EP0204656A1 - Process for dyeing hydrophobic fibrous material - Google Patents

Abstract

A process is described for dyeing hydrophobic fiber material with unformed disperse dyes from an aqueous liquor, which is characterized in that one or more of these dyes is used by means of a surfactant or surfactant mixture having a hydrotropic or solubilizing effect on disperse dyes at a temperature of 50 ° to 150 ° C. Water dissolves, the dye solution is brought together with the substrate in a dyeing machine, then the dyeing liquor is heated to the dyeing temperature and the dyeing is completed at this temperature, and then the substrate is removed and the extracted dyeing liquor is returned to the original by adding / water, surfactant and dye Set composition and used again for dyeing.

Description

The present invention relates to a method for dyeing hydrophobic fiber material with unformed disperse dyes, and to the fiber material dyed by the method.

Hydrophobic fiber material, primarily polyester yarns or fabrics or knits made of polyester fibers, are dyed with disperse dyes either under normal pressure, at temperatures up to 100 ° C in the presence of a carrier or in a closed dyeing machine at temperatures from 120 to 150 ° C under pressure. Both processes have the disadvantage that disperse dyes are required to carry them out, which are in a finely divided, stable dispersed form. Accordingly, the dyes have to be subjected to lengthy grinding operations after synthesis, for example in agitator ball mills or sand mills, together with suitable dispersants. Finally, the ground-down disperse dye must be transferred to a stable, storable liquid formulation which does not tend to reagglomeration or be subjected to a gentle drying process in order to obtain a dye powder which can be dispersed rapidly in the dye liquor without lump formation.

In order to avoid this complex grinding and formulation process, an HT dyeing process for polyester piece goods is already proposed in European patent application 0060433, which is carried out with disperse dyes which are unformed, ie after the synthesis, no aftertreatment, especially none Nasal grinding. It is essential in this known method that the dye is largely present as an undissolved solid in the liquor during the dyeing. This means that this process is practically limited to general cargo dyeing in jet machines. When dyeing bobbins or packages in circulation equipment, the undissolved dye is inevitably filtered off on the yarn or fabric.

It has now been found that, surprisingly, hydrophobic fiber material, in particular polyester and polyamide fiber material, can be dyed with unformed disperse dyes, regardless of the form and dyeing apparatus, if these are dissolved in water with the aid of a surfactant or surfactant mixture having a hydrotropic or solubilizing effect and that the drawn dye liquor can be used again for dyeing after adding the consumed amounts of water, surfactant and dye.

The method according to the invention offers considerable advantages. By using unformed dyes, i.e. Dyes which are free of dispersants can be dispensed with the dispersants and the complex grinding, thermal stabilization and drying of the dyes. The amount of waste water is greatly reduced because the dye baths are used several times. In addition to saving water, this also entails a considerable reduction in energy costs, since the dyed baths that are pulled out do not have to be re-heated from room temperature to the dyeing temperature if they are used again. Only the cooling, which may be necessary without a device for the hot extension of the goods and which occurs during the change of the goods, has to be compensated. Since the undrawn part of the dye is available again for the next dyeing, overall there is less dye and chemical consumption.

Further advantages of the method according to the invention are that there are no longer any problems with the dispersion stability, that the absorption curves are very little dependent or independent of the dye concentration, depending on the amount of surfactant used, and that the absorption rate of the dyes is more uniform and lower in the critical temperature range Has values than when dyeing with conventional disperse dyes. This makes it possible to put together a trichromatic curve consisting of individual components whose overlap curves instead of primary mixtures with a good tone-on-tone structure for any nuances and color strengths. In this way, level dyeings in the critical temperature range can be achieved even at higher heating speeds and / or lower circulation rates without having to calculate special time-temperature programs.

• Da sich keine Dispergatoren im System anreichern, kann die Farbstoffkonzentration-in der Restflotte genauer bestimmt werden, die Reproduzierbarkeit der Färbungen sind nicht gefährdet und die Herabsetzung des Energie-, Wasser-, Farbstoff- und Chemikalienverbrauchs kann mehr herabgesetzt werden.

Further advantages over recycling the liquor when dyeing with conventional disperse dyes:

• Since no dispersants accumulate in the system, the dye concentration in the remaining liquor can be determined more precisely, the reproducibility of the dyeings are not endangered and the reduction in energy, water, dye and chemical consumption can be reduced more.

The invention thus relates to a process for dyeing hydrophobic fiber material with unformed disperse dyes from an aqueous liquor, which is characterized in that one or more of these dyes is hydrotroped or stabilized by a surfactant or surfactant mixture on disperse dyes at a temperature of 50 ° to 150 ° C, in particular 70-100 ° C and preferably 90-99 ° C at normal or positive pressure, in water, the dye solution in a dyeing machine with substrate, then the dyeing liquor heated to dyeing temperature and the dyeing (for example HT or carrier) completed at this temperature, and that you then remove the substrate and the extracted dye liquor by adding water, surfactant and dye, the dye being either the same or optionally restores the original composition together with another or only with another and used again for dyeing.

The dye liquor is preferably used 5 to 100 times, in particular 5 to 15 times.

The disperse dyes which can be used according to the invention can belong to a wide variety of dye classes. In particular, it is azo, anthraquinone, nitro, methine, styryl, azostyryl; Naphthoperinone, quinophthalone, acridone or naphthoquinoneimine dyes that are free from water-solubilizing groups. Preferred dispersion dyes are metal-free mono- or disazo dyes, nitro dyes, acridone dyes, anthraquinone dyes or quinophthalone dyes. Dyes which have sufficient water solubility in the presence of hydrotroping or solubilizing surfactants for use in the present process can easily be selected by appropriate preliminary tests.

The dyes can in principle be used without any aftertreatment, i.e. directly from the synthesis, e.g. in the form of a moist press cake or as an aqueous suspension.

The disperse dye or dyes are introduced into the dyeing apparatus in the form of a hot aqueous solution or dissolved in the dyeing apparatus before the introduction of the fiber material. In the following, the term solution is understood to mean a true monomolecular solution, a colloidal solution and a microdispersion. The dye is thus fed to the dye liquor in dissolved, solubilized, hydrotroped or microdispersed form.

The dye solution can, for example, be fed into the liquor circulating in the dyeing apparatus either by adding all of it, for example in one, connected to the dyeing apparatus Batch container, prepared solution or by metering in portions. The latter can be done by appropriate control, for example in relation to the number of pumping cycles, or also as a function of the heating rate, if the dye solution is added to the dye liquor little by little during heating to the dyeing temperature. Moreover, it is advantageous if the dye solution has the same temperature as the circulating liquor when it is metered into the dyeing apparatus. The method according to the invention can also be carried out using the sluice method or by changing the direction of the fleet.

In order to dissolve the disperse dye (in principle it is also possible to dissolve dispersed dyes) in water at from 50 ° to 150 ° C., a surfactant or surfactant mixture having a hydrotroping or solubilizing effect is used according to the invention. First and foremost, they are anionic, nonionic and cationic surfactants. In addition, amphoteric surfactants can also be used. However, mixtures of a nonionic and an anionic surfactant have proven to be particularly favorable. Mixtures of a nonionic and a cationic surfactant are also suitable.

worin R ein aliphatischer Kohlenwasserstoffrest mit 8 bis 22 Kohlenstoffatomen oder ein cycloaliphatischer oder aliphatisch-aromatischer Kohlenwasserstoffrest mit 10 bis 22 Kohlenstoffatomen, R₁ Wasserstoff oder Methyl, A -0-,-NH- oder

X der Säurerest einer anorganischen, Sauerstoff enthaltenden Säure oder der Rest einer mehrbasischen Carbonsäure und m eine Zahl von 1 bis 20, insbesondere 1 bis 5, ist. Der Rest R-A- leitet sich z.B. ab von höheren Alkoholen wie Decyl-, Lauryl-, Tridecyl-, Myristyl-, Cetyl-, Stearyl-, Oleyl-, Arachidyl-, Hydroabietylalkohol oder Behenylalkohol; ferner von Fettaminen wie Stearylamin, Palmitylamin oder Oleylamin; von Fettsäuren, wie Capryl-, Caprin-, Laurin-, Myristin-, Palmitin-, Stearin-, Arachin-, Behen-, Kokosfett-(C₈-C₁₈), Decen-, Dodecen-, Tetradecen-, Hexadecen-, Oel-, Linol-, Linolen-, Eikosen-, Dokosen- oder Clupanodonsäure; von Alkylphenolen, wie Butyl-, Hexyl-, n-Octyl-, n-Nonyl-, p-tert.Qctyl, p-tert.Nonyl-, Decyl-, Dodecyl-, Tetradecyl- oder Hexadecylphenol. Bevorzugt sind Reste mit 10 bis 18 Kohlenstoffatomen, insbesondere solche, die sich von den Alkylphenolen ableiten.The hydrotroping or solubilizing anionic surfactants used are preferably reaction products of ethylene oxide and / or propylene oxide with saturated or unsaturated fatty acids, fatty alcohols, fatty amines, alicyclic alcohols or aliphatic-aromatic hydrocarbons which are terminally esterified by an inorganic oxygen-containing acid or a polybasic carboxylic acid. These are compounds of the formula I.

wherein R is an aliphatic hydrocarbon radical with 8 to 22 carbon atoms or a cycloaliphatic or aliphatic-aromatic hydrocarbon radical with 10 to 22 carbon atoms, R _{1 is} hydrogen or methyl, A -0 -, - NH- or

X the acid residue an inorganic, oxygen-containing acid or the rest of a polybasic carboxylic acid and m is a number from 1 to 20, in particular 1 to 5. The rest RA- is derived, for example, from higher alcohols such as decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl, hydroabietyl alcohol or behenyl alcohol; also of fatty amines such as stearylamine, palmitylamine or oleylamine; of fatty acids, such as caprylic, capric, lauric, myristic, palmitic, stearic, arachine, behen, coconut fat (C ₈ -C ₁₈ ), decene, dodecene, tetradecene, hexadecene, Oleic, linoleic, linolenic, eicotonic, docosonic or clupanodonic acid; of alkylphenols such as butyl, hexyl, n-octyl, n-nonyl, p-tert-octyl, p-tert-nonyl, decyl, dodecyl, tetradecyl or hexadecylphenol. Residues having 10 to 18 carbon atoms are preferred, in particular those which are derived from the alkylphenols.

The acid residue X is usually derived from low molecular weight dicarboxylic acids, such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is connected to the residue RA- (CH ₂ CHR _i O) - via an ester bridge. In particular, X is derived from inorganic polybasic acids such as orthophosphoric acid and sulfuric acid. The acid residue X is preferably in salt form, ie, for example, as an alkali metal, ammonium or amine salt. Examples of such salts are sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.

These compounds are prepared by known methods by adding to the alcohols, fatty amines, acids and alkylphenols mentioned, ethylene oxide and / or propylene oxide and then esterifying the alkoxylates thus obtained and optionally converting the esters into their salts. Such surfactants are e.g. known from U.S. Patent 3,211,514.

Of this group of anionic surfactants, the acidic sulfuric acid esters of alkylphenol ethoxylates are in turn preferably used, that is to say those compounds of the formula given in which RA- is an alkylphenol radical, R _{1 is} hydrogen, m has the meaning given and X represents a sulfuric acid radical.

Specifically mentioned are the reaction products esterified with sulfuric acid of 1 mol butylphenol and 3 mol ethylene oxide, 1 mol tributylphenol and 5 mol ethylene oxide, 1 mol nonylphenol and 2 mol ethylene oxide, 1 mol nonylphenol and 10 mol propylene or ethylene oxide, 1 mol nonylphenol and 20 moles of ethylene oxide, 1 mole of dodecylphenol and 4 moles of ethylene oxide or 1 mole of pentadecylphenol and 5 moles of ethylene oxide. The sulfuric acid half-esters of the alkoxylates mentioned are preferably in the form of the ammonium salt. If appropriate, mixtures of the anionic surfactants can also be used.

in Frage, wobei die Substituenten R₁ bis R₃ und das Symbol X⊖ die folgende Bedeutung haben:

• R₁ ein gesättigter und/oder ungesättigter Alkylrest mit 8 bis 22 Kohlenstoffatomen;
• Rz unabhängig voneinander jeweils ein Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine Polyalkylenoxidkette mit 3 bis 30 Aethylenoxid- und/oder Propylenoxideinheiten oder Aethylenoxid-und Styroloxideinheiten;
• R₃ ein gegebenenfalls durch eine Hydroxy-, Methoxy- oder Aethoxygruppe oder durch einen Carbamoyl- oder Phenylrest substituierter Alkylrest mit 1 bis 4 Kohlenstoffatomen;
• X das Anion einer organischen oder anorganischen Säure, wie z.B. Chlorid, Bromid, Sulfat oder Methosulfat.

The hydrotroping or solubilizing cationic surfactants are primarily quaternary ammonium compounds of the formula II which have a higher alkyl radical

in question, where the substituents R ₁ to R ₃ and the symbol X⊖ have the following meaning:

• R _{1 is} a saturated and / or unsaturated alkyl radical having 8 to 22 carbon atoms;
• Rz independently of one another in each case an alkyl radical with 1 to 4 carbon atoms or a polyalkylene oxide chain with 3 to 30 ethylene oxide and / or propylene oxide units or ethylene oxide and styrene oxide units;
• R _{3 is} an alkyl radical which is optionally substituted by a hydroxyl, methoxy or ethoxy group or by a carbamoyl or phenyl radical and has 1 to 4 carbon atoms;
• X is the anion of an organic or inorganic acid, such as chloride, bromide, sulfate or methosulfate.

Such compounds are known or can be obtained by known processes, for example by reacting a fatty amine or a mixture of fatty amines, such as, for example, coconut fatty amine with ethylene oxide and / or propylene oxide and then quaternizing the alkoxylate thus obtained, e.g. with dimethyl sulfate (see e.g. H. Stache, Tensid-Taschenbuch; Carl Hanser Verlag 1981).

• Mit Chloracetamid quaterniertes Anlagerungsprodukt von 8 Mol Aethylenoxid an 1 Mol Talgfettamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 30 Mol Aethylenoxid an 1 Mol eines CIB-C22-Fettamins;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 30 Mol Aethylenoxid an 1 Mol Laurylamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 15 Mol Aethylenoxid an 1 Mol Laurylamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 15 Mol Aethylenoxid an 1 Mol Stearylamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 1 Mol Styroloxid und 30 Mol Aethylenoxid an 1 Mol Stearylamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 6 Mol Propylenoxid und 30 Mol Aethylenoxid an 1 Mol Caprylamin;
• mit Dimethylsulfat quaterniertes Anlagerungsprodukt von 1 Mol Styroloxid und 20 Mol Aethylenoxid an 1 Mol Stearylamin;

The following are mentioned as quaternary fatty amine alkoxylates:

• Addition product of 8 mol of ethylene oxide with 1 mol of tallow fatty amine quaternized with chloroacetamide;
• adduct of 30 moles of ethylene oxide and 1 mole of a CIB-C22 fatty amine quaternized with dimethyl sulfate;
• adduct of 30 moles of ethylene oxide and 1 mole of laurylamine quaternized with dimethyl sulfate;
• adduct of 15 moles of ethylene oxide and 1 mole of laurylamine quaternized with dimethyl sulfate;
• adduct of 15 moles of ethylene oxide and 1 mole of stearylamine quaternized with dimethyl sulfate;
• adduct of 1 mol of styrene oxide and 30 mol of ethylene oxide and 1 mol of stearylamine quaternized with dimethyl sulfate;
• adduct of 6 moles of propylene oxide and 30 moles of ethylene oxide and 1 mole of caprylamine quaternized with dimethyl sulfate;
• adduct of 1 mol of styrene oxide and 20 mol of ethylene oxide and 1 mol of stearylamine quaternized with dimethyl sulfate;

Because of their good solubilizing effect, however, those cationic surfactants of the formula II have proven particularly useful which, in addition to the higher alkyl radical R ₁ as substituents R _{2, have} a methyl or ethyl radical and in which R _{3 is} 1 to 4 for an alkyl radical substituted by the phenyl group Carbon atoms; X has the meaning already given. Mixtures of such compounds are also suitable, which are obtained, for example, when starting from fatty amine mixtures, such as coconut fatty amine, for the production of these surfactants.

• Ammoniumsalz des sauren Monoschwefelsäureesters des Anlagerungsproduktes von 2,5 Mol Aethylenoxid an 1 Mol Talgfettamin;
• Ammoniumsalz des sauren Monoschwefelsäureesters des Anlagerungsproduktes von 4 Mol Aethylenoxid an 1 Mol Talgfettamin;
• Ammoniumsalz des sauren Monoschwefelsäureesters des Anlagerungsproduktes von 6 Mol Aethylenoxid an 1 Mol Talgfettamin,
• Ammoniumsalz des sauren Monoschwefelsäureesters des Anlagerungsproduktes von 8 Mol Aethylenoxid an 1 Mol Talgfettamin;
• mit Chloracetamid quaterniertes Ammoniumsalz des amphoteren Schwefelsäureesters des Anlagerungsproduktes von 8 Mol Aethylenoxid an 1 Mol Talgfettamin;
• mit Dimethylsulfat quaternisiertes Ammoniumsalz des amphoteren Schwefelsäureesters des Anlagerungsproduktes von 30 Mol Aethylenoxid an 1 Mol eines C₁₈-C₂₂ Fettamins.

In addition to the purely anionic or cationic surfactants, amphoteric surfactants are also suitable as solubilizing agents. The following compounds are mentioned as examples:

• Ammonium salt of the acid monosulfuric acid ester of the adduct of 2.5 moles of ethylene oxide and 1 mole of tallow fatty amine;
• Ammonium salt of the acid monosulfuric acid ester of the adduct of 4 moles of ethylene oxide and 1 mole of tallow fatty amine;
• Ammonium salt of the acidic monosulfuric acid ester of the adduct of 6 moles of ethylene oxide with 1 mole of tallow fatty amine,
• Ammonium salt of the acidic monosulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• ammonium salt quaternized with chloroacetamide of the amphoteric sulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• ammonium salt quaternized with dimethyl sulfate of the amphoteric sulfuric acid ester of the adduct of 30 moles of ethylene oxide with 1 mole of a C ₁₈ -C ₂₂ fatty amine.

Surfactants from the group of amine oxides have also proven to be effective. Depending on the pH of the dyebath, such compounds have a nonionic (neutral to basic liquor) or cationic (acidic liquor) character. For example, N-dodecyl-N, N-dimethylamine oxide N-myristyl-N, N-dimethylamine oxide N-dodecyl-N, N-di-2-hydroxyethylamine oxide N-hexadecyl-N, N-di-2-hydroxyethylamine oxide N- Hexadecyl-N, N-dimethylamine oxide N-oleyl-N, N-di-2-hydroxyethylamine oxide N-stearyl-N, N-di-2-hydroxyethylamine oxide N-coconut fatty acid amidopropyl-N, N-dimethylamine oxide N-tallow fatty acid amidopropyl-N, N- dimethylamine oxide.

• a) einem niedermolekularen, aliphatischen Polyol, oder
• b) einem gesättigten und/oder ungesättigten Fettalkohol mit 6 bis 20 C-Atomen, oder
• c) einem Alkylphenol mit 4 bis 12 C-Atomen im Alkylrest, oder
• d) einem Hydroxybiphenyl, oder
• e) einem gesättigten und/oder ungesättigten Fettamin mit 14 bis 20 C-Atomen, oder
• f) einer gesättigten und/oder ungesättigten Fettsäure mit 14 bis 20 C-Atomen, oder
• g) einem gesättigten und/oder ungesättigten Fettsäure-(N,N-bis- hydroxyalkyl)amid

in Frage, wobei auf 1 Mol der unter a) bis g) genannten Verbindungen 2 bis 10 Mol, insbesondere 4 bis 8 Mol, Aethylenoxid und/oder Propylenoxid kommen.As hydrotroping or solubilizing nonionic surfactants which, as mentioned, are used in a mixture with anionic surfactants, reaction products of ethylene oxide and / or propylene oxide are preferred

• a) a low molecular weight, aliphatic polyol, or
• b) a saturated and / or unsaturated fatty alcohol having 6 to 20 carbon atoms, or
• c) an alkylphenol with 4 to 12 carbon atoms in the alkyl radical, or
• d) a hydroxybiphenyl, or
• e) a saturated and / or unsaturated fatty amine with 14 to 20 carbon atoms, or
• f) a saturated and / or unsaturated fatty acid with 14 to 20 carbon atoms, or
• g) a saturated and / or unsaturated fatty acid (N, N-bis-hydroxyalkyl) amide

into question, 2 to 10 mol, in particular 4 to 8 mol, of ethylene oxide and / or propylene oxide being added to 1 mol of the compounds mentioned under a) to g).

• a) Umsetzungsprodukte von Aethylenglykol, Propylenglykol, Glycerin oder Pentaerythrit mit 5 bis 10 Mol an Aethylenoxid und/oder Propylenoxid pro Mol an Polyol;
• b) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettalkoholen mit 6 bis 20 C-Atomen mit 2 bis 10 Mol Aethylenoxid und/oder 2 bis 10 Mol Propylenoxid je Mol Fettalkohol, vorzugsweise von gesättigten Fettalkoholen mit 6 bis 10 C-Atomen, mit 2 bis 10 Mol Aethylenoxid pro Mol Fettalkohol;
• c) Umsetzungsprodukte von Alkylphenolen mit 4 bis 12 C-Atomen im Alkylrest, mit 2 bis 10 Mol Aethylenoxid und/oder 2 bis 10 Mol Propylenoxid je Mol phenolische Hydroxylgruppe;
• d) Umsetzungsprodukte von o-, m- oder p-Phenylphenol mit 2 bis 10 Mol Aethylenoxid und/oder Propylenoxid pro Mol Hydroxybiphenyl;
• e) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettaminen mit 14 bis 20 C-Atomen mit 2 bis 10 Mol Aethylenoxid und/oder 2 bis 10 Mol Propylenoxid je Mol Fettamin;
• f) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäuren mit 14 bis 20 C-Atomen, mit 2 bis 10 Mol Aethylenoxid und/oder 2 bis 10 Mol Propylenoxid je Mol Fettsäure;
• g) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäure-(N,N-bis-hydroxyalkyl)amiden, wie z.B. Kokosölfettsäure-(N,N-bis-ß-hydroxyäthyl)amid mit 2 bis 10 Mol Aethylenoxid und/oder Propylenoxid pro Mol Fettsäurehydoxyalkylamid.

Examples of such alkoxylation products are:

• a) reaction products of ethylene glycol, propylene glycol, glycerol or pentaerythritol with 5 to 10 moles of ethylene oxide and / or propylene oxide per mole of polyol;
• b) reaction products of saturated and / or unsaturated fatty alcohols with 6 to 20 carbon atoms with 2 to 10 moles of ethylene oxide and / or 2 to 10 moles of propylene oxide per mole of fatty alcohol, preferably of saturated fatty alcohols with 6 to 10 carbon atoms, with 2 to 10 moles of ethylene oxide per mole of fatty alcohol;
• c) reaction products of alkylphenols with 4 to 12 carbon atoms in the alkyl radical, with 2 to 10 moles of ethylene oxide and / or 2 to 10 moles of propylene oxide per mole of phenolic hydroxyl group;
• d) reaction products of o-, m- or p-phenylphenol with 2 to 10 moles of ethylene oxide and / or propylene oxide per mole of hydroxybiphenyl;
• e) reaction products of saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms with 2 to 10 moles of ethylene oxide and / or 2 to 10 moles of propylene oxide per mole of fatty amine;
• f) reaction products of saturated and / or unsaturated fatty acids with 14 to 20 carbon atoms, with 2 to 10 moles of ethylene oxide and / or 2 to 10 moles of propylene oxide per mole of fatty acid;
• g) reaction products of saturated and / or unsaturated fatty acid (N, N-bis-hydroxyalkyl) amides, such as coconut oil fatty acid (N, N-bis-β-hydroxyethyl) amide with 2 to 10 moles of ethylene oxide and / or propylene oxide per mole Fatty acid hydoxyalkylamide.

Mixtures of the reaction products according to a) to g) can also be used. These mixtures are obtained by mixing individual reaction products or directly by alkoxylating a mixture of the compounds on which the reaction products are based.

Suitable saturated and / or unsaturated fatty alcohols for b) are dodecanol, hexadecyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol or tallow fatty alcohols, hexanol, 2-ethylhexanol and decanol.

As alkylphenols for c) n-butylphenol, tert-butylphenol, tributylphenol, octylphenol, p-amylphenol, hexalphenol, isooctylphenol, nonylphenol and dodecylphenol are mentioned.

As fatty amine for e) come e.g. in addition to stearylamine, palmitylamine and especially oleylamine.

For f), saturated and / or unsaturated fatty acids are e.g. Palmitic acid, especially stearic acid and oleic acid.

Reaction products of groups c) and d) have proven to be particularly effective, and especially hydroxybiphenyl ethoxylates, such as reaction products of 6 or 8 moles of ethylene oxide with one mole of o-phenylphenol or C ₄ to c ₉ alkylphenol ethoxylates, for example Reaction products of 6 to 8 moles of ethylene oxide with one mole of butylphenol.

The ethylene / propylene oxide reaction products are known or can be prepared by processes known per se (see, for example: N. Schönfeldt, interfacially active ethylene oxide adducts; Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart; 1976).

The mixing ratio of nonionic to anionic surfactant is advantageously between 1: 4 and 4: 1. Those surfactant mixtures which contain about twice as much nonionic as anionic surfactant are preferably used.

A particularly pronounced solubilizing effect has a mixture which contains, as a nonionic component, a reaction product of 1 mol of o-phenylphenol or 1 mol of tert-butylphenol and 6 mol of ethylene oxide and a nonylphenol diglycol ether sulfate as the anionic component; also a mixture of a cationic and a nonionic surfactant, for example a reaction product of 1 mol of o-phenylphenol + 6 mol of ethylene oxide and a product of the formula

With regard to the amount of surfactant or surfactant mixture, 5 to 100, preferably 10 to 80 and in particular 25 to 45 parts of surfactant or surfactant mixture are used, based on 1 part of disperse dye.

The amounts in which the disperse dyes are used can vary within wide limits depending on the desired depth of color; in general, amounts of 0.01 to 10 percent by weight of one or more of the stated disperse dyes, based on the material to be dyed, are used.

The hydrophobic fiber materials that can be dyed by the present process are primarily those made from linear, high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols, for example from terephthalic acid and ethylene glycol or dimethylolcyclohexane and mixed polymers from terephthalic acid and isophthalic acid and ethylene glycol. Provided the appropriate equipment is available, these materials can be used at any stage of processing, e.g. in the form of flakes, sliver, yarn, textured threads, woven or knitted fabrics, as well as a mixed fabric among themselves or with other fibers, for example as a mixed fabric made of polyester / polyamide or polyester / cotton. The dyeing temperature for these materials is preferably 120 to 150 ° C for the HT process and up to 100 ° C for the carrier process.

Furthermore, polyamide material can be dyed by the process according to the invention, e.g. Polyamide-6, polyamide-6,6 or also polyamide 12. The dyeing temperature for these materials is preferably 98 to 100 ° C.

If necessary, the aqueous liquor can contain customary coloring auxiliaries, advantageously in small amounts, such as acids, in particular an organic lower monocarboxylic acid, e.g. Formic acid or acetic acid, buffer salts such as ammonium sulfate or sodium acetate, wetting agents, emulsifiers or anti-foaming agents.

The liquor ratio is usually 1: 5 to 1:50; the dyeing time is 5 to 60 minutes.

The process according to the invention is preferably carried out in circulation apparatus as follows: the unformed dyestuff or dyes are in the form of an aqueous suspension, a press cake or also in solid form, for example powder, in a batch vessel connected to the dyeing apparatus in about 50 ° to 150 ° C. hot water, for example dissolved or solubilized by means of a mixture of nonionic and anionic surfactant. By adding acetic acid and sodium acetate, the pH of the dye solution is adjusted to a value of 4 to 5.5. Then, by opening a valve, the dye solution, if necessary after passing through a filter, is let into the dyeing apparatus, where the polyester material to be colored is present, for example in the form of a bobbin, such as muff, cheese, dyeing tree, or as an endless web. If necessary, the substrate is preheated with steam. With further constant liquor circulation, advantageously from the inside out or alternately, for example with 5-minute periods, the dyebath is at a rate of approx. 1 ° C / minute to a temperature of 120 ° to 150 ° C, advantageously 125 ° to 135 ° C, heated. After the desired depth of color has been achieved or when the dye bath is completely exhausted - dyeing time approx. 1 hour - the hot liquor is cooled to such an extent that the goods can be removed from the liquor and the entrained liquor portion is reduced to less than 1% (e.g. by suction or centrifuging) the entire fleet can be reduced). Weighing the wet goods determines how much of the used dye liquor is removed and adds the corresponding amount of water and surfactant to the liquor remaining in the dye bath.

The dye content of the remaining liquor is determined in the usual way, preferably photometrically, and the remaining liquor is then mixed with sufficient dye to achieve the liquor composition required for the next dyeing. The dyeing cycle described above can then be repeated.

The following examples serve to illustrate the invention; Parts mean parts by weight and percentages percent by weight. The temperatures are given in degrees Celsius.

Example 1: In the metal container of a laboratory dyeing machine (Callebaut de Blicquy) 28.44 mg of the unformed dye of the formula

in 100 ml einer wässrigen Flotte, enthaltend 1 ml (1,08 g) einer Tensidlösung, bestehend aus 42,7 % Umsetzungsprodukt von 1 Mol o-Phenylphenol + 6 Mol Aethylenoxid, 42,7 % Nonylphenol-diglykoläthersulfat als 40%ige wässrige Lösung, 14,2 % Wasser und 0,4 % Antischaummittel, bei 98°C gelöst. Der pH-Wert der Farbstofflösung wird durch Zusatz von Ammoniumsulfat und Ameisensäure auf 4,6 bis 5 eingestellt und anschliessend werden 10 g Polyestergewebe (Crimplene®)) in die Flotte gegeben und der Metallbehälter verschlossen. Man heizt innerhalb von 6 Minuten auf 130°C auf und hält diese Temperatur 30 Minuten aufrecht. Dann wird auf eine Temperatur unter 100° abgekühlt und das Substrat aus der Flotte herausgenommen.

in 100 ml of an aqueous liquor, containing 1 ml (1.08 g) of a surfactant solution, consisting of 42.7% reaction product of 1 mol of o-phenylphenol + 6 mol of ethylene oxide, 42.7% nonylphenol diglycol ether sulfate as a 40% aqueous solution , 14.2% water and 0.4% anti-foaming agent, dissolved at 98 ° C. The pH of the dye solution is adjusted to 4.6 to 5 by adding ammonium sulfate and formic acid, and then 10 g of polyester fabric (Crimplene®) are added to the liquor and the metal container is closed. The mixture is heated to 130 ° C. in the course of 6 minutes and this temperature is maintained for 30 minutes. Then it is cooled to a temperature below 100 ° and the substrate is removed from the liquor.

The amount of entrained dye liquor (28.44 g) is determined by weighing the moist substrate; the residual dye content in the extracted dye liquor is determined photometrically (2.46 mg).

Then add as much water (28.25 g) and surfactant (0.184 g) as was removed by the entrained remaining liquor to the extracted dye liquor. In addition, so much dye is added that the original content of 28.44 mg is reached again.

Another 10 g of polyester fabric are added to this dyeing liquor and the dyeing process described above is repeated. This is done a total of 10 times.

The colorations obtained are irrelevant and practically identical in color strength. The total degree of dye exhaustion after 10 dyeings was over 96%.

The following Table 1 shows the amounts of water, dye and surfactant used or replaced and the photometrically determined relative color strength of the dyeings obtained, based on the first dyeing.

Example 2: 22.29 mg of the dried press cake of the dye of the formula are in the metal container of a laboratory dyeing machine (Callebaut de Blicquy)

in 100 ml einer wässrigen Flotte, enthaltend 1,2 ml (1,3 g) einer Tensidlösung (60 % Wirksubstanz), bestehend aus 42,7 % Umsetzungsprodukt von 1 Mol o-Phenylphenol + 6 Mol Aethylenoxid, 42,7 % Nonylphenol-diglykoläthersulfat als 40%ige wässrige Lösung, 14,2 % Wasser und 0,4 % Antischaummittel, bei 98°C gelöst. Der pH-Wert der Farbstofflösung wird durch Zusatz von Ammoniumsulfat und Ameisensäure auf 4,6 bis 5 eingestellt und anschliessend werden 10 g Polyestergewebe (Crimplene^m)) in die Flotte gegeben und der Metallbehälter verschlossen. Man heizt innerhalb von 6 Minuten auf 130°C auf und hält diese Temperatur 30 Minuten aufrecht. Dann wird auf eine Temperatur unter 100° abgekühlt und das Substrat aus der Flotte herausgenommen.

in 100 ml of an aqueous liquor, containing 1.2 ml (1.3 g) of a surfactant solution (60% active substance), consisting of 42.7% reaction product of 1 mol of o-phenylphenol + 6 mol of ethylene oxide, 42.7% of nonylphenol diglycol ether sulfate as 40% aqueous solution, 14.2% water and 0.4% anti-foaming agent, dissolved at 98 ° C. The pH of the dye solution is adjusted to 4.6 to 5 by adding ammonium sulfate and formic acid, and 10 g of polyester fabric (Crimplene ^m )) are then added to the liquor and the metal container is closed. The mixture is heated to 130 ° C. in the course of 6 minutes and this temperature is maintained for 30 minutes. Then it is cooled to a temperature below 100 ° and the substrate is removed from the liquor.

The amount of entrained dye liquor is determined by weighing the moist substrate; the residual dye content in the extracted dye liquor is determined photometrically (see Table 2).

Then add as much water and surfactant to the extracted dye liquor as was removed by the entrained remaining liquor. In addition, so much dye is added that the original content is reached again (see Table 2).

Another 10 g of polyester fabric are added to this dyeing liquor and the dyeing process described above is repeated. This is done a total of 10 times.

The colorations obtained are irrelevant and practically identical in color strength.

Table 2 shows the amounts of water, dye and surfactant used or replaced, as well as the photometrically determined relative color strength of the dyeings obtained, based on the first dyeing.

Examples 3-7: In Examples 3-7, polyester material (PES) was dyed using the same method and under the same conditions as in Example 2. Dye (dried press cake), amount of dye used, surfactant, surfactant concentration and number of colors can be found in Table 3.

The colorations obtained are irrelevant and the repetitions of the color strength are practically identical.

Example 8: The procedure of Example 2 is followed. 22.29 mg of the dye of the formula

are dissolved in 100 ml of an aqueous liquor containing 5 g / 1 of a carrier obtained by mixing in dodecylbenzenesulfonic acid, triethanolamine, diphenyl, uniperol EL, xylene, n-hexanol and ethylene glycol at 60 ° C, in 1.2.4-trichlorobenzene at 78 ° C . After the pH had been adjusted (see Example 2), the temperature of the liquor was brought to 100 ° C. in about 1 minute. The polyester substrate was colored at 100 ° C for 60 minutes. You get a no matter red colored polyester material.

Example 9: The procedure of Example 2 is repeated. 10 mg of the dye of the formula

werden in 100 ml einer wässrigen Flotte enthaltend 10 ml/1 Tensides 42,7 % Umsetzungsprodukt von 1 Mol o-Phenylphenol + 6 Mol Aethylenoxid, 42,7 % Nonylphenol-diglykoläthersulfat als 40%ige wässrige Lösung, 14,2 % Wasser und 0,4 % Antischaummittel bei 98°C gelöst. Nach der Einstellung des pH-Wertes (s. Beispiel 2) wurde die Temperatur der Flotte ca. in einer Minute auf 100°C gebracht. Das Polyamid 6.6 Substrat wurde 45 Minuten bei 100°C gefärbt. Man erhält ein egal scharlach gefärbtes Polyamidmaterial.

are in 100 ml of an aqueous liquor containing 10 ml / 1 surfactants 42.7% reaction product of 1 mol o-phenylphenol + 6 mol ethylene oxide, 42.7% nonylphenol diglycol ether sulfate as 40% aqueous solution, 14.2% water and 0 , 4% antifoam dissolved at 98 ° C. After the pH had been adjusted (see Example 2), the temperature of the liquor was brought to 100 ° C. in about one minute. The polyamide 6.6 substrate was dyed at 100 ° C for 45 minutes. A scarlet colored polyamide material is obtained.

Claims (22)

1. A process for dyeing hydrophobic fiber material with unformed disperse dyes from an aqueous liquor, characterized in that one or more such dyes are dissolved in water by means of a surfactant or surfactant mixture which has a hydrotropic or solubilizing effect on disperse dyes at a temperature of 50 ° to 150 ° C, the dye solution is brought together with the substrate in a dyeing machine, then the dyeing liquor is heated to the dyeing temperature and the dyeing is completed at this temperature, and then the substrate is removed and the dyeing liquor is extracted by adding water, surfactant and dye to the composition required for the next dyeing adjusted and used again for dyeing. 2. The method according to claim 1, characterized in that the dye solution is introduced into the dyeing apparatus or metered in in portions. 3. The method according to claim 1, characterized in that a nonionic, anionic or a cationic surfactant or a mixture of a nonionic and an anionic surfactant or a nonionic and a cationic surfactant is used as a surfactant having a hydrotroping or solubilizing effect on disperse dyes. 4. The method according to claim 3, characterized in that one uses a mixture of a nonionic and an anionic surfactant. 5. Process according to claims 3 and 4, characterized in that the anionic surfactant is one of the formula 1

used, wherein R is an aliphatic hydrocarbon radical having 8 to 22 carbon atoms or a cycloaliphatic or aliphatic-aromatic hydrocarbon radical having 10 to 22 carbon atoms, R _{1 is} hydrogen or methyl, A -O-, -NH- or

X is the acid residue of an inorganic, oxygen-containing acid or the rest of a polybasic carboxylic acid and m is a number from 1 to 20. in particular 1 to 5. 6. The method according to claim 5, characterized in that one uses the acidic sulfuric acid ester of an alkylphenol ethoxylate. 7. The method according to claim 3, characterized in that quaternary ammonium compounds of the formula II are used as the cationic surfactant

used where R _{1 is} a saturated and / or unsaturated alkyl radical having 8 to 22 carbon atoms; Rz independently of one another in each case an alkyl radical with 1 to 4 carbon atoms or a polyalkylene oxide chain with 3 to 30 ethylene oxide and / or propylene oxide units or ethylene oxide and styrene oxide units; R _{3 is} an alkyl radical which is optionally substituted by a hydroxyl, methoxy or ethoxy group or by a carbamoyl or phenyl radical and has 1 to 4 carbon atoms; X represents the anion of an organic or inorganic acid. 8. The method according to claim 7, characterized in that the cationic surfactant of the formula II is one in which R _{2 is} methyl or ethyl and R ₃ is phenyl-substituted alkyl C ₁ to G ₄ and R ₁ or X⊖ the im Claim 6 have the meaning given. 9. The method according to claims 3 and 4, characterized in that a nonionic surfactant is a reaction product of ethylene oxide and / or propylene oxide a) a low molecular weight, aliphatic polyol, or b) a saturated and / or unsaturated fatty alcohol having 6 to 20 carbon atoms, or c) an alkylphenol with 4 to 12 carbon atoms in the alkyl radical, or d) a hydroxybiphenyl, or e) a saturated and / or unsaturated fatty amine with 14 to 20 carbon atoms, or f) a saturated and / or unsaturated fatty acid with 14 to 20 carbon atoms, or g) a saturated and / or unsaturated fatty acid (N, N-bis-hydroxyalkyl) amide
used, 2 to 10 mol, in particular 4 to 8 mol, of ethylene oxide and / or propylene oxide being used for 1 mol of the compounds mentioned under a) to g). 10. The method according to claim 7, characterized in that one uses a reaction product of ethylene oxide with a hydroxybiphenyl or a C ₄ to C ₉ alkylphenol. 11. The method according to claim 4, characterized in that a nonionic surfactant is a reaction product of 1 mol of o-phenylphenol or 1 mol of tert-butylphenol, each with 6 mol of ethylene oxide and a nonylphenol diglycol ether sulfate as the anionic surfactant. 12. The method according to claim 4, characterized in that a reaction product of 1 mol of o-phenylphenol + 6 mol of ethylene oxide as the nonionic surfactant and one of the formula as the cationic surfactant

used. 13. The method according to claim 1, characterized in that one uses 10 to 80 parts of surfactant or surfactant mixture for 1 part of dye. 14. The method according to claim 13, characterized in that 25 parts to 45 parts of surfactant or surfactant mixture are used for 1 part of dye. 15. The method according to claim 4, characterized in that nonionic and anionic surfactant is used in a ratio of 1: 4 to 4: 1, in particular of 2: 1. 16. The method according to claim 1, characterized in that metal-free mono- or disazo dyes, nitro dyes, acridone dyes, anthraquinone dyes or quinophthalone dyes are used as the dispersion dye. 17. The method according to claim 1, characterized in that polyester material, in particular that of polyethylene glycol terephthalate fibers, is used as the hydrophobic fiber material. 18. The method according to any one of claims 1 to 17, characterized _ characterized in that the extracted dye liquor after adding water, surfactant, dye and chemicals to adjust the composition required for the next dyeing 5 to 100 times, preferably 5 to 15 times used. 19. The method according to any one of claims 1 to 18, characterized in that the dye content in the remaining liquor is determined photometrically. 20. The method according to any one of claims 1 to 19, characterized in that dyeing polyester material at 100 to 150 ° C. 21. The method according to any one of claims 1 to 19, characterized in that dyeing material made of synthetic polyamide at 98 to 100 ° C. 22. The fiber material dyed according to the method according to one of claims 1 to 21.