EP0033715A1 - Auxiliary and its use in the dyeing or optical brightening of polyester fibre materials - Google Patents

Abstract

Novel auxiliary mixture containing at least (I) one dicarboxyimidoester of the formula <IMAGE> where W is a radical of dicarboxylic acid of at least 2 carbon atoms, T is an aliphatic, cycloaliphatic or araliphatic radical of not more than 24 carbon atoms and n is from 2 to 5, and as component (II) (A) an acid ester or salt thereof of a polyadduct of propylene oxide with a polyfunctional aliphatic amino or hydroxyl compound which has from 2 to 9 carbon atoms and at least one amino or hydroxyl group capable of addition, or (B) an acid ester or salt thereof of a polyadduct of an alkylene oxide with a phenyl having at least one alkyl, benzyl or phenyl group, and (C) an anionic or amphoteric ester or salt thereof of a polyadduct of 2 to 50 mol of an alkylene oxide with an aliphatic monoamine of from 8 to 24 carbon atoms, or a mixture of two or more of these substances, in particular a mixture of surfactant compounds (A), (B) and (C) together. The auxiliary mixture is used in the optical brightening or preferably dyeing of polyester fibre materials to increase the rate of migration of optical brighteners or disperse dyes.

Description

The present invention relates to a novel aid and its use in dyeing or optically brightening polyester fiber materials.

In DE-OS 2758417 a Migrationsfärbeverfahren will be described with selected disperse dyes, where ^p without dyeing assistant and without a specific control of the Tem eratursteige- tion in the heating level dyeings can be generated at delicate light and medium shades.

Surprisingly, new auxiliaries have now been found which allow a broader class of disperse dyes, in particular also highly sublimation-resistant dyes, to be used which, without the addition of auxiliaries, have a migration rate which is too low and, as a result, tend to irregular dyeing when the temperature is not controlled in the heating phase. By using the auxiliaries according to the invention, the migration rate is increased in such a way that even colorations are achieved with these disperse dyes. Thanks to the new tools, it is now possible to dye not only light and medium tones, but also deep tones with high fastness properties.

The present invention accordingly relates to an aid which at least

(I) a dicarboxyimido ester of the formula

worin W einen mindestens 2 Kohlenstoffatome aufweisenden Rest einer Dicarbonsäure,

• T einen aliphatischen, araliphatischen oder cycloaliphatischen Rest mit höchstens 24, vorzugsweise 12 Kohlenstoffatomen und
• n 2 bis 5 bedeuten, und
• als Komponente (II)
  • (A) einen sauren Ester oder dessen Salz eines Polyadduktes von Propylenoxyd an eine polyfunktionelle aliphatische Amino- oder Hydroxyverbindung, die 2 bis 9, vorzugsweise 2 bis 6 Kohlenstoffatome und mindestens eine additionsfähige Amino- oder Hydroxygruppe aufweist oder
  • (B) einen sauren Ester oder dessen Salz eines Polyadduktes von einem Alkylenoxyd an ein mindestens eine Alkyl-, Benzyl- oder Phenyl- gruppe aufweisendes Phenol oder
  • (C) einen anionischen oder amphoteren Ester oder dessen Salz eines Polyadduktes von 2 bis 50 Mol eines Alkylenoxydes an ein aliphatisches Monoamin von 8 bis 24 Kohlenstoffatomen, insbesondere 10 bis 18 Kohlenstoffatomen oder
  
  ein Gemisch von zwei oder mehreren dieser Stoffe enthält.

in which W is a radical of a dicarboxylic acid which has at least 2 carbon atoms,

• T is an aliphatic, araliphatic or cycloaliphatic radical with at most 24, preferably 12 carbon atoms and
• n is 2 to 5, and
• as component (II)
  • (A) an acidic ester or its salt of a polyadduct of propylene oxide with a polyfunctional aliphatic amino or hydroxy compound which has 2 to 9, preferably 2 to 6 carbon atoms and at least one amino or hydroxy group capable of addition, or
  • (B) an acidic ester or its salt of a polyadduct of an alkylene oxide with a phenol having at least one alkyl, benzyl or phenyl group or
  • (C) an anionic or amphoteric ester or its salt of a polyadduct of 2 to 50 moles of an alkylene oxide with an aliphatic monoamine of 8 to 24 carbon atoms, in particular 10 to 18 carbon atoms or
  
  contains a mixture of two or more of these substances.

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 the 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, glutaric, adipic, pinelin, cork, azelaic or sebacic acid. Aethylenically unsaturated dicarboxylic acids are preferably those. Maleic, itaconic, mesaconic, gitraconic, glutaconic or methylene malonic acid.

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

Preferably W represents the divalent residue of an aromatic dicarboxylic acid such as e.g. a naphthalenedicarboxylic acid or phthalic acid.

W preferably represents a phenylene radical which can be substituted by halogen, such as chlorine or bromine, methyl or methoxy. W in particular denotes an unsubstituted phenylene radical.

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

• worin W 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
• T₁ Alkyl mit 1 bis 12 Kohlenstoffatomen, vorzugsweise 3 bis 6 Kohlenstoffatomen, Cyclohexyl oder Benzyl
  bedeuten.

Practically important dicarboxyimido esters of the formula (1) correspond to the formula

• wherein W 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
• T ₁ alkyl having 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, cyclohexyl or benzyl
  mean.

• Phthalimidoessigsäurebutylester,
• Phthalimidopropionsäureäthylester, Phthalimidobuttersäuremethylester,
• Phthalimido-hexansäuremethylester,
• Phthalimido-hexansäureäthylester,
• Phthalimido-hexansäurepropylester,
• Phthalimido-hexansäure-n-butylester,
• Phthalimido-hexansäure-2-äthylhexylester,
• Hexahydrophthalimido-hexansäure-n-butylester,
• Tetrahydrophthalimido-hexansäure-n-butylester,
• Tetrachlorophthalimido-hexansäure-n-butylester,
• Succinimido-hexansäure-n-butylester und
• Tetrahydrophthalimido-hexansäure-2-äthylhexylester.

Typical representatives of the dicarboximido esters used according to the invention are

• Butyl phthalimidoacetate,
• Ethyl phthalimidopropionate, methyl phthalimidobutyrate,
• 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,
• Tetrahydrophthalimido-hexanoic acid n-butyl ester,
• N-butyl tetrachlorophthalimido-hexanoate,
• N-butyl succinimido hexanoate and
• 2-ethylhexyl tetrahydrophthalimido-hexanoate.

Among these representatives, the c ₁ -C ₈ -alkyl phthalimido-hexanoic acid and especially C ₃ -C ₆ -alkyl phthalimido-hexanoate, such as the n-butyl phthalimido-hexanoate in particular, are particularly preferred.

mit einer Verbindung der Formel (4)

in Gegenwart eines Alkohols der Formel (5) T-OH umsetzt.The compounds of the formulas (1) and (2) 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 formula (4)

in the presence of an alcohol of formula (5) T-OH.

Compounds of formulas (1) and (2) and their preparation are e.g. in U.S. Patent 3,210,313.

Individual examples of starting materials of the formula (3) are maleic anhydride, succinic anhydride, dimethylsuccinic anhydride, glutaric anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

Individual examples of starting materials of the formula (4) are a-pyrrolidone, α-piperidone or preferably ε-caprolactam.

Individual examples of alcohols of the formula (5) are methanol, ethanol, n-butanol, sec-butanol, tert-butanol, amyl alcohol, hexanols, 2-ethyl hexanol, octyl alcohols, decyl alcohols, dodecyl alcohols, cyclohexanol or benzyl alcohol. These alcohols can be used alone or as mixtures.

The esters suitable as component II can be used alone, as mixtures among themselves of two or more compounds or preferably as mixtures of components (A), (B) and (C) together.

The acidic esters of the polypropylene oxide adducts of component (A) can be present as free acids or preferably as salts, for example alkali metal or ammonium salts. The alkali metal salts include, in particular, the sodium or potassium salts and the ammonium salts are the ammonium (NH ₄ ), trimethylammonium, monoethanolammonium, diethanolammonium and triethanolammonium salts. The sodium or ammonium (NH ₄ ) salts are preferred.

The acidic esters of polypropylene oxide adducts that can be used as component (A) are prepared by adding propylene oxide to an aliphatic amino or hydroxy compound as defined and the adduct with an at least dibasic oxygenic acid or a functional derivative of this acid in the acidic esters and, if appropriate, those obtained acidic esters in the transferred salts mentioned above.

For example, acidic esters, in particular sulfuric acid esters, or their salts of polypropylene oxide adducts, where the polyadduct has an average molecular weight of 1000 to 6000, preferably 2300 to 4600, have proven particularly useful for use in accordance with the present invention. Such polyadducts can be prepared, for example, by adding 15 to 100 moles, preferably 40 to 80 moles, of propylene oxide to 1 mole of the aliphatic amino or preferably hydroxy compound as defined.

As according to the definition hydroxy practical _e come rweise polyhydric aliphatic alcohols containing at least 2, advantageously from 2 to 6 hydroxyl groups and preferably 2 to 6 carbon atoms, such as alkylene diols having an alkylene radical of 2 to 6 carbon atoms, such as ethylene glycol, 1,3- or 1,2 Propylene glycol or 1,5-pentanediol, and also glycerol, trimethylolethane or propane, erythritol, pentaerythritol, mannitol or sorbitol. Aliphatic alcohols which have three carbon atoms and two or three hydroxyl groups, such as, for example, propylene glycol and in particular glycerol, are preferably used.

Suitable amino compounds which can be reacted with the propylene oxide as starting materials are in principle polyfunctional amines which either have at least one reactive amino group or at least one reactive hydroxyl group, the reactive amino group being primary and / or secondary. To be suitable have especially alkylene polyamines 2 to 6 carbon _s t _o ffatome and 2 to 4 amino groups have proven particularly advantageous. Suitable _alk y _l enpolyamine are for example ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylenetriamine, _T riäthylentetramin, 1,2-propylenediamine, dipropylenetriamine, tripropylene _l entetramin, dibutylenetriamine. Preferred polyamines are alkylenediamines with 2 or 3 carbon atoms, such as propylenediamine and especially ethylenediamine.

At least one hydroxyalkyl-containing amine of 2 to 6 carbon atoms, e.g. Hydroxyalkylamines, such as β-hydroxyethylamine, β- or y-hydroxypropylamine or β, y-dihydroxypropylamine; Bishydroxyalkylamines, such as bis (ß-hydroxyethyl) amine, bis (y-hydroxypropyl) amine or bis (a-methyl-ß-hydroxyethyl) amine; Tris-hydroxyalkylamines, such as tris (β-hydroxyethyl) amine; N-alkyl-N-hydroxyalkylamines, such as N-methyl- or N-ethyl-N-y-hydroxypropylamine. Monoisopropanolamine and β-ethanolamine are preferred.

Both the propylene oxide addition and the esterification can be carried out by known methods.

As polybasic oxygen acids for the formation of the acidic esters, sulfonated, organic, preferably aliphatic, mono- or dicarboxylic acids of 3 to 6 carbon atoms, such as e.g. Maleic acid or sulfosuccinic acid or in particular polybasic, inorganic oxygen acids, such as e.g. Serve sulfuric acid. Instead of the acids, their functional derivatives, such as acid anhydrides, acid halides, acid esters or acid amides, can be used. Examples of these functional derivatives are sulfur trioxide, in particular chlorosulfonic acid and sulfamic acid.

The esterification is generally carried out by simply mixing the reactants with heating, expediently to a temperature between 25 ° C. and 100 ° C. The free acids initially formed can then be converted into the corresponding alkali metal or ammonium salts. The conversion into the salts is carried out in the usual way by adding bases, such as ammonia, monoethanolamine, triethanolamine or alkali metal hydroxides, for example sodium or potassium hydroxide. According to a particularly preferred embodiment, the acidic sulfuric acid esters are prepared directly in the form of their ammonium salts, by adding the propylene oxide addition products, conveniently in the presence of urea, heated with sulfamic acid.

Te _NEN Further details about the composition of the com- (A) eligible acidic esters, including their preparation, are described in German Offenlegungsschriften 2,521,106 and 2,624,431.

In the component (B) in question anionic phenol glycol ethers is suitably acidic, Estergruppen from inorganic or organic acids adducts containing from 1 to 60 moles of alkylene oxides, particularly 1 to 60 moles of _A ethylene oxide and / or propylene oxide and optionally additionally 1 mol Styrene oxide on phenols which have at least one benzyl group, a phenyl group or preferably an alkyl group of at least 4 carbon atoms, such as, for example, benzylphenol, dibenzylphenol, dibenzyl- (nonyl) phenol, o-phenylphenol, butylphenol, tributylphenol, octylphenol, nonylphenol, dodecylphenol or pentadecylphenol.

Preferred components (B) correspond to the formula

• wherein R is alkylphenyl having 4 to 16 carbon atoms in the alkyl moiety or _o - _Ph e ylphenyl _n, of Y ₁ and Y ₂ is hydrogen or methyl and the other is hydrogen,
• X is the acid residue of an inorganic, oxygen-containing acid, e.g. Orthophosphoric acid or sulfuric acid,
• m 1 to 30, preferably 2 to 15
  mean.

The alkyl radical in alkylphenyl is preferably in the para position.

• worin R₁ Octyl oder Nonyl bedeutet,
• m 2 bis 15 ist, und
• X₁ sich von der Schwefelsäure oder vorzugsweise von o-Phosphorsäure ableitet und die Tenside als freie Säuren, Natrium-oder Ammoniumsalze vorliegen.

The acid residue can be in salt form, ie, for example, as an alkali metal, alkaline earth metal, ammonium or amine salt. Particularly preferred components (B) are anionic surfactants of the formula

• where R _{1 is} octyl or nonyl,
• m is 2 to 15, and
• X _{1 is} derived from sulfuric acid or preferably from o-phosphoric acid and the surfactants are present as free acids, sodium or ammonium salts.

Of particular interest is the acidic phosphoric acid ester of the adduct of 10 moles of ethylene oxide with 1 mole of p-nonylphenol.

Component (C) can be represented by the formula

dargestellt werden,

• worin Z einen aliphatischen Kohlenwasserstoffrest mit 8 bis 24, vorzugsweise 10 bis 18 Kohlenstoffatomen,
• von _Y3 und _Y4 eines Wasserstoff, Methyl oder Phenyl und das andere Wasserstoff,
• die beiden Q einzeln oder zusammen den Säurerest einer anorganischen Sauerstoff enthaltenden Säure oder einer aliphatischen Dicarbonsäure,
• p 1 oder 2 und r und s ganze Zahlen bedeuten, wobei die Summe von r und s 2 bis 50, vorzugsweise 2 bis 15 beträgt.

being represented,

• in which Z is an aliphatic hydrocarbon radical having 8 to 24, preferably 10 to 18, carbon atoms,
• of _Y3 and _Y4 one hydrogen, methyl or phenyl and the other hydrogen,
• the two Q, individually or together, the acid residue of an inorganic oxygen-containing acid or an aliphatic dicarboxylic acid,
• p is 1 or 2 and r and s are integers, the sum of r and s being 2 to 50, preferably 2 to 15.

In formula (8), Z preferably denotes an alkyl or alkenyl radical having 8 to 22, especially 10 to 18, carbon atoms. Y ₃ and Y ₄ are preferably hydrogen. The sum of r + s is advantageously 6 to 15, p is preferably 2.

If Z is alkyl, then these are residues, such as e.g. Octyl, decyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl. As alkenyl residues for Z are e.g. Dodecenyl, hexadecenyl, oleyl or octadecenyl.

The aliphatic amines which are required as starting materials for the preparation of the adducts of the formula (8) can have saturated or unsaturated, branched or unbranched hydrocarbon radicals. The amines can be chemically uniform or can be considered in the form of mixtures. As amine mixtures, preference is given to those used in the transfer of natural fats or oils, e.g. Tallow fat, soybean oil or coconut oil, in the corresponding amines. Dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, arachidylamine, behenylamine and octadecenylamine (oleylamine) may be mentioned as amines.

Ethylene oxide, propylene oxide or styrene oxide can be added to the amines. It is useful to use 1 mol of amine, 2 to 30 mol of ethylene oxide, propylene oxide, styrene oxide or mixtures thereof. Propylene oxide and styrene oxide are preferably used in mixtures with ethylene oxide. In this case, 1 mol of amine, 1 to 3 mol of propylene oxide or styrene oxide and at least 3 mol or 5 mol of ethylene oxide are expediently used.

The acid residue Q of the formula (8) is derived, for example, from aliphatic dicarboxylic acids having preferably 2 to 6 carbon atoms, such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is via an ester bridge with the alkyleneoxy part of the Linked molecule. In particular, however, Q is derived from inorganic polybasic acids, such as sulfuric acid or preferably orthophosphoric acid.

The acid residue Q is preferably in salt form, i.e. e.g. as an alkali metal, alkaline earth metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, calcium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts. Sodium salts and ammonium salts are preferred.

Particularly suitable components (C) are compounds of the formula

worin Z Alkenyl oder vor allem Alkyl mit 10 bis 18 Kohlenstoffatomen und p 1 oder 2 bedeuten, die Summe von r und s₁ 2 bis 15, insbesondere 6 bis 10 ist und die zwei Q sich von Schwefelsäure oder einzeln oder zusammen von o-Phosphorsäure ableiten und die Verbindungen als freie Säuren, Natrium- oder Ammoniumsalze vorliegen. Bei der Veresterung mit Orthophosphorsäure bilden sich vorwiegend Gemische, die z.B. aus Verbindungen der Formeln

und

bestehen, worin Z₁, _rl und s₁ die angegebene Bedeutung haben und M Wasserstoff, Ammonium oder Natrium bedeutet. Das Gewichtsverhältnis der Verbindungen der Formel (9a) zu der Verbindung der Formel (9b) ist vorteilhafterweise 2:1 bis 1:1.

wherein Z is alkenyl or especially alkyl having 10 to 18 carbon atoms and p 1 or 2, the sum of r and s _{1 is} 2 to 15, in particular 6 to 10 and the two Q are sulfuric acid or individually or together from o-phosphoric acid derive and the compounds are present as free acids, sodium or ammonium salts. In the esterification with orthophosphoric acid, predominantly mixtures are formed which, for example, consist of compounds of the formulas

and

exist in which Z ₁ , _rl and s _{1 have} the meaning given and M is hydrogen, ammonium or sodium. The weight ratio of the compounds of formula (9a) to the compound of formula (9b) is advantageously 2: 1 to 1: 1.

Of particular interest is the phosphoric acid ester of the adduct of 8 moles of ethylene oxide with 1 mole of dodecylamine.

• (Ia) einen Dicarboxyimidoester der Formel (2) ,
• (Aa) einen Schwefelsäureester oder dessen Salz eines Polyadduktes von 40 bis 80 Mol Propylenoxyd an einen zwei- bis sechswertigen aliphatischen Alkohol von 2 bis 6 Kohlenstoffatomen,
• (Bb) einen sauren Ester, vorzugsweise Phosphorsäureester, oder dessen Salz eines Polyadduktes von 2 bis 20 Mol Aethylenoxyd und/oder Propylenoxyd an ein p-Alkylphenol mit 4 bis 16 Kohlenstoffatomen im Alkylrest und
• (Cc) eine Tensidverbindung der Formel (9).

Preferred auxiliaries contain at least the following components:

• (Ia) a dicarboxyimido ester of the formula (2),
• (Aa) a sulfuric acid ester or its salt of a polyadduct of 40 to 80 mol of propylene oxide with a dihydric to hexavalent aliphatic alcohol of 2 to 6 carbon atoms,
• (Bb) an acidic ester, preferably phosphoric acid ester, or its salt of a polyadduct of 2 to 20 moles of ethylene oxide and / or propylene oxide with a p-alkylphenol with 4 to 16 carbon atoms in the alkyl radical and
• (Cc) a surfactant compound of formula (9).

In addition to components (I) and (II), such as (A), (B) and (C), the auxiliary mixture can additionally contain, as component (III), polypropylene glycol or an adduct of propylene oxide with a tris-hexavalent aliphatic alcohol of 3 to 6 carbon atoms , such as Contain glycerin or pentaerythritol, both the polypropylene glycol and the polypropylene oxide adduct having an average molecular weight of 250 to 1800, preferably 400 to 900. Such an addition serves to improve the homogeneity of the emulsion formed in the dye bath.

As a further additional auxiliary substances: acid esters are suitable, especially organophosphate of addition products of from 2 up to 15 _m ol ethylene oxide and / or Propylenoxydvorzugsweise 2 to 10 moles of ethylene oxide with higher fatty alcohols that alkanols or alkenols each having 8 to 22 carbon atoms and in particular Alfols as well Dimethylmethanphosphat. Some of the Alfole representatives are Alfol (8-10), (10-14) and (16-18).

The new auxiliary preparations can be prepared by simply stirring the above-mentioned components I, II ((A), (B), (C)) and optionally III together with water, homogeneous clear mixtures being obtained which are stable in storage at room temperature. Clear preparations can also be made without water. The weight ratio of component (I) to component (A) advantageously ranges from 6: 1 to 2: 1, preferably 4: 1 to 3: 1, to component (B), advantageously between 8: 1 to 2: 1, preferably 4: 1 to 3: 1 and to component (C) advantageously 6: 1 to 3: 1, preferably 4: 1 to 2: 1.

The auxiliary preparations advantageously contain, based in each case on the preparation,

• 15 to 60 percent by weight of component (I)
• 5 to 25 percent by weight of component (A)
• 10 to 40 percent by weight of component (B)
• 0 to 30 preferably 2 to 25 percent by weight of component (C)
• 0 to 15, preferably 3 to 10 percent by weight of component (III) and
• 0 to 40, preferably 5 to 30 weight percent water.

The new auxiliary preparations increase the rate of diffusion of the dyes in the fibers and thereby accelerate the migration of the dyes when dyeing polyester fiber materials, preferably linear polyester fibers. Subject of the present The invention is therefore also a process for level dyeing or optical brightening of polyester fiber material with disperse dyes or optical brighteners, which is characterized in that this material is colored or optically brightened in the presence of the auxiliary according to the invention.

The amounts used in which the auxiliary preparation according to the invention is added to the dyebaths or lightening liquors range from 0.5 to 6 g, preferably 2 to 4 g, per liter of dyebath or lightening liquor.

As polyester fiber material, in particular textile material, which can be dyed or optically brightened in the presence of the new auxiliary mixture, e.g. Cellulose ester fibers, such as cellulose 2 1/2 acetate fibers and triacetate fibers and particularly linear polyester fibers, should be mentioned. Linear polyester fibers are to be understood as synthetic fibers which e.g. can be obtained by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, and also 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, or yarn in the form of a wrap or sleeve. The latter can have winding densities of 300 to 600 g / cm ³ , in particular 400 to 450 g / cm.

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, naphtho-quinonimine, styryl or nitro dyes.

Mixtures of disperse dyes can also be used according to the invention.

The new auxiliary mixtures can also be used for whitening undyed polyester fiber materials with optical brighteners dispersed in water.

The optical brighteners which can be used according to the invention are in particular water-poorly soluble optical brighteners from the coumarin, benzocoumarin, pyrazine, pyrazoline, oxazine, triazolyl, benzoxazolyl, benzofuran, benzimidazolyl or naphthalimide series.

Disperse dyes or optical brighteners which have a migration half-life t / 2 of at least 40, preferably at least 50 minutes at 130 ° C. without the addition of auxiliaries are particularly suitable. The migration half-life t / 2 is the time in which an undyed polyester fiber material, which is treated together with an equally sized piece of the same material at 130 ° C in an aqueous liquor, is dyed so that its amount of dye is 50% of the amount of the dyed material is. These dyes are particularly suitable 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 fleet or opti brightener depends on the desired color strength; in all _- a g _em, amounts to have from 0.001 to 10 preferably 0.001 to 5 weight percent, based on the textile material employed proven.

The present invention to be used assistant _D iphenyläther, chlorodiphenyl, methyldiphenyl, cyclohexanone, acetophenone, Alkylphenoxyäthanol, mono-, di- can also be in a mixture with known carrier based on, for example, di- or trichlorobenzene, methyl or ethyl benzene, o-phenylphenol, benzylphenol, or trichlorophenoxyethanol or propanol, pentachlorophenoxyethanol, alkylphenyl benzoates, or in particular based on diphenyl, methyl diphenyl ether, dibenzyl ether, methyl benzoate, butyl benzoate or phenyl benzoate. 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.

The dyebaths or brightening baths may also oligomer inhibitors, antifoaming agents, wrinkle-free medium according to the textile material to be treated in addition to the dyes or optical brighteners and the inventive tool _- preferably contain and dispersant.

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. Suitable dispersants are, for example, anionic surfactants, which can be present alone or as mixtures.

• - sulfatierte aliphatische Alkohole, deren Alkylkette 8 bis 18 Kohlenstoffatome aufweist; z.B. sulfatierter Laurylalkohol, Oleylalkohol oder Kokosfettalkohol;
• - sulfatierte ungesättigte Fettsäuren oder Fettsäureniederalkylester, die im Fettrest 8 bis 20 Kohlenstoffatome aufweisen, z.B.Oelsäure oder Rizinolsäure und solche Fettsäuren enthaltende Oele, z.B. Rizinusöl;
• - Alkylsulfonate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält, z.B. Dodecylsulfonat;
• - Alkylarylsulfonate mit geradkettiger oder verzweigter Alkylkette mit mindestens 6 Kohlenstoffatomen, z.B. Nonyl- oder Dodecylbenzolsulfonate oder 3,7-Diisobutyl-naphthalinsulfonate;
• - Sulfonate von Polycarbonsäureestern, z.B. Dioctylsulfosuccinate;
• - die als Seifen bezeichneten Alkalimetall-, Ammonium- oder Aminsalze von Fettsäuren mit 10 bis 20 Kohlenstoffatomen, z.B. Kolophoniumsalze;
• - Ester von Polyalkoholen, insbesondere Mono- oder Diglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen, z.B. Monoglyceride der Laurin-, Stearin- oder Oelsäure; und
• - die mit einer organischen Dicarbonsäure, wie z.B. Maleinsäure, Malonsäure oder Sulfobernsteinsäure, vorzugsweise jedoch mit einer anorganischen mehrbasischen Säure, wie o-Phosphorsäure oder insbesondere Schwefelsäure in einen sauren Ester übergeführten Anlagerungsprodukte von 1 bis 60 Mol Aethylenoxyd und/oder Propylenoxyd an Fettsäuren, Fettsäureamide oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen.

Examples of suitable anionic surfactants are:

• sulfated aliphatic alcohols whose alkyl chain has 8 to 18 carbon atoms; eg sulfated lauryl alcohol, oleyl alcohol or coconut oil alcohol;
• - Sulphated unsaturated fatty acids or fatty acid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, eg oleic acid or ricinoleic acid and oils containing such fatty acids, for example castor oil;
• Alkyl sulfonates whose alkyl chain contains 8 to 20 carbon atoms, for example dodecyl sulfonate;
• Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 6 carbon atoms, for example nonyl- or dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
• - Sulfonates of polycarboxylic acid esters, for example dioctyl sulfosuccinates;
• - The so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, for example rosin salts;
• - Esters of polyalcohols, especially mono- or diglycerides of fatty acids with 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid; and
• - The addition products of 1 to 60 mol of ethylene oxide and / or propylene oxide with fatty acids, fatty acid amides converted into an acidic ester with an organic dicarboxylic acid, such as maleic acid, malonic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid, such as o-phosphoric acid or in particular sulfuric acid or fatty alcohols each with 8 to 22 carbon atoms.

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, ß-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- (6-sulfonaphthyl-2-) methane is preferred.

Mixtures of anionic dispersants can also be used are 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 0.1 to 5 g / 1 liquor.

The dyebaths or brightening baths may also contain a water- soluble _l iches alkaline earth metal, aluminum or ammonium salt of an organic mono- or polyhydric aliphatic carboxylic acid, or a monovalent or polyvalent inorganic acid. The addition of these salts, the dispersion stability in the dye bath, depending on the _Fa rbstofftyp be greatly improved, especially in the dyeing of polyester bobbin with a very high winding density. Thus, material deposits _color can 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, Fluorwasser- _s t _of fsäure, nitric acid, sulfuric acid, phosphoric acid or formic acid, acetic acid and thiocyanic acid. As such salts, for example, are suitable: calcium nitrate, magnesium nitrate, aluminum _m i _n iumnitrat, calcium chloride, magnesium chloride, magnesium thiocyanate, _Kalz i _umth i _o cyanate or organic ammonium chlorides, bromides or iodides, such as Methoniumsalze (alkane-bis-trimethylammonium ). Examples of suitable Methoniumsalze are the Fentamethoniumiodid, _D ecamethoniumbromid and particularly hexamethonium.

Salts are also to be understood as meaning the complexes of the abovementioned cations with mono- or polyvalent organic acids which are capable of releasing the cation under the dyeing conditions.

The best results are with alkaline earth metal salts, before all achieved with calcium or magnesium salts, monovalent inorganic acids or monovalent aliphatic carboxylic acids, but especially with calcium or magnesium chloride.

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

Furthermore, the dyebaths or lightening liquors can be conventional additives, advantageously electrolytes, such as salts, 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 or oxalic 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 5.5.

The dyeing or lightening is 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: 4 to 1: 100, preferably 1:10 to 1:50. The temperature at which dyeing or lightening is at least 70 ° C and is usually 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 by 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., and optionally under pressure. Circulation apparatuses such as cross-wound or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels.

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

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

Preferably, the dyed material can for 5 minutes at 60-80 ° C in the bath which contains the dyes of the adjuvant mixture and optionally other additives, and to a pH _- value is adjusted from 4.5 to 5.5, pre-run, the temperature is within 15 to 60, preferably 20 to 35 minutes to 110 to 135 ° C., preferably 130 ° C., and the dye liquor is kept at this temperature for 30 to 120 minutes, preferably 60 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. In the event of any use of carriers, the dyeings are advantageously heat-treated to improve the lightfastness, e.g. Thermosolieren, subjected, which is preferably carried out at 160 to 180 ° C and for 30 to 90 seconds.

According to the method according to the invention, uniform and vivid colorations are obtained on polyester fiber material, in particular on linear polyester fibers. Due to the fact that dyes that are suitable for sublimation can also be used, high fastness properties are achieved even in deep shades. The light fastness is hardly influenced by the addition of the auxiliary mixture used according to the invention.

• - ein unkontrolliertes Aufheizen der Flotte auf Färbetemperatur ohne besondere Berücksichtigung der signifikanten oder kritischen Färbegeschwindigkeit;
• - ein ausgeprägt schnelles Migrieren der Dispersionsfarbstoffe unter HT-Bedingungen, wobei die Migration Ton-in-Ton erfolgt mit sehr geringer Rückhaltung unter Erzielung eines gleichmässigen Farbtons;
• - eine Nuancierung unter üblichen HT-Bedingungen dank der verbesserten Migration der Dispersionsfarbstoffe;
• - eine einfache, rationelle und sichere Durchführung;
• - eine einfache Korrektur von Fehlfärbungen, da besserer Ausgleich stattfindet;
• - die Erzielung egaler Einzel- und insbesondere Mischtonfärbungen einschliesslich Trichromiefärbungen mit guten Echtheiten, wie z.B. Licht-, Reib- und Sublimierechtheit unter Vermeidung von Streifigkeiten und auch unter schwierigen Umständen;
• - ein vorwiegendes Arbeiten ohne Zusatz von üblichen Carriern, Dispergatoren und/oder Egalisiermitteln;
• - die Erzielung egaler Färbungen bei heiklen hellen und mittleren Tönen und vor allem bei tiefen Tönen unter Verwendung sublimierechter Farbstoffe.

This distinguishes itself from known processes which also use disperse dyes which do not migrate or only migrate moderately Process according to the invention by a shortened heating phase and by the possibility of adding the dye to the liquor at any temperature. In particular, by using the auxiliary mixture used according to the invention, the migration half-life t / 2 of disperse dyes, which is generally in the range from 50 to 120 minutes without the addition of auxiliary agents, can be reduced to less than 45 minutes. 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;
• - A markedly fast migration of the disperse dyes under HT conditions, the migration tone-on-tone takes place with very little retention while achieving a uniform color tone;
• - 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;
• - Achieving 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 streaks and even 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 examples below, parts are parts by weight and percentages are percentages by weight. The following reaction products are examples of the components (A), (B) and (C).

Component (A)

• A ammonium salt of the formula
  
• A ₂ ammonium salt of the formula
  
• _A3 ammonium salt of the acid sulfuric acid ester of the adduct of 43 moles of propylene oxide with 1 mole of trimethylolpropane;
• A ₄ ammonium salt of the acid sulfuric acid ester of the adduct of 8 moles of propylene oxide and 1 mole of pentaerythritol;
• _A ammonium salt of the acid sulfuric acid ester of the adduct of 75 moles of propylene oxide and 1 mole of glycerol;
• A ₆ sodium salt of the acidic monosulfosuccinic acid ester of the adduct of 60 moles of propylene oxide with 1 mole of glycerol;
• A ₇ ammonium salt of the acid sulfur _b äureesters of the adduct of 50 moles of propylene oxide with 1 mole of ethylene glycol;
• A ₈ ammonium salt of the acid sulfuric acid ester of the adduct of 50 moles of propylene oxide with 1 mole of 1,2-propylene glycol;
• A ₉ ammonium salt of the acid sulfuric acid ester of the adduct of 60 moles of propylene oxide with 1 mole of ethylenediamine;
• A ₁₀ ammonium salt of the acid sulfuric acid ester of the adduct of 60 moles of propylene oxide with 1 mole of monoisopropanolamine.

Component (B):

• B ₁ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of butylphenol;
• B ₂ ammonium salt of the acid sulfuric acid ester of the adduct of 5 moles of ethylene oxide and 1 mole of tributylphenol;
• B ₃ ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₄ ammonium salt of the acidic sulfuric acid ester of the adduct of 10 moles of propylene oxide and 10 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₅ ammonium salt of the acidic sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₆ ammonium salt of the acid sulfuric acid ester of the adduct of 50 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₇ ammonium salt of the acid sulfuric acid ester of the adduct of 15 moles of propylene oxide and 1 mole of nonylphenol;
• B ₈ ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of dodecylphenol;
• B ₉ ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of pentadecylphenol;
• _B10 ammonium salt of the acid sulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of o-phenylphenol;
• B ₁₁ sodium salt of the acid M _al einsäureesters of the adduct of 2 mols of ethylene oxide and 1 mole of p-nonylphenol;
• B ₁₂ sodium salt of the acidic monosulfosuccinic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol;
• B ₁₃ ammonium salt of the acidic phosphoric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol;
• B acidic phosphoric acid ester of the adduct of 10 moles of ethylene oxide and 1 mole of p-nonylphenol;
• B ₁₅ sodium salt of the acid sulfuric acid ester of the adduct of 15 moles of ethylene oxide and 1 mole of dibenzyl- (nonyl) phenol;
• B ₁₆ sodium salt of the acidic sulfuric acid ester of the adduct of 12 moles of ethylene oxide and 1 mole of dibenzylphenol.

Component (C):

• C ₁ ammonium salt of the acidic disulfuric acid ester of the adduct of 2.5 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₂ ammonium salt of the acidic disulfuric acid ester of the adduct of 4 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₃ ammonium salt of the acidic disulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₄ ammonium salt of the acidic disulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₅ ammonium salt of the monosulfuric acid ester of the adduct of 4, 6 or 8 moles of ethylene oxide with 1 mole of tallow fatty amine;
• C ₆ ammonium salt of the acidic disulfuric acid ester of the adduct of 3 moles of propylene oxide and 5 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₇ mixture of the mono- and di-phosphoric acid ester (1: 2) of the adduct of 8 moles of ethylene oxide and 1 mole of dodecylamine;
• C mixture of the mono- and di-phosphoric acid ester (1: 2) of the adduct of 4 moles of ethylene oxide and 1 mole of laurylamine;
• C ₉ ammonium salt of the acidic phosphoric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• C ₁₀ sodium salt of the acidic di (sulfosuccinic acid) half ester of Adduct of 8 moles of ethylene oxide with 1 mole of tallow fatty amine;
• C ₁₁ ammonium salt of the acidic disulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of stearylamine;
• C ₁₂ ammonium salt of the acidic disulfuric acid ester of the adduct of 1 mol of styrene oxide and 8 mol of ethylene oxide and 1 mol of dodecylamine.

• 52 % 6-Phthalimido-hexansäure-n-butylester,
• 16 % der Komponente A₁
• 16 % der Komponente B₁₄ und
• 16 % der Komponente C₇

enthält. Hierauf werden zur Flotte 7,14 g eines gelben Farbstoffes der Formel

13,44 g eines roten Farbstoffes der Formel

und 4,83 g eines blauen Farbstoffes der Formel

zugegeben, worauf die Flotte während 10 Minuten bei 80°C zirkulieren gelassen wird. Darauf wird die Färbeflotte im Verlauf von 35 Minuten, bei einer Flottenumwälzung von 2,5 Umwälzungen pro Minute, von 80°C auf 130°C aufgeheizt und während 60 Minuten bei dieser Temperatur belassen. Anschliessend kühlt man das Färbebad auf 80° C ab und spült und stellt die Färbung auf übliche Art fertig.Example 1: In an HT circulation apparatus, 2.1 kg of a textured polyester (polyethylene glycol terephthalate) in the form of a winding body with a winding density of 425 g / cm ³ , in a liquor ratio of 1: 8, are treated with an aqueous liquor at 80 ° C. , the 32 g of ammonium sulfate, 15 ml of 80% formic acid and 48 g of a preparation (1) consisting of

• 52% n-butyl 6-phthalimido-hexanoate,
• 16% of component A ₁
• 16% of component B ₁₄ and
• 16% of component C ₇

contains. 7.14 g of a yellow dye of the formula are then added to the liquor

13.44 g of a red dye of the formula

and 4.83 g of a blue dye of the formula

added, whereupon the liquor is circulated at 80 ° C. for 10 minutes. The dye liquor is then heated from 80 ° C. to 130 ° C. in the course of 35 minutes, with a liquor circulation of 2.5 circulations per minute, and left at this temperature for 60 minutes. The dye bath is then cooled to 80 ° C. and rinsed and the dyeing is completed in the usual way.

If you knit separately the outer, middle and inner layers of the brown-colored polyester bobbin to form a piece of knitting, it will be completely colored regardless, and the individual layers can practically no longer be distinguished. In addition, the lightfastness of the dyeings is not adversely affected.

With the same procedure, but with the addition of 21 g of the disodium salt of di- (6-sulfonaphthyl-2) -methane instead of the auxiliary preparation (1) indicated, unevenly colored polyester knitted pieces are obtained after knitting.

If you compare the migration half-life t / 2 of the dyes used with or without a mixture of auxiliaries, the following migration half-lives result: (t / 2 without a mixture of auxiliaries; t '/ ₂ with a mixture of auxiliaries).

Instead of components A ₁ , B ₁₄ and C ₇ , components A ₂ to ^A ₉ ^or B ₁ to B ₁₃ , B ₁₅ and B ₁₆ ^or C ₁ to C can also be used in the auxiliary preparation (1) with similar success ₆ and C ₈ to C ₁₁ are used.

Beispiel 14: Verfährt man wie in Beispiel 1 angegeben, ersetzt jedoch die 48 g des Hilfsmittels (1) durch dieselbe Menge folgenden Hilfsmittels (2) der Zusammensetzung

• 52% 6-Phthalimido-hexansäure-n-butylester
• 14% der Komponente A
• 14% der Komponente ^B ₁₄
• 14% der Komponente C₇ und
• 6% Polypropylenglykol mit einem durchschnittlichen Molekulargewicht von 400

und führt die Färbung wie im Beispiel 1 beschrieben durch, so erhält man ebenso egale braune Wickelkörper und daraus hergestellte Strickstücke.Examples 2 to 13: If the procedure is as described in Example 1, but instead of the dye mixture given there in each case the dyes listed in the following table in the amount specified there (3rd column), knitting pieces of any color obtained after knitting listed in the last column of the table. In the fourth column the migration half-life t / 2 of the dye without the auxiliary mixture is given, while in the fifth column the migration half-life t '/ _{2 is} reduced in minutes of the dye due to the presence of the auxiliary mixture. The dyeings obtained according to Examples 2 to 13 are lightfast and have no dye deposits.

EXAMPLE 14 The procedure is as described in Example 1, but the 48 g of auxiliary (1) are replaced by the same amount of auxiliary (2) of the composition below

• 52% n-butyl 6-phthalimido-hexanoate
• 14% of component A
• 14% of component ^B ₁₄
• 14% of component C ₇ and
• 6% polypropylene glycol with an average molecular weight of 400

and if the dyeing is carried out as described in Example 1, level brown bobbins and knitted pieces made therefrom are also obtained.

• (3) 52 % 6-Phthalimido-hexansäure-n-butylester, ¹⁶ % der Komponente A₁ 16 % der Komponente ^B ₁₄ 16 % der Komponente C₈;
• (4) 52 % 6-Phthalimido-hexansäure-n-butylester, 13 % der Komponente A₅ 13 % der Komponente B₁₄ 13 % der Komponente C₇ 9 % Dimethylmethan-phosphat; oder
• (5) 52 % 6-Phthalimido-hexansäure-n-butylester 16 % der Komponente A₂ 16 % der Komponente B₁₄ 16 % des sauren Phosphorsäureesters des Analgerungsproduktes von 3 Mol Aethylenoxyd an 1 Mol Alfol (8-10)

und führt die Färbung wie in Beispiel 1 beschrieben durch, so erhält man ebenso egale braune Wickelkörper und daraus hergestellte Strickstücke.Example 15: The procedure described in Example 1 is followed, but the 48 g of auxiliary (1) are replaced by the same amount of one of auxiliary (3), (4) or (5) of the following compositions

• (3) 52% n-butyl 6-phthalimido-hexanoate, ¹⁶ % of component A ₁ 16% of component ^B ₁₄ 16% of component C ₈ ;
• (4) 52% n-butyl 6-phthalimido-hexanoate, 13% of component A ₅ 13% of component B ₁₄ 13% of component C ₇ 9% dimethyl methane phosphate; or
• (5) 52% n-butyl 6-phthalimido-hexanoate 16% of component A ₂ 16% of component B ₁₄ 16% of the acidic phosphoric acid ester of the analgesic product of 3 moles of ethylene oxide and 1 mole of alfol (8-10)

and if the dyeing is carried out as described in Example 1, level brown bobbins and knitted pieces made therefrom are also obtained.

in 1000 ml Wasser vordispersiert, zugegeben, worauf die Flotte während 5 Minuten zirkulieren gelassen wird. Mit einer Aufheizrate von 1,5°C pro Minute erhöht man die Färbetemperatur auf 130°C und färbt dann während 60 Minuten bei einer Flottenumwälzung von 3 Umwälzungen pro Minute bei dieser Temperatur. Anschliessend kühlt man das Färbebad auf 80°C ab und spült und trocknet die gefärbte Ware.Example 16: In an HT circulation dyeing machine, 2000 g of a textured polyester (polyethylene glycol terephthalate) in the form of a winding body with a winding density of 450 g / cm in a liquor ratio of 1: 7 are treated with an aqueous liquor, the 7 ml 80 / -Aqueous formic acid, 28 g of ammonium sulfate, 200 g of an aqueous preparation containing 42 g of the auxiliary (1), and 7 g of calcium chloride dissolved in 500 ml of water. Then the liquor 20 g of a red dye of the formula

Predispersed in 1000 ml of water, added and the liquor was allowed to circulate for 5 minutes. With a heating rate of 1.5 ° C per minute, the dyeing temperature is increased to 130 ° C and then dyed for 60 minutes with a liquor circulation of 3 circulations per minute at this temperature. The dye bath is then cooled to 80 ° C. and the dyed goods are rinsed and dried.

If you knit the outer, middle and inner layers of the red-colored polyester bobbin separately into a knitted piece, it will be completely colored regardless, and the individual layers can practically no longer be distinguished. In addition, no dye deposits are visible. Likewise, the light fastness is not negatively affected and remains unchanged.

With the same procedure, the same amount of magnesium chloride can be used instead of 7 g of calcium chloride. Level dyeings which are free of dye deposits are also obtained.

• 10,5 ml 80%iger Essigsäure
• 52,5 g der wässerigen Hilfsmittelzubereitung (1) und
• 14 g einer wässerigen 20%igen Sandmahlung enthaltend den optischen Aufheller der Formel
  

und das Anlagerungsprodukt von 35 Mol Aethylenoxyd an 1 Mol Nonylphenol (1:1), Teilchengrösse<2µ, enthält. Danach erhitzt man die Flotte im Verlauf von 20 Minuten bei einer Flottenumwälzrate von 3 Umwälzungen pro Minute auf 130°C und belässt sie 30 Minuten bei dieser Temperatur. Nach Abkühlen der Flotte auf 80°C wird die Ware zweimal mit warmem Wasser gespült, darauf zentrifugiert und bei 120°C getrocknet. Verstrickt man jeweils getrennt die äusseren, mittleren und inneren Lagen des aufgehellten Polyester-wickelkörpers zu einem Strickstück, so kann man keinen Unterschied im Weissgrad bei den drei Strickstücken feststellen. Das ganze Strickstück ist vollständig egal aufgehellt.Example 17: 1400 g of a textured polyester yarn in the form of a bobbin with a liquor ratio of 1:15 are allowed to circulate in 21 liters of an aqueous liquor in a Hr circulation dyeing machine (HT coil dyeing machine) at 70 ° C. for 5 minutes

• 10.5 ml 80% acetic acid
• 52.5 g of the aqueous auxiliary preparation (1) and
• 14 g of an aqueous 20% sand grinding containing the optical brightener of the formula
  

and the adduct of 35 moles of ethylene oxide with 1 mole of nonylphenol (1: 1), particle size <2μ, contains. The liquor is then heated to 130 ° C. over a period of 20 minutes at a liquor circulation rate of 3 circulations per minute and left at this temperature for 30 minutes. After the liquor has cooled to 80 ° C., the goods are rinsed twice with warm water, then centrifuged and dried at 120 ° C. If you knit the outer, middle and inner layers of the lightened polyester bobbin separately into a knitted piece, you can see no difference in the whiteness of the three knitted pieces. The whole knitted piece is lightened completely no matter.

With the same procedure, but without the addition of the auxiliary preparation (1), unevenly lightened polyester knitted pieces are obtained after knitting, which also have a low degree of whiteness.

EXAMPLE 18 The procedure is as described in Example 17, an additional 8.5 g of calcium chloride are added to the liquor and the optical brightening is completed as described in Example 17.

If the outer, middle and inner layers of the lightened polyester wrap are knitted separately to form a knitted piece, no difference in the degree of whiteness can be found for the three knitted pieces. The whole knit piece is completely lightened no matter what and has an unchanged light fastness, and no precipitations.

Claims (30)

1. Aid for dyeing or optical brightening, characterized in that there is at least (I) a dicarboxyimido ester of the formula

in which W is a radical of a dicarboxylic acid which has at least 2 carbon atoms, T is an aliphatic, cycloaliphatic or araliphatic radical with at most 24 carbon atoms and n is 2 to 5, and as component (II) (A) an acidic ester or its salt of a polyadduct of propylene oxide with a polyfunctional aliphatic amino or hydroxy compound which has 2 to 9 carbon atoms and at least one amino or hydroxyl group capable of addition; or (B) an acidic ester or its salt of a polyadduct of an alkylene oxide with a phenol or at least one alkyl, benzyl or phenyl group (C) an anionic or amphoteric ester or its salt of a polyadduct of 2 to 50 moles of an alkylene oxide with an aliphatic monoamine of 8 to 24 carbon atoms or
contains a mixture of two or more of these substances (A), (B) and (C). 2. Aid according to claim 1, characterized in that in formula (1) W is phenylene which is unsubstituted or substituted by halogen, methyl or methoxy. 3. Aid according to one of claims 1 and 2, characterized in that in formula (1) T is alkyl having 1 to 12 carbon atoms. 4. Aid according to one of claims 1 to 3, characterized in that in formula (1) n is 5. 5. Aid according to claim 1, characterized in that the dicarboxyimido ester of the formula

corresponds to wherein W ₁ alkylene or alkenylene having 2 to 4 carbon atoms, cyclohexylene or phenylene which is unsubstituted or substituted by halogen, methyl or methoxy and T _l alkyl having 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, cyclohexyl or benzyl. 6. aid according to one of claims 1 to 5, characterized in that component (I) a phthalimido-hexanoic acid-C ₁ -C ₈ alkyl esters, and preferably a phthalimido hexanoic acid ^C ₃ - ^C ₆ alkyl. 7. Aid according to one of claims 1 to 6, characterized in that component (II) is a mixture of the surfactant compounds (A), (B) and (C). 8. Aid according to one of claims 1 to 7, characterized in that component (A) is an acidic ester, preferably sulfuric acid ester, or its salt of a polypropyleneoxy adduct, which has an average molecular weight of 1000 to 6000, preferably 2300 to 4600. 9. Aid according to claim 8, characterized in that the polypropylene oxide adduct has been obtained by adding 40 to 80 mol of propylene oxide to 1 mol of a polyfunctional aliphatic hydroxy compound having 2 to 9 carbon atoms. 10. Aid according to claim 9, characterized in that the aliphatic hydroxy compound is a polyhydric aliphatic alcohol which has 2 to 6 hydroxyl groups and 2 to 6 carbon atoms. 11. Aid according to claim 10, characterized in that the polyhydric aliphatic alcohol has 2 or 3 hydroxyl groups and 3 carbon atoms. ₁ 2. Aid according to one of claims 1 to 11, characterized in that component (B) is an acidic ester or its salt of a polyalkylene oxide adduct, which by addition of 1 to 60 moles of alkylene oxide to 1 mole of a phenol which has at least one benzyl group, contains a phenyl group or an alkyl group of at least 4 carbon atoms. 13. Aid according to claim 12, characterized in that component (B) is an anionic surfactant of the formula

-st, in what R alkylphenyl with 4 to 16 carbon atoms in the alkyl part or o-phenylphenyl, of Y ₁ and Y _{2 is} hydrogen or methyl and the other hydrogen, X is the acid residue of an inorganic, oxygen-containing acid and m is 1 to 30. 14. Aid according to claim 13, characterized in that component (B) is an anionic surfactant of the formula

is in which R is octyl or nonyl, m ₁ 2 to 15 and X _{1 is} derived from sulfuric acid or o-phosphoric acid and the surfactant is present as the free acid, sodium or ammonium salt. 15. Aid according to one of claims 1 to 14, characterized in that component (C) is a compound of the formula

in which of Y ₃ and Y ₄ one is hydrogen, methyl or phenyl and the other hydrogen, Z is an aliphatic hydrocarbon radical having 8 to 24 carbon atoms, the two Q individually or together are the acid radical of an inorganic oxygen-containing acid or an aliphatic dicarboxylic acid, p 1 or 2 and r and s are integers, the sum of r and s being 2 to 50. ₁₆ . Aid according to claim 15, characterized in that component (C) is a compound of the formula

is in which Z _{1 is} alkyl or alkenyl, each having 10 to 18 carbon atoms and p 1 or 2, the sum of r and s _{1 is} 2 to 15 and the two Q ₁ are derived from sulfuric acid or individually or together from o-phosphoric acid and the compound of formula (9) is present as the free acid, sodium or ammonium salt. _17th Aid according to claim 16, characterized in that component (C) is a mixture of the compounds of the formulas

and

in which Z ₁ , r ₁ and s _{1 have} the meaning given in claim 16 and M is hydrogen, ammonium or sodium. 18. Aid according to any one of claims 1 to 17, characterized in that it is at least (Ia) a dicarboxyimido ester of the formula

wherein W ₁ alkylene or alkenylene having 2 to 4 carbon atoms, cyclohexylene or phenylene which is unsubstituted or substituted by halogen, methyl or methoxy, and T _{1 is} alkyl having 1 to 12 carbon atoms, preferably 3 to 6 carbon atoms, cyclohexyl or benzyl, (Aa) a sulfuric acid ester or its salt of a polyadduct of 40 to 80 mol of propylene oxide with a dihydric to hexavalent aliphatic alcohol of 2 to 6 carbon atoms, (Bb) an acidic ester, preferably phosphoric acid ester, or its salt of a polyadduct of 2 to 20 moles of ethylene oxide and / or propylene oxide with a p-alkylphenol with 4 to 16 carbon atoms in the alkyl part and (Cc) a surfactant compound of the formula

wherein Z _{1 is} alkyl or alkenyl each having 10 to 18 carbon atoms and p is 1 or 2, the sum of r and s is 2 to 15 and the two Q ₁ are derived from sulfuric acid or individually or together from o-phosphoric acid. _19th Aid according to one of claims 1 to 18, characterized in that it additionally contains, as component (III), a polypropylene glycol or an adduct of propylene oxide with a three to six-valent aliphatic alcohol of 3 to 6 carbon atoms. 2 ₀ . Aid according to one of claims 1 to 19, characterized in that it is based on the agent 15 to 60 percent by weight of component (I), 5 to 20 percent by weight of component (A), 10 to 40 percent by weight of component (B), 2 to 25 percent by weight of component (C), 0 to 15 percent by weight of component (III) and 0 to 40 weight percent water
contains. 21. Use of the aid according to one of claims 1 to 20 in the dyeing or optical brightening of polyester fiber materials with disperse dyes or dispersed optical brighteners. 22. A process for dyeing or optically brightening polyester fiber materials with disperse dyes or dispersed optical brighteners, characterized in that the materials are colored or optically brightened in the presence of an auxiliary which at least (I) a dicarboxyimido ester of the formula

in which W is a radical of a dicarboxylic acid which has at least 2 carbon atoms, T is an aliphatic, cycloaliphatic or araliphatic radical with at most 24 carbon atoms and n 2 to 5
mean and as component (II) (A) an acidic ester or its salt of a polyadduct of propylene oxide with a polyfunctional aliphatic amino or hydroxy compound which has 2 to 9 carbon atoms and at least one amino or hydroxyl group capable of addition; or (B) an acidic ester or its salt of a polyadduct of an alkylene oxide with a phenol or at least one alkyl, benzyl or phenyl group (C) an anionic or amphoteric ester or its salt of a polyadduct of 2 to 50 moles of an alkylene oxide or an aliphatic monoamine of 8 to 24 carbon atoms or the like
contains a mixture of two or more of these substances (A), (B) and (C). 23. The method according to claim 22, characterized in that the auxiliary additionally contains as component (III) a polypropylene glycol or an adduct of propylene oxide with a trihydric to hexavalent aliphatic alcohol of 3 to 6 carbon atoms. _24th Method according to one of claims 22 and 23, characterized in that the auxiliary is used in an amount of 0.5 to 6 g per liter of dyeing liquor or lightening liquor. _{25. The} method according to any one of claims 22 to 24, characterized in that the dyeing liquor or lightening liquor additionally contains an anionic dispersant :. ₂₆ . Method according to one of claims 22 to 25, characterized g _e - indicates that the dye liquor additionally contains a brightening or carriers. _27th Method according to one of claims 22 to 26, characterized in that dispersion dyes or optical brighteners are used which have a migration half-life t / 2 of at least 40 minutes at 130 ° C without auxiliary agents. 28. The method according to any one of claims 22 to 27, characterized in that at least two or three disperse dyes are used. 29. The method according to any one of claims 22 to 28, characterized in that the dyeing or optical brightening is carried out at a temperature of 80 to 135 ° C, preferably 110 to 135 ° C. 30. The method according to any one of claims 22 to 29, characterized in that the fiber material is introduced into the liquor at 60 to 80 ° C, this is heated to 110 to 135 ° C in the course of 15 to 60 minutes and for 30 to 120 minutes colors at this temperature.