DE3221951A1 - Dyeing with basic dyes - Google Patents

Abstract

Process for the dyeing, padding or printing of hydroxyl-containing textile material with a basic dye while simultaneously treating the textile material with a fixing agent, or subsequent treatment of the textile material dyed or printed with a basic dye with a fixing agent or an aftertreatment agent, characterised in that the fixing agent is a precondensation product or a mixture either A) of a compound of a reaction product of mono- or polyfunctional, primary or secondary amino groups with cyanamide, dicyandiamide, guanidine or bisguanidine, or of ammonia with cyanamide or dicyandiamide, it being possible for up to 50 mol per cent of the cyanamide, dicyandiamide, guanidine or bisguanidine to be replaced by dicarboxylic acids or mono- or diesters thereof, as long as the product A) contains free hydrogen atoms bound to nitrogen atoms, or B) of a quaternary polyalkylenepolyamine, with C) formaldehyde or a formaldehyde-releasing compound and/or D) an N-methylol compound of a urea, melamine, guanamine, triazinane, urone, carbamide or acid amide, if desired, together with E) a catalyst for crosslinking the N-methylol derivatives mentioned under D). a

Description

Coloring with basic dyes

The invention relates to a process for improving fastness properties in textile treatment, especially light and wash fastness, especially when dyeing and printing substrates containing hydroxyl groups with basic dyes.

The present invention relates to a method for dyeing, Padding or printing of textile material containing hydroxyl groups using a basic dye with simultaneous treatment of the textile material with a fixative or subsequent treatment with a basic dye dyed or printed textile material with a fixing agent or post-treatment agent, characterized in that the fixing agent is a precondensate or a mixture is either A) from a compound of a reaction product of mono- or polyfunctional, primary or secondary amino groups with cyanamide, dicyandiamide; Guanidine or Bisguanidine, or of ammonia with cyanamide or dicyandiamide, with up to 50 mole percent of cyanamide, dicyandiamide, guanidine or bisguanidine by dicarboxylic acids or whose mono- or diesters can be replaced as long as the product A) is free Contains nitrogen atoms bonded hydrogen atoms, or B) a quaternary polyalkylenepolyamine, with C) formaldehyde or a formaldehyde-releasing compound and / or D) a N-methylol compound of a urea, melamine, guanamine, triazinons, urons, carbamides or acid amide, optionally together with E) a catalyst for crosslinking the N-methylol derivatives mentioned under D).

Advantageous fixing agents are precondensates or mixtures of A) with D), B) with D) and A) with C), optionally together with D).

It is advantageous to implement in the presence of the catalyst E). Beneficial Fixatives are precondensates, i.e. those reaction products that are water-soluble are not gel-like and can be further networked.

The substrate can be used simultaneously with the basic dye and with treated with the fixative, e.g. in the same bath using the exhaust or padding process or in the same printing paste in the printing process. The fixative can also be used at can be used in an aftertreatment process, i.e. one with a basic Dye-colored or printed substrate. In both cases, the fixative the catalyst E) or it can contain the catalyst E) separately in a subsequent Step can be used. If the fixative is a precondensate and a catalyst contains, the catalyst can before, during or after the reaction in which the Precondensate is formed, are added; but the reaction is advantageous instead of in the presence of the catalyst.

Component A) is advantageously a reaction product of a polyalkylene polyamine of the formula RRN-t-Z X-LZ - NRR I, in which R independently of one another is hydrogen or a (l-1OC) -alkyl radical optionally substituted by hydroxy, (1-4C) -alkoxy or cyano, n is a number from 0 to 100, Z independently of one another when n is 0, (l-4C) -alkylene or (1-4C) -Hydroxyalkylene and X independently of one another when n is 1, -O-, -S- or -NR-, provided that at least one -NH- or -NH2- group is present, with cyanamide, Dicyandiamide, guanidine or bisguanidine, especially with dicyandiamide.

In preferred polyalkylenepolyamines of the formula I, each R is hydrogen pder (1-4C) -alkyl- or hydroxyalkyl, but advantageously hydrogen, n is a number from 0 to 30, especially 0 to 6 and especially 0 to 4, X independently of one another -NR-, especially -NH- or -N (CH3) - and Z independently of one another if n is zero is (1-4C) -alkylene, in particular 1,2-ethylene, 1,3-propylene or 1,3- (2-hydroxy) propylene.

Particularly preferred compounds of the formula I are diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, 2-aminoethyl-3-aminopropylamine, dipropylenetriamine or N, N-bis- (3-aminpropyl) .methylamine.

Particularly valuable components A) are reaction products of dicyandiamide with diethylenetri- or triethylenetetramine. Such products are in the PCT publication 81/02423 described. Likewise their conversion products with. N-methylol components D) to produce the corresponding precondensation products.

In component A) up to 50 mol percent, in particular up to 20 mole percent of dicyandiamide or another reactive with an amine Compound can be replaced by a dicarboxylic acid or its mono- or diester. Suitable acids are adipic, oxalic or terephthalic acid or, for example, their dimethyl esters.

Advantageous compounds of component B) have the repeating unit of the formula wherein R1 is a (1-4C) -alkyl radical, R2 is H or OH, and X2 - CH2 - CH2 - O - CH2 - CH2 - or - (CH2) b - mean, in which m stands for a number between 7 to 75, b stands for a number between 1 to 5 and 3 for an anion.

Particularly advantageous compounds of component B) have the repeating unit of the formula where R1 is a (1-4C) -alkyl radical, in particular methyl, and m 'is a number between 20 and 30, advantageously an average value of about 25.

The components B) are known and can be according to known Methods can be prepared, e.g., by reacting an N, N'-tetralkylalkylenediamine with a dichloroalkane, or a secondary amine with an epihalohydrin according to English patent 1,396,195.

Components B) and their reaction products with N-methylol components D) for the corresponding precondensates are in the English Offenlegungsschrift 2,084,597 A.

The invention also relates to a textile auxiliary containing components A) or B), C) and / or D) as individual components or the corresponding ones Precondensates and possibly E).

The reaction of a component A) with formaldehyde or a formaldehyde releasing compound, e.g. paraformaldehyde, can be beneficial at pH from above 4, preferably between 7 and 11 and at a temperature between 20 and 60 "C, especially between 40-50" C.

Formaldehyde can be in the form of a concentrated, e.g. 37% solution can be used. Between 1: 2-1: 6 formaldehyde is used per mole of component A) used based on the number of moles of amines used at the beginning.

Particularly suitable N-methylol compounds D) are those used as crosslinkers for cellulose known compounds, as they are from the PCT published patent application 81/2423 are known. Examples of such methylol compounds are acyclic or cyclic N-methylolureas, which can be etherified. Etherified derivatives contain alkyl ethers with, for example, 1-4 carbon atoms.

Urea derivatives with N-methylol are used as N-methylolureas groups in question, e.g. those of ethylene urea, propylene urea, acetylene urea, Dihydroxyäthylenurstoffs, urone or triazone derivatives, urethanes, carbamates, such as e.g. acrylic acids. Examples include: N, N'-dimethylolurea, N, N'-dimethylolurea-dimethyl ether, N, N'-Tetramethylolacetylenediurea, N, N'-Dimethylolpropylenurea, 4,5-dihydroxy-N, N'-dimethyloläthylenurea> 4,5-dihydroxy-N, N'-dimethylolethylene urea dimethyl ether> N, N'-dimethylol-5-hydroxypropylene urea, 4-methoxy-5,5-dimethylolpropyleneurea, N, N'-dimethylolethyleneurea, methoxymethylmelamine, Dimethylolalkanediol-diurethane, Dimethylolhexahydrotriazinone, Dimethylolurone, Dimethylol carbamates, etc. These compounds can be used alone or in admixture with one another can be used for the implementation.

Hydrolysis-resistant crosslinkers or reactant resins are particularly suitable, such as N-dimethylol or N-dialkoxymethyl derivatives of 4,5-dihydroxy or 4,5-dimethoxyethylene urea, 4-methoxy-5,5-dimethylpropyleneurea and N-dimethylol or. N-dialkoxymethyl derivatives of carbamates. N-methylol compounds are described, for example, in "Textilveredlung 3, No. 8, pp. 414-415 (1968).

Catalysts (E) are advantageously used for curing or

Crosslinking catalysts, such as those used in the refinement of cellulose are known, e.g. from PCT laid-open specification 81/2423. This is it acidic salts of polyvalent metals, such as nitrates, sulfates, chlorides or hydrogen phosphates of aluminum, magnesium or zinc, for example aluminum nitrate, sulfate, chloride or dihydrogen phosphate, magnesium or zinc nitrate, sulfate, -chloride or dihydrogen phosphate or mixtures of these salts, such as magnesium, aluminum and aluminum hydroxychloride, zinc nitrate and Aluminum sulfate, etc. Other suitable catalysts are zinc fluoroborate, zirconium oxychloride. The aforementioned catalysts in a mixture with neutral inorganic ones are also suitable water-soluble salts, especially with alkali metal sulfates, such as sodium or Potassium sulfate or alkaline earth sulfates or chlorides, such as those of calcium. Suitable are also combinations of acids and salts, such as phosphoric acid ammonium chloride, Calcium chloride and organic acids such as citric acid. More examples of catalysts Sodium bisulfate, the tetrafluoroborates of zinc and magnesium, are organic Hydrochlorides, e.g., 2-amino-2-methylpropanol hydrochloride. Organic acids, such as Citric acid, oxalic acid, maleic acid, glycolic acid, trichloroacetic acid and inorganic Acids such as phosphoric acid and hydrochloric acid can be used either alone or in combination be used with metal salts. Ammonium salts are also suitable catalysts inorganic acids such as ammonium nitrate, chloride, sulfate, mono- and diammonium phosphate, Ammonium oxalate, etc. The selection of the catalyst is largely dependent on the Selection of component A) and the methylol compound (D). Preferred catalysts are Al, Mg or Zn salts, especially Mg salts, especially MgCl2, optionally together with alkali, especially sodium sulfate, the optimal catalyst of the Choice of the methylol component (D) is dependent.

If A) or B) with D) in the absence of formaldehyde C) is used is, the preferred amount of A) or B) to D) and the catalyst F) is im Range from 1: 0.625-22: 0.025-6, advantageously in the range from 1: 1.75-7.5: 0.25-1.5, based on the dry weight of the active component. If the N-methylol component D) is used together with a precondensate of A) and formaldehyde C) to use them in a range of 50-200% parts by weight of A) + C). The amount of the catalyst is in these cases about 7.5-12.5 percent by weight of the dry weight from D).

The aftertreatment can be carried out in accordance with PCT Offenlegungsschrift 81/2423 e.g. on a padder or from a short or long liquor. In long Liquors (over 1:10) 1 to 10 g / l liquor, advantageously 2-5 g / l liquor, are used, in the case of short liquors or when impregnating on the padder are generally Quantities of 20 g / l to 100 g / l of the fixing agent are necessary. (All values refer to based on 100% active ingredient). One can also print one with a basic dye Post-treat textile material on the padder or from a short or long liquor.

The post-treatment according to the invention takes place after the fixation of the Dye, or the dyeing instead, the dyed, padded or printed Textile material can be dried in between or post-treated in a moist state can; the conditions should be chosen so that there is sufficient penetration the goods (pick-up) takes place. The precondensate is used together with the catalyst and optionally a methylol compound onto the substrate by known methods brought, or the substrate is impregnated, e.g. by padding, such as by patting, Spraying, dipping, foam application and similar application methods, such as from long or short liquor, and advantageously at room temperature. The fixation, or the Crosslinking of the textile auxiliary applied to the textile material takes place according to one of the known dry crosslinking processes. You can, for example, at Room temperature with a liquor containing the agent according to the invention, if appropriate impregnate with the addition of a plasticizer, leveling agent and / or handle agent, squeeze off and then through a shock drying process pre-drying and condensing in one operation at temperatures between 100-200 "C, especially between 140-180" C carry out. You can also predry at temperatures of 70-120 "C and then Crosslink at temperatures of 130-180 ° C for 2 to 8 minutes.

The amount of the auxiliary to be crosslinked is largely dependent on the color depth of the color to be fixed, i.e. to be post-treated. For staining, e.g. from 1/1 standard type thickness these amounts are 30-200 grams per liter of impregnation liquor, with a squeeze effect after impregnation of about 70-100% on dry weight the crowd.

About coloring. rijit a washable wet fastness improvement, To obtain sufficient crease resistance in cotton, you need about 70-140 9/1; in the case of regenerated cellulose, this amount should be increased by about 50% to 100-200 gll. In the case of mixed fabrics with a cellulose content, the amount is on the Calculate cellulose content.

The aftertreatment is mainly used for padded, colored with or printed natural or regenerated cellulose, e.g. cotton or viscose, carried out, or in the case of blended fabrics with synthetic fibers, e.g. with basic dyeable fibers, such as acrylonitrile or polyamide modified by acid groups or polyester fibers.

The textile material containing hydroxyl groups is made according to known methods colored with the basic dyes mentioned. The simultaneous dyeing and padding or printing, i.e. in a bath or in printing with components A), B), C) and / or 0), and optionally E) can by known methods, such as those when dyeing with basic dyes is customary to be carried out and in principle the same as in post-treatment, i.e. by padding, or from a long or short liquor or with the help of a printing paste. The fixation is also carried out according to known methods Methods.

Basic dyes can have one or more protonatable amino groups and / or one or more cationic groups, such as quaternary ammonium groups, and / or contain one or more cycloimmonimum groups, these cycloimmonimum groups Is part of the chromophoric system, e.g. in the case of the Fischerbase, in the case of the pyridine, quinoline, Isoquinoline, diazole, triazole, tetrazole, thiazole, thiadiazole, Benzothiazole, Benzoxazole or dehydrothio-toluidinsystemen, or cycloimmonium groups, which are bound to the chromophoric system directly or via a bridge, such as pyridine, Picoline, lutidine, quinoline, or isoquinoline.

The basic dyes can be of the mono- or polyazo series, if necessary May contain metal complex atoms and be of the 1: 1 or 1: 2 metal complex series, e.g. Cu> Cr, Co, Ni, Zn, Fe, Mn, also dyes of the anthraquinone, diphenyl or triphenylmethane, styryl, azomethine, hydrazone, nitro, phthalocyanine, naphthoquinone, Chi nophthalone series.

Mainly there are those dyes, which directly or via a Bridge link to an aromatic-carbocyclic or aromatic-heterocyclic Core, e.g. phenyl, naphthyl, pyridone, either as a diazo and / or coupling component one or more protonatable and / or one or more quaternary ammonium groups bound included. There are also azo compounds in question, which an aceto-acetyl-alkyl or arylamide coupling component included.

As a rule, basic dyes are free from sulfonic acid groups and are mainly suitable for dyeing and printing cellulose, but especially of polyacrylonitrile, paper, leather or of polyamide modified by acid groups or polyester fibers; but there are also such basic dyes, which in addition to a basic group carry a sulfonic acid group, e.g., basic phthalocyanine dyes or, for example, dyes in DOS-29 15 323, 30 30 196 and 30 30 197, respectively Claims and all the examples.

Protonable groups are primary, secondary or tertiary amino groups, in particular the alkylamino groups are suitable, or cyclic amines, such as morpholine, Piperidine, pyrrolidine, piperazine or aziridine.

Suitable basic dyes are those in the Couleur Index are named under CI Basic Dyes, (e.g. CI Basic Red 27). Furthermore, dyes such as they are covered by the claims and examples in the following patents are: German patent 852'588, 1 011 396, 1 014 519, 1 029 965, 1 061 010, 1064 661, 1 444 715, 1 444 716, 2 054 697, German Offenlegungsschriften 1 924 7702, 2 548 009, 2 061 964, 2627 680, 2 809 601, French patents 1 495 232, 1,541,429, 1,563,323, 2,000,639, British patents 576,270, 1,568,767 Belgian Patents 553 773, 633 447, the hydrazinium dyes described therein by the corresponding known ammonium dyes can be used.

Swiss patents 464 392, 534 773, 546 269, 547 337, 554 398, 554 399, 560 241, 563 430, European Offenlegungsschrift 41 040.

Further suitable basic dyes are those of the formula wherein A1, A2, A, X, Y, Z, n, R3, Me have the meanings given in DOS 31 17 127 and R1 is an aromatic or heterocyclic diazo or coupling component, with the additional proviso that if each A represents the radical -CONH- a) and each R3 represents (1-4C) -alkyl, R1 represents an aromatic or aromatic heterocyclic diazo component.

In this DOS 31 17 127 are in particular the dyes of the formulas III, IV, V and VI as well as the examples of particular importance.

Furthermore, according to the process according to the invention, basic Dyes are used that have a metal-free cationic or

protonic molecular weight of 400 to 1200, advantageously 450 to 1000 and especially 500-950 and after 90 minutes at cooking temperature, in electrolyte-free bath with a liquor ratio of 1:20 in 1/1 standard type strength dyed on mercerized cotton, a draw-up quotient (ratio between exhausted dye and dye in the bath) from 50 to 100S, or 70-100S, or $ 0 to 100%, or 90-100%. The 1/1 standard thickness is according to DIN 54,000, resp. ISO standard, RIOS / I, 1959, Part. 1.

Most dyes from the DOS correspond to such conditions 2 000 639, 2 548 009, 2 627 680, 2 915 323, 3 117 127, 3 030 196, 3 020 197, DP 1 621 702, Brit. Patents 576'270, FP 1 495 232, Europ. OS 41 040.

Dyeings and prints with basic dyes often show insufficient results Wet fastness and wash fastness.

The dye that is superficially bound to the cellulose is. of the Fiber gradually loosened through repeated washing processes. When bleeding into the The washing liquor can partially absorb the dye back onto the undyed cellulose.

There has been no lack of attempts to remedy these disadvantages, e.g.

Treatment of the dye and / or the fiber with formaldehyde.

The disadvantage of all methods used so far is that although an improvement in the abovementioned fastness properties is actually achieved can, the results are only temporary.

Those with the new polymeric reaction products or those according to the invention Means achievable wash-resistant improvements in the wet fastness of dyeings and printing on cellulosic textiles are repeated with alkaline and acidic, respectively Wash at temperatures between 40-90 "C, especially at and above 60" C extremely resistant. Wash liquors (liquor e.g. 1:50) with e.g. 5 g / l soap and 2 g / l soda calc. and repeated washing processes of 30 minutes each are tolerated without any problems. Pure Cellulose of all common types, as well as mixed fabrics of cellulose fibers with other native or synthetic fibers can be dyed or dyed so that they are washable and wet-fast. be treated afterwards.

The inventive treatment or aftertreatment of the colored or printed textiles, a fixation is achieved that has not been achieved before possible improvement of the wet fastness with it. At the same time a Cross-linking of the cellulose fibers (refinement), combined with reduced swelling achieved in aqueous and alkaline solutions. This achieves a faster one Drying, improved dimensional stability and increased crease resistance.

In the following examples, the parts mean part-e by weight, the Percentages by weight, the temperatures are given in degrees Celsius.

Preparation of fixatives A) 103 parts of diethylenetriamine and 84 Parts of dicyandiamide are heated to 110 °. As soon as this temperature is reached. an exothermic reaction takes place, with ammonia escaping. The temperature will slowly brought to 160 ° and left at this temperature for 6 hours no more ammonia escapes. The ammonia content is 34 parts.

The liquid reaction product is poured onto a metal plate and pulverized after cooling.

69.3 parts of this powder become 35 "warm water under steady conditions Stirring given. Thereupon 53.4 parts of 44.6% strength sulfuric acid with 45.0 parts are added Ice added so that the temperature does not rise above 48-50 °. Then one adds a further 69.3 parts of powder are added and the mixture is neutralized with 78.8 parts of 44.6 % sulfuric acid and 45.0 parts of ice, so that the temperature remains below 50 °. The yellow solution has a pH of 7.5 and is then spray-dried. Man receives a white powder. 18.3 dicyandiamide and 362.6 parts of a 50% solution of Dimethyloldihydroxyäthylenurea are together with 147.2 parts of water solved. 54.3 parts of magnesium chloride hexahydrate are added, followed by 72.6 parts of the above spray-dried powder, and the whole mixture stirred at 30 ° for so long until all solid components are dissolved and the solution has a pH of about 4.5 owns.

The mixture is then heated at 70 "for 45 minutes while Held for 1 1/2 hours at 70-74 ° and finally cooled, leaving a clear stable yellow solution is obtained.

B) - D) The reaction product of epichlorohydrin and dimethylamine is reacted with dimethyloldihydroxyethylene urea in the presence of magnesium chloride, as shown in Examples 1-3 of British Patent Application No. 2,084,597 described will.

E) The reaction product of 1,2-bis (dimethylamino) ethane and 2,2'-dichlorodiethyl ether is with dimethyloldihydroxyäthylenurea and magnesium chloride according to the example 4. of British patent application 2,084,597 implemented.

F) 103 parts of diethylenetriamine and 84 parts of dicyandiamide are added 110 ° heated. At this temperature an exothermic reaction begins and it escapes Ammonia. The temperature is brought to 1500 and the reaction at 1600 during Finished 6 hours. During cooling, the product solidifies; one pulverizes it. 156 parts of this powder are suspended in 400 parts of water and the mixture heated to 80-90 °.

The powder gradually dissolves and a solution is obtained with a pH value of about 11. After cooling to 50 °, 343 parts of a 35% aqueous Formaldehyde solution added dropwise.

The reaction mixture is then stirred for two more hours at 50 °, then cooled to room temperature and neutralized with hydrochloric acid, whereby one 930 parts of a clear yellow solution, which is about 30% (based on the dry weight) contains a precondensate of diethylenetriamine / dicyandiamide with formaldehyde.

G-I). The product is prepared according to F), but the pH values are established by adding hydrochloric acid to 8.6 or 4 before adding formaldehyde.

J) K). The solid product of diethylenetriamine and dicyandiamide will according to F). 90 parts of this powder are each in 330 parts of water dissolved and at a pH of 11 with 227 parts or 340 parts of a 35% strength aqueous formaldehyde solution implemented.

Example 1 Cotton is mixed with the dye by known methods of example 42 of British application 2,076,421 in metal-free form. The colored material is mixed with a solution containing 100 g / l of the fixing agent A) padded, and squeezed off to a liquor pick-up of about 80%. The impregnated The fabric is then placed on a tenter at a temperature of 175-180 " shock dried that the condensation time is about 30-45 seconds.

The aftertreated cotton dye has good wet, washing and and lightfastness. It can withstand repeated 60 "washes and even one hot wash. At the same time, the crease resistance is improved and you get a reduced one Swelling value of the cellulose fibers.

Example 2-5 Example 1 is repeated by mixing cotton with the The copper phthalocyanine dye of British Patent 1,185,791 colors. The aftercare is carried out with fixatives B) -E). Dyeings with good fastness properties are obtained.

Example 6 Cotton is made with the dye of Example 68 of the European Patent application 51 041 dyed, rinsed and dried. The dyed fabric will with a solution containing 30 g / l of fixative F (as 100% active ingredient), 50 g / l dimethyloldihydroxyethylene urea and 15 g / l MgCl2.6H20 padded and the solution with acetic acid adjusted to a pH value of 4 and then to a Wet pick-up of about 80% squeezed off. The impregnated fabric is after shock-dried on a tenter at a temperature of 1800, the Condensation time is 30-45 seconds. The fixed color is easy to wash and lightfastness.

Examples 7-10 Example 6 is repeated using the fixatives G) -K). You get similarly good results.

Example 11 Cotton is made with the dye of Example 80 of the European Patent application 51 041 dyed, rinsed and dried.

The dyeing is treated as described in Example 6, using a padding liquor containing 50 g / l of the fixing agent F), but 15 g / l MgCl2.6H20 without N-methylol component. The fixed dye is washfast and lightfast.

Example 12 The fabric dyed according to Example 1 is mixed with a liquor containing 70 g / l (as 100% active substance) of the fixative F) and 15 g / l MgCl2.6H20 padded and squeezed to a liquor pick-up of 80 ".

The fabric impregnated in this way is retained down to a residual moisture of 2-4% dried and then condensed at 1800 for 60 seconds. You get similar good fastness properties as in the previous examples.

Example 13 A cotton fabric is exhausted in an aqueous liquor in the presence of the dye from Example 1 of British Patent 1,547,900, 40 g / l of fixative A) and 0.25 g / l 80% acetic acid for 90 minutes Colored at boiling temperature so that a 2% coloration is obtained. The dyed fabric is rinsed and dried and has improved wash and lightfastness.

Example 14 A 100% zeliwool fabric is dyed according to the information in Example 13, but uses 80 g / l of fixative B) instead of 40 g / l A), a 3% coloration is obtained. The dyed fabric is rinsed and dried and has improved wash and lightfastness.

Claims (21)

Dyeing with basic dyes Patent claims 1. Method for Dyeing, padding or printing of textile material containing hydroxyl groups Use of a basic dye with simultaneous treatment of the textile material with a fixative or subsequent treatment of the colored with a dye or printed textile material with a fixing agent or post-treatment agent, characterized in that the fixing agent is a precondensate or a mixture is either A) from a compound of a reaction product of mono- or polyfunctional, primary or secondary amino groups with cyanamide, dicyandiamide, guanidine or Bisguanidine, or from Anunonlak with cyanamide or dicyandiamide, with up to 50 Mol percent of the cyanamide, diacandlamide, guanidine or bisguanidine due to dicarboxylic acids or their mono- or diesters can be replaced, as long as the product A) free, Contains hydrogen atoms bonded to nitrogen atoms, or B) a quaternary Polyalkylenepolyamine, with C) formaldehyde or a formaldehyde-releasing compound and / or D) an N-methylol compound of a urea, melamine, guanamine, triazinone, Urons, carbamides or acid amides, optionally together with E) a catalyst for the crosslinking of the N-Methylolderi mentioned under D) derivatives. 2. The method according to claim 1, characterized in that the with a basic dye dyed, padded or printed substrate with a Fixative is aftertreated. 3. The method according to.Anspruch 1, characterized in that the fixing agent is a precondensate or a mixture of A) with D), B) with D) or A) with C), if appropriate together with D). 4. The method according to claim 1, characterized in that the fixing agent contains a catalyst E). 5. The method according to claim 1, characterized in that the component A) a reaction product of a polyalkylenepolyamine of the formula RRN-t-Z-X + Z-NRR I, in which R independently of one another is hydrogen or an optionally substituted by hydroxy, (1-4C) -Alkoxy or cyano-substituted (l-10C) -alkyl radical, n is a number from 0 to 100, Z independently of one another if n> O, (1-4C) -alkylene or (1-4C) -hydroxyalkylene and X independently of one another if n> 1, -O-, -S- or -NR-, provided that at least one -NH- or -NH2- group is present, with cyanamide, dicyandiamide, Is guanidine or bisguanidine, especially with dicyandiamide. 6. The method according to claim 1, characterized in that the component A) a reaction product of dicyandiamide with diethylenetriamine or triethylenetetramine is. 7. The method according to.Anspruch 1, characterized in that component B) is the repeating unit of the formula wherein R1 is a (1-4C) -alkyl radical, R2 is H or OH, and X2 -CH2 - CH2 - O-CH2 - CH2 - or - (CH2) b - mean, in which m stands for a number between 7 to 75, b stands for a number between 1 to 5 and AO stands for an anion. 8. The method according to claim 1, characterized in that component B) is the repeating unit of the formula where R1 is a (1-4C) -alkyl radical, in particular methyl, and m 'is a number between 20 and 30, advantageously an average value of about 25. 9. The method according to claim 1, characterized in that the component D) N, N'-dimethylol-4,5-dihydroxy- or 4,5-dimethoxyethylene urea, N, N'-dimethylol-4-methoxy-5,5-dimethylpropylene urea, N, N'-dimethylol carbamate or its methyl or ethyl ether. 10. The method according to claim 1, characterized in that one magnesium chloride is used as catalyst E). 11. The method according to claims 1 to 6 and 9, characterized in that that a precondensate of a component A) with D) is used as the fixing agent. 12. The method according to claim 11, characterized in that the Pre-condensate is formed in the presence of a catalyst E). 13. The method according to claims 1 to 4 and 7 to 9, characterized in that that the fixative is a precondensate from components B) and D). 14. The method according to claim 13, characterized in that the Pre-condensate is formed in the presence of a catalyst E). 15. The method according to claims 1 and 11 to 14, characterized in that that the weight ratios of A) or B) to D and the catalyst E) in the range from 1: 0.625-22: 0.625-6. 16. The method according to claim 1, characterized in that the Fixing agent is a precondensate from components A) and C). 17. The method according to claim 16, characterized in that the Molar ratio of component A) to formaldehyde C) is in the range of 1: 2-6, calculated on the number of moles of the amines used in component A). 18. The method according to claim 1, characterized in that basic Dyes are used that have a metal-free cationic or protonic Molecular weight from 400 to 1200, advantageously 450 to 1000 and especially 500-950 own and after 90 minutes at boiling temperature, in an electrolyte-free bath with a Liquor ratio of 1:20 dyed in 1/1 standard type thickness on mercerized cotton, an absorption quotient (ratio between extracted dye and dye in the bath) from 50 to 100%, or 70-100%, or 80 to 100%, or 90-100%. 19. The method according to claim 1, characterized in that the Substrate is subjected to a heat treatment. 20. The method according to claim 1, that cotton is used. 21. The textile material treated according to claim 1.