MXPA06009344A - Method of increasing depth of shade - Google Patents

Abstract

The present invention relates to a method of increasing the depth of shade of dyed natural or synthetic polyamide fibre materials, which comprises treating the fibre material - before, during or after dyeing - with an aqueous liquor comprising a polyamine, the polyamine being the product of reaction of a compound containing at least two primary amino groups with ethylene oxide, propylene oxide, 1,2-epoxybutane, a chloroalkylamine or an aromatic compound having at least one -COCI, -S03CI or -S02-Z substituent wherein Z is vinyl, 2-chloroethyl or 2-sulfatoethyl, or the product of reaction of a compound containing at least two primary amino groups with an unsaturated aliphatic cyano compound and subsequent hydrogenation.

Description

METHOD TO INCREASE THE DEPTH OF SHADOW The present invention relates to a method for increasing the shading depth of polyamide fiber materials, natural or synthetic, by treatment with specific polyamines, before, during or after dyeing. In the dyeing of polyamide fibers, especially polyamide microfibers, dark shades can be obtained by using acidic dyes, although at the expense of good washing properties. Conversely, good washing properties are obtained when dyeing with reactive dyes, although in this case, dark shadows are not easily obtained. It has now been found that dark shades, which have a high degree of firmness to washing, can be obtained if the polyamide fiber material is treated with a liquor comprising specific polyamines, before, during or after dyeing. The present invention relates to a method of increasing the shading depth of dyed, natural or synthetic polyamide fiber materials, this method comprises treating the fiber material, before, during or after dyeing, with an aqueous liquor, comprising a polyamine, this polyamine being the product of the reaction of a compound containing at least two primary amino groups with ethylene oxide, propylene oxide, 1,2-epoxybutane, a chloryalkylamine or an aromatic compound, which has at least a substituent of -COCÍ, -S02C1 or -S02-Z, wherein Z is vinyl, 2-chloroethyl or 2-sulfatoethyl, or the reaction product of a compound containing at least two primary amino groups with an unsaturated cyanoaliphatic compound and the subsequent hydrogenation. A large number of compounds, which contain at least two primary amino groups, are known and commercially available. The aliphatic, aromatic, araliphatic or cycloaliphatic di- or polyamines can be used to prepare the polyamines, which can be used in the method according to the invention. In this context, aromatic si- and polyamines are understood to include both carbocyclic and heterocyclic compounds. Similarly, the term "cycloaliphatic compounds" includes both carbocyclic and heterocyclic ring systems. Examples of suitable diamines are aliphatic diamines, such as, for example, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane. Other suitable di- or polyamines, aliphatic, are the dimeric, oligomeric or polymeric ethylene amines. Aromatic diamines are, for example, 4-aminobenzylamine, 4- (2-aminoethyl) -aniline and 1,4-bis (aminomethyl) benzene.

Suitable cycloaliphatic diamines are, for example, among others, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane and isophorone diamine. For the preparation of polyamines, which can be used in the method according to the invention, the primary amino groups of the diamines are reacted, according to methods known per se, with epoxides, such as ethylene oxide, propylene oxide or 1,2-epoxybutane, with chloroalkylamines, such as, for example, l-dimethylamino-2-chloropropane or l-dimethylamino-2-chloroethane, with chlorides of aromatic carboxylic acids, such as benzoyl chloride or 4-aminobenzoyl chloride, with aromatic sulfonic acid chlorides, such as benzene sulfochloride or 4-aminobenzene sulfochloride or with reactive aromatic sulphonyl compounds, such as, for example, 4- (2-sulfatoethylsulfonyl) -aniline . It is also possible first to add said compounds containing at least two primary amino groups to an unsaturated aliphatic cyano compound, such as, for example, acrylonitrile or methacrylonitrile and then hydrogenating the intermediate compound obtained. In the method, according to the invention, preference is given to the use, such as polyamine, of a compound of the formula (1) or (2): wherein A is a divalent, aliphatic, aromatic, araliphatic or cycloaliphatic radical, and the radicals Xi, X2, X3 and X4 are each, independently of the others, a divalent, linear or branched aliphatic radical, containing from 2 to 6 carbon atoms, and the radicals Ri to R8 are each, independently of the other hydrogen, Ci-Cealkyl or amino- (C2-C6) alkyl, or the reaction product of a compound of the formula (1) or (2), in which at least one of the radicals Ri to R8 is hydrogen, with the ethylene oxide, propylene oxide, 1,2-epoxybutane, a chloryalkylamine or an aromatic compound having at least one substituent of -COCÍ, -S03C1 or -S02-Z, wherein Z is vinyl, 2-chloroethyl or 2-sulfatoethyl.

Aliphatic radicals S in formulas (1) and (2) are, for example, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, decamethylene or alkylene, linear or branched, interrupted by one or more groups of -NH-, -N-alkyl- or -N-alkylene-NH2-. Suitable aromatic radicals A, of the formulas (1) or (2), are, for example, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-1. , 5-diyl, naphthalene-1,6-diyl and pyridine-2,4-diyl.

Suitable aliphatic radicals Xi, X2, X3 and X4 in formulas (1) and (2) are, for example, ethylene, propylene, trimethylene, propan-1,1-diyl or tetramethylene. The C? -C6alkyl, as one of the radicals Ri to Rg can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl or n-hexyl.

A, in formula (1) or (2), is preferably an aliphatic radical. Preferred polyamines are the compounds of formulas (1) or (2), in which A is C2-C? 0alkylene, or C4-Csoalkylene, linear or branched, interrupted by one or more groups of -NH-, -N-Ci- -Calkyl- or -NC? -Cealkylene-NH2-. Special preference is given to the compounds of formulas (1) or (2), wherein A is ethylene, tetramethylene, hexamethylene or a group of the formula (3): where x is a number from 1 to 20, and y is a number from 0 to 20, Y is a C2-C6alkylene radical, straight or branched, and R7 and R8 are, each independently of the other, hydrogen, Ci-C-alkyl or amino- (C2-Ce) alkyl. R7 and R3 in formula (3) are preferably hydrogen, methyl or ethyl. In the method, according to the invention, preference is also given to the use, such as polyamine, of a compound of the formula (1) or (2), in which Ri to R8 are hydrogen or methyl. In addition, preference is given to the compounds of the formula (1) or (2), in which X? R X2, X3 and X4 are ethylene, propylene, 1,1-propandiyl or trimethylene. In another preferred embodiment of the method, according to the invention, it is used, as the polyamine, the reaction product of a compound of the formula (1) or (2), wherein at least one of the radicals Ri to R8 is hydrogen , with a compound of formulas (4) to (9): wherein Z is vinyl, 2-chloroethyl or 2-sulfatoethyl, w is 0 or 1, Rn and Ri2 are each, independently of the other hydrogen or Ci-Cealkyl, z is 0 or 1, Y is C2-C6alkylene, preferably ethylene, propylene, trimethylene or tetramethylene, R13 and R14 are each, independently of the other halogen, -OR15, -NH2, -NHR? 5 or -NR? 5R? 6 in which R15 and RX6 are, each independently on the other a C? -C? 2alkyl radical, linear or branched, which is unsubstituted or can be substituted by one or more hydroxyl, amino, sulfo or C6-C24aryl groups. As the polyamine, special preference is given to the reaction product of a compound of the formula (1) or (2), in which at least one of the radicals Ri to R8 is hydrogen, with the compound of the formula (10) H2N-ff \ -s2 / 0-SO, 3H (10).

Especially preferred polyamines are the compounds of the formulas (100) - (109): The compounds of the formulas (1) and (2) are known or can be prepared according to known methods, for example by the reaction of the diamine of the formula H2N-A-NH2 with the appropriate aminoalkyl chlorides, of the formulas Cl-X? -NR? R2, C1-X2-NR3R4, Cl-Xx-NRsRe and C1-X4-NR7R8 in which A, X to X and Rx to R8 have the above definitions. The polyamines used in the method, according to the invention, are advantageously used independently of the liquor ratio, in an amount of 0.01 to 15% by weight, preferably 0.1 to 10% by weight and especially 0.5 to 7% by weight. % by weight, based on the weight of the polyamide fiber material. The treatment of the polyamide fiber material with the polyamine can be carried out after, during or, preferably, before dyeing. When the treatment of the polyamide fiber material with the polyamines is carried out during the dyeing process, the method, according to the invention, is advantageously carried out by adding polyamine to the dye liquor, in the aforementioned amount, and dyeing the fiber material in the usual way. However, preferably the treatment of the polyamide fiber material with the polyamines is carried out before dyeing. After the pre-treatment, the textile material is advantageously rinsed with water at room temperature or slightly elevated temperature.

Suitable material of polyamide fiber includes the natural polyamide fiber material, for example wool or silk, and synthetic polyamide fiber material, for example polyamide-6 or polyamide-6, 6, and fiber blends, by Example of wool / cellulose or polyamide / cellulose, blends of polyamide / wool fibers or blends of polyamide / elastane fibers. The material of is preferably a synthetic polyamide fiber material. The textile material can be used in any form, for example in the form of fibers, yarns, woven fabrics or knitted fabrics. The treatment of the polyamide fiber material with the polyamines is preferably carried out according to the depletion process, in this case, the liquor ratio can be selected within a wide range and is, for example, from 1: 4 to 1: 100, preferably from 1: 5 to 1:40. No special device is required. For example, the usual dyeing apparatus, such as open baths, handlebars, pattern or pallet, injection or circulation, etc. can be used. The process is advantageously carried out at a temperature of, for example, 20 to 130 ° C, preferably 50 to 120 ° C and especially 60 120 ° C. The treatment time can be, for example, 10 to 50 minutes and preferably 15 to 40 minutes. The pH of the liquor is generally from 7 to 13, preferably from 8 to 12.5 and especially from 10 to 12. The liquor may comprise, in addition to the auxiliary and, according to the invention, other customary additives, such as electrolytes, for example the sodium chloride or sodium sulfate, dispersants and wetting agents, pH regulators and antifoams. The dyeing is carried out using, for example, anionic dyes or reactive dyes, any customary anionic dye or reactive dye, as described, for example, in the Color Index, 3rd edition (1971) is suitable. Examples of anionic dyes include the sulfo group, which contains monoazo, polyazo, azo metal complexes, anthraquinone, phthalocyanine and formazan dyes. The anionic dyes used in the dyeing of the polyamide fiber material are either in the form of their free sulfonic acids or, preferably, in the form of their salts.

The dyes used in the dyeing of the polyamide fiber material may comprise other additives, for example sodium chloride or dextrin. The dyeing of the polyamide fiber material can be carried out in accordance with customary dyeing or printing methods, for example, according to the padding or depletion process. The dyeing liquors of the pastes being printed may comprise, in addition to water and dyes, other additives for example, wetting agents, defoamers, leveling agents or agents having an influence on the characteristics of the textile, for example, softeners, flame retardants or repellents of dirt, water and oil, and also water softeners and natural or synthetic thickeners, for example, alginates and cellulose ethers. The amounts in which the dyes are used in the dyeing baths may be within wide limits, depending on the required depth of the shade, in general, amounts of 0.01 to 15% by weight, especially 0.01 to 10% by weight. Weight, based on the material to be dyed, have proven to be advantageous. The dyeing with anionic dyes or reactive dyes is preferably carried out at a pH of 1 to 8, and especially of 2 to 7. The liquor ratio can be selected within wide ranges, for example from 1: 3 to 1:50. , preferably from 1: 5 to 1:30. The dyeing is preferably carried out at a temperature of 50 to 130 ° C and especially of 80 to 120 ° C. Following the method, according to the invention, dyeings of dyes are obtained, for example anionic dyes or reactive dyes, on polyamide fiber material, these dyes exhibit a substantial improvement in terms of the depth of the shadow, without the properties of firmness to wash or firmness to light, are adversely affected. The invention also relates to a textile auxiliary, comprising an aqueous solution of a polyamine, as defined above. The textile auxiliaries, according to the invention, can comprise, as other additives, for example, wetting agents, dispersants or pH regulators. The following Examples serve to illustrate the invention. The temperatures are given in degrees Celsius, the parts are parts by weight and the percentages refer to percentages by weight, unless otherwise specified. The parts by weight are related to the parts by volume, in the same ratio of kilograms to liters.

I. Preparation Examples 1. 1 174.3 g of pentaethylenehexamine, 5 drops of Triton B (40% aqueous solution of benzyltrimethylammonium hydroxide) and 0.2 g of hydroquinone were introduced into a 350 ml sulfonation flask and heated to 40 ° C. In the course of 70 minutes, 159.3 g of acrylonitrile were added in drops. The reaction is exothermic and the temperature was maintained at 40-45 ° C. After the addition, the reaction mixture was stirred for 90 minutes at 45 ° C and then for 3 more hours at 70 ° C. The product is then hydrogenated at 150 ° C and 80 bars in ethanol, using Raney nickel and ammonia as catalyst. After filtering off the catalyst, the ethanol was removed using a rotary evaporator. 275 g of a light brown, slightly viscous liquid were obtained. 1. 10.9 g of the pentaethylenehexamine and 20 g of water were introduced into a 100 ml sulfonation flask and heated to 40 ° C. Then, in the course of 40 minutes, a solution of 29.2 g of the 2-chloro-l-dimethylaminopropane hydrochloride and 20 g of water were added in drops. During the dropwise addition, a constant pH of 9.5 was maintained, adding 4N NaOH. After the addition was complete, the stirring was carried out for a further 3 hours at 80 ° C and at a pH of 9.5. 168 g of a thin, yellow, clear solution having a test value of about 17% was obtained. 1. 10.9 g of the pentaethylenehexamine and 20 g of water were introduced into a 100 ml sulfonation flask and heated to 40 ° C. Then, over the course of 40 minutes, a solution of 26.6 g of the 2-chloro-l-dimethylaminoethane hydrochloride and 20 g of water were added in drops. During the dropwise addition, a constant pH of 9.5 was maintained, adding 4N NaOH. After the addition was complete, the stirring was carried out for a further 3 hours at 80 ° C and at a pH of 9.5. 137 g of a thin, yellow, clear solution having a test value of about 21% was obtained. 1. 4 14.86 g of pentaethylenehexamine, having a molecular weight of 800, and 5 drops of Triton B (40% of an aqueous solution of benzyltrimethylammonium hydroxide) were placed in a 350 ml sulfonation flask and heated to 70 ° C. . Then, over the course of 70 minutes, a solution of 58.5 g of 4- (2-sulfatoethylsulfonyl) -aniline and 80 g of water was neutralized to a pH of 4.5 and filtered, then added in drops at 70 ° C. C. During the addition, the pH value fell. When the pH of 9.6 was reached, the pH remained consistent by adding 4N NaOH. After stirring for 2 hours at 70 ° C and a pH of 9.5, a cloudy solution was obtained. After cooling to room temperature, the organic phase was separated and collected. A clear, light brown, slightly viscous solution was obtained, which has a test value of 40%. 1. 5 34.4 g of polyethylenimine, having a molecular weight of 800, 49.1 g of water and 3 drops of Triton B, were introduced into a 380 ml sulfonation flask and heated to 70 ° C. After adding 58.5 g of 4- (2-sulfatoethylsulfonyl) -aniline, the mixture was stirred at 70 ° C for 2 hours. A cloudy brown solution of medium viscosity, which has a test value of 30% was obtained. 1. 6 6.3 g of N, N, N ', N' -tetrakis (3-aminopropyl) -1,4-diaminobutane, 7.5 g of water and 1 drop of Triton B were introduced into a 100 ml sulfonation flask and heated at 70 ° C. After adding 5.8 g of the 4- (2-sulfatoethylsulfonyl) -aniline, the mixture was stirred at 70 ° C for 2 hours. A clear, brown solution was obtained, which has a test value of 51%. 1. 7 174.3 g of pentaethylenehexamine, 5 drops of Triton B and 0.2 g of hydroquinone were placed in a 350 ml sulfonation flask and heated to 40 ° C. In the course of 70 minutes, 169.3 g of acrylonitrile were added in drops. The reaction is exothermic and the temperature was maintained at 40-45 ° C. After the addition, the reaction mixture was stirred for 90 minutes at 45 ° C and then for 3 more hours at 70 ° C. The intermediate product was then hydrogenated at 150 ° C and 80 bar, in ethanol, using Raney nickel and ammonia as a catalyst. After filtering off the catalyst, the ethanol was removed using a rotary evaporator. 21.5 g of the resulting product, 29 g of water and 5 drops of Triton B were introduced into the 100 ml sulfonation flask and heated to 70 ° C. After adding 29.2 g of the 4- (2-sulfatoethylsulfonyl) -aniline, the mixture was stirred at 70 ° C for 2 hours. A turbid brown, medium viscosity solution having a test value of 60% was obtained. 1. 8. Example 1.4 was repeated using 43 g of pentaethylenehexamine in place of the polyethylenimine. A light brown solution was obtained, which has a test value of 27%. 1. 9. 4.61 g of cyanuric chloride, 25 g of water, 25 g of ice and 1 drop of a dispersant were placed in a 350 ml sulfonation flask and stirred for 30 minutes at 0 ° C. In the course of about 35 minutes, a solution of 1.53 g of ethanolamine and 5.0 g of water was added in drops, so that the pH remained constant at 7.5. The mixture was stirred at 0 ° C for a further 90 minutes. A consistent pH of 7.5 was maintained by adding 1N NaOH. Then a neutralized solution was added at a pH of 4.0, and filtered, of 7.4 g of 4- (2-sulfato-ethylsulfonyl) -aniline and 20 g of water. The pH was kept constant at 5.0 and the temperature was slowly increased to 40 ° C. After about 6 hours, the reaction was complete. A solution of 43.1 g of 1 polyethyleneimine, having a molecular weight of 800, and 20 g of water were then added. After reacting at a pH of 0.5 for 3 hours, the solution was filtered. 225 g of a clear solution was obtained, which has a test value of 14%.

I.10 47.9 g of diethylenetriamine, 5 drops of Triton B and 0.1 g of hydroquinone onomethyl ether were placed in a 350 ml sulfonation flask and heated to 40 ° C. In the course of 60 minutes, 98.5 g of acrylonitrile were added in drops. The reaction is exothermic and the temperature was maintained at 40-45 ° C. After the addition, the reaction mixture was stirred for 90 minutes at 45 ° C, then for 90 minutes at 70 ° C and then for 90 more minuets at 90 ° C. The product was then hydrogenated in ethanol at 70 ° C and 60 bar, using Raney cobalt. After filtering the Raney cobalt, the ethanol was separated using a rotary evaporator. 148 g of a light yellow liquid was obtained. 19. 9 g of the resulting product, 47.5 g of water, 1 drop of Triton B and 17.4 g of the 4- (2-sulfatoethylsulfonyl) -aniline were introduced into a 350 ml sulfonation flask and heated to 70 ° C. The reaction mixture was stirred at that temperature for 2 hours. 86.2 g of water were added; The product solution was cooled, filtered and collected. 167 g of a clear, reddish-brown liquid was obtained. 1. 11 127 g of 1,6-diaminohexane, 5 drops of Triton B and 0.1 g of hydroquinone monomethyl ether were introduced into a 750 ml sulfonation flask and heated to 40 ° C. After the mixture melted, 232 g of acrylonitrile were added dropwise over the course of 80 minutes. The reaction is exothermic and the temperature was maintained at 40-45 ° C. After the addition, the reaction mixture was stirred for 90 minutes at 45 ° C, then for 90 minutes at 70 ° C and then for a further 90 minutes at 90 ° C. The product was then hydrogenated in ethanol at 70 ° C and 80 bars, using Raney cobalt. After separating the Raney cobalt by filtration, the ethanol was separated using a rotary evaporator. 32 g of a light yellow liquid were obtained. . 6 g of the resulting product, 47.5 g of water, 1 drop of Triton B and 17.4 g of the 4- (2-sulfatoethylsulfonyl) -aniline were introduced into a sulfonation flask and heated to 70 ° C. The reaction mixture was stirred for 2 hours at that temperature. 100.2 g of water were added, the product solution was cooled, filtered and collected. 180 g of a light brown liquid were obtained.

II. Application Examples II.1 Pretreatment and dyeing of microfibers (a) Pretreatment 5 g of a polyamide microfiber fabric (PA-Meryl microfibre 5-3101) were immersed, at room temperature, in a liquid containing 0.25 g of the product of Preparation Example I. a (5% of the active product, based on the weight of the fibers) and 45 g of water, adjusted to a pH of 11, using NaOH. The liquor was then heated to 98 ° C at a heating rate of 3 ° C / minute. After 30 minutes at 98 ° C, the liquor was cooled to 60 ° C at 3 ° C / minute. After pretreatment, the tissue was rinsed with water, first at 25 ° C then at 50-60 ° C and subsequently with dilute acetic acid (pH 6.0) at 25 ° C. (b) Dyeing The previously treated fabric was immersed, at room temperature, in 60 g of a liquor, adjusted to a pH of 3, using 80% acetic acid and containing 8% of Eriofast Red 2B (Ciba Specialty Chemicals) and 1 g / liter of Tinovetin JUN (wetting agent, Ciba Specialty Chemicals). The liquor was then heated to 98 ° C with a heating rate of 2 ° C / minute. After 60 minutes at 98 ° C, the liquor was cooled to 60 ° C at a rate of 3 ° C / minute. After staining, the fabric was first rinsed at 50 ° C with water, then for 20 minutes at 70 ° C with an aqueous solution of Na 2 CO 3 (1 g / liter), at 30-40 ° C with water and finally at room temperature environment with dilute acetic acid (0.5 ml of 80% acetic acid per liter) and again with water. II.2. Example II.1 was repeated using 1.50 g of the product of Preparation Example 1.2. II.3. Example II.1 was repeated using 1.20 g of the product of Preparation Example 1.3. II.4. Example II.1 was repeated using 0.62 g of the product of Preparation Example 1.4. 11. 5. Example II.1 was repeated using 0.50 g of the product of Preparation Example 1.5 11.6. Example II.1 was repeated using 0.30 g of the product of Preparation Example 1.6. II.7. Example II.1 was repeated using 0.30 g of the product of Preparation Example 1.7. 11.8. Example II.1 was repeated using 0.95 g of the product of Preparation Example 1.8. 11.9. Example II.1 was repeated using 1.70 g of the product of Preparation Example 1.9. 11.10. Example II.1 was repeated using 0.25 g of the product of Preparation Example 1.10. 11.11. Example II.1 was repeated using 0.25 g of the product of Preparation Example 1.11. Test Results: Dyeings were obtained that have dark shadows, without adversely affecting the firmness to washing and firmness to light.

Claims (16)

1. A method for increasing the shading depth of dyed, natural or synthetic polyamide fiber materials, this method comprises treating the fiber material, before, during or after dyeing, with an aqueous liquor comprising a polyamide, this polyamide is the product of the reaction of a compound, which contains at least two primary amino groups, with ethylene oxide, propylene oxide, 1,2-epoxybutane, a chloryalkylamine or an aromatic compound, having at least one substituent of - COCÍ, -S03C1 or -S02-Z in which Z is vinyl, 2-chloromethyl or ethyl 2-sulfate, or the reaction product of a compound containing at least two primary amino groups with an unsaturated aliphatic cyano compound, and the subsequent hydrogenation.

2. A method, according to claim 1, wherein the polyamide is a compound of the formulas (1) or (2): wherein A is a divalent, aliphatic, aromatic, araliphatic or cycloaliphatic radical, and the radicals Xi, X2, X3 and X4 are each, independently of the others, a divalent, linear or branched aliphatic radical, containing from 2 to 6 carbon atoms, and the radicals Ri to R8 are each, independently of the other hydrogen, Ci-Cealkyl or amino- (C2-C6) alkyl, or the reaction product of a compound of the formula (1) or (2), in which at least one of the radicals Ri to R8 is hydrogen, with the ethylene oxide, propylene oxide, 1,2-epoxybutane, a chloryalkylamine or an aromatic compound having at least one substituent of -COCÍ, -S03C1 or -S0-Z, where Z is vinyl, 2-chloroethyl or 2-sulfatoethyl.

3. A method, according to claim 2, wherein the polyamine is a compound of the formulas (1) or (2), wherein A is an aliphatic radical.

4. A method, according to claim 2, wherein the polyamine is a compound of the formulas (1) or (29, in which A is C2-C? 0alkylene or C4-Csoalkylene, linear or branched, interrupted by one or more groups of -NH-, -N-Ci-Cdalkyl- or -N-Cj- C6alkylene-NH2-

5. A method, according to claim 2, wherein the polyamide is a compound of the formulas (1) or (2), wherein A is ethylene, tetramethylene, hexamethylene or a group of the formula (3): where x is a number from 1 to 20 and y is a number from 0 to 20, Y is a Ci-Cealkylene radical and R7 and R8 are each independently of the other, C-C-alkyl or amino- (C2) hydrogen -C6) alkyl.

6. A method, according to claim 2, wherein the polyamine is a compound of the formulas (1) or (2), in which Ri to RQ are hydrogen or methyl.

7. A method, according to any of claims 2 to 5, wherein Xi, X2, X3 and X are ethylene, propylene, 1,1-propanediyl or trimethylene.

8. A method, according to claim 2, wherein the psiamine is the product of the reaction of a compound of the formulas (1) or (2), wherein at least one of the radicals Ri to R8 is hydrogen, with a compound of the formulas (4) to (9): wherein Z is vinyl, 2-chloroethyl or 2-sulfatoethyl, w is 0 or 1, Rn and R? 2 are each, independently of the other hydrogen or Ci-Cdalkyl, z is 0 or 1, Y is C2- Cealkylene, R13 and R14 are each, independently of the other halogen, -ORi5, -NH2, -NHR15 or -NR? 5R? 6 in which Ri5 and R6 are each, independently of the other, a radical C? -C12alkyl, linear or branched, which is unsubstituted or may be substituted by one or more hydroxyl, amino, sulfo or C6-C24aryl groups.

A method, according to claim 2, wherein the polyamine is the reaction product of a compound of the formulas (1) or (2), wherein at least one of the radicals Ri to R8 is hydrogen, with the compound of the formula (10):

10. A method, according to any of the preceding claims, wherein the polyamine is present in the liquor, in an amount of 0.01 to 15% by weight, based on the weight of the polyamide fiber material.

11. A method, according to any of the preceding claims, in which the fiber material is treated before dyeing.

12. A method, according to any of the preceding claims, wherein the treatment of the liquor comprising the polyamine, is carried out at a temperature of 20 to 130 ° C,

13. A method, according to claim 11, wherein the pretreatment is carried out at a pH of 7 to 13.

14. A method, according to any of the preceding claims, wherein the treatment with the liquor, which comprises the polyamine, is carried out according to the depletion process.

15. A method, according to any of the preceding claims, wherein the polyamide fiber material is in the form of microfibers.

16. A textile auxiliary, comprising an aqueous solution of a polyamide, according to claim 1.