EP0204656A1 - Process for dyeing hydrophobic fibrous material - Google Patents
Process for dyeing hydrophobic fibrous material Download PDFInfo
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- EP0204656A1 EP0204656A1 EP86810208A EP86810208A EP0204656A1 EP 0204656 A1 EP0204656 A1 EP 0204656A1 EP 86810208 A EP86810208 A EP 86810208A EP 86810208 A EP86810208 A EP 86810208A EP 0204656 A1 EP0204656 A1 EP 0204656A1
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- EP
- European Patent Office
- Prior art keywords
- surfactant
- dyeing
- mol
- dye
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/002—Processing by repeated dyeing, e.g. in different baths
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/904—Mixed anionic and nonionic emulsifiers for dyeing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/906—Mixed cationic and nonionic emulsifiers for dyeing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/907—Nonionic emulsifiers for dyeing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/908—Anionic emulsifiers for dyeing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
Definitions
- 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.
- 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.
- 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.
- hydrophobic fiber material in particular polyester and polyamide fiber material
- the method according to the invention offers considerable advantages.
- 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.
- 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.
- 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
- 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.
- 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.
- 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.
- 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.
- a surfactant or surfactant mixture having a hydrotroping or solubilizing effect is used according to the invention.
- they are anionic, nonionic and cationic surfactants.
- amphoteric surfactants can also be used.
- 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.
- 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.
- 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
- 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-
- 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.
- 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.
- 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.
- 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.
- 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).
- 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.
- 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.
- 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.
- alkylphenols for c) n-butylphenol, tert-butylphenol, tributylphenol, octylphenol, p-amylphenol, hexalphenol, isooctylphenol, nonylphenol and dodecylphenol are mentioned.
- fatty amine for e come e.g. in addition to stearylamine, palmitylamine and especially oleylamine.
- 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.
- 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;ticianliche 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
- 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.
- 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.
- 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.
- 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.
- 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.
- the pH of the dye solution is adjusted to a value of 4 to 5.5.
- 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.
- the substrate is preheated with steam.
- 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.
- 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.
- Example 1 In the metal container of a laboratory dyeing machine (Callebaut de Blicquy) 28.44 mg of the unformed dye of the formula
- 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).
- polyester fabric 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%.
- 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)
- 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).
- polyester fabric 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.
- 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.
- Example 8 The procedure of Example 2 is followed. 22.29 mg of the dye of the formula
- 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 .
- 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
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Abstract
Beschrieben wird ein Verfahren zum Färben von hydrophobem Fasermaterial mit unformierten Dispersionsfarbstoffen aus wässriger Flotte, das dadurch gekennzeichnet ist, dass man einen oder mehrere solcher Farbstoffe mittels eines auf Dispersionsfarbstoffe hydrotropierend oder solubilisierend wirkenden Tensids oder Tensidgemisches bei einer Temperatur von 50° bis 150°C in Wasser löst, die Farbstofflösung in einem Färbeapparat mit dem Substrat zusammenbringt, anschliessend die Färbeflotte auf Färbetemperatur erhitzt und die Färbung bei dieser Temperatur fertigstellt und dass man danach das Substrat entnimmt und die ausgezogene Färbeflotte durch Zusatz von /Wasser, Tensid und Farbstoff wieder auf die ursprüngliche Zusammensetzung einstellt und erneut zum Färben verwendet.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
Die vorliegende Erfindung betrifft ein Verfahren zum Färben von hydrophobem Fasermaterial mit unformierten Dispersionsfarbstoffen, sowie das nach dem Verfahren gefärbte Fasermaterial.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.
Hydrophobes Fasermaterial, in erster Linie Polyestergarne oder auch Gewebe oder Gewirke aus Polyesterfasern, werden mit Dispersionsfarbstoffen entweder unter Normaldruck, bei Temperaturen bis zu 100°C in Gegenwart eines Carriers oder in einem geschlossenen Färbeapparat bei Temperaturen von 120 bis 150°C unter Druck gefärbt. Beide Verfahren haben den Nachteil, dass zu ihrer Durchführung Dispersionsfarbstoffe benötigt werden, die in einer möglichst feinteiligen, stabil dispergierten Form vorliegen. Demzufolge müssen die Farbstoffe nach der Synthese langwierigen Mahloperationen unterworfen werden, beispielsweise in Rührwerks-Kugelmühlen oder Sandmühlen, zusammen mit geeigneten Dispergiermitteln. Schliesslich muss der heruntergemahlene Dispersionsfarbstoff in eine stabile, nicht zur Reagglomeration neigende, lagerfähige Flüssigformulierung überführt oder einem schonenden Trocknungsverfahren unterworfen werden, damit ein Farbstoffpulver erhalten wird, das in der Färbeflotte ohne Klumpenbildung rasch dispergierbar ist.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.
Um diesen aufwendigen Mahl- und Formulierungsprozess zu umgehen, wird in der europäischen Patentanmeldung 0060433 bereits ein HT-Färbeverfahren für Polyester-Stückware vorgeschlagen, das mit Dispersionsfarbstoffen durchgeführt wird, die unformiert sind, d.h. im Anschluss an die Synthese keiner Nachbehandlung, vor allem keiner Nasamahlung, unterworfen werden. Wesentlich an diesem bekannten Verfahren ist, dass der Farbstoff während des Färbens zum grössten Teil als ungelöster Feststoff in der Flotte vorliegt. Damit ist dieses Verfahren praktisch auf die Stückgutfärberei in Jet-Apparaten beschränkt. Beim Färben von Spulen oder Wickelkörpern in Zirkulationsapparaten kommt es unweigerlich zur Abfiltration des ungelösten Farbstoffs auf dem Garn oder Gewebe.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.
Es wurde nun gefunden, dass überraschenderweise hydrophobes Fasermaterial, insbesondere Polyester- und Polyamidfasermaterial, unabhängig von Aufmachungsform und Färbeapparatur mit unformierten Dispersionsfarbstoffen gefärbt werden kann, wenn diese mit Hilfe eines auf Dispersionsfarbstoffe hydrotropierend oder solubilisierend wirkenden Tensids oder Tensidgemisches in Wasser gelöst werden und dass man die ausgezogene Färbeflotte nach Zugabe der verbrauchten Mengen an Wasser, Tensid und Farbstoff erneut zum Färben verwenden kann.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.
Das erfindungsgemässe Verfahren bietet erhebliche Vorteile. Durch die Verwendung unformierter Farbstoffe, d.h. Farbstoffe welche frei von Dispergatoren sind, kann auf die Dispergatoren und das aufwendige Mahlen, Thermostabilisation und Trocknen der Farbstoffe verzichtet werden. Die Abwassermenge wird stark reduziert, da die Färbebäder mehrmals verwendet werden. Dies bringt neben der Einsparung an Wasser auch eine erhebliche Reduzierung der Energiekosten mit sich, da die ausgezogenen Färbebäder bei nochmaliger Verwendung nicht jeweils erneut von Raumtemperatur auf die Färbetemperatur erhitzt werden müssen. Lediglich die Abkühlung, die ohne Vorrichtung zum heissen Ausfahren der Ware eventuell notwendig ist und die während des Wechsels der Ware eintritt, muss ausgeglichen werden. Da der nicht ausgezogene Teil des Farbstoffes für die nächste Färbung erneut zur Verfügung steht, ergibt sich insgesamt gesehen ein kleinerer Farbstoff- und Chemikalienverbrauch.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.
Weitere Vorteile des erfindungsgemässen Verfahrens liegen darin, dass es keine Probleme mehr mit der Dispersionsstabilität gibt, dass die Aufziehkurven sehr wenig abhängig oder unabhängig von der Farbstoffkonzentration sind, je nach der eingesetzten Tensidmenge, und dass die Aufziehgeschwindigkeit der Farbstoffe gleichmässiger ist und im kritischen Temperaturbereich kleinere Werte aufweist als beim Färben mit herkömmlichen Dispersionsfarbstoffen. Dadurch ist es möglich, eine aus Einzelkomponenten deren Ausziehkurven sich überlappen anstatt aus Primärmischungen bestehende Trichromie mit gutem Ton-in-Ton-Aufbau für beliebige Nuancen und Farbstärken zusammenzustellen. Dabei erreicht man egale Färbungen im kritischen Temperaturbereich auch bei grösseren Aufheizgeschwindigkeiten und/oder kleineren Umwälzraten ohne spezielle Zeit-Temperatur Programme zu berechnen.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.
Weitere Vorteile gegenüber dem Recyclieren der Flotte beim Färben mit herkömmlichen Dispersfarbstoffen:
- 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.
- 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.
Gegenstand der Erfindung ist somit ein Verfahren zum Färben von hydrophobem Fasermaterial mit unformierten Dispersionsfarbstoffen aus wässriger Flotte, das dadurch gekennzeichnet ist, dass man einen oder mehrere solcher Farbstoffe mittels eines auf Dispersionsfarbstoffe hydrotropierend oder stabilisierend wirken Tensids oder Tensidgemisches bei einer Temperatur von 50° bis 150°C, insbesondere 70-100°C und vorzugsweise 90-99°C bei Normal- oder Ueberdruck, in Wasser löst, die Farbstofflösung in einem Färbeapparat mit Substrat zusammenbringt, anschliessend die Färbeflotte auf Färbetemperatur erhitzt und die Färbung (z.B. HT oder Carrier) bei dieser Temperatur fertigstellt, und dass man danach das Substrat entnimmt und die ausgezogene Färbeflotte durch Zusatz von Wasser, Tensid und Farbstoff, wobei als Farbstoff entweder derselbe oder gegebenenfalls zusammen mit einem anderen oder nur mit einem anderen wieder auf die ursprüngliche Zusammensetzung einstellt und erneut zum Färben verwendet.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.
Vorzugsweise wird die Färbeflotte 5 bis 100 mal, insbesondere 5 bis 15 mal verwendet.The dye liquor is preferably used 5 to 100 times, in particular 5 to 15 times.
Die erfindungsgemäss verwendbaren Dispersionsfarbstoffe können den verschiedensten Farbstoffklassen angehören. Insbesondere handelt es sich um Azo-, Anthrachinon-, Nitro-, Methin-, Styryl-, Azostyryl-; Naphthoperinon-, Chinophthalon-, Acridon- oder Naphthochinonimin-Farbstoffe, die frei von wasserlöslichmachenden Gruppen sind. Bevorzugte Dispersionsfarbstoffe sind metallfreie Mono- oder Disazofarbstoffe, Nitrofarbstoffe, Acridonfarbstoffe, Anthrachinonfarbstoffe oder Chinophthalonfarbstoffe. Farbstoffe die in Gegenwart von hydrotropierend oder solubilisierend wirkenden Tensiden eine zur Verwendung in vorliegendem Verfahren ausreichende Wasserlöslichkeit aufweisen, lassen sich leicht durch entsprechende Vorversuche auswählen.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.
Die Farbstoffe können grundsätzlich ohne jede Nachbehandlung, d.h. direkt von der Synthese her, z.B. in Form des feuchten Presskuchens oder auch als wässrige Suspension, eingesetzt werden.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.
Der oder die Dispersionsfarbstoffe werden in Form einer heissen wässrigen Lösung in den Färbeapparat eingebracht oder vor dem Einbringen des Fasermaterials im Färbeapparat gelöst, dabei soll im folgenden unter dem Begriff Lösung eine echte monomolekulare Lösung, eine kolloidale Lösung, sowie eine Mikrodispersion verstanden werden. Der Farbstoff wird der Färbeflotte somit in gelöster, solubilisierter, hydrotropierter oder mikrodispergierter Form zugeführt.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.
Die Einspeisung der Farbstofflösung kann z.B. in die im Färbeapparat zirkulierende Flotte erfolgen entweder durch einmalige Zugabe der gesamten, beispielsweise in einem, mit dem Färbeapparat verbundenen Ansatzbehälter, vorbereiteten Lösung oder durch portionsweises Zudosieren. Letzteres kann durch entsprechende Steuerung, z.B. in Relation zur Anzahl der Umpumpzyklen, geschehen oder auch in Abhängigkeit von der Aufheizgeschwindigkeit erfolgen, wenn die Farbstofflösung der Färbeflotte nach und nach, während dem Aufheizen auf Färbetemperatur zugesetzt wird. Im übrigen ist es vorteilhaft, wenn die Farbstofflösung beim Eindosieren in den Färbeapparat die gleiche Temperatur aufweist, wie die zirkulierende Flotte. Das erfindungsgemässe Verfahren kann auch nach der Einschleusmethode oder mittels Flottenrichtungswechsel durchgeführt werden.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.
Um den Dispersionsfarbstoff (man kann prinzipiell auch dispergierte Farbstoffe lösen) bei Temperaturen von 50° bis 150°C in Wasser zu lösen, wird erfindungsgemäss ein auf diesen hydrotropierend oder solubilisierend wirkendes Tensid oder Tensidgemisch verwendet. In erster Linie handelt es sich um anionische, nichtionogene, wie auch kationische Tenside. Daneben kommen auch Amphotenside in Frage. Als besonders günstig haben sich jedoch Gemische aus einem nichtionischen und einem anionischen Tensid erwiesen. Auch Gemische aus einem nichtionogenen und einem kationischen Tensid kommen in Frage.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.
Als hydrotropierend oder solubilisierend wirkende anionische Tenside gelangen bevorzugt Umsetzungsprodukte von Aethylenoxid und/oder Propylenoxid mit gesättigten oder ungesättigten Fettsäuren, Fettalkoholen, Fettaminen, alicyclischen Alkoholen oder aliphatischaromatischen Kohlenwasserstoffen zur Anwendung, die endständig durch eine anorganische sauerstoffhaltige Säure oder eine mehrbasische Carbonsäure verestert sind. Und zwar handelt es sich um Verbindungen der Formel I
Der Säurerest X leitet sich in der Regel von niedermolekularen Dicarbonsäuren ab, wie z.B. Maleinsäure, Malonsäure, Bernsteinsäure oder Sulfobernsteinsäure, und ist über eine Esterbrücke mit dem Rest R-A-(CH2CHRiO) - verbunden. Insbesondere leitet sich X jedoch von anorganischen mehrbasischen Säuren, wie Orthophosphorsäure und Schwefelsäure ab. Der Säurerest X liegt vorzugsweise in Salzform, d.h. z.B. als Alkalimetall-, Ammonium- oder Aminsalz, vor. Beispiele für solche Salze sind Natrium-, Kalium-, Ammonium-, Trimethylamin-, Aethanolamin-, Diäthanolamin- oder Triäthanolaminsalze.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.
Die Herstellung dieser Verbindungen erfolgt nach bekannten Methoden, indem man an die genannten Alkohole, Fettamine, Säuren und Alkylphenole, Aethylenoxid und/oder Propylenoxid anlagert und die so erhaltenen Alkoxylate anschliessend verestert und die Ester gegebenenfalls in ihre Salze überführt. Derartige Tenside sind z.B. aus der US-Patentschrift 3 211 514 bekannt.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.
Von dieser Gruppe anionischer Tenside werden wiederum bevorzugt die sauren Schwefelsäureester von Alkylphenoläthoxylaten verwendet, also solche Verbindungen der angegebenen Formel, worin R-A- ein Alkylphenolrest ist, R1 Wasserstoff bedeutet, m die angegebene Bedeutung hat und X für einen Schwefelsäurerest steht.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.
Im einzelnen genannt sind die mit Schwefelsäure veresterten Umsetzungsprodukte von 1 Mol Butylphenol und 3 Mol Aethylenoxid, 1 Mol Tributylphenol und 5 Mol Aethylenoxid, 1 Mol Nonylphenol und 2 Mol Aethylenoxid, 1 Mol Nonylphenol und 10 Mol Propylen- bzw. Aethylenoxid, 1 Mol Nonylphenol und 20 Mol Aethylenoxid, 1 Mol Dodecylphenol und 4 Mol Aethylenoxid oder 1 Mol Pentadecylphenol und 5 Mol Aethylenoxid. Die Schwefelsäurehalbester der genannten Alkoxylate liegen bevorzugt als Ammoniumsalz vor. Gegebenenfalls können auch Mischungen der anionischen Tenside eingesetzt werden.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.
Als hydrotropierend oder solubilisierend wirkende kationische Tenside kommen in erster Linie einen höheren Alkylrest aufweisende quaternäre Ammoniumverbindungen der Formel II
- 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.
- 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.
Derartige Verbindungen sind bekannt oder nach bekannten Verfahren zugänglich, beispielsweise durch Umsetzen eines Fettamins oder einer Mischung von Fettaminen, wie beispielsweise Kokosfettamin mit Aethylenoxid und/oder Propylenoxid und anschliessendes Quaternieren des so erhaltenen Alkoxylats z.B. mit Dimethylsulfat (siehe z.B. H. Stache, Tensid-Taschenbuch; Carl Hanser Verlag 1981).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).
Als quaternäre Fettaminalkoxylate sind beispielsweise die folgenden genannt:
- 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;
- 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;
Aufgrund ihrer guten solubilisierenden Wirkung haben sich jedoch insbesondere solche kationischen Tenside der Formel II bewährt, die neben dem höheren Alkylrest R1 als Substituenten R2 einen Methyl-oder Aethylrest aufweisen und bei denen R3 für einen durch die Phenylgruppe substituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen steht; X hat die bereits angegebene Bedeutung. Auch Mischungen derartiger Verbindungen kommen in Frage, die beispielsweise erhalten werden, wenn man bei der Herstellung dieser Tenside von Fettamingemischen, wie z.B. Kokosfettamin, ausgeht.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.
Neben den rein anionischen bzw. kationischen Tensiden kommen als Solubilisierungsmittel auch Amphotenside in Betracht. Beispielhaft genannt sind die folgenden Verbindungen:
- 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.
- 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.
Als wirksam erweisen sich ferner Tenside aus der Gruppe der Aminoxide. Derartige Verbindungen zeigen je nach pH des Färbebades nichtionischen (neutrale bis basische Flotte) bzw. kationischen (saure Flotte) Charakter. In Frage kommen beispielsweise N-Dodecyl-N,N-dimethylaminoxid N-Myristyl-N,N-dimethylaminoxid N-Dodecyl-N,N-di-2-hydroxyethylaminoxid N-Hexadecyl-N,N-di-2-hydroxyethylaminoxid N-Hexadecyl-N,N-dimethylaminoxid N-Oleyl-N,N-di-2-hydroxyethylaminoxid N-Stearyl-N,N-di-2-hydroxyethylaminoxid N-Kokosfettsäureamidopropyl-N,N-dimethylaminoxid N-Talgfettsäureamidopropyl-N,N-dimethylaminoxid.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.
Als hydrotropierend oder solubilisierend wirkende nichtionische Tenside, die, wie erwähnt, im Gemisch mit anionischen Tensiden verwendet werden, kommen bevorzugt Umsetzungsprodukte von Aethylenoxid und/oder Propylenoxid mit
- 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).
Als derartige Alkoxylierungsprodukte seien im einzelnen genannt:
- 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.
- 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.
Auch Gemische der Umsetzungsprodukte nach a) bis g) untereinander sind verwendbar. Diese Gemische erhält man durch Mischen einzelner Umsetzungsprodukte oder direkt durch Alkoxylierung eines Gemsiches der den Umsetzungsprodukten zugrunde liegenden Verbindungen.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.
Als gesättigte und/oder ungesättigte Fettalkohole kommen für b) Dodecanol, Hexadecylalkohol, Palmitylalkohol, Stearylalkohol, Oleylalkohol oder Talgfettalkohole, Hexanol, 2-Aethylhexanol und Decanol in Betracht.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.
Als Alkylphenole für c) sind n-Butylphenol, tert.-Butylphenol, Tributylphenol, Octylphenol, p-Amylphenol, Hexalphenol, Isooctylphenol, Nonylphenol und Dodecylphenol zu nennen.As alkylphenols for c) n-butylphenol, tert-butylphenol, tributylphenol, octylphenol, p-amylphenol, hexalphenol, isooctylphenol, nonylphenol and dodecylphenol are mentioned.
Als Fettamin für e) kommen z.B. neben Stearylamin, Palmitylamin vor allem Oleylamin in Betracht.As fatty amine for e) come e.g. in addition to stearylamine, palmitylamine and especially oleylamine.
Für f) sind als gesättigte und/oder ungesättigte Fettsäuren z.B. Palmitinsäure, vor allem Stearinsäure und Oelsäure zu nennen.For f), saturated and / or unsaturated fatty acids are e.g. Palmitic acid, especially stearic acid and oleic acid.
Als besonders wirksam haben sich Umsetzungsprodukte der Gruppen c) und d) erwiesen und hier vor allem Hydroxybiphenyl-äthoxylate, wie z.B. Umsetzungsprodukte von 6 oder 8 Mol Aethylenoxid mit einem Mol o-Phenyl-phenol bzw. C4 bis c9 Alkylphenoläthoxylate, wie z.B. Umsetzungsprodukte von 6 bis 8 Mol Aethylenoxid mit einem Mol Butylphenol.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.
Die Aethylen/Propylenoxid-Umsetzungsprodukte sind bekannt oder können nach an sich bekannten Verfahren hergestellt werden (siehe z.B.: N. Schönfeldt, Grenzflächenaktive Aethylenoxid-Addukte; Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart; 1976).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).
Das Mischungsverhältnis von nichtionischem zu anionischem Tensid bewegt sich vorteilhaft zwischen 1:4 und 4:1. Dabei gelangen bevorzugt solche Tensidgemische zur Anwendung, die etwa doppelt so viel nichtionisches wie anionisches Tensid enthalten.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.
Eine besonders stark ausgeprägte solubilisierende Wirkung hat ein Gemisch, das als nichtionische Komponente ein Umsetzungsprodukt aus 1 Mol o-Phenyl-phenol oder 1 Mol tert.-Butylphenol und 6 Mol Aethylenoxid und als anionische Komponente ein Nonylphenol-diglykoläthersulfat enthält; ferner ein Gemisch aus einem kationischen und einem nichtionischen Tensid, beispielsweise ein Umsetzungsprodukt von 1 Mol o-phenylphenol + 6 Mol Aethylenoxid und ein Produkt der Formel
Was die Menge an Tensid bzw. Tensidgemisch betrifft, so werden, bezogen auf 1 Teil Dispersionsfarbstoff 5 bis 100, vorzugsweise 10 bis 80 und insbesondere 25 bis 45 Teile Tensid bzw. Tensidgemisch verwendet.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.
Die Mengen, in denen die Dispersionsfarbstoffe eingesetzt werden, können je nach der gewünschten Farbtiefe in weiten Grenzen schwanken, im allgemeinen werden Mengen von 0,01 bis 10 Gewichtsprozent eines oder mehrerer der genannten Dispersionsfarbstoffe, bezogen auf das Färbegut, verwendet.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.
Bei den nach vorliegendem Verfahren färbbaren hydrophoben Fasermaterialien handelt es sich in erster Linie um solche aus linearen hochmolekularen Estern aromatischer Polycarbonsäuren mit polyfunktionellen Alkoholen, beispielsweise aus Terephthalsäure und Aethylenglykol oder Dimethylolcyclohexan und Mischpolymere aus Terephthalsäure und Isophthalsäure und Aethylenglykol. Diese Materialien können, sofern die hierfür geeigneten Apparaturen vorhanden sind, in beliebigen Verarbeitungsstadien, z.B. in Form von Flocken, Kammzug, Garn, texturierten Fäden, Gewebe oder Gewirke, wie auch als Mischgewebe unter sich oder mit anderen Fasern vorliegen, beispielsweise als Mischgewebe aus Polyester/Polyamid oder Polyester/Baumwolle. Die Färbetemperatur für diese Materialien liegt vorzugseise bei 120 bis 150°C für das HT-Verfahren und bis zu 100°C für das Carrier-Verfahren.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.
Ferner kann nach dem erfindungsgemässen Verfahren Polyamidmaterial gefärbt werden, z.B. Polyamid-6, Polyamid-6,6 oder auch Polyamid 12. Die Färbetemperatur beträgt für diese Materialien vorzugsweise 98 bis 100°C.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.
Falls erforderlich, kann die wässrige Flotte übliche Färbehilfsmittel, vorteilhaft in kleinen Mengen, enthalten, wie Säuren, insbesondere eine organische niedere Monocarbonsäure, z.B. Ameisensäure oder Essigsäure, Puffersalze, wie Ammonsulfat oder Natriumacetat, Netzmittel, Emulgiermittel oder Antischaummittel.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.
Das Flottenverhältnis liegt üblicherweise bei 1:5 bis 1:50; die Färbezeit beträgt 5 bis 60 Minuten.The liquor ratio is usually 1: 5 to 1:50; the dyeing time is 5 to 60 minutes.
Das erfindungsgemässe Verfahren wird vorzugsweise in Zirkulationsapparaten folgendermassen durchgeführt: Der oder die unformierten Farbstoffe werden als wässrige Suspension, als Presskuchen oder auch in fester Form, beispielsweise Pulver, in einem mit der Färbeapparatur verbundenen Ansatzgefäss in ca. 50° bis 150°C heissem Wasser z.B. mittels eines Gemisches aus nichtionischem und anionischem Tensid gelöst bzw. solubilisiert. Durch Zugabe von Essigsäure und Natriumacetat stellt man den pH der Farbstofflösung auf einen Wert von 4 bis 5,5 ein. Hierauf wird durch Oeffnen eines Ventils die Farbstofflösung, gegebenenfalls nach Passieren eines Filters, in den Färbeapparat eingelassen, wo das zu färbende Polyestermaterial, das z.B. in Form eines Wickelkörpers, wie z.B. Muff, Kreuzspule, Färbebaum, oder als endlose Warenbahn vorliegt. Wenn nötig, wird das Substrat mit Dampf vorgewärmt. Unter weiterer stetiger Flottenzirkulation, vorteilhaft von innen nach aussen oder auch wechselseitig, z.B. mit 5-minütigen Perioden, wird das Färbebad mit einer Geschwindigkeit von ca. 1°C/Minute auf eine Temperatur von 120° bis 150°C, vorteilhaft 125° bis 135°C, aufgeheizt. Nach Erzielung der gewünschten Farbtiefe oder bei vollständiger Erschöpfung des Färbebades - Färbezeit ca. 1 Stunde - wird die heisse Flotte so weit abgekühlt, dass die Ware der Flotte entnommen werden kann und der mitgerissene Flottenanteil z.B. durch Absaugen oder Abschleudern auf weniger als 1 % (auf die ganze Flotte bezogen) herabgesetzt werden kann. Durch Wiegen der nassen Ware bestimmt man, wieviel der verbrauchten Färbeflotte herausgenommen wird und setzt der im Färbebad verbliebenene Flotte die entsprechende Menge an Wasser und Tensid wieder zu.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.
Der Farbstoffgehalt der Restflotte wird auf übliche Weise, vorzugsweise fotometrisch, ermittelt und die Restflotte anschliessend mit soviel Farbstoff versetzt, dass die für die nächste Färbung erforderliche Flottenzusammensetzung erreicht ist. Anschliessend kann der oben beschriebene Färbecyclus wiederholt werden.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.
Die folgenden Beispiele dienen der Veranschaulichung der Erfindung; Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente. Die Temperaturen sind in Grad Celsius angegeben.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.
Durch Wiegen des feuchten Substrates bestimmt man die Menge an mitgerissener Färbflotte (28,44 g); der Restgehalt an Farbstoff in der ausgezogenen Färbeflotte wird photometrisch bestimmt (2,46 mg).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).
In die ausgezogene Färbflotte gibt man anschliessend wieder so viel Wasser (28,25 g) und Tensid (0,184 g) wie durch die mitgerissene Restflotte entfernt wurden. Ausserdem wird so viel Farbstoff wieder zugesetzt, dass der ursprüngliche Gehalt von 28,44 mg wieder erreicht ist.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.
In diese Färbflotte gibt man erneut 10 g Polyestergewebe und wiederholt den oben beschriebenen Färbeprozess. Dies wird insgesamt 10 mal durchgeführt.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.
Die erhaltenen Färbungen sind egal und in der Farbstärke praktisch identisch. Der Gesamtausziehgrad an Farbstoff nach 10 Färbungen betrug über 96 %.The colorations obtained are irrelevant and practically identical in color strength. The total degree of dye exhaustion after 10 dyeings was over 96%.
Die folgende Tabelle 1 zeigt die jeweils eingesetzten bzw. ersetzten Mengen an Wasser, Farbstoff und Tensid sowie die fotometrisch bestimmte relative Farbstärke der erhaltenen Färbungen, bezogen auf die erste Färbung.
Durch Wiegen des feuchten Substrates bestimmt man die Menge an mitgerissener Färbflotte; der Restgehalt an Farbstoff in der ausgezogenen Färbeflotte wird photometrisch bestimmt (siehe Tabelle 2).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).
In die ausgezogene Färbflotte gibt man anschliessend wieder so viel Wasser und Tensid wie durch die mitgerissene Restflotte entfernt wurden. Ausserdem wird so viel Farbstoff wieder zugesetzt, dass der ursprüngliche Gehalt wieder erreicht ist (siehe Tabelle 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).
In diese Färbflotte gibt man erneut 10 g Polyestergewebe und wiederholt den oben beschriebenen Färbeprozess. Dies wird insgesamt 10 mal durchgeführt.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.
Die erhaltenen Färbungen sind egal und in der Farbstärke praktisch identisch.The colorations obtained are irrelevant and practically identical in color strength.
Tabelle 2 zeigt die jeweils eingesetzten bzw. ersetzten Mengen an Wasser, Farbstoff und Tensid sowie die fotometrisch bestimmte relative Farbstärke der erhaltenen Färbungen, bezogen auf die erste Färbung.
Die erhaltenen Färbungen sind egal und die jeweiligen Wiederholungen in der Farbstärke praktisch identisch.
werden in 100 ml einer wässrigen Flotte enthaltend 5 g/1 eines Carriers erhalten aus Einmischen von Dodecylbenzolsulfonsäure, Triäthanolamin, Diphenyl, Uniperol EL, Xylol, n-Hexanol und Aethylenglykol bei 60°C, in 1.2.4-Trichlorbenzol bei 78°C gelöst. Nach der Einstellung des pH-Wertes (siehe Beispiel 2) wurde die Temperatur der Flotte ca. in 1 Minute auf 100°C gebracht. Das Polyestersubstrat wurde 60 Minuten bei 100°C gefärbt. Man erhält ein egal rot gefärbtes Polyestermaterial.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.
Claims (22)
verwendet, 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.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
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).
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CH2049/85 | 1985-05-14 |
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EP86810208A Withdrawn EP0204656A1 (en) | 1985-05-14 | 1986-05-07 | Process for dyeing hydrophobic fibrous material |
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US (1) | US4715863A (en) |
EP (1) | EP0204656A1 (en) |
JP (1) | JPS61266684A (en) |
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ZA (1) | ZA863556B (en) |
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EP0455055A2 (en) * | 1990-05-01 | 1991-11-06 | Bayer Ag | Dyeing with reactive dyestuffs in standing baths following the exhaustion process |
DE112009001369B4 (en) | 2008-08-11 | 2022-02-03 | Golden Quimica Do Brasil Ltda. | Process for dyeing textiles made from cellulosic fibers and their blends and polyester and their blends with recycled dye liquors without carrying out subsequent cleaning treatments |
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EP0490814A1 (en) * | 1990-12-11 | 1992-06-17 | Ciba-Geigy Ag | Pastry to solid dyestuff-melt |
EP0555182B1 (en) * | 1992-02-06 | 1998-03-04 | Ciba SC Holding AG | Process for dyeing of natural or synthetic polyamide fibers |
US5427589A (en) * | 1993-03-03 | 1995-06-27 | Springs Industries, Inc. | Method for dyeing fibrous materials |
US5437690A (en) * | 1994-05-25 | 1995-08-01 | Springs Industries, Inc. | Method for dyeing fibrous materials and dye assistant relating to the same |
US6113656A (en) * | 1995-01-17 | 2000-09-05 | Milliken & Company | Method of dyeing low pill polyester |
US5540740A (en) * | 1995-09-06 | 1996-07-30 | China Textile Institute | Low temperature microemulsion dyeing process for polyester fibers |
US5830240A (en) * | 1996-10-23 | 1998-11-03 | Solutia Inc. | Fibers and textile materials having enhanced dyeability and finish compositions used thereon |
US5944852A (en) * | 1996-10-23 | 1999-08-31 | Solutia Inc. | Dyeing process |
EP0881324A3 (en) * | 1997-05-26 | 1999-12-01 | Bayer Ag | Process for simultaneously dyeing and removing brightening agents from synthetic fibers |
US6753956B2 (en) | 1998-05-27 | 2004-06-22 | Georgia Tech Research Corp. | Automated analysis system for a dyebath |
US6056790A (en) * | 1998-05-27 | 2000-05-02 | Georgia Tech Research Corp. | Method for automated dyebath reuse |
JP2008291384A (en) * | 2007-05-24 | 2008-12-04 | Teijin Techno Products Ltd | Method for dyeing wholly aromatic polyamide fiber |
CN101949099A (en) * | 2010-09-14 | 2011-01-19 | 冠宏股份有限公司 | Production technology of superfine-denier nylon fabric |
JP7140070B2 (en) * | 2019-07-24 | 2022-09-21 | 日東紡績株式会社 | Mixed dyed fabric and its manufacturing method |
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- 1986-05-09 US US06/861,676 patent/US4715863A/en not_active Expired - Fee Related
- 1986-05-14 JP JP61108726A patent/JPS61266684A/en active Pending
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EP0090272A2 (en) * | 1982-03-20 | 1983-10-05 | Hoechst Aktiengesellschaft | Process for the level-dyeing of polyester fibres by the exhaust method |
EP0143077A1 (en) * | 1983-11-15 | 1985-05-29 | Ciba-Geigy Ag | Process for dyeing hydrophobic fibrous material |
Non-Patent Citations (1)
Title |
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MELLIAND TEXTILBERICHTE, Band 65, Nr. 5, Mai 1984, Seiten 336-337, Würzburg, DE; T. PICKFORD: "Sparen mit Auffrisch-Folgebädern in der Färberei" * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0455055A2 (en) * | 1990-05-01 | 1991-11-06 | Bayer Ag | Dyeing with reactive dyestuffs in standing baths following the exhaustion process |
EP0455055A3 (en) * | 1990-05-01 | 1992-02-26 | Bayer Ag | Dyeing with reactive dyestuffs in standing baths following the exhaustion process |
DE112009001369B4 (en) | 2008-08-11 | 2022-02-03 | Golden Quimica Do Brasil Ltda. | Process for dyeing textiles made from cellulosic fibers and their blends and polyester and their blends with recycled dye liquors without carrying out subsequent cleaning treatments |
Also Published As
Publication number | Publication date |
---|---|
ZA863556B (en) | 1986-12-30 |
JPS61266684A (en) | 1986-11-26 |
KR860009186A (en) | 1986-12-20 |
US4715863A (en) | 1987-12-29 |
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