EP0359188B1 - Dyeing and printing process of cellulose fibres in the absence of alkali or reducing agents - Google Patents

Abstract

Process for the alkali-free dyeing and printing of cellulose fibres with reactive dyes, direct dyes, acid dyes, water-soluble sulphur dyes or sulphur vat dyes, wherein the textile material to be dyed is pretreated with a wetting agent and a reaction product of an epihalogenohydrin and ammonia or an amine of the formula <IMAGE> where A is hydrogen, alkyl having 1 to 5 carbon atoms or hydroxyalkyl having 1 to 5 carbon atoms, R is alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, a group of the formula <IMAGE> (n = 0 to 5), a group of the formula <IMAGE> (X = oxygen or sulphur) (n = 0 to 5), or R and A together are <IMAGE> then dyed with the dyes mentioned in a conventional manner but without alkali, and the dyeing is finished by rinsing, soaping and drying.

Description

The dyeing of textile materials, such as, for example, woven fabrics, knitted fabrics or yarns and threads, consisting of or containing cellulose fibers with reactive dyes, can be carried out according to known methods in that the textile material is drawn out with a dyeing liquor containing reactive dye, usually at elevated temperature and in most commercially available reactive dye types in the presence of alkali, or continuous or discontinuous processes, such as the so-called pad-steam process, or the cold retention process can be used. In the pad-steam process, as well as in the cold dwell process, the textile material is first padded with a reactive dye liquor, the alkali required for fixation being usually applied in a separate impregnation step. In the pad-steam process, the dye fixation is then carried out by a steaming process, in the cold dwell process by docking the impregnated goods and lingering for several hours at room temperature. Other fixation options, such as The treatment of the goods, which have been sealed with an alkali-free reactive dye liquor, using sodium hydroxide solution / water glass solution have become known and are practiced industrially.

In all of the reactive dyeing processes mentioned, a covalent chemical bond between the dye molecule and the cellulose molecule is produced in the course of the dyeing process. The presence of alkali is absolutely necessary for this.

In US-A-4 806 126 is a process for dyeing cellulosic fibers with reactive dyes described in which the presence of alkali is not required. The fixation of the dyes on the fibers is achieved in this process in that the fibers are pretreated with a reaction product of polyethylene amine and a bifunctional alkylating agent before dyeing.

worin

A

Wasserstoff, Alkyl mit 1 bis 5 C-Atomen, Hydroxyalkyl mit 1 bis 5 C-Atomen,

R

Alkyl mit 1 bis 5 C-Atomen, Hydroxyalkyl mit 1 bis 5 C-Atomen,
eine Gruppe der Formel

(n = 0 bis 5),
eine Gruppe der Formel

(X = Sauerstoff oder Schwefel) (n = 0 bis 5),

oder R und A zusammen

und alkylen jeweils C₁-C₆-, vorzugsweise C₂-C₃-alkylen, bedeuten, vorbehandelte anschließend nach üblichen Methoden, jedoch ohne Alkali, mit den genannten Farbstoffen färbt und die Färbung durch Spülen, Seifen und Trocknen fertigstellt.It has now been found that cellulose fibers can be dyed and printed with reactive dyes, direct dyes, acid dyes, water-soluble sulfur dyes or sulfur vat dyes without the use of alkali or a reducing agent if they are mixed with a wetting agent and a reaction product of an epihalohydrin and ammonia or an amine of the formula

wherein

A

Hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms,

R

Alkyl with 1 to 5 carbon atoms, hydroxyalkyl with 1 to 5 carbon atoms,
a group of the formula

(n = 0 to 5),
a group of the formula

(X = oxygen or sulfur) (n = 0 to 5),

or R and A together

and alkylene in each case mean C₁-C₆-, preferably C₂-C₃-alkylene, pretreated subsequently using customary methods, but without alkali, with the dyes mentioned and the dyeing done by rinsing, soaping and drying.

The auxiliary agent required for the pretreatment is known from US-A-3 544 363. The tool is used there exclusively for the improvement of the wet fastness properties of dyeings with sulfur dyes. Pretreatment with this aid and subsequent dyeing without alkali is not described there.

The pretreatment agents to be used according to the invention are prepared by reacting an epihalohydrin, preferably epichlorohydrin, with ammonia or an amine of the formula given at temperatures of about 60 to 70 ° C. in water or a lower alcohol as solvent. These pretreatment agents can optionally be quaternized with C₁-C₄, preferably C₁-C₃ alkyl groups. The quaternization can be carried out using alkyl halides, preferably alkyl chlorides, or dialkyl sulfonates by known methods.

Examples of amines which correspond to the formula given above are: monomethyl, ethyl, propyl, isopropyl, butyl, isobutylamine, monooxethyl, monooxypropylamine, ethylenediamine, diaminopropanes, diaminobutanes, diaminohexanes, 3 , 3'-diaminodipropyl ether, piperazine, monooxethyl and di-oxätätätätätäthendiamin, diethylenetriamine, dipropylenetriamine, triethylenetetramine and. a.

The preparation of these pretreatment agents is described in detail in US-A-3,544,363.

This previously described aid is applied to the textile material to be dyed or printed together with a wetting or padding aid from an aqueous liquor which is customary in the textile industry. Alkane sulfonates, dialkyl sulfosuccinates, dialkyl phosphates or propylene oxide / ethylene oxide block polymers with a proportion of 40-80% by weight of ethylene oxide, but in particular nonionic compounds, for example oxyethylated nonylphenol, are taken as such wetting or padding aids. Raw or pre-treated cotton or mixed fabrics containing cotton are possible as textile materials. The process according to the invention is particularly interesting for the pretreatment of cotton warp yarns with the aid described in the size. After weaving with untreated weft yarns and the subsequent alkali-free over-dyeing with reactive dyes, a denim effect is then achieved after washing out the fabric.

The pretreatment with the auxiliary together with a nonionic wetting agent is carried out from an aqueous liquor by customary methods by padding or in the exhaust process at temperatures of approximately 20 to 70 ° C., preferably 40 to 60 ° C., in the size from 80 ° C. to cooking temperature. The liquor is adjusted to a weakly acidic pH, preferably pH 6. The amount of auxiliary is about 3 to 10%, preferably 3 to 8%, based on the weight of the goods. The amount of wetting agent is preferably 2 to 4 g / l. The pretreatment liquor is then squeezed off and the goods are dried.

The goods pretreated in this way are then dyed with reactive dyes using customary methods and on customary dyeing units, for example using the cold dwelling method, the exhaust method or the heat setting method. The fleet ratio can be about 1: 3 to 1:40. However, it is important here that, in contrast to the previously customary procedure, no alkali is used in the present case. Suitable reactive dyes in this process are all known types of reactive dyes which contain groups which are reactive with the hydroxyl groups of cellulose and which, under the dyeing conditions described according to the invention, preferably react by reaction with the polymers described and fixed on the cellulose material. The reactive groups are, for example, groups with easily removable substituents which leave an electrophilic radical, such as reactive groups of the vinylsulfone type, groups of the ring systems quinoxaline, phthalazine, triazine, pyrimidine or pyridazone substituted with halogen atoms or reactive groups substituted with alkylsulfonyl radicals in the case of sulfonylpyrimidothiazole or sulfonylbenzonylbenzene . Specifically, dyes with the reactive groups ß-sulfatoethylsulfone, ß-thiosulfatoethylsulfone, ß-phosphatoethylsulfone, chlorotriazinylamino, trichloropyrimidylamino, dichloropyrimidylamino, dichloro-pyrid amino, 2-methylsulfonyl-benzothiazol-6-yl-amino, 2,3-dichloroquinoxalin-6-yl-carbonylamino or 4-chloro-5-methyl-2-methylsulfonylpyrimid-3-yl-amino.

Suitable basic dye bodies of the reactive dyes are, for example, water-soluble azo, disazo, formazan, anthraquinone, dioxazine or phthalocyanine dyes. Water-soluble azo and disazo reactive dyes, which can also be metal complex reactive dyes, are preferably used. After dyeing, the goods are finished by rinsing, possibly soaping and drying.

The process according to the invention can be carried out not only with reactive dyes, but also in the same way with other types of dyes which contain anionic, for example sulfo groups, such as, for example, direct dyes, acid dyes and water-soluble sulfur dyes. Similar effects and fastness properties are achieved with these dyes as with the reactive dyes. In addition, sulfur vat dyes can also be used in the process.

The method according to the invention is not only suitable for dyeing textile material, but also for printing. Here, the textile material is printed with a printing paste which contains a marking dye and the auxiliary agent to be used according to the invention. After drying and fixing, the textile material is then over-dyed with reactive dyes without alkali, preferably using the pad-steam process or the exhaust process. Another possibility is that the cotton chains or cotton fabrics preheated with the aid described are printed with a printing paste which contains the reactive dye but no alkali and then the dyeing, for. B. fixed by steaming at 102-105 ° C for 8 minutes. The subsequent aftertreatment is carried out analogously to the dyeings.

The main advantage of the process according to the invention is that, as a result of the pretreatment with the auxiliary described, no alkali or reducing agent is required in the subsequent dyeing. When the goods are finally washed out after dyeing, no alkali then goes into the wastewater, so that the salt pollution of the wastewater in the dyeing plants is significantly reduced. In addition, the pretreatment described also partially results in a significant color deepening of the color compared to a coloration with the same amount of reactive dye in one conventional dyeing process. Among other things, water glass is used to a large extent as the alkali for fixing the reactive dyes. If this water glass is not carefully washed out after fixing, it can lead to annoying SiO₂ deposits on the goods and thus impair the grip. This disadvantage is also eliminated in the method according to the invention. This new process also makes washing out the unfixed dye residues easier by dispensing with alkali, since in the presence of alkali the cotton fiber swells and the unfixed dye is more strongly absorbed. This does not apply to the method according to the invention.
The solubility of the reactive dyes, which is severely restricted by the alkali, is significantly improved and the stability of the neutral dye liquors is increased.

The dyeings produced by the process according to the invention described above show good wet fastness properties, but especially in the case of denim effects and individual dyestuffs, a partial slight discoloration of the undyed weft thread and, above all, a cloudy color tone is evident.

Surprisingly, it was found that a washing process immediately following the soaping process with detergents containing perborate significantly increases the brilliance of the dyeings and the weft thread, which has not been dyed or, depending on the color shade, is slightly soiled, so that a dyeing with high brilliance and white weft yarn is obtained. The use of optical brighteners in the wash liquor further increases the brilliance of the dyeings and the weft yarns.

These effects are achieved in particular when the washing is carried out between 20-50 ° C., preferably between 40-50 ° C. You wash with the perborate-containing Detergents at higher temperatures, for example 50 ° to 100 ° C., preferably 85 ° to 100 ° C., the dyeing can be lightened in stages until the fabric is almost completely decolorized. In this way, uneven dyeing (stone-washed effect) is achieved in a way that is very gentle on the fibers. This effect can otherwise only be achieved with alkaline hypochlorite solutions and possibly with washing in the presence of pumice stones.

The amount of alkali perborate in the detergents is between about 4 and 25% by weight. Such detergents containing perborate, which are suitable here, are described in detail in "Tenside" 18, p. 246 (1981).

example 1

On a sizing machine, cotton warp yarns are treated with a fleet of the following composition in the trough provided:
30 g / l polyvinyl alcohol (PVA)
5 g / l polyethylene glycol
4 g / l di-2-ethylhexyl phosphate potassium salt
60 g / l of reaction product from NH₃ and epichlorohydrin according to DE-A-1 619 391, Example 1.

The fleet intake is 100-120% (high-performance crushing unit).

The yarn runs at a speed of 15 m / sec, the liquor temperature is 80 - 90 ° C.

After leaving the sizing trough, the cotton chains are dried with contact heat at approx. 130 ° C.

Instead of PVA, starch, modified starch or mixtures of these products can also be used. The cotton chains are then woven with the weft cotton yarn and the fabric obtained is padded with a solution having the following composition on a cold residence unit consisting of dyeing pad and docking device:
10 g / l CJ Reactive Blue 19 (CI No. 61200)
4g / l wetting agent (4-nonylphenol polyglycol ether).

The goods padded in this way are wrapped in an airtight manner on a dock with a polyethylene film and left to rotate for a maximum of 24 hours.

After the aftertreatment customary in the case of reactive dyes by rinsing, boiling soap and subsequent repeated rinsing, a dyeing with good fastness properties is obtained even without the amount of alkali normally required for fixing the reactive dyes. The pretreatment of the cotton chains with the reaction product described according to the invention moreover achieves a significantly deeper shade than with the previously customary fixation with alkalis. The weft of the colored material becomes practically white during the aftertreatment in the rinsing or rinsing process. A fabric with a denim effect is obtained.

Example 2

A bleached cotton fabric is placed on a 2 or 3-roll pad with a solution
60 g / l of the reaction product according to DE-A-1 619 391, Example 1 and
2 g / l di-2-ethylhexyl phosphate potassium salt
contains, padded and after drying padded with a liquor which
10 g / l Reactive Red 1 (CI No. 18158) and
2 g / l wetting agent (4-nonylphenol polyglycol ether)
contains.

The dyeing is lingered and treated according to Example 1 of this application. A deep red color is obtained with good fastness properties. The corresponding cold dyed dye, which was stained with the normal amount of alkali (NaOH / water glass), on the other hand, shows only a light pink shade.

The following table describes further examples that are made with different pretreatment agents. In all cases, dyeings are obtained which are distinguished from the conventional method of fixation with alkali by a deepening of color and by good fastness properties.

Claims (4)

1. A process for the dyeing and printing of cellulose fibers by means of reactive dyes, direct dyes, acid dyes, water-soluble sulfur dyes or sulfur vat dyes in the absence of alkali or reducing agents, which comprises pretreating the textile material to be dyed with a wetting agent and a reaction product of an epihalogenohydrin with ammonia or an amine of the formula

   

   in which

   A   is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms,

   R   is alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms,
   a group of the formula

   

   (n = 0 to 5),
   a group of the formula

   

   (X = oxygen or sulfur) (n = 0 to 5),

   or R and A together are

   

   and alkylene is in each case C₁-C₆-alkylene, preferably C₂-C₃-alkylene, subsequently dyeing them by conventional methods, but without alkali, by means of the dyes mentioned, and completing the dyeing by rinsing, soaping and drying.
2. The process as claimed in claim 1, wherein warp yarn is pretreated with the wetting agent and the reaction product together with the sizing liquor in a sizing bath.
3. The process as claimed in claim 1, wherein the reaction product is preferably used in an amount of 3 to 10 % of the weight of the material.
4. The process as claimed in claim 1, wherein a polymeric padding auxiliary is added to the dye padding liquor.