EP0636742B1 - Process for modifying and dyeing of modified fibre materials - Google Patents

Description

In conventional dyeing processes for cellulose-containing substrates with anionic Dyes are used urea, electrolyte salts and alkali. Is cellulose only sufficiently alkalophilic in alkaline to react with reactive dyes react. Urea and electrolyte salts are needed for one Increase in the substantivity of the dyes. In the case of amino groups At neutral pH, fiber materials already suffice for using Reactive dyes to react. With direct and acid dyes you dye in weakly acidic pH with addition of electrolyte so that the anionic dyes are good pull on the substrate. The in the procedures mentioned after the end of Wastewater from the dyeing process contains large quantities of the above Auxiliaries and are often no longer justifiable from an ecological perspective.

It was therefore an object of the present invention to provide a method for dyeing (including printing) to find textile fiber materials, only with the smallest possible amount of electrolyte salts, such as sodium chloride and sodium sulfate, or completely without electrolyte salts and at the same time with only small amounts of an alkaline agent, such as sodium carbonate, Sodium hydroxide or water glass, or entirely without such an alkaline effective agent can be carried out. A dyeing process that is low in salt or completely without salt and at the same time only using small amounts Amounts of an alkaline agent or entirely without one alkaline auxiliary can be carried out, is therefore particularly at the dyeing process using fiber-reactive dyes advantageous. Because in addition to the fixing process of the fiber-reactive dye in the aqueous, often strongly alkaline dyeing liquors can additionally Hydrolysis reactions of the fiber-reactive dye take place, which is why Fixation on the fiber material is not complete. For this reason following the dyeing process must be partly extensive and time consuming washing and rinsing processes are carried out like that multiple rinses with cold and hot water and one Excess neutralization treatment in between Alkali on the colored material and further, for example, one Cook with a non-ionic detergent to ensure good fastness to ensure the coloring.

It is already known (see text. Res. J. 17 (1947), 645; loc. Cit. 23, 522 (1953) and 39, 686 (1969) and EP-A-0 546 476) that cellulose with Modify aminoethylsulfuric acid via the stage of ethyleneimine and can then dye with direct dyes. Further work showed later (see Melliand Textilber. 6, 641 (1964)) that such modified fibers can also be dyed with monochlorotriazine dyes. The one in these known methods used for the treatment of cotton alkaline However, the active substance solutions were 25% sodium hydroxide in all cases, and the liquor absorption of the impregnated fabric was more than 100% by weight. After a long predrying, the fixation was carried out via several minutes at temperatures above 100 ° C. This procedure for Modification of cotton is extremely uneconomical; furthermore it is not possible to dye the textile fabric treated in this way and uniform Generate goods images.

GB-A-979,279 describes a method for improving color fastness of cellulose textiles in the presence of primary and / or secondary amines and one bifunctional crosslinking agent. Examples of such crosslinking agents are dicarboxylic acid esters such as dimethyl oxalate, diethyl tartrate and urea oxalate.

From DE-A-3 831 139 and DE-A-3 709 766 it is known that one can Pretreatment of textiles with alkylated polyethyleneimines to uneven Colorings come with a denim effect. The toxicity of this alkylating agent used is out of the question and a complete, residue-free removal of these agents is essential.

CH-A-747 954 and CH-A-574 536 describe reaction products of Polyethyleneimine with dicyandiamide or cyanamide and their fixation. DE-A-2 214 966 also pretreates with polyimines and polyamines, but immediately afterwards dyed with fiber-reactive dyes. Here it comes in In the case of pull-out dyeing to undesirable flocculation, since the polyamines and polyimines can be detached from the fiber and with the dyes then react and flocculate.

With the present invention it has now been found that in Surprisingly, with anionic textile dyes, especially those with fiber-reactive groups, without or with little use of alkaline agents and electrolyte salts level and strong colorings with good fastness properties when you get a textile material Fiber material used, which is pretreated by a polymeric compound and is modified, the at least one secondary or primary amino group contains, and by a suitable bifunctional connection on the fiber cross-linked and thus insoluble in water.

A

eine chemische Bindung oder eine Methylengruppe,

X

eine Gruppe der Formel (-CH₂-)_m, -CH₂-NR¹-CH₂- oder -CH₂-O-CH₂-, worin m eine Zahl von 1 bis 6, vorzugsweise 1 bis 4, und R¹ Wasserstoff oder C₁-C₄-Alkyl ist, und

n

eine Zahl von 2 bis 1000, vorzugsweise 10 bis 500, ist,

wobei gleiche oder verschiedene der als X bezeichneten Gruppen in beliebiger Reihenfolge verknüpft sein können,
sowie einem bifunktionellen Vernetzungsmittel der Formel (II) Z-Q-Z worin

Z

eine Gruppe der Formel -CHO oder -CH(OR¹)₂, worin R¹ jeweils gleich oder verschieden ist und Wasserstoff oder C₁-C₄-Alkyl bedeutet und

Q

eine Phenylengruppe oder eine Gruppe der Formel (-CH₂-)_a, worin a eine Zahl von 0 bis 4, vorzugsweise 0 bis 2, ist,

in Kontakt bringt.The present invention relates to a process for modifying fiber materials, characterized in that the fiber material is treated with a polymer of the formula (I) containing at least one primary or secondary amino group. (-AXA-) _n wherein

A

a chemical bond or a methylene group,

X

a group of the formula (-CH ₂ -) _m , -CH ₂ -NR ¹ -CH ₂ - or -CH ₂ -O-CH ₂ -, where m is a number from 1 to 6, preferably 1 to 4, and R ¹ Is hydrogen or C ₁ -C ₄ alkyl, and

n

is a number from 2 to 1000, preferably 10 to 500,

the same or different groups referred to as X can be linked in any order,
and a bifunctional crosslinking agent of the formula (II) ZQZ wherein

Z.

a group of the formula -CHO or -CH (OR ¹ ) ₂ , in which R ^{1 is in} each case the same or different and is hydrogen or C ₁ -C ₄ -alkyl and

Q

a phenylene group or a group of the formula (-CH ₂ -) _a , in which a is a number from 0 to 4, preferably 0 to 2,

brings in contact.

The number of primary or secondary amino groups in the polymer of the formula (I) is preferably 10 to 500.

The distance between the amino groups in the polymer can be determined by intervening Alkylene or alkyleneoxy groups can be varied within a wide range. Preferred polymers of the formula (I) are polyethyleneimines with a molecular weight from 500 to 2000 and polypropyleneimines with a molecular weight of 500 to 1000.

The preferred bifunctional crosslinking agent of the formula (II) is glyoxal. Dialdehydes can too present as acetals or hemiacetals.

Fiber materials include natural and synthetic fiber materials understood that contain hydroxyl and / or carbonamide groups, such as silk, Wool and other animal hair as well as synthetic polyamide fiber materials and Polyurethane fiber materials, for example polyamide-4, polyamide-6 and Polyamide-11, and in particular fiber materials that make up the main body of the contain α, β-glucose, such as cellulose fiber materials, for example cotton, Hemp, jute and linen, and their regenerated derivatives, such as viscose silk and cellulose, or mixtures of such fiber materials.

a) eine Mischung eines Polymers der Formel (I) und einer Verbindung der Formel (II) in wäßriger oder wäßrig-alkalischer Lösung mit dem Fasermaterial in Kontakt bringt oder

b) zuerst ein Polymer der Formel (I) mit dem Fasermaterial in Kontakt bringt und anschließend mit oder ohne Zwischentrocknung eine Verbindung der Formel (II) auf das Fasermaterial aufbringt.

The modification of the fiber material according to the invention takes place in such a way that

a) a mixture of a polymer of formula (I) and a compound of formula (II) in aqueous or aqueous alkaline solution in contact with the fiber material or

b) first bringing a polymer of formula (I) into contact with the fiber material and then applying a compound of formula (II) to the fiber material with or without intermediate drying.

a) eine Mischung eines Polymers der Formel (I) und einer Verbindung der Formel (II) in wäßriger oder wäßrig-alkalischer Lösung mit dem Fasermaterial vor dem Färben in Kontakt bringt oder

b) zuerst ein Polymer der Formel (I) mit dem Fasermaterial in Kontakt bringt und anschließend mit oder ohne Zwischentrocknung eine Verbindung der Formel (II) auf das Fasermaterial aufbringt, wobei gegebenenfalls der Farbstoff zusammen mit der Verbindung der Formel (II) oder in einem anschließenden separaten Schritt aufgebracht wird. Das Aufbringen der Behandlungsmittel und des Farbstoffs auf das Fasermaterial erfolgt durch ein Ausziehverfahren oder Klotzverfahren, durch Versprühung oder mit Hilfe eines Ink-Jet-Verfahrens.

The invention further relates to a method for dyeing the fiber material modified according to the invention.
The term "dyeing" is understood to mean both dyeing processes and processes for printing fiber materials. The modification and dyeing of the fiber material takes place in such a way that

a) a mixture of a polymer of formula (I) and a compound of formula (II) in aqueous or aqueous alkaline solution in contact with the fiber material before dyeing or

b) first bringing a polymer of formula (I) into contact with the fiber material and then applying a compound of formula (II) to the fiber material with or without intermediate drying, the dye optionally together with the compound of formula (II) or in one subsequent separate step is applied. The treatment agents and the dye are applied to the fiber material by means of an exhaust process or block process, by spraying or with the aid of an ink jet process.

The compounds of formulas (I) and (II) and the dye are dissolved in water, optionally the aqueous solution is a small amount of alkali, electrolyte or other conventional additives, such as. B. wetting agents (surfactants) added. The concentration of the polymers of the formula (I) in the aqueous treatment solution is advantageously 1 to 30% by weight, preferably 2 to 20% by weight, and that of the compounds of the formula (II) 0.5 to 20% by weight , preferably 1 to 10% by weight. In order to prevent the compounds of the formulas (I) and (II) from reacting too quickly with one another, the solution can be cooled and / or made alkaline. This is conveniently done with Na ₂ CO ₃ or NaOH. The concentration of the alkali in the treatment solution is in the range from 0 to 20% by weight, preferably 0 to 5% by weight, and depends on the stability of the solution to be achieved. The lower the content of compounds of formula (I) and (II) in the solution, the more stable the mixtures are even without additives.

The treatment solution and the dye solution are expedient at temperatures between 10 and 100 ° C, preferably between 20 and 50 ° C, brought into contact with the fiber material.

The fiber material that is modified according to the invention as well as in the modified form used in the dyeing process can be used in all Processing conditions, such as yarn, flake, sliver and piece goods (Tissue), and also in a mixture with other fiber materials, such as for example in the form of cotton / polyester fiber materials and in the form of blended fabrics with other fiber materials.

The fiber material is impregnated with an alkaline aqueous solution Solution by introducing the fiber material into this solution or by Padding (padding), the impregnated material is then from excess liquor squeezed out, so that the intake of this aqueous, alkaline solution between 50 and 120 wt .-%, preferably between 70 and 100 wt .-%, based on the fiber material. Usually the impregnation takes place (by padding, splashing or treatment in the Solution itself) at a temperature between 10 and 60 ° C, preferably at a temperature between 15 and 30 ° C. When spraying the solution on the Fiber material, usually at a temperature between 10 and 40 ° C takes place, a liquid intake of preferably between 10 and 50 wt .-% selected.

After impregnating the fiber material on one of the above the impregnated material can be dried in various ways, whereby a temperature between 20 and 100 ° C. is preferred for drying between 30 and 50 ° C. As a rule, drying takes place through Hot air treatment for 0.5 to 3 minutes. The fiber material can but also directly after the reaction with the compounds of the formulas (I) and (II) processed wet.

The customary aftertreatment of the modified fiber material is carried out by Rinse with cold and hot water and if necessary by treating in an aqueous bath containing a small amount of a surfactant Removal of only superficially adhering compounds from the fiber material and possibly subsequent drying. In the dyeing process should be as possible neutral reacting fiber material can be used.

The dyeing of such modified fiber materials according to the invention is carried out analogously to the known dyeing methods and printing processes for dyeing or Printing of fiber materials with water-soluble textile dyes, such as anionic dyes, especially fiber-reactive dyes, and under Application of the temperature ranges known for this and usual amounts of dye, but with the exception of the invention that for the dye baths, padding liquors and printing pastes of the invention Dyeing process an addition of alkaline compounds, such as usually used to fix fiber-reactive dyes, such as for example sodium carbonate, potassium carbonate, sodium hydroxide solution and water glass, can be largely or entirely excluded and the further the usual addition of electrolyte salts, especially migration of the dye on the fiber should increase, not or only to a small extent, for example up to a maximum of 10 g per liter of dye bath or dye liquor, is required. The dyeing process according to the invention is carried out accordingly within a pH range between 4 and 8, preferably between 4.5 and 7.

Dyeing processes that can be used according to the invention are for example the different extraction processes, such as dyeing on the Jigger and on the reel runner or dyeing from a long or short fleet, the Dyeing in jet dyeing machines, dyeing using the block-cold-dwell process or after a block-hot steam fixing process. When pulling out can you work in the usual fleet ratio of 1: 3 to 1:20. The Dyeing temperature can be between 30 and 90 ° C, preferably it is a temperature below 60 ° C; as evidenced from the above application of the block cold dwelling method according to the invention, that is Dyeing is also advantageously possible at room temperature (10 to 30 ° C).

In the dyeing process according to the invention, the use of customary, often necessary dyeing aids, such as surfactants (wetting agents), Thiourea, thiodiethylene glycol, thickeners, leveling agents, Aids that determine the solubility of dyes in the concentrated padding liquors improve, such as condensation products from formaldehyde and optionally alkyl-substituted naphthalenesulfonic acids, and in particular Urea, to be omitted entirely or to a considerable extent. Usually the modified fiber material according to the invention can only be found under Use of a purely aqueous dye solution, in which only extremely small amounts of electrolyte salts (such as sodium chloride and sodium sulfate) that are contained, dissolved, colored as adjusting agents in the dye powders will.

The present invention can also be advantageous for single bath dyeing processes for dyeing mixtures of cellulose and polyester fibers find if, in addition, a disperse dye used for dyeing Polyester fiber materials is suitable with a reactive dye in the common dye bath is used. Because many disperse dyes are sensitive to alkali, especially when using higher temperatures, they can be used for single-bath dyeing of cellulose / polyester mixed fiber materials not used because the application of high Temperatures in the alkaline bath when dyeing the polyester fiber through the Disperse dye leads to damage to the disperse dye. The However, the present invention makes it possible to dye free of alkali, so that in the aqueous, alkali-free dye liquor first at low temperature, such as for example at a dyeing temperature between 30 and 80 ° C, the Reactive dye can be fixed on the modified fiber material and then the polyester fiber with the disperse dye in the usual way at temperatures above 100 ° C, such as between 110 and 140 ° C, is colored.

For the dyeing methods according to the invention, all water-soluble ones are preferred anionic dyes, preferably one or more sulfo- and / or Have carboxy groups and the optionally fiber-reactive groups may contain, suitable. You can save the class of fiber reactive Dyes of the class of azo development dyes, the direct dyes, the Vat dyes and acid dyes belong to it, for example Azo dyes, copper complex, cobalt complex and chromium complex azo dyes, Copper and nickel phthalocyanine dyes, anthraquinone, Copper formazane, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and Stilbene dyes can be. Such dyes are numerous in the Literature described, for example in EP-A-0 513 656, and the expert familiar on all sides.

The colorings of the modified obtained in the manner according to the invention Cellulose fiber materials require after removal from the dyebath or after the fixation of the dye on the substrate is finished, no more Post-treatment, especially no complex post-treatment process including a wash. As a rule, a normal one or one is sufficient repeated rinsing of the colored substrate with warm or hot and optionally cold water, which may be a nonionic Can contain wetting agents or a fiber-reactive aftertreatment agent, such as for example, condensation products from one mole of cyanuric chloride and two Moles of 4- (β-sulfatoethylsulfonyl) aniline, from equivalent amounts of cyanuric chloride, 4- (β-sulfatoethylsulfonyl) aniline and 4,8-disulfo-2-amino-naphthalene or from equivalent amounts of cyanuric chloride, 4-sulfo-aniline and 4,8-disulfo-2-aminonaphthalene. The use of a fiber-reactive aftertreatment agent is recommended if the fiber material modified according to the invention only was stained in slight depths of color or a dye was used which does not have satisfactory fiber reactivity. In these cases are still there are sufficient dye-reactive spots on the modified fiber, which for example with other dyes in contaminated with these dyes Rinsing baths are able to react. Through this after-treatment still active areas of the fiber modified according to the invention deactivated, and one also obtains with one used in a technical process Dyes contaminate the rinse water to give the originally desired clear Coloring. In addition there is a final cooking treatment of the colored substrate not with a washing solution to improve the fastness properties required.

In cases where there is an oversupply of dye such. B. when printing, for Bleeding white, non-colored goods can come after the Fix diethanolamine or ammonia in the wash solution. This improves the Washing properties (staining) of the goods, as these additives make them too clear less soiling effects.

Compared to the known methods of modifying cotton to refrain from using alkali; the same can be said Reduce fixing times drastically. Furthermore, the invention allows Process for dyeing fiber materials modified according to the invention especially in the exhaust process, the one-time dyeing of Polyester / cotton blended fabrics with reactive and disperse dyes, without causing damage to the disperse dye, precisely because Alkali is not present in this single bath dyeing process.

The method according to the invention is ecological and economical Aspects advantageous because the impregnation and dyeing in can be carried out in a simple manner and the polymers of the formula (I) if they not in the same solution with the compound of formula (II) from which aqueous solution can be concentrated and regenerated.

The present invention also relates to a Modified fiber material according to the invention and a modified and dyed fiber material according to the invention.

Furthermore, the invention relates to the use of such above defined polymers and crosslinking agents containing amino groups Modification of fiber materials, especially with the aim of making them Dyeing with water-soluble, anionic dyes with little or no To be able to use amounts of electrolyte salts and alkaline agents.

The following examples serve to illustrate the invention. The one in it The parts mentioned are parts by weight that give percentages Percentages by weight, unless otherwise noted. Obtain parts by weight to parts by volume like kilograms to liters. "MG" means middle Molecular weight.

example 1

a) A fabric made of mercerized and bleached cotton is with a Dissolve 10% polyethyleneimine (MW: 1000) in water Impregnated for 5 minutes. Then the fabric is on Squeezed 80% liquor pickup and into a solution of 2% glyoxal immersed in water for 5 minutes. The diving procedure is based on to ensure a good mix of the fleets, otherwise irregularities result. After the diving process, the temperature is increased to 80% Squeezed liquor pickup and then dried at 45 ° C.

b) The modified cotton fabric is dyed analogously to a conventional exhaust dyeing process: 100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution, the 2 parts of a 50% electrolyte-containing (predominantly sodium chloride) dye powder from EP-A-0 061 151 known dye of the formula

in the form of the alkali metal salt (ie 1 part of this dye and 1 part of the electrolyte) dissolved, the dyebath is heated to 60 ° C within 30 minutes, and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then rinsed with cold and hot water, the hot water may contain a commercially available wetting agent, and if necessary, it is rinsed again with cold water and dried.

A strong, uniformly colored orange color is obtained, which is good Possesses general realities.

Example 2

a) A fabric made of mercerized and bleached cotton is with a Solution of 5% polyethyleneimine (MG: 2000) in a foulard with 80% Padded fleet pickup. Then the tissue is covered with a Solution of 2% glyoxal in water padded. The tissue thus obtained is dried at 30 ° C in a circulating air cabinet.

b) The modified cotton fabric is made according to a pad cold-dyeing process colored. For this purpose, an aqueous dye solution, which in 1000 parts by volume 20 parts of that described in Example 1 Dye powder, 100 parts of urea and 3 parts of a commercially available contains non-ionic wetting agent dissolved, by means of a padder with a liquor intake of 80%, based on the weight of the Fabric, applied to the fabric at 25 ° C. The one with the Dyeed fabric padded fabric is wound onto a dock, in wrapped in a plastic sheet and kept at 20 to 25 ° C for 16 hours left and then with cold and with hot water, the may optionally contain a commercially available wetting agent, and if necessary, rinse again with cold water and dried.

A strong, uniformly colored orange color is obtained, which is good General fastness properties, especially good rub and light fastness properties.

Example 3

a) A fabric made of mercerized and bleached cotton is with the Mixture of a solution of 3% polyethyleneimine (MW: 1000) and 1% Glyoxal in water padded with 80% liquor absorption. The fabric thus obtained is dried at 60 ° C.

b) The fabric modified in this way is dyed according to a conventional padding process, for example analogously to the procedure of Example 2. For this purpose, an aqueous dye liquor containing 28 parts of 1000 parts by volume of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the dye of the formula known from Belgian Patent No. 715,420

and contains 3 parts of a commercially available nonionic wetting agent dissolved, by means of a padder with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 20 ° C. The padded fabric is then wound up on a dock, wrapped in a plastic film and left at 30 to 40 ° C for eight hours and then with cold and with hot water, which may optionally contain a commercially available nonionic surfactant, and optionally again with cold water washed and dried.

It becomes a strong, uniformly colored yellow color with the usual get good fastness properties.

Example 4

a) A fabric of mercerized and bleached cotton is mixed with a mixture of a solution of 10% polyethyleneimine (MW: 500), in which 4% Na ₂ CO ₃ was previously added, and 4% glyoxal in water in a padder with 80% liquor absorption padded. The tissue thus obtained is dried at 50 ° C. in a circulating air cabinet.

b) The modified, dried material is dyed in a conventional exhaust process. For this purpose, 10 parts of this material in 200 parts by volume of an aqueous dye solution, the 0.2 parts of a 50% electrolyte-containing dye powder of the dye of the formula known from German Offenlegungsschrift No. 24 12 964

contains dissolved. The dyeing takes place at 60 ° C. for 60 minutes. The dyed fabric is then rinsed with cold and warm water at 30 to 35 ° C, which may optionally contain a commercially available nonionic surfactant, then washed again with cold water and dried if necessary.

Example 5

A fabric made of mercerized and bleached cotton is mixed with a mixture consisting of a solution of 5% polyethyleneimine (MG: 2000), into which 4% Na ₂ CO ₃ had previously been added, and 4% glyoxal in water, using a commercially available inkjet printer, which works according to a non-thermal process (e.g. piezo), printed. The printing can take place over the entire fabric or even in patterns. In the case of a sample print, colorful patterns are created on a white background after coloring. The tissue thus obtained is dried at 50 ° C. in a circulating air cabinet.

und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eines Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Das mit der Farbstofflösung geklotzte Gewebe wird auf eine Docke aufgewickelt, in eine Plastikfolie gehüllt und während 16 Stunden bei 20 bis 25°C liegen gelassen und danach mit kaltem und mit heißem Wasser, das gegebenenfalls ein handelsübliches Netzmittel enthalten kann, und gegebenenfalls nochmals mit kaltem Wasser gewaschen und getrocknet.A cotton fabric modified in accordance with the above information is dyed in accordance with a block-cold-dyeing process. For this purpose, an aqueous dye solution containing 20 parts of 1000 parts by volume of a 50% electrolyte-containing dye powder of, for example, copper phthalocyanine dye of the formula known from German Patent No. 1,179,317

and contains 3 parts of a commercially available nonionic wetting agent dissolved, by means of a padder with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 25 ° C. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and optionally again with cold water Washed water and dried.

There is a strong, uniformly colored turquoise color that has good general fastness, in particular good fastness to rubbing and light.

Example 6

a) A fabric made of mercerized and bleached cotton is in a Mixture of a solution of 5% polyethyleneimine (MW: 1000) and 1% Glyoxal submerged in water (e.g. in a jigger). The so obtained The fabric is dried at 50 ° C in a circulating air cabinet.

b) A cotton fabric modified in this way is printed with an aqueous printing paste containing 20 parts of the dye of the formula in 1000 parts

(known from Example 258 of German Offenlegungsschrift No. 1 644 204) and contains 400 parts of an approximately 4% aqueous sodium alginate thickener. The printed cotton fabric is first dried at 60 to 80 ° C and then steamed for 5 minutes with superheated steam from 101 to 103 ° C, then treated by rinsing with cold and hot water, by boiling treatment in a bath containing a neutral, nonionic detergent, again rinsed with cold and hot water and dried. A uniform, scarlet-colored print is obtained which has good fastness properties.

Example 7

(bekannt aus Beispiel 3 der deutschen Offenlegungsschrift Nr. 2 557 141) und 400 Teile einer wäßrigen, 4 %igen Natriumalginat-Verdickung enthält. Das bedruckte Gewebe wird zunächst bei etwa 60 bis 80°C getrocknet und sodann 5 Minuten mit Heißdampf von 101 bis 103°C gedämpft. Der erhaltene Druck, der gemäß den Angaben des Beispieles 6 fertiggestellt wird, zeigt ein brillantes, blaues Druckmuster, das gute Allgemeinechtheiten, insbesondere gute Reib- und Lichtechtheiten, aufweist.A cotton fabric modified as described in Example 4a) is printed with an aqueous printing paste containing 20 parts of the dye of the formula in 1000 parts

(known from Example 3 of German Offenlegungsschrift No. 2 557 141) and contains 400 parts of an aqueous, 4% strength sodium alginate thickener. The printed fabric is first dried at about 60 to 80 ° C and then steamed for 5 minutes with superheated steam at 101 to 103 ° C. The print obtained, which is completed in accordance with the information in Example 6, shows a brilliant, blue print pattern which has good general fastness properties, in particular good fastness to rubbing and light.

Example 8

(bekannt aus Colour Index unter C.I. Nr. 51320) gegeben. Man färbt das Baumwollgewebe in dieser Farbstofflösung während 60 Minuten bei 60°C. Die Nachbehandlung der erhaltenen Färbung erfolgt in üblicher Weise, wie beispielsweise analog den Angaben des Beispieles 6. Es wird eine farbstarke blaue Färbung erhalten, die sehr gute Gebrauchsechtheiten, wie insbesondere eine gute Waschechtheit, aufweist.10 parts of a cotton fabric modified according to the information in Example 1 a) is dissolved in 200 parts of an aqueous solution of 0.2 part of the dye of the formula

(known from Color Index under CI No. 51320). The cotton fabric is dyed in this dye solution for 60 minutes at 60 ° C. The aftertreatment of the dyeing obtained is carried out in a customary manner, for example analogously to the instructions in Example 6. A strong blue dyeing is obtained which has very good fastness to use, in particular good fastness to washing.

Example 9

gegeben und während 60 Minuten bei einer Färbetemperatur von 80°C gefärbt. Die erhaltene Färbung wird danach mit kaltem und warmen Wasser von 30 bis 35°C, das ein handelsübliches nichtionogenes Tensid enthalten kann, und anschließend nochmals mit kaltem Wasser gespült und getrocknet. Man erhält eine hochwertige türkisfarbene Färbung mit guten Echtheiten.10 parts of a cotton fabric modified as described in Example 3a) are dissolved in 200 parts of an aqueous solution of 0.2 parts of the copper phthalocyanine dye of the formula known, for example, from British Patent No. 1,046,520

given and dyed for 60 minutes at a dyeing temperature of 80 ° C. The dyeing obtained is then rinsed with cold and warm water at 30 to 35 ° C., which may contain a commercially available nonionic surfactant, and then rinsed again with cold water and dried. You get a high quality turquoise color with good fastness properties.

Example 10

a) 100 parts of a cotton jersey are placed in a jet apparatus continuous goods management with 1500 parts of an aqueous fleet of 75 parts of polyethyleneimine (MW: 1000) and 45 parts of glyoxal treated, by placing the liquor on the material at this temperature 30 minutes. The fleet is then removed from the equipment drained and the modified material in the apparatus with cold, then with hot water, which is a commercially available Wetting agent can be added, and then again with cold Water rinsed thoroughly.

b) 2000 parts of water are then let into the jet dyeing machine and heated to 60 ° C. It is dosed over a period of 60 minutes a total of 20 parts of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder of the in Example 5 Azo dye described in EP-A 0 144 766 leads to the coloring then continue for about 5 minutes and then leave the colorless Residual liquor from the apparatus. The colored jersey is rinsed with cold and hot water, through boiling treatment in one bath containing nonionic detergent, by rinsing again hot and cold water and drying finished in the usual way. A deep red color with very good coloration is obtained Fastness to use.

Example 11

a) 10 parts of a polyester / cotton blend are saturated with CO ₂ and 20 parts of glyoxal per 1000 parts of water using a conventional pull-out process in a liquor ratio of 1:10 with an aqueous solution containing 50 parts of polyethyleneimine (MW: 500) , treated at 30 ° C for 15 minutes. The modified fabric was then rinsed thoroughly with cold and hot water, to which a commercially available non-ionic surfactant can be added, and again with cold water.

b) The modified goods can be fed in the wet state to a single-bath dyeing process in a jet dyeing machine. For this purpose, 10 parts of the modified blended fabric in the apparatus with 0.1 part of a 50% electrolyte-containing fiber-reactive azo dye described in Example 1 of European Patent 0 032 187 and 0.1 part of the disperse dye known from DE-OS 23 63 376 formula

in 200 parts of water heated to 60 ° C, held at this temperature for 15 minutes and then heated to 130 ° C. It is dyed for 30 minutes at 130 ° C., cooled to 60 ° C., the now colorless dyeing liquor is removed and the dyed material is washed in a conventional manner, for example by rinsing with cold and hot water, by boiling treatment in a nonionic detergent Bath, by rinsing again with water and drying.

One obtains a strong, level, level red coloration in their Authenticity properties the authenticity of according to the methods of the prior art Technique available colorings is equivalent in all points.

Example 12

a) A package with 30 parts of bleached cotton yarn is in one Yarn dyeing apparatus in 450 parts of an aqueous solution of 50 parts Polyethyleneimine (MW: 1000) and 30 parts of glyoxal in 1000 parts of water with mutual pumping around the fleet through the cheese treated at a temperature of 30 ° C for 20 minutes. After that the liquor cooled, drained and the bobbin thoroughly with cold Rinsed water.

b) After a new rinse with cold water, the yarn on the cheese is subjected directly to a dyeing process: the dyeing machine is with 450 parts of an aqueous dye solution with 0.6 part of the fiber-reactive azo dye of the formula known from DE-OS 28 40 380

loaded and heated to 60 ° C. The dyeing is carried out at 60 ° C for 30 minutes by pumping the liquor through the cheese. The yarn on the bobbin is then finished in the same way with cold and hot water, to which a non-ionic detergent can be added, and by rinsing again with cold water. An irrespective yellow colored fiber is obtained with good fastness properties for the dye.

Example 13

a) Direkt Blue 108 (C. I. No. 51320) oder

b) Direkt Blue 199 (GB-A-1046520)

enthält. Die resultierenden Färbungen werden abwechselnd heiß und kalt gespült und getrocknet. Sie zeigen ein gutes Echtheitsbild.A cotton jersey is impregnated with a mixture consisting of an aqueous solution of 3% polyethyleneimine (MW: 1000) and 1% glyoxal in water in a washing machine. Then carry out a household wash with a full detergent at 60 ° C to remove any yellowing. The knitted fabric thus obtained is dried at 60 ° C. in a tumbler.
The dried fabric is dyed analogously to a conventional exhaust process: 100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution, and the 2 parts of the 50% electrolyte-containing (predominantly sodium chloride) dye powder

a) Direct Blue 108 (CI No. 51320) or

b) Direct Blue 199 (GB-A-1046520)

contains. The resulting dyeings are alternately rinsed hot and cold and dried. They show a good authenticity picture.

Claims (17)

1. A process for modifying fiber materials, which comprises contacting the fiber material with a polymer which contains at least one primary or secondary amino group and has the formula (I) (-A-X-A-)_n where

   A

   is a chemical bond or a methylene group,

   X

   is a group of the formula (-CH₂-)_m, -CH₂-NR¹-CH₂- or -CH₂-O-CH₂- where m is from 1 to 6 and R¹ is hydrogen or C₁-C₄-alkyl, and

   n

   is from 2 to 1000,

   and identical or different groups X can be joined together in any desired order,
   and with a bifunctional crosslinking agent of the formula (II) Z-Q-Z where

   Z

   is a group of the formula -CHO or -CH(OR¹)₂ where R¹ is in each case identically or differently hydrogen or C₁-C₄-alkyl, and

   Q

   is a phenylene group or a group of the formula (-CH₂-)_a where a is from 0 to 4.

2. The process of claim 1, wherein the number of primary or secondary amino groups in the polymer of the formula (I) is from 10 to 500.
3. The process of claim 1 or 2, wherein

   m

   is from 1 to 4,

   n

   is from 10 to 500 and

   a

   is from 0 to 2.

4. The process of at least one of claims 1 to 3, wherein the polymer of the formula (I) is a polyethyleneimine having a molecular weight from 500 to 2000 or a polypropyleneimine having a molecular weight from 500 to 1000.
5. The process of at least one of claims 1 to 4, wherein the bifunctional crosslinking agent of the formula (II) is glyoxal.
6. The process of at least one of claims 1 to 5, wherein the concentration of the polymers of the formula (I) in aqueous solution is from 1 to 30% by weight, preferably from 2 to 20% by weight, and that of the compounds of the formula (II) is from 0.5 to 20% by weight, preferably from 1 to 10% by weight.
7. The process of at least one of claims 1 to 6, wherein the fiber materials are polyester fibers, synthetic polyamide fibers and polyurethane fibers, cellulose fibers, regenerated cellulose or a mixture thereof, preferably cotton.
8. The process of at least one of claims 1 to 7, wherein

   a) the fiber material is contacted with a mixture of a polymer of the formula (I) and of a compound of the formula (II) in aqueous or aqueously alkaline solution, or

   b) the fiber material is contacted first with a polymer of the formula (I) and then with or without intermediary drying with a compound of the formula (II).
9. A process for dyeing fiber materials with watersoluble, anionic dyes, which comprises carrying out the dyeing using low-electrolyte or completely electrolyte-free and/or low-alkali or completely alkali-free dye solutions (dyeing liquors, print pastes) and using a fiber material modified as claimed in at least one of claims 1 to 8.
10. The process of claim 9, wherein the dye is applied to the fiber material together with the compound of the formula (II) or in a subsequent separate step.
11. The process of at least one of claims 8 to 10, wherein the aqueous or aqueously alkaline solution contains from 0 to 20% by weight, preferably from 0 to 5% by weight, of NaOH or Na₂CO₃.
12. The process of at least one of claims 1 to 11, wherein the application of the treatment agent and/or of the dye to the fiber material is effected by an exhaust method or padding process, by spraying, or by means of an inkjet process.
13. The process of at least one of claims 9 to 12, wherein the water-soluble, anionic dye is a reactive dye.
14. The process of at least one of claims 9 to 13, wherein a fiber mixture of cellulose and polyester fibers is initially modified and dyed or printed with a reactive dye and then dyed with a disperse dye.
15. A fiber material modified by a process as claimed in at least one of claims 1 to 8.
16. A fiber material dyed by a process as claimed in at least one of claims 9 to 14.
17. The use of compounds of the formulae (I) and (II) as set forth in at least one of claims 1 to 5 for modifying a fiber material.