DE4114052A1 - Alkaline treatment or mercerisation and dyeing of cellulose - by wet on wet impregnation with one or two baths, eliminating need for washing - Google Patents

Abstract

Alkaline treatment/mercerisation and dyeing or printing of cellulose fibre materials and mixed fibre materials contg. these is carried out by wet-on-wet impregnation with the relevant liquor(s) in one or two baths, squeezing or stripping to 60-200, pref. 70-150% pick-up and then fixing the dyestuff. The material is dyed or printed with reactive dyestuff(s). Mercerisation is carried out with KOH soln. with an alkalinity of 5-32oBe, pt. of which may be replaced by an alkali salt, pref. up to 75% of the KOH soln. by KCl. In particular, a 2-bath method is used and the mercerisation liquor contains KOH and KCl in 3:1 to 1:3 wt. ratio, whilst the pick-up is 50-110, pref. 60-100%. The swell time for impregnation with alkali is 3-30 s. Cold dyeing reactive dyestuffs are used and fixing is carried out by the cold dwell technique. A reactive dyestuff with a reactive difluoromonochloropyrimidine, dichloroquinoxaline, methylsulphonyl-chloromethylpyrimidine or monofluorotriazine system and opt. a second reactive gp. is pref. used. USE/ADVANTAGE - The technique is claimed for treating natural cellulose. It avoids the need for costly and time-consuming rinsing, washing, rinsing and drying after mercerisation.

Description

The invention relates to the one-bath or two-bath wet-in-wet Leaching / mercerization and dyeing of cellulose fiber material.

According to the prior art, leaching / mercerizing is essential and dyeing in two separate individual processes, d. H. it is independent of other pretreatment processes such as singeing, washing, Desizing and bleaching using various processes first leached or mercerized. In any case, the goods must then be rinsed well and dried if they are subsequently (continuously) colored shall be. The basic variants come as continuous dyeing processes such as cold dwell, warm dwell, pad steam, pad dry or pad thermofix Procedure in question. Known processes using ammonia will come in practice because of the smell / health impairment out of the question.

It is known to leach / mercerize to increase fiber affinity as well as swelling of the fiber, which leads to the following advantages:

• - higher dyeability,
• - Mercerising gloss,
• - soft, flowing handle,
• - improvement of the dyeing of immature / dead cotton,
• - Less wrinkling in subsequent strand forming processes (washing),
• - Uniform, calmer and clear image of goods and structure,
• - improved dimensional stability,  
• - For knitwear, no edge compression and compensation of spiral distortion in the case of single jersey,
• - Good dimensional stability and
• - Less fluid after washing treatments.

To this day, leaching / mercerizing is self-contained Process in which the goods are rinsed well at the end (costly and time-consuming), must be soaped, rinsed again and dried.

According to the invention, a method for alloying or mercerizing has now been and dyeing or printing cellulose fiber materials, which is characterized in that one-bath or two-bath-wet-in wet the substrate with the corresponding (short) liquor (s), to a total dry weight gain of 60 to 200%, preferably 70 to 150, in particular 75 to 110% squeezed or stripped, and then performs dye fixation. This is the two-bath Wet-on-wet process preferred because only for the single bath process a very limited number of dyes are suitable. Such dyes namely must be extremely stable to hydrolysis or electrolytes. The new Process without intermediate treatment between leaching / mercerizing and Coloring improves u. a. the color yield and brilliance of the dyeings.

Dyeing or printing is preferably carried out with reactive dyes.

Under liquor / mercerizing liquor is a liquor, the alkali contains in a concentration intended for mercerization. Both caustic soda and potassium hydroxide as well as a Mix of both can be used. Potassium hydroxide solution is preferably used. The liquor / mercerizing liquor preferably has an alkalinity from 5 to 42 ° B´, especially (for mercerizing) between 20 and 30 ° B´, or if the lye is partially replaced by salt, 6 to 25 ° B´, on. It advantageously contains 120 to 400 g / l of an alkali metal hydroxide (Sodium and / or potassium hydroxide), especially 200 to 400 g / l potassium hydroxide. However, it has been shown that part of the alkali solution by salts of alkali metals, preferably potassium salts, in particular  Potassium chloride, can replace. The partial replacement of the alkali hydroxide can, if the coloring is fixed in the cold residence process, up to one Mixing ratio of 1: 3, in some cases up to 1:10 (1 part by weight Lye to 3, possibly up to 10 parts by weight of salt). Preferably the ratio of potassium hydroxide solution to potassium chloride is in the range of 3: 1 to 1: 3 parts by weight, that is, generally from those mentioned above 120 to 400 g / l potassium hydroxide a quarter to three quarters through potassium chloride can be replaced. The advantage of replacing lye with a salt is obvious: the baths contain less aggressive alkali making it less dangerous in every way.

If the staining is fixed by heat treatment e.g. B. Steaming made at 100 to 150 ° C, about 10 to 50% of the potassium hydroxide solution Potassium chloride to be replaced.

The liquor / mercerizing liquor thus contains, according to the invention Mixture of alkali lye and alkali salt in the weight ratio between 1:10 and 10: 1.

In principle, according to the two-bath process, both with the first Lye / mercerizing bath and then with the dye liquor, but also in reverse Order are impregnated.

It is preferably leached / mercerized first, that is with the alkaline liquor / mercerizing liquor impregnated and 3 to 30 seconds in the alkali liquor to swell the fiber, and then (after the Squeezing / stripping off the excess alkali liquor) the dye liquor, or printing paste applied.

The high dry weight gains indicated are particularly due to so-called Double foulards of various types, e.g. B. Horizontal, vertical and gusset foulards and their different combinations Equipment for spraying liquors, foam application, electrostatic Fleet orders and their combinations with a pad concept possible.  

As particularly favorable for the two-phase process concept according to the invention of leaching / mercerizing and coloring (and vice versa) described in DE-OS 36 20 864, 37 33 997 and 37 33 996 Machine concepts for the addition fleet order in combination with proven the foulard concept.

The wet-on-wet fleet order concepts mentioned are subject to certain Restrictions, especially since in the case of paint fleet orders especially high demands on uniformity must be made. Solubility problems also exist if the fleet order differences are too small of active substances in the second foulard. The introduction of incompatible Active substances in the fleet of second foulers can continue to affect dyeing results.

The fleet order for this innovative fleet order concept is carried out in generally in an upright trough, in which the web always only with a very small amount of constantly supplied treatment fleet is in contact. The trough is horizontal down through two each other opposite inflatable lips sealed on both sides of the web, which lie against the web and the treatment fleet carried by it down to a predeterminable total moisture content wipe off. The special advantage of this system is the possibility of immediate fleet turnover with no or only a very small fleet stock, so that the strong alkali is introduced into the dyebath and the possibly resulting undesirable reactions such as uncontrolled Hydrolysis and / or substantivity can be prevented. A Another advantage of the addition fleet order is that solubility limits do not limit the color depths easily.

The separate alkali and dye liquor routing gives you more options the liquor or mercerizing liquor design in order to To influence fixing conditions favorably. In the subject of the invention therefore a fully continuous cold retention process is included, where the dye has no heat energy (e.g. steaming or heat setting), can be fixed at room temperature in the minute range. Required is just an open goods store like slide, J-box,  Roller air duct, unheated dampers, empty roller skids and the like Requirement is the use of fast-reacting reactive dyes.

The alkali liquor used in the process according to the invention can also be a Alkali metal silicate (water glass), preferably sodium or potassium silicate contain. In this case the alkalinity given above applies of the liquor / mercerizing liquor to the entire concentration, alkali metal hydroxide and alkali metal silicate. The amount of alkali metal silicate in the liquor / mercerizing liquor is adjusted accordingly and can up to 200 ml / l water glass from 38 to 41 ° B´, preferably one Amount from 50 to 200 ml / l, especially 100 to 200 ml / l water glass from 38 to 41 ° B´ used. The reason for adding water glasses is primarily that Prevention of excessive shrinkage of the goods due to swelling.

The leaching / Mercerizing liquor still other auxiliaries, for example a usual alkali-resistant wetting agent used in dyeing processes in order to a quick and even wetting of the goods with the alkaline solution to reach. The wetting agent or mixture is preferably used in an amount from 0.1 to 10 g / l, particularly 2 to 6 g / l.

The mercerizing liquor can also use a complexing agent as a further aid contain, which is able to sequester heavy metal ions, without impairing metal-containing dyes, and at the same time is stable under the alkaline conditions described.

The complexing agent is advantageously used in an amount of up to 40 g / l used with the water hardness. The complexing agent is preferred in an amount of 0.2 to 20, especially 0.5 to 10, especially 2.5 to 5 g / l used.

It is advantageous to mix the complexing agent with a dispersant, especially an anionic dispersant, e.g. B. a sulfonated fatty acid amide, add to the treatment bath. As an example of such a preferred one Mixture is an aqueous preparation containing 15% (weight) sodium gluconate and contains 5% (weight) of a sulfonated fatty acid amide.  

The liquor / mercerizing liquor used in the process according to the invention can also contain a lubricant. This lubricant can be dispersing and optionally as a retardant / leveling agent for Reactive dyes work. Such means are known. Are preferred those products that are anionic, for example sulfonated or sulfated castor oil. The lubricant, if present, is preferred in an amount of 0.1 to 15 g / l, especially 1 to 15 g / l of the treatment bath admitted. Furthermore, the liquor / mercerizing liquor can still be a conventional one Contain bleach, for example hydrogen peroxide.

As dyes that are used according to the invention, such come Use under the leaching / mercerizing conditions without loss, for example, by hydrolysis, can be fixed on the goods. This includes especially cold dye reactive dyes, as well as those on the market Sulfur and vat dyes and reactant-fixable direct dyes (Indosol dyes), in any case dyes caused by the alkali not be affected.

The following simple dyes are particularly suitable reactive dyes Multiple reactive systems:

Difluoromonochloropyrimidines, dichloroquinoxalines, methylsulfonchloromethylpyrimidines, Monofluorotriazines, monochlorotriazines (the latter in particular for the single bath process), vinyl sulfones and their combinations (double anchor Reactive dyes). The difluoromonochloropyrimidine are particularly preferred Reactive dyes.

If fiber-reactive or substantive metal complex dyes are used it is advantageous not to have a complexing agent in the liquor / mercerizing liquor to use. The dye liquor can also be used for dyeing usual dye chemicals, in particular solubility-promoting products, e.g. B. urea, and liquor retention agents, foam prevention and wetting agents as described, etc. included.

The aqueous leaching / mercerizing and dyeing liquor is advantageous for a temperature of 10 to 100 ° C, preferably 15 to 80 ° C, especially 15  up to 40 ° C the same or different on the goods as described Methods applied.

After the treatment according to the invention, an impregnated product is so long subjected to a dwell or fix process until the desired one Leaching or mercerizing and dye fixation has occurred. Suitable leaching / mercerizing and dye fixing processes come in Question:

• 1. Cold and warm dwell processes, single-phase and two-phase wet-on-wet, with or without (mechanical or thermal) partial drainage, with short and long-term fixation with residence times from 30 s to 48 h at temperatures from room temperature to 230 ° C in air and / or steam atmosphere, where the steam atmosphere of over 100 ° C HT conditions or overheating Subject to atmospheric pressure. The cold retention process has proven particularly useful with residence times between 30 s to 48 h, preferably between 10 min to 48 h. Treatment can also be done after the pad roll and warm Processes with preferred temperatures between 20 and 100 ° C at Residence times between 30 sec to 8 h can be carried out.
• 2. Pad dry process, single-phase or two-phase wet-on-wet, with or without Partial drainage, with subsequent drying fixation at drying temperatures between 100 to 150 ° C in hot air or superheated steam at times between 1 sec and 30 min.
• 3. Pad heat setting process, single-phase or two-phase wet-on-wet.
• The subsequent heat setting process must be carried out:
  • a) In hot air at temperatures between 100 to 230 ° C in times between 1 sec to 30 in.
  • b) In superheated steam at temperatures between 100 and 230 ° C for times between 1 sec and 30 min.
• 4. Pad steam process, single-phase and two-phase wet-on-wet.  
• The subsequent steaming process must be carried out:
  • - In saturated steam under normal pressure around 100 ° C,
  • - In saturated steam under pressure conditions from 100 to 150 ° C, each 1 sec to 30 min.

After the treatment, the goods can be washed and dried in a known manner will. It is advantageous to use demineralized (softened) Washed water. The washout can take place at a temperature between and cooking temperature, preferably at 60 to 95 ° C. If desired, the goods can be acid bathed at the end of the washing process be neutralized.

A bleaching agent, for example hydrogen peroxide, can also be used Wash out can be used.

The preferred two-stage wet-on-wet method uses the first Impregnation in general to a dry weight gain between about 50 and 110%, preferably squeezed to 60 to 100%, in the second Impregnation are still (based on the dry weight of the substrate) once applied between about 5 and 110%, preferably 10 to 60%, overall, the impregnations should increase 70 to a maximum of 200% dry weight bring.

If a printing paste is used in the second order, its share is usually between 5 and 15% (based on the weight of the dry substrate).

In general, there is less overall dry weight gain with woven fabrics (e.g.: 50 to 110%), for knitwear a greater increase in dry weight (e.g. 80 to 200%).

The method according to the invention comes for all textile materials from natural or regenerated cellulose fibers and their mixtures as well Mixtures with synthetic fibers, especially textile fabrics in question.  

Of particular interest are:

• - mixtures of cotton and regenerated cellulose fibers,
• - Cotton and regenerated cellulose fibers with acrylic fibers or polyester mixed,
• - raw material qualities as knitted and woven goods,
• - Pretreated qualities as knitted and woven goods,
• - tubular knitted fabric,
• - warp knitted fabrics,
• - Terry, velvet, cord and plush items.

When treating raw cotton, the dead cotton is well covered. The crease mark on tubular goods is higher Fleet application and better dye diffusion immediately during the Prevents fiber swelling in the crease area.

It was further shown that in the case of the preferred wet-on-wet Fleet order based on the Flex-Nip concept with first-phase mercerising liquor Impregnation and the associated extremely light sliding fabric surface also impregnated knitted fabric on the Flex-Nip can be. In general, the use of the Flex-Nip system for knitted fabrics not recommended due to excessive longitudinal tension.

The following examples illustrate the invention without limiting it. Percentages are percentages by weight, temperatures are given in Centigrade.

Example 1

A bleached 100% co-fabric became wet-on-wet on one conventional double foulard, in the first foulard with a fleet containing

63 g / l potassium hydroxide 100%,
188 g / l potassium chloride,
100 g / l sodium water glass 38 ° B´,
50 g / l of a mixture of wetting agent and sodium gluconate / sulfonated fatty acid amide mixture,

padded with a pickup of 72%, in the second foulard with a fleet containing

30 g / l C.I. Reactive Green 21

and a pickup of 31% padded and then at room temperature Lingered for 20 min, rinsed and dried.

A level, brilliant deep green was achieved. In comparison to conventional pad batch staining with 30 g / l C.I. Reactive Green 21, 50 cc / l sodium water glass 38 ° B´ and 10 cc / l sodium hydroxide 36 ° B´ at 24 h Residence time and the same range of dyes could not only be one more brilliant, but also essential with a dwell time of only 20 min deeper green coloring can be achieved.

Example 2

A bleached 100% co-fabric became wet-on-wet in the addition liquor application (Flex-Nip concept), in the first conventional foulard with one Containing fleet

125 g / l potassium hydroxide 100%,
125 g / l potassium chloride,
100 ml / l sodium water glass 38 ° B´,
50 ml / l of an aqueous mixture of wetting agent and sodium gluconate / sulfonated fatty acid amide mixture,

padded with an 80% pickup in the second fleet applicator Flex-Nip (addition fleet order) with

40 g / l C.I. Reactive Blue 225,

padded with a pickup from 26% to a total of 106% and then  lingers at room temperature for 20 min, rinsed and dried. A level, deep navy blue coloration was achieved which compared to a conventional pad batch staining with sodium water glass / sodium hydroxide solution with a 6-hour dwell one about four times (100% to 400%) lower Staining revealed.

Example 3

A non-leached CV tissue (cellulose regenerated) got wet-on-wet on a conventional double foulard concept, in the first foulard containing a fleet

250 g / l potassium hydroxide 100%,
100 ml / l sodium water glass 38 ° B´,
50 ml / l of a mixture of wetting agent with sodium gluconate / sulfonated fatty acid amide mixture,

in the second foulard

40 g / l C.I. Reactive Blue 225

padded, in the first conventional foulad to 65% dry weight gain squeezed, in the second conventional foulard with 21% impregnated a total of 86% dry weight gain and then at Room temperature is cold, rinsed and dried for 10 min.

It has a deep navy blue tint compared to a conventional one Pad batch dyeing with a 6-hour dwell and the same range of dyes was 4 times lower.

Example 4

A non-leached CV fabric became wet-on-wet on a conventional one Double foulard conception, in the first foulard with a fleet containing

220 g / l potassium hydroxide 100%,
30 g / l potassium chloride,
100 ml / l sodium water glass 38 ° B´,
50 ml / l of a mixture of wetting agent with sodium gluconate / sulfonated fatty acid amide mixture,

in the second foulard

80 g / l C.I. Reactive Orange 69

padded, in the first conventional padder to a 65% increase in dry weight squeezed, in the second conventional foulad with 23% impregnated to a total of 88% dry weight gain and then without intermediate drying for 30 seconds at 102 ° C in saturated steam under atmospheric pressure steamed, rinsed and dried.

It became a very deep, brilliant orange color compared to a conventional pad batch staining with 6 h residence time with the same Dye range had a shade 4 times lower.

Example 5

The same coloring as described in Example 4 was carried out with a bleached 100% co-fabric. The result corresponded to that of the Example 4.

Example 6

An unleached cotton renforc product was included with a fleet

125 g / l potassium chloride,
125 g / l potassium hydroxide 100%,
100 g / l water glass 38 ° B´,
50 g / l of a mixture of wetting agent with sodium gluconate / sulfonated fatty acid amide mixture

with a pickup of 80% (based on the dry weight of the goods) at 20 sec diving time and then wet-on-wet with a printing paste containing

40 g CI Reactive Blue 225,
10 g sodium metanitrobenzenesulfonate,
400 g of a starch ether thickening,
580 g water

with an additional paste pickup of 10% (based on the dry Goods) overprinted with a flat stencil. The mixture then became cold for 30 minutes lingers, rinsed and dried.

A deep navy blue print was achieved compared to one conventional direct printing following the procedure

• 1.Print with a flat stencil of the following printing paste 400 g starch ether 12%,
  10 g sodium metanitrobenzenesulfonate,
  10 g CI Reactive Blue 225,
  580 g water, with a paste application (based on the dry goods weight) of 40%.
• 2. drying at 110 ° C,
• 3. Over-fouling with a fleet of 650 g of water,
  200 g soda soda,
  200 g Glauber's salt,
  Make up to 1000 g with xg water,
• 4. Cold stay at 30 min,  
• 5. soaping, rinsing and drying,

was four times darker and more brilliant.

Example 7

A 100% bleached cotton weave was wet-on-wet addition liquor order (Flex-nip concept) in the first conventional foulard a fleet containing

100 g / l water glass 38-41 ° B´,
250 g / l potassium hydroxide 100%,
50 g / l of an aqueous mixture containing
0.25 g / l of a commercially available anionic wetting agent,
1 g / l of a sodium gluconate / sulfonated fatty acid amide mixture,

impregnated with 20 sec immersion time, after 25 seconds of air in the second Fleet application device Flex-Nip (addition fleet application) with

50 g / l C.I. Reactive Red 147

padded, in the first fleet applicator to 96% increase in dry weight squeezed, in the second fleet applicator with 60% to a total of 156% Impregnated dry weight gain, then at room temperature 10 Minutes fixed, rinsed and dried.

It became a brilliant, deep red and level coloring with a typical mercerizing effect receive. Compared to conventional pad batch staining With

50 g / l CI Reactive Red 147,
50 g / l water glass 38-41 ° B´ and
11 g / l NaOH 36 ° B '

with a 24-hour dwell time, not only could a much more brilliant, but a 20% deeper coloring can also be achieved.  

Example 8

Based on example 7, only the Flex-Nip system was used replaced by a conventional foulard with soft rollers (50 ° Sh), with a pickup of 69% on the lye paddle and in the second dyeing paddle a pickup of 119% with soft rollers and low squeeze pressure (Pickup difference of 50%) was achieved. The residence time was 10 minutes. Compared to the conventional pad batch method, it could not only a much more brilliant, but also a 20% deeper red color can be achieved.

Example 9

A bleached 100% cotton fabric got wet-on-wet in the addition liquor order (Flex-nip concept) in the first conventional foulard a fleet containing

250 g / l potassium hydroxide solution 100%,
50 g / l of an aqueous mixture containing
0.25 g / l of a commercially available anionic wetting agent,
and a sodium gluconate / sulfonated fatty acid amide mixture,

in the second fleet application device Flex-Nip (addition order)

50 g / l C.I. Reactive Blue 136, a low-reactive pull-out Reactive dye

padded, in the first fleet applicator to 88% increase in dry weight squeezed, in the second fleet applicator (Flex-Nip) with 52% of total Impregnated 140% dry weight gain and then at Room temperature lingers for 24 h, rinsed and dried. It became a very Get brilliant level green color with typical mercerizing effect.

Example 10

On the basis of the 9th example, instead of the cold retention,  Steaming process with a steaming time of 1 min connected to dye fixation.

It became a level, very brilliant green color with typical Mercerizing effect created.

Example 11

A bleached 100% cotton knitwear was wet-on-wet Addition fleet order (Flex-Nip concept) in the first conventional Foulard with a fleet containing

100 g / l water glass 38-41 ° B´,
300 g / l potash lye 100%,
50 g / l of an aqueous mixture containing
0.25 g / l of a commercially available anionic wetting agent,
1 g / l of a sodium gluconate / sulfonated fatty acid amide mixture,

in the second fleet application device Flex-Nip (addition fleet order)

40 g / l reactive golden yellow 125, a highly reactive reactive dye,

padded, in the first fleet applicator to 95% increase in dry weight squeezed, in the second fleet applicator with 105% to a total of 200% Impregnated dry weight gain and then at room temperature 10 Minutes lingered.

Compared to conventional pad batch staining with

40 g / l CI Reactive Golden Yellow 125R,
50 g / l water glass 38 ° B´ and
10 g / l caustic soda 36 ° B´,

at 24 h dwell time, could not only be a much more brilliant, but a deeper color can be achieved even with a dwell time of only 10 minutes.  

Example 12

A 100% cotton knitted fabric, bleached, was bathed with a lye and dye liquor containing

40 g / l CI Reactive Red 190,
200 g / l potassium hydroxide solution conc. 100%,
100 g / l water glass 38-41 ° B´,
50 g / l of a mixture of wetting agent and sodium gluconate / sulfonated fatty acid amide mixture padded,

squeezed with 151% dry weight gain and then at room temperature lingered, rinsed and dried for 6 hours.

It became a brilliant, deep red and level coloring with a typical mercerizing effect created. Compared to conventional staining, one Colorimetric yield increase of 20% can be achieved. In the same way, instead of C.I. Reactive Red 190, C.I. Reactive Blue 13, C.I. Reactive Red 13 or the dye according to Example 1 DE-OS 35 45 555 can be used.

The potassium hydroxide solution can also be replaced up to 2/3 with potassium chloride. So you get the same color results if you replace the 200 g / l KOH uses only 100 g / l KOH and 100 g KCl, or 70 g / l KOH and 130 g / l KCl.

Claims (11)

1. A process for leaching or mercerizing and dyeing or printing cellulosic fiber materials and mixed fiber materials containing them, characterized in that one-bath or two-bath wet-on-wet impregnated the substrate with the corresponding liquor (s), to a dry weight gain of 60 to 200%, preferably 70 to 150% squeezed or stripped, and then the dye fixation is carried out. 2. The method according to claim 1, characterized in that with colors or prints one or more reactive dyes. 3. The method according to claim 1 or 2, characterized in that one leached or mercerized with potassium hydroxide solution at an alkalinity of 5 to 32 ° B´. 4.A method according to one of the preceding claims, characterized in that that a part of the alkali lye during leaching / mercerization is replaced by an alkali salt. 5. The method according to any one of claims 3 or 4, characterized in that up to 75% of the potassium hydroxide solution is replaced by potassium chloride. 6. The method according to any one of the preceding claims, characterized characterized in that one leached / mercerized and stained in one bath. 7. The method according to any one of claims 1 to 5, characterized in that that in two baths wet-on-wet leaching / mercerizing and Dyeing with a liquor / mercerizing liquor containing potassium hydroxide and Impregnated potassium chloride in a weight ratio between 3: 1 and 1: 3 and impregnation to a dry weight gain of 50 to 110%, preferably 60 to 100% squeezed or stripped.   8. The method according to any one of the preceding claims, characterized characterized in that for dyeing reactive dyes, the one Reactive system of difluoromonochloropyrimidine, dichloroquinoxaline, Methylsulfonochloromethyl pyrimidine or monofluorotriazine series and optionally contain a second reactive group used. 9. The method according to one of the preceding claims, characterized in that that you dye with cold dye reactive dyes and the Fixation carried out in the cold residence process. 10.The method according to any one of claims 1 to 5 and 7, characterized in that a residence time of 3 for the alkali impregnation up to 30 seconds. 11. The method according to any one of the preceding claims, characterized in that that you treat materials made from native cellulose.