phthalimido-hexanoate,
Hexahydrophthalimido-hexanoic acid n-butyl ester,
2-ethylhexyl hexahydrophthalimido-hexanoate,
Tetrahydrophthalimido-hexanoic acid n-butyl ester,
N-butyl tetrachlorophthalimido-hexanoate,
2-ethylhexyl tetrachlorophthalimido-hexanoate,
N-butyl succinimido hexanoate and
2-ethylhexyl tetrahydrophthalimido-hexanoate.

Among these representatives, the above-mentioned phthalimido-hexanoic acid C₁-C₈-alkyl esters and especially phthalimido-hexanoic acid-C₃-C₈-alkyl esters such as in particular the phthalimido-hexanoic acid-2-ethylhexyl ester.

mit einer Verbindung der Formel

in Gegenwart eines Alkohols der Formel (1c) R-OH umsetzt.The compounds of the formulas (1) and (3) are prepared in a manner known per se. The preparation can preferably be carried out by using a dicarboxylic anhydride of the formula

with a compound of the formula

in the presence of an alcohol of formula (1c) R-OH.

Compounds of formulas (1) and (3) and their preparation are e.g. in U.S. Patent 3,210,313.

Specific examples of starting materials of the formula (1a) are maleic anhydride, dimethylmaleic anhydride, dichloromaleic anhydride, succinic anhydride, dimethylsuccinic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, glutaconic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

Individual examples of starting materials of the formula (1b) are α-pyrrolidone, α-piperidone or preferably ε-caprolactam.

Individual examples of alcohols of the formula (1c) are methanol, ethanol, n-butanol, sec-butanol, tert-butanol, amyl alcohol, hexanols, 2-ethylhexanol, octyl alcohols, decyl alcohols, dodecyl alcohols, cyclohexanol or benzyl alcohol. These alcohols can be used alone or as mixtures.

The substituent Y in formula (2) advantageously has 8 to 12 carbon atoms and is in particular α-methylbenzyl, α, α-dimethylbenzyl, α-tolylethyl or α-xylylethyl. Α-Methylbenzyl is particularly preferred.

Ketten sind bevorzugt vom Ethylenglykol-, Propylenethylen­glykol- oder Ethylenpropylenglykol-Typus; besonders bevorzugt ist ersterer.(Alkylene-O) ̵

Chains are preferably of the ethylene glycol, propylene ethylene glycol or ethylene propylene glycol type; the former is particularly preferred.

n 1 is preferably 4 to 40.

The acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as of maleic acid, succinic acid or sulfosuccinic acid, and is connected to the alkyleneoxy part of the molecule via an ester bridge. In particular, however, X is derived from inorganic polybasic acids, such as sulfuric acid or orthophosphoric acid.

The acid residue X can be in the form of a free acid or in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, diethylamine, ethanolamine, diethanolamine or triethanolamine salts. Alkali metal salts or triethanolamine salts are preferred. The mono- or diethanolamine salts can be etherified further with 1 to 4 oxethylene units.

worin Y₁ α-Methylbenzyl, α,α-Dimethylbenzyl oder α-Tolylethyl bedeutet,
X₁ ein Säurerest ist, der sich von Schwefelsäure oder vorzugsweise o-Phosphorsäure ableitet, und
m 1 bis 3 und n₂ 4 bis 40 sind.Preferred acid esters of component (B) correspond to the formula

where Y₁ is α-methylbenzyl, α, α-dimethylbenzyl or α-tolylethyl,
X₁ is an acid residue which is derived from sulfuric acid or preferably o-phosphoric acid, and
m are 1 to 3 and n₂ are 4 to 40.

These acidic esters are preferably in the form of sodium, potassium, ammonium, diethylamine, triethylamine, diethanolamine or triethanolamine salts.

The acidic esters of formula (2) or (4) which are suitable as components (B) are prepared by adding alkylene oxide (ethylene oxide or propylene oxide) to a phenol compound which is substituted by definition and the adduct with a polybasic oxygen acid or a functional derivative of this acid , such as Acid anhydrides, acid halides, acid esters or acid amides are converted into the acidic esters and, if appropriate, the acidic ester obtained into the abovementioned salts. Examples of these functional derivatives are phosphorus pentoxide, phosphorus oxytrichloride, chlorosulfonic acid or sulfamic acid. Both the alkylene oxide addition and the esterification can be carried out by known methods.

Highly suitable components (B) are acidic esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one α-tolylethyl group, an α-methylbenzyl group or an α, α-dimethylbenzyl group, e.g. α-Tolylethylphenol, α-methylbenzylphenol, bis- (α-methylbenzyl) -phenol or tris-α- (methylbenzyl) -phenol, whereby these acidic esters can be used individually or in a mixture.

Of particular interest are acidic phosphoric acid esters or sulfuric acid esters of the adducts of 8 to 30 moles of ethylene oxide with 1 mole of compounds which are prepared by the addition of 1 to 3 moles of styrenes to 1 mole of phenols, the phosphoric acid esters expediently as mixtures of the corresponding salts of a mono - and diesters are present.

The styrene addition products are prepared in a known manner, preferably in the presence of catalysts, such as sulfuric acid, p-toluenesulfonic acid or zinc chloride. Suitable styrenes are suitably styrene, α-methylstyrene or vinyltoluene (4-methylstyrene). Examples of the phenols are phenol, cresols or xylenols.

worin m 1 bis 3 und n₃ 12 bis 30 bedeuten.Acidic phosphoric acid esters (mono- and diesters) or sulfuric acid esters or their salts of oxyalkylation products of the formula are very particularly preferred

wherein m is 1 to 3 and n₃ 12 to 30.

The following may be mentioned as examples of oxyalkylation products of the formulas (4) and (5):
- Oxalkylation product with 18 ethylene oxide units of the adduct of 2 moles of styrene and 1 mole of phenol
- Oxalkylation product with 18 ethylene oxide units of the adduct of 3 moles of styrene with 1 mole of phenol
- Oxalkylation product with 27 ethylene oxide units of the adduct of 2 moles of 4-methylstyrene with 1 mole of phenol
- Oxalkylation product with 17 ethylene oxide units of the adduct of 3 moles of 4-methylstyrene with 1 mole of phenol
- Oxalkylation product with 18 ethylene oxide units of the mixture of an adduct of 2 moles of styrene with 1 mole of phenol and an adduct of 3 moles of styrene with 1 mole of phenol
Oxyalkylation product of 13 ethylene oxide units of the mixture of an adduct of 2 moles of styrene with 1 mole of phenol and an adduct of 3 moles of styrene with 1 mole of phenol.

The nonionic surfactant used as component (C) is advantageously an alkylene oxide addition product of 2 to 100 moles of alkylene oxide, for example ethylene oxide and / or propylene oxide, on 1 mole of an aliphatic Monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol with preferably 3 to 6 carbon atoms, one optionally substituted by C₄-C₁₂-alkyl, phenyl, α-tolylethyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl or a fatty acid with 8 to 22 carbon atoms.

Examples of nonionic surfactants are:
- Addition products of preferably 2 to 80 mol of alkylene oxide, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides each having 8 to 22 carbon atoms or to benzyl alcohols, phenylphenols, benzylphenols, β-phenethylphenols, α-methylbenzylphenols, α, α-dimethylbenzylphenols, α-tolylethylphenols or alkylphenols, the alkyl radicals of which have at least 4 carbon atoms;
- Alkylene oxide, in particular ethylene oxide and / or propylene oxide condensation products (block polymers);
- Ethylene oxide-propylene oxide adducts with fatty amines or diamines, especially ethylenediamine;
- Reaction products from a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group of these reaction products containing hydroxyalkyl groups, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and can be greater than 1, for example 1: 1 to 2: 1, and
- Sorbitan esters preferably with C₆-₂₄ fatty acid ester groups or polyethoxylated sorbitan esters, such as polyoxethylene sorbitan monolaurate or monooleate or monostearate, each with 4 to 20 ethylene oxide units or polyoxethylene sorbitan trioleate with 4 to 20 ethylene oxide units.
- Fatty alcohol polyglycol mixed ethers, in particular addition products of 3 to 30 moles of ethylene oxide and 3 to 30 moles of propylene oxide with aliphatic monoalcohols of 8 to 22 carbon atoms, preferably alkanols of 8 to 16 carbon atoms.

Of these, the above-mentioned oxyalkylation products of the formula (5) derived from styrene addition products are particularly preferred as nonionic surfactants.

oder durch die Formel

dargestellt werden, worin
R′ einen Alkyl- oder Alkenylrest mit jeweils 8 bis 24 Kohlenstoffatomen oder einen Rest der Formel

T einen aliphatischen Rest mit 8 bis 30 Kohlenstoffatomen und
z 1 bis 25 bedeuten und
Y, m, n₁ und "Alkylen" die oben angegebene Bedeutung haben.Further particularly preferred nonionic surfactants can be represented by the formula

or by the formula

are shown in what
R 'is an alkyl or alkenyl radical each having 8 to 24 carbon atoms or a radical of the formula

T is an aliphatic radical with 8 to 30 carbon atoms and
z mean 1 to 25 and
Y, m, n₁ and "alkylene" have the meaning given above.

mit einer Fettsäure T-COOH oder durch Umsetzung einer alkoholischen oder phenolischen Verbindung R′-OH mit einem Fettsäureester der Formel

hergestellt werden.The compounds of formula (6) can by reacting the adduct of the formula

with a fatty acid T-COOH or by reacting an alcoholic or phenolic compound R'-OH with a fatty acid ester of the formula

getting produced.

Formaldehyd oder einer Formaldehyd abgebenden Verbindung, z.B. Paraformaldehyd und einem Fettsäureester der Formel T-CO-O(̵CH₂CH₂O)̵

H und werden teilweise in der japanischen Offenlegungsschrift JP-A-83-18486 beschrieben. Dort nicht genannte Verbindungen, die unter Formel (7) fallen, lassen sich entsprechend herstellen, wobei die in der japanischen Offenlegungsschrift genannten Reaktionsbedingungen zu den gewünschten Produkten der Formel (7) führen.The compounds of the formula (7) are reaction products from addition products of the formula

Formaldehyde or a formaldehyde-releasing compound, for example paraformaldehyde and a fatty acid ester of the formula T-CO-O (̵CH₂CH₂O) ̵

H and are partially described in Japanese Patent Application Laid-Open No. 83-18486. Compounds which are not mentioned there and fall under formula (7) can be prepared accordingly, the reaction conditions mentioned in the Japanese laid-open publication leading to the desired products of the formula (7).

worin
R₁ Alkyl oder Alkenyl mit jeweils 8 bis 22 Kohlenstoffatomen, von Z₁ und Z₂ eines Phenyl und das andere Wasserstoff und
s 4 bis 80 bedeuten.Well-suited components (C) also correspond to the formula

wherein
R₁ alkyl or alkenyl each having 8 to 22 carbon atoms, of Z₁ and Z₂ a phenyl and the other hydrogen and
s mean 4 to 80.

H anlagert.The compounds of formula (8) are prepared by adding styrene oxide to the polyethylene glycol ether of the formula R˝-O (̵CH₂CH₂O) ̵

H attaches.

The new auxiliary preparations can be prepared by simply stirring the components (A), (B), (C) and, if appropriate, together with water, giving homogeneous, clear mixtures which are notable for good transport and storage stability. The auxiliary mixtures according to the invention are particularly very stable at higher temperatures up to 130 ° C. when they are used in dye baths. They increase the rate of diffusion of the dyes when dyeing polyester fiber materials, preferably linear polyester fibers.

The present invention accordingly also relates to a process for dyeing polyester fiber material with disperse dyes, which is characterized in that this material is dyed in the presence of the auxiliary mixture according to the invention.

The amounts used in which the auxiliary combination according to the invention is added to the dyebaths range from 0.3 to 6 g, preferably 0.5 to 4 g, per liter of dye liquor.

As polyester fiber material, in particular textile material, which can be dyed in the presence of the new auxiliary mixture, e.g. Cellulose ester fibers, such as cellulose-2 ½ acetate fibers and triacetate fibers and particularly linear polyester fibers, should be mentioned. Linear polyester fibers are to be understood as synthetic fibers which are obtained, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear polyester used almost exclusively in the textile industry so far consists of terephthalic acid and ethylene glycol.

The fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool can be used.

The textile material to be dyed can be in various stages of processing. Examples include: loose material, piece goods, such as knitted or woven fabrics, yarn in the form of a wrap or muff. The latter can have winding densities of 200 to 600 g / cm³, in particular 400 to 450 g / cm³.

The disperse dyes to be used, which are only sparingly soluble in water and are present in the dyeing liquor for the most part in the form of a fine dispersion, can belong to a wide variety of dye classes, for example the acridone, azo, anthraquinone, coumarin, methine, Perinone, quinophthalone, naphthoquinoneimine, styryl or nitro dyes.

Mixtures of disperse dyes can also be used according to the invention. The mixtures are used in particular for the production of level mixed tone dyeings, including a dichromatic or trichromatic dyeing. Trichromatic is primarily understood to mean a three-way combination of the basic colors yellow (or orange), red and blue.

The amount of dyes to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.05 to 5 percent by weight, based on the textile material used, have proven successful.

The auxiliaries to be used according to the invention can also be mixed with known carriers based on e.g. Di- or trichlorobenzene, methyl- or ethylbenzene, o-phenylphenol, benzylphenol, diphenyl ether, chlorodiphenyl, methyldiphenyl, cyclohexanone, acetophenone, alkylphenoxyethanol, mono-, di- or trichlorophenoxyethanol or propanol, pentachlorophenoxyethene, or in particular, based on methyl, from phenhenyl or Dibenzyl ether can be used. The carriers are preferably used in an amount of 0.5 g to 2 g / l of liquor or 10 to 60 percent by weight, based on the auxiliary preparation.

Depending on the textile material to be treated, the dyebaths can also contain oligomer inhibitors, anti-foaming agents (e.g. silicone oils or ethylene bis fatty acid amides), wrinkle-free agents and preferably dispersants, in addition to the dyes and the auxiliary mixture according to the invention.

The dispersants are used primarily to achieve a good fine distribution of the disperse dyes. The dispersants generally used for dyeing with disperse dyes can be used.

The dispersants used are preferably sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols having 2 to 6 carbon atoms, such as ethylene glycol, glycerol or pentaerythritol or with at least two amino groups or one amino group and one hydroxyl group with amines having 2 up to 9 carbon atoms as well Alkyl sulfonates with 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates with straight-chain or branched alkyl chain with 8 to 20 carbon atoms in the alkyl chain, such as, for example, nonyl- or dodecylbenzenesulfonate, 1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate, such as alkylnaphthalene acid or sulfonate, such as naphthalenesulfonate, such as naphthalenesulfonate or alkyl naphthalenesate, such as sulfate or naphthalenesate, such as naphthalenesulfonate or alkyl naphthalenes, such as naphthalenesulfonates, such as naphthalenesulfonate or alkyl naphthalenes, such as naphthalenesulfonate or eg sodium dioctyl sulfosuccinate or sodium di-2-ethylhexyl sulfosuccinate.

Lignin sulfonates, polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, β-naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenesulfonic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. The disodium salt of di- or tri- (6-sulfonaphthyl-2-) methane is preferred.

Mixtures of anionic dispersants can also be used. The anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amine salts. These dispersants are preferably used in an amount of 0.5 to 8 g / l of liquor.

The dye baths can also contain a water-soluble alkaline earth metal, aluminum or organic ammonium salt of a mono- or polyvalent aliphatic carboxylic acid or a mono- or polyvalent inorganic acid. The addition of these salts can greatly improve the dispersion stability in the dyebath, depending on the type of dye used, especially when dyeing polyester bobbins with a very high winding density. Dye deposits can thus be prevented or significantly reduced. These additional salts are water-soluble salts, for example the magnesium, calcium, barium, strontium, aluminum or organic ammonium salts of mono- or polyvalent inorganic acids or mono- or polyvalent aliphatic carboxylic acids such as hydrochloric acid, hydrobromic acid , Hydrofluoric acid, nitric acid, sulfuric acid, phosphoric acid or formic acid, acetic acid and rhodanhydric acid. As such Salts are possible, for example: calcium nitrate, magnesium nitrate, aluminum nitrate, calcium chloride, magnesium chloride, magnesium thiocyanate, calcium thiocyanate or organic ammonium chlorides, bromides or iodides, such as, for example, methonium salts (alkane-bis-trimethylammonium salts). Examples of suitable methonium salts are pentamethonium iodide, decamethonium bromide and in particular hexamethonium chloride.

These salts are preferably used in an amount of 0.1 to 3 g per liter of dye liquor or 0.2 to 5 percent by weight, based on the fiber material.

The dyebaths can also contain conventional additives, suitably electrolytes, such as salts, e.g. Sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, ammonium acetate or sodium acetate and / or acids, e.g. Mineral acids, such as sulfuric acid or phosphoric acid, or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic, oxalic or citric acid. The acids primarily serve to adjust the pH of the liquors used according to the invention, which is generally 4 to 6.5, preferably 4.5 to 6.

The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio can accordingly be chosen within a wide range, e.g. 1: 3 to 1: 100, preferably 1: 7 to 1:50. The temperature at which dyeing is carried out is at least 70 ° C and usually it is not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.

Linear polyester fibers and cellulose triacetate fibers are preferably dyed according to the so-called high-temperature process in closed and expediently also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., under pressure. As closed vessels, for example, circulation apparatuses such as cross-wound or tree dyeing machines, reel runners, jet or drum dyeing machines, jet or muff dyeing machines, paddles or jiggers are suitable.

Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.

The dyeing process can be carried out by either briefly treating the material to be dyed first with the auxiliary mixture and then dyeing it, or preferably treating it simultaneously with the auxiliary mixture and the dye.

The material to be dyed is preferably allowed to run for 5-10 minutes at 40-80 ° C. in a bath which contains the dye, the auxiliary mixture and, if appropriate, further additives and is adjusted to a pH of 4.5 to 6, the temperature increases within 15 to 30 minutes to 110 to 135 ° C, preferably 125-130 ° C and leaves the dye liquor at this temperature for 15 to 30 minutes, preferably 15 to 20 minutes.

The dyeings are completed by cooling the dye liquor to 60 to 80 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a conventional manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried. Uniform and vivid colorations are obtained on synthetic fiber material, in particular on linear polyester fibers, which are furthermore distinguished by good light fastness and rub fastness. During the dyeing process, the dyeing liquor remains stable and there are no deposits inside the dyeing equipment.

Compared to known processes, which likewise use disperse dyes which do not migrate or only migrate moderately, the process according to the invention is distinguished by a shortened heating phase and by the possibility of adding the dye to the liquor at any temperature. In particular, the migration of disperse dyes can be improved by using the auxiliary mixture used according to the invention. Due to the improved migration capacity of the dyes, any unevenness in the dipping phase of the dyes in the dwell phase at the final temperature can be compensated for by subsequent migration. In summary, the dyeing process with the auxiliary mixture according to the invention offers the following advantages:
- an uncontrolled heating of the liquor to the dyeing temperature without taking into account the significant or critical dyeing speed;
- shading under normal HT conditions thanks to the improved migration of the disperse dyes;
- an easy, rational and safe implementation;
- a simple correction of incorrect stains, since better compensation takes place;
- Rapid achievement of level single and in particular mixed tone dyeings including trichromatic dyeings with good fastness properties, such as fastness to light, rubbing and sublimation, while avoiding streakiness and also under difficult circumstances;
- a predominant work without the addition of conventional carriers, dispersants and / or leveling agents;
- Achieving level colorations for delicate light and medium tones and especially for deep tones using sublimation-resistant dyes.

In the following examples, parts are parts by weight and percentages are percentages by weight.

Example 1:

0,28 g/l eines Farbstoffes der Formel

0,19 g/l eines Farbstoffes der Formel

und 1 g/l einer Hilfsmittelformulierung bestehend aus
60 % 6-Phthalimido-hexansäure-2-ethylhexylester
20 % Triethanolaminsalz eines Gemisches von Mono- und Diesterphosphat eines Oxalkylierungsproduktes mit 18 Ethylenoxideinheiten des Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol und
20 % eines Oxalkylierungsproduktes von 18 Mol Ethylenoxid mit 1 Mol eines Anlagerungsproduktes von 3 Mol Styrol an 1 Mol Phenol
enthält und mit Ameisensäure auf pH 5 gestellt ist.80 parts of a polyester knitted fabric (225 g / m²) are placed in a 70 ° C. bath containing 1000 parts of water, 2 g / l of ammonium sulfate (anhydrous), a dispersed dye mixture of the composition
0.24 g / l of a dye of the formula

0.28 g / l of a dye of the formula

0.19 g / l of a dye of the formula

and 1 g / l of an auxiliary formulation consisting of
60% 2-ethylhexyl 6-phthalimido-hexanoate
20% triethanolamine salt of a mixture of mono- and diester phosphate of an oxyalkylation product with 18 ethylene oxide units of the adduct of 3 moles of styrene with 1 mole of phenol and
20% of an oxyalkylation product of 18 moles of ethylene oxide with 1 mole of an adduct of 3 moles of styrene and 1 mole of phenol
contains and is adjusted to pH 5 with formic acid.

The liquor is heated, with constant circulation, to 130 ° C. within 20 minutes and dyed at this temperature for 15 minutes. The liquor is then cooled, drained and the goods rinsed and dried. A level brown color is obtained with a high dye yield and good fastness properties. The usual reductive post-cleaning is not necessary.

The 2-ethylhexyl 6-phthalimido-hexanoate used is prepared as follows.

als braunes Oel. Säurezahl: 6148 g of phthalic anhydride are heated to 180 ° C. together with 113 g of ε-caprolactam, 132 g of 2-ethylhexanol, 1.9 g of p-toluenesulfonic acid and 70 g of 1,3-xylene. The resulting water is removed azeotropically. The reaction is complete after 12 hours, 18 ml of water being removed. The solvent is then removed in vacuo. 370 g of the compound of the formula are obtained

as a brown oil. Acid number: 6

Example 2:

und
0,23 Teile des Farbstoffes der Formel

und
1g/l der Hilfmittelformulierung gemäss Beispiel 1
enthält und mit Ameisensäure auf pH 5 gestellt ist. Danach wird die Flotte im Verlauf von 30 Minuten auf 130°C erhöht und bei dieser Tempe­ratur 60 Minuten gefärbt. Alsdann wird die Flotte auf 90°C abgekühlt, abgelassen und die Ware gespült und ohne eine reduktive Nachreinigung getrocknet.
Man erhält eine egale braune Färbung mit guten Gebrauchsechtheiten.100 parts of a knitted fabric made of textured polyester fibers are placed in a not fully flooded jet dyeing machine, which contains 1000 parts of 60 ° C warm water, 2 parts of ammonium sulfate, a finely dispersed dye mixture of the composition:
0.5 part of the dye Disperse Yellow 23 CI 26070
0.14 parts of the dye of the formula

and
0.23 parts of the dye of the formula

and
1g / l of the auxiliary formulation according to Example 1
contains and is adjusted to pH 5 with formic acid. The liquor is then increased to 130 ° C. in the course of 30 minutes and dyed at this temperature for 60 minutes. The liquor is then cooled to 90 ° C., drained and the goods are rinsed and dried without reductive post-cleaning.
A level brown coloring with good fastness properties is obtained.

Example 3:

100 parts of a knitted fabric made of textured polyester fibers are placed in a not fully flooded jet dyeing machine, which contains 1000 parts of 60 ° C warm water, 2 parts of ammonium sulfate, 2.5 parts of the contains finely dispersed dye Disperse Yellow 42 CI 10338 and 1.5 parts of the auxiliary formulation according to Example 1 and is adjusted to pH 5 with formic acid.

zum Nuancieren in die Flotte eingebracht, worauf die Ware weitere 30 Minuten bei 130°C gefärbt wird. Alsdann wird die Flotte abgekühlt und die Färbung gespült und wie üblich fertiggestellt.
Man erhält eine egale brillante grüne Färbung mit guten Echtheiten. Durch den Zusatz der genannten Hilfsmittelformulierung muss die Flotte vor der Nuancierzugabe nicht abgekühlt werden. Man kann mit dieser Arbeitsweise Zeit und Energie sparen.The temperature of the liquor is increased to 130 ° C. in the course of 30 minutes and dyeing is carried out at this temperature for 30 minutes. Then 0.1 part of the dye of the formula

introduced into the fleet for nuance, after which the goods are dyed for a further 30 minutes at 130 ° C. The liquor is then cooled and the dyeing rinsed and finished as usual.
A level, brilliant green dyeing with good fastness properties is obtained. By adding the auxiliary formulation mentioned, the liquor does not have to be cooled down before adding the nuance. This way of working can save time and energy.

Claims (20)

1. dyeing aid mixture, characterized in that it is at least
(A) a dicarboxyimido ester of the formula

in which W is a radical of a dicarboxylic acid which has at least 2 carbon atoms,
R is an aliphatic, araliphatic or cycloaliphatic radical with at most 24 carbon atoms and
n is 2 to 5,
(B) an acidic ester or its salts of an alkylene oxide adduct of the formula

wherein
V is hydrogen or methyl,
X is the acid residue of an inorganic, oxygen-containing acid or the rest of an organic acid and
Y is an α-methylaralkyl radical
mean,
"Alkylene" stands for the ethylene radical or propylene radical and
m are 1 to 3, m₁ 1 or 2 and n₁ 4 to 50 and
(C) a nonionic surfactant
contains. 2. Auxiliary mixture according to claim 1, characterized in that in formula (1) W is phenylene which is unsubstituted or substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy. 3. Auxiliary mixture according to one of claims 1 and 2, characterized in that in formula (1) R is alkyl having 1 to 12 carbon atoms. 4. Auxiliary mixture according to one of claims 1 to 3, characterized in that in formula (1) n is 5. 5. Auxiliary mixture according to claim 1, characterized in that the dicarboxyimido ester of the formula

corresponds to what
W₁ alkylene or alkenylene having 2 to 4 carbon atoms, cyclohexylene or phenylene which is unsubstituted or substituted by halogen, methyl or methoxy and
R₁ alkyl having 1 to 12 carbon atoms, cyclohexyl or benzyl
mean. 6. Auxiliary mixture according to one of claims 1 to 5, characterized in that component (A) is a C₃-C₈ alkyl phthalimido-hexanoate and preferably 2-ethylhexyl phthalimido-hexanoate. 7. Auxiliary mixture according to one of claims 1 to 6, characterized in that in formula (2) Y represents α-tolylethyl, α-xylylethyl, α, α-dimethylbenzyl or α-methylbenzyl. 8. Auxiliary mixture according to one of claims 1 to 7, characterized in that in formula (2) n₁ is 4 to 40. 9. A mixture of adjuvants according to one of claims 1 to 8, characterized in that the acid residue X in formula (2) is derived from sulfuric acid or o-phosphoric acid. 10. Auxiliary mixture according to one of claims 1 to 9, characterized in that component (B) of a compound of the formula

corresponds to what
Y₁ denotes α-methylbenzyl, α, α-dimethylbenzyl or α-tolylethyl,
X₁ is an acid residue which is derived from sulfuric acid or preferably o-phosphoric acid, and
m are 1 to 3 and n₂ are 4 to 40. 11. A mixture of adjuvants according to claim 1, characterized in that component (B) is an acidic phosphoric acid ester or sulfuric acid ester or the salts thereof of an oxyalkylation product of 8 to 30 moles of ethylene oxide with 1 mole of a compound obtained by addition of 1 to 3 moles of styrene, α- Methyl styrene or vinyl toluene has been produced on 1 mol of phenol, cresol or xylenol. 12. A mixture of auxiliaries according to one of claims 1 to 11, characterized in that component (B) is an acidic phosphoric acid ester or sulfuric acid ester or the salts thereof of an oxyalkylation product of the formula

is where m is 1 to 3 and n₃ 12 to 30. 13. A mixture of adjuvants according to one of claims 1 to 12, characterized in that component (C) is an alkylene oxide addition product of 2 to 100 moles of alkylene oxide with 1 mole of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol with 3 to 6 carbon atoms, one optionally substituted by C₄-C₁₂-alkyl, phenyl, α-tolylethyl, benzyl, α-methylbenzyl or α, α-dimethylbenzyl or a fatty acid having 8 to 22 carbon atoms. 14. Auxiliary mixture according to one of claims 1 to 12, characterized in that component (C) is an oxyalkylation product of the formula

is where m are 1 to 3 and n₃ 12 to 30. 15. Auxiliary mixture according to one of claims 1 to 12, characterized in that component (C) is a compound of the formula

is what
R 'is an alkyl or alkenyl radical each having 8 to 24 carbon atoms or a radical of the formula

and
T is an aliphatic radical having 8 to 30 carbon atoms and
Y, m, n₁ and "alkylene" have the meaning given in claim 1. 16. Auxiliary mixture according to one of claims 1 to 12, characterized in that component (C) is a compound of the formula

is what
T is an aliphatic radical having 8 to 30 carbon atoms and z is 1 to 25 and
Y, m, n₁ and "alkylene" have the meaning given in claim 1. 17. Auxiliary mixture according to one of claims 1 to 12, characterized in that component (C) is a compound of the formula

is what
R˝ alkyl or alkenyl each having 8 to 22 carbon atoms, of Z₁ and Z₂ a phenyl and the other hydrogen and
s mean 4 to 80. 18. Auxiliary mixture according to one of claims 1 to 17, characterized in that it is based on the entire mixture
20 to 70 percent by weight of component (A)
15 to 40 percent by weight of component (B)
and 15 to 40 percent by weight of component (C)
contains. 19. Use of the auxiliary mixture according to one of claims 1 to 18 in the dyeing of textile material containing polyester fibers. 20. A process for dyeing textile material containing polyester fibers with disperse dyes, characterized in that this material is dyed in the presence of the auxiliary mixture according to one of claims 1 to 18.