EP0358174A2 - Thermofixation process for dyeing and printing with reactive dyes or water soluble sulfur dyes in the absence of alkali or reducing agents - Google Patents

Abstract

The textile material is treated first with a wetting agent and a reaction product of polyethyleeimine and a bifunctional alkylating agent. Then it is dyed with reactive dyes or water-soluble sulphur dyes, thermofixed in the absence of alkali and finished in a conventional manner.

Description

In US Pat. No. 4,806,126 it was described that cellulose fibers can be dyed and printed with reactive dyes and also with water-soluble sulfur dyes without alkali and reducing agents if the textile material is pretreated with a wetting agent and a quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent. then dyes by conventional methods, but without alkali and reducing agents, with reactive dyes or water-soluble sulfur dyes and the dyeing is completed by rinsing, soaping and drying. Common methods are the block-cold dwell process and dyeing using the exhaust process.

It has now been found that the dyes mentioned in this process can be fixed not only on the fiber by the block-cold dwell process and on the pull-out process, but also by means of a heat-setting process.

The invention thus relates to a process for dyeing and printing with reactive dyes or water-soluble sulfur dyes in the absence of alkali or reducing agents, in which the textile material to be dyed is pretreated with a wetting agent and an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent, then with the aforementioned Dyes dye, dry, heat set and finished in the usual way.

The process according to the invention has the advantage that the long residence times of the block-cold residence process (for example 8 to 12 hours) are avoided.

A preferred auxiliary for the pretreatment is known from US 4,588,413. The aid is used there exclusively for the aftertreatment of dyeings with reactive dyes. Pretreatment with this aid and subsequent dyeing without alkali is not described there. A method exclusively for the aftertreatment of reactive dyeings with compounds of a similar structure is also described in GB-PS 2 006 279.

)_b-H      (I)

worin
X ein Rest der Formel -(CH₂-CH₂-NH)_c-H
a und b unabhängig voneinander Zahlen von 0 bis 600 sind
wobei die Summe a+b eine Zahl von 50 bis 600 ist und
c eine Zahl von 0 bis 50 ist.The polyethyleneimine required for the preparation of the pretreatment agent to be used preferably corresponds to formula I.
H- (CH₂-CH₂-NH) _a · - (CH₂-CH₂-

) _b -H (I)

wherein
X is a radical of the formula - (CH₂-CH₂-NH) _c -H
a and b are independently numbers from 0 to 600
where the sum a + b is a number from 50 to 600 and
c is a number from 0 to 50.

This means that the polyethyleneimine used is a molecule in which there are -NH₂,> NH and -N <building blocks which are linked together by ethylene groups. In total, the polyethyleneimine contains about 50 to 600 ethyleneimine units. In conventional commercial products, primary, secondary and tertiary nitrogen functions are in a numerical ratio of approximately 1: 2: 1.

In principle, all known bifunctional alkylating agents can be used for the reaction with the ethyleneimine of the formula I. Such known bifunctional alkylating agents correspond to formula II
A - Z - A (II)

In this formula, A is the residue of an alkylating agent and Z is either a direct bond or a divalent bridge member.

bedeutet und Z, sofern es keine direkte Bindung ist, für einen zweiwertigen geradkettigen oder verzweigten Rest der Formel III
-C_nH_2n-      (III)
worin n eine Zahl von 1 bis 4 ist, einen zweiwertigen Rest der Formel IV
-C_mH_2m-D-C_mH_2m-      (IV)
worin m die Zahlen 1 oder 2 bedeutet und D für -O-, -S-, -NH-, -CO-, -SO-, -SO₂-, oder für Phenylen steht.Particularly suitable for the reaction with the polyethyleneimines to assistants to be used according to the invention are those functional alkylating agents of the formula II in which A is a group of the formula -CH₂-Y, in which Y is a substituent which can be removed as an anion, in particular chlorine, bromine, iodine or -0H or a group which can be split off as an anion, in particular the sulfato group or a sulfonyloxy group, in particular phenylsulfonyloxy or p-tolylsulfonyloxy, or the epoxy group

means and Z, if it is not a direct bond, for a divalent straight-chain or branched radical of the formula III
-C _n H _2n - (III)
wherein n is a number from 1 to 4, a divalent radical of the formula IV
-C _m H _2m -DC _m H _2m - (IV)
wherein m represents the numbers 1 or 2 and D represents -O-, -S-, -NH-, -CO-, -SO-, -SO₂-, or phenylene.

Preferred for the reaction with polyethyleneimine to be used according to the invention are those bifunctional alkylating agents in which A are groups of the formula -CH₂-Y which are linked to one another via a bridge member of the formula IV, or those in which one of the radicals A is a group of Formula is -CH₂-Y, which is bonded directly to an epoxy group.

Examples of such bifunctional alkylating agents are epichlorohydrin, glycid, 1,3-dichloropropan-2-ol, ß, ß'-dichloro-diethyl ether, ß, ß'-dichloro-diethylamine, ß, ß'-dichloro-diethyl sulfide , ß, ß'-dichloro-diethylsulfoxide, ß, ß'-dichloro-diethylsulfone, ß, ß'-sulfatoethyl ether, ß, ß'-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzo, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxybutane -2-methylbutane, diepoxypropylamine.

To prepare the pretreatment agents to be used according to the invention, the polyethyleneimine and the bifunctional alkylating agent are reacted with one another in a weight ratio of from 100: 0.01 to 100: 2.0, preferably from 100: 0.1 to 100: 1.0.

It can be assumed that this reaction involves the installation of crosslinking bridging links between the polyethyleneimine chains. An external indication of this is that the viscosity of the aqueous solutions rises significantly when the crosslinked polyethyleneimine changes to the product crosslinked by the bifunctional alkylating agent. In principle, the polyethyleneimine can be reacted with the bifunctional alkylating agents without a solvent. In view of the better possibility of controlling the reaction and the more favorable heat dissipation, it is expedient to carry out the reaction in the presence of an inert solvent. Both organic solvents in which the reactants are soluble, such as, for example, lower alcohols, and in particular water, are suitable for this. The reaction can be carried out in the temperature range between -10 and about 100 ° C. The implementation in the environment of normal room temperature, ie in the range between 15 and 45 ° C., is particularly advantageous. This results in a reaction process with good control options, very good product quality and the lowest possible energy consumption. The reaction is essentially completed in about 1 to 2 hours.

In order to obtain aids to be used which have particularly narrowly tolerated specifications, i.e. In order to achieve particularly good reproducibility of the production process, it is advantageous, after the main reaction has ended, for the reaction mixture to have a defined pH between 9 and 10 for several hours, usually 2 to 6 hours, at elevated temperature, advantageously between 60 and 100 ° C afterwards.

The reaction products of polyethyleneimine used with a bifunctional alkylating agent can optionally also be quaternized with C₁-C₄, preferably C₁-C₃ alkyl groups. The quaternization can be carried out using alkyl halides, preferably alkyl chlorides, or dialkyl sulfates by known methods.

This aid described above is applied to the textile material to be dyed or printed together with a wetting and 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 to 80% by weight of ethylene oxide are used as such wetting or padding aids, but in particular nonionic compounds, for example oxyethylated nonylphenol. Raw or pretreated cotton or mixed fabrics containing cotton are suitable 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 or reducing agent-free over-dyeing with reactive dyes or water-soluble sulfur 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 padded with a padding liquor which contains dyes of the types mentioned. The goods are then dried, heat-set at 120 to 200 ° C for 0.5 to 1 minute and washed out cold and hot.

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 that leave an electrophilic residue, 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 groups in the case of sulfonylpyrimidothiazole or sulfonylbenzylbenzene . Specifically, dyes with the reactive groups ß-sulfatoethyl sulfone, ß-chloroethyl sulfone, ß-thiosulfatoethyl sulfone, ß-phosphatoethyl sulfone, chlorotriazinylamino, dichlorotriazinylamino, chlorotriazinyldiamino, trichloropyrimidylamino, Dichloropyrimidylamino, dichloropyridazinylamino, trichloropyridazinylamino, dichloropyridazinylcarbonylamino, 2-chloro-benzothiazol-6-yl-amino, 2-methylsulfonylbenzthiazol-6-yl-amino, 2,3-dichloroquinoxylin-6-yl-carbonylamino To mention 2-methylsulfonyl-pyrimid-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 and with water-soluble sulfur dyes, but also with sulfur vat dyes.

When dyeing with water-soluble sulfur dyes and sulfur vat dyes, the reducing agents used there, such as e.g. Na hydrogen sulfide, Na dithionite, Na sulfide, which leads to a reduction in wastewater pollution.

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 that contains a marking dye and the cationic aid to be used. After drying and fixing, the textile material is then over-dyed with reactive dyes or water-soluble dyes, preferably using the heat setting method. Another possibility is that one with the aid described pre-stained cotton fabric printed with a printing paste that contains the dye but no alkali. The dye is then fixed by heat treatment at 130 to 200 ° C. The 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 reducing agents, no alkali and no fixing agents are required in the subsequent dyeing. When the goods are subsequently washed out after dyeing, no alkali then goes into the wastewater, so that the salt load in the wastewater in the dyeing plants is substantially reduced. In addition, the pretreatment described also partially results in a significant deepening of the color of the dyeing compared to dyeing with the same amount of reactive dye in a 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 in the conventional processes, is significantly improved here 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.

Surprisingly, it would also be found that a washing process directly after the soaping process with detergents containing perborate significantly increases the brilliance of the dyeings. If the warp yarn in a denim fabric has been pretreated in the manner according to the invention, the weft thread, which has not been dyed or, depending on the dye shade, is slightly soiled, becomes white again due to the detergent containing perborate, and 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 and 50 ° C., preferably between 40 and 50 ° C. If the perborate-containing detergent is washed at higher temperatures, for example from 50 ° C. to 100 ° C., preferably from 85 ° C. to 100 ° C., the dyeing can be gradually lightened in stages to completely decolorize the fabric. In this way, uneven coloring or fashionable color changes (stone wash effect) are achieved in a way that is very gentle on the fibers. This effect can otherwise only be achieved with alkaline hypochlorite solution 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). Two formulations are described below as examples. 2. Soap 35 - 50% Tetrapropylene benzene sulfonate Fatty alcohol sulfate Fatty acid ethanolamide Na carbonate 14-18% Na water glass 6 - 10% Na diphosphate 5 - 8% Na triphosphate Na perborate 4 - 6% Magnesium silicate 1 - 3% Opt. Brightener 0.03% Carboxymethyl cellulose Perfume oil

example 1

Cotton warp yarns are treated as follows on a sizing machine in the trough provided:
40 g / l polyvinyl alcohol (PVA)
5 g / l polyethylene glycol
4 g / l di-2-ethylhexyl phosphate potassium salt
100 g / l polyethyleneimine condensation product according to the example in Table 1, last line of patent application EP 0 133 933
Fleet intake 100 to 120% (high-performance crushers)

The yarn runs at a speed of 60 m / min, the liquor temperature is 80 to 90 ° C.
After leaving the sizing trough, the cotton chains are dried with contact heat at approx. 130 ° C.
Instead of PVA, native and modified starch or mixtures of native or modified starch and PVA can also be used. The use of carboxymethyl cellulose or carboxymethyl starch as a sizing agent is not possible, since the cationic alkyl ethyleneimine Condensate can precipitate. The cotton chains are then woven with the weft of cotton and the fabric obtained is padded with a solution, for example 10 g / l CI Reactive Blue 19 (CI No. 61200) and on a system consisting of dyeing pad and dryer
4 g / l wetting agent (ethoxylated nonylphenol)
contains.

After drying, the fabric is heat set at 200 ° C for 1 min. In the aftertreatment customary for reactive dyes by rinsing, boiling soap and repeated rinsing, the chains are colored with good fastness to use even without the amount of alkali normally required for fixing the reactive dyes. The pretreatment of these cotton chains with the polyethyleneimine condensation product also results in a much deeper shade than with normal fixation with alkali. The shot practically turns white again after rinsing and soaping. A fabric with a denim effect is thus obtained.

Example 2

After the final rinsing and soaping process, the denim fabric sized and dyed as in Example 1 is treated with 5 g / l of a conventional detergent containing perborate (content of Na perborate 20% by weight) at 50-60 ° C. for 10 to 20 minutes .

This results in a much more brilliant shade of this denim fabric while maintaining the full strength and intensity of the dyeing. In addition, the whiteness of the weft yarn is again significantly improved compared to a denim fabric dyed in the same way, but which has not been washed with a detergent containing perborate.

Example 3

Instead of the recipe with Reactive Blue 19 mentioned in Example 1, the
25 g / l Solubilized Sulfur Red 11
impregnated. Aftertreatment and completion as under 1. An intense red color is obtained.

Example 4

A bleached cotton fabric is placed on a 2- or 3-roll pad with a solution that
60 g / l of the polyethyleneimine condensation product as in Example 1 and
2 g / l di-2-ethylhexyl phosphate potassium salt
contains, padded cold and after drying padded with a liquor which
10 g / l Reactive Red 1 (CI No. 18158) and
2 g / l of a wetting agent (ethoxylated nonylphenol)
contains.

The dyeing is dried according to Example 1 and 1 '200 ° C heat set. A deep red color is obtained with good fastness properties.

Instead of the Reactive Red 1
10 g / l Solubilized Sulfur Blue 7 (CI No. 53441)
used, dried and heat set at 1 '20 ° C. A deep blue color is obtained with good fastness properties.

Example 5

A bleached PES / cotton fabric is placed on a 2- or 3-roll pad with a solution of
60 g / l polyethyleneimine condensation product as in Example 1 and
2 g / l di-2-ethylhexyl phosphate potassium salt
cold padded and padded with a liquor after drying
150 g / l Solubilized Sulfur Red 11
30 g / l of a black dye consisting of
disperse blue 165 (CI 11077),
disperse orange 29 (CI 26077),
disperse red 184
2 g / l of oxyethylated nonylphenol
contains. Then it is dried at 120 ° C, 1 'heat set at 200 ° C, rinsed, soaped and rinsed again. A black-red bicolor color is obtained.

Claims (8)

1. A method for dyeing and printing with reactive dyes or water-soluble sulfur dyes in the absence of alkali or reducing agents, characterized in that the textile material to be dyed with a wetting agent and an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent, then dyed with the dyes mentioned , dries, heat-set and finished in the usual way. 2. The method according to claim 1, characterized in that warp yarn is pretreated with a wetting agent and a reaction product of polyethyleneimine with a bifunctional alkylating agent together with the size in a size bath. 3. The method according to claim 1, characterized in that the reaction product is preferably used in an amount of 3 to 10% of the weight of the goods. 4. Process according to claims 1 to 3, characterized in that a reaction product of polyethyleneimine with epichlorohydrin, 1,3-dichloropropan-2-ol or mixtures thereof is used. 5. Process according to claims 1 to 4, characterized in that a reaction product of polyethyleneimine with a bifunctional alkylating agent is used in a reactant weight ratio of 100: 0.01 to 100: 2. 6. The method according to claim 1, characterized in that a polymeric padding aid is added to the dye padding liquor. 7. Process according to claims 1 to 6, characterized in that the dyeings or prints are then washed with a detergent which contains a perborate and optionally a perborate activator and optical brightener. 8. The method according to claim 1, characterized in that heat-setting at 120 to 200 ° C for 0.5 to 1 minute.