EP0359104A2 - Uneven dyeing process of cellulose fibres in the absence of alkali or reducing agents - Google Patents

Abstract

The cellulose fibres are treated with an aqueous liquor containing a wetting agent, an optionally quaternised reaction product of polyethyleneimine with a bifunctional alkylating agent, and an anionic surfactant, and the material is dried and dyed without addition of alkali. This process can also be combined with a sizing process. The dyeings obtained are unlevel, making the textile materials suitable for making up into fashionable articles.

Description

The dyeing of textile materials, e.g. Woven fabrics, knitted fabrics or yarns and threads, consisting of or containing cellulose fibers with reactive dyes, can be carried out according to known processes in that the textile material is drawn out with a dyeing liquor containing a reactive dye, usually at elevated temperature and in most commercial reactive dye types in the presence of Alkali, is treated, 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 fixing 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 residence process by docking the impregnated goods and staying 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 has become known and is practiced industrially.

All of these dyeing processes are designed to obtain the most uniform possible distribution of the dyes over the length and width of the textile fabric.

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.

U.S. Patent 4,806,126 describes a process for dyeing cellulosic fibers with reactive dyes in which the presence of alkali is not required. The fixation of the dyes on the fibers is achieved in this process by pretreating the fibers with a reaction product of polyethyleneimine and a bifunctional alkylating agent before dyeing.

In a further embodiment of this process, it has now been found that uneven colorations are obtained if an additional anionic surfactant is added to the liquor which contains the stripper. In this way, dyeings with light-dark effects are obtained, which open up new possibilities for the fashionable design of textiles.

The invention relates to a process for the uneven dyeing of cellulose fibers in the absence of alkali or a reducing agent, characterized in that the cellulose fibers are treated with a liquor which contains a wetting agent, an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent and an anionic surfactant, dries and dyes with reactive, direct or water-soluble sulfur dyes without the addition of alkali.

The auxiliary device required for the pretreatment is known from US Pat. No. 4,588,413. The aid is used there exclusively for the aftertreatment of dyeings with reactive dyes. Pretreatment with this auxiliary and subsequent dyeing without alkali or reducing agent 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 to produce the pretreatment agent to be used according to the invention 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, the sum a + b being 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 -NH₂, and> NH and -N <building blocks are present, 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, einen zweiwertigen Rest der Formel IV
-C_mH_2m-D-D_mH_2m- (IV)
worin m die Zahlen 1 oder 2 bedeutet und D für -O-, -S-, -NH-, -CO-, -SO-, SO₂-, oder für Phenylen steht.Those bifunctional 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 split off as an anion, in particular chlorine, bromine, iodine or -OH 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 -DD _m H _2m - (IV)
wherein m represents the numbers 1 or 2 and D represents -O-, -S-, -NH-, -CO-, -SO-, SO₂-, or phenylene.

Those preferred for the reaction with polyethyleneimine to auxiliaries to be used according to the invention are those bifunctional alkylating agents in which A are groups of the formula -CR₂-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 the formula -CH₂-Y which is directly attached to an epoxy group is bound.

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

To produce 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 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 increases significantly when the non-crosslinked polyethyleneimine is transferred 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 lower alcohols and especially water. 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 according to the invention which have particularly narrow-tolerance 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 according to the invention 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 together with a wetting or padding agent customary in the textile industry and an anionic surfactant from an aqueous liquor. Such wetting or padding aids are, for example, propylene oxide / ethylene oxide block polymers with a proportion of 40-80% by weight of ethylene oxide, but especially ethoxylated nonylphenol.

All known compounds of this type are suitable as anionic surfactants, for example sec. Alkanesulfonates, alkyl sulfates, alkyl ether sulfates, fatty acids, alkylbenzenesulfonates, olefin sulfonates, di-alkyl sulfosuccinates or di-alkyl phosphates. The presence of the anionic surfactants is of crucial importance for the process according to the invention, because the anionic surfactants form agglomerates and precipitates with the optionally quaternized reaction products of polyethyleneimine with a bifunctional alkylating agent, which deposit on the fibers in an uneven form and thus ensure an uneven coloring .

The pretreatment with the auxiliary, together with the nonionic wetting agent and the anionic surfactant, is carried out from an aqueous liquor by customary methods by padding or in the exhaust process at temperatures of about 20 to 70 ° C., preferably 40 to 60 ° C. The liquor is adjusted to a weakly acidic pH, preferably pH 6. The amount of auxiliary is about 5 to 100 g / l, preferably 30 to 80 g / l. The amount of wetting agent is preferably 0.5 to 4 g / l and the amount of anionic surfactant is approximately 1 to 80 g / l. The pretreatment liquor is then squeezed off and the goods are dried.

Raw or pretreated cotton or mixed fabrics containing cotton are suitable as textile materials.

The goods pretreated in this way are then dyed using customary processes and on customary dyeing units with direct dyes, reactive dyes or sulfur dyes containing sulfo groups, for example using the cold residence process or an exhaust process. The Fleet ratio can be about 1: 3 to 1:40. It is important, however, that, in contrast to the previously customary procedure, no alkali and no reducing agent 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 towards 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 sulfonylpyrimzthiazonyl or sulfonylcarbonyl sulfonyl or sulfonyl sulfonyl . In particular dyes are sulfatoethylsulfone β-with the reactive groups, β-chloroethyl, β-Thiosulfatoethylsulfon, β-Phosphatoethylsulfon, Chlortriazinylamino, Dichlortriazinylamino, Chlortriazinyldiamino, Dichlorpyridazinylamino, Trichlorpyridazinylamino, Dichlorpyridazinylcarbonylamino, 2-chloro-benzothiazole-6-yl-amino, 2, To mention 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. To 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 and water-soluble sulfur dyes. Similar effects and fastness properties are achieved with these dyes as with the reactive dyes. In addition, pigment dyes such as vat and sulfur vat dyes can also be used in the process.

A variant of the method according to the invention is that it is not a finished fabric that is pretreated and dyed, but only the warp yarns, expediently in combination with a sizing treatment. In this variant, the warp yarn made of cellulose is treated according to customary methods with a size liquor which, in addition to the usual wetting agent, contains an anionic size and the pretreatment agent described above. The amount of sizing agent is usually 10 to 100, preferably 20 to 40 g / l. The warp yarn is then dried and woven with a white weft yarn. When this fabric is over-dyed using customary methods, but in the absence of alkali, a denim fabric is obtained which has an interesting fashionable effect due to the uneven dyeing of the warp yarn. In this process, in which the pretreatment with the special pretreatment agent is combined with the size, the anionic surfactant is replaced by an anionic size agent. Examples of such anionic sizing agents are carboxymethyl cellulose, carboxymethyl starch, degraded starches, polysaccharides, galactomanes, acrylates or polyesters.

Through a washing process immediately following the soaping process with detergents containing perborate, the brilliance of the dyeings can be increased significantly and the weft thread, which has not been dyed or, depending on the dye shade, slightly soiled, can become white, 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 if the washing is carried out between 20 - 25 ° C. If you wash with the detergent containing perborate at elevated temperatures, for example 50 to 100 ° C., the dyeing can be gradually lightened until the fabric is almost completely decolorized. In this way, spotty dyeings 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 by washing in the presence of pumice stones. However, stones, sand and / or surfactants can be added to the treatment bath to discolor or modify the washing effect.

example 1

Cotton warp yarns are treated as follows on a sizing machine in the trough provided:
30 g / l sodium carboxymethyl cellulose (CMC)
3 g / l non-ionic wetting agent (nonylphenol + 10 EO)
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 - 120% (high-performance crushing unit)

The sodium carboxymethyl cellulose used has a viscosity of 300 mPa · s in a 2% strength aqueous solution at 20 ° C., measured in a falling ball viscometer (commercial product Tylose C 300).

The yarn runs at a speed of 60 m / min, the temperature of the sizing liquor is 80 - 90 ° C. After leaving the sizing trough, the yarns run over drying cylinders and are dried by contact heat at approx. 130 ° C.

Instead of the CMC size, a mixture of CMC and modified starch can also be used.

Then the so-sized cotton chains are woven with raw white cotton weft and the fabric obtained is padded with a solution on a cold dwelling system consisting of dyeing pad and docking device

10 g / l CI Reactive Blue 19 (CI No. 61200)
and 3 g / l non-ionic wetting agent (nonylphenol + 10 EO)
contains.

The goods padded in this way are wrapped airtight on the dock with a polyethylene film and left to rotate for up to 24 hours.

After the aftertreatment customary for reactive dyes by rinsing, boiling soap with a surfactant and rinsing again, an uneven coloring of the cotton chains with good fastness properties is obtained even without the amounts of alkali normally required for fixing the reactive dyes. In addition, this process does not produce this with the polyethyleneimine condensation product pre-pickled weft practically white again. A fabric with a denim effect is thus obtained.

Example 2

On a sizing machine, cotton warp yarns are treated as follows in the trough provided:
60 g / l carboxymethyl starch (CMS)
3 g / l non-ionic wetting agent (nonylphenol + 10 EO)
80 g / l of a reaction product of polyethylene lmin with a bifunctional alkylating agent quaternized with dimethyl sulfate / commercial product: ^(R) Solidogen FFL)
Fleet absorption 100 - 130% (high-performance crushing unit).

The yarn runs at a speed of 60 m / min, the temperature of the sizing liquor is 80 - 90 ° C. After leaving the sizing trough, the yarns run over drying cylinders and are dried by contact heat at approx. 130 ° C.

Then the cotton chains, which are so simply sized, are woven with raw white cotton weft. The tissue obtained is padded on a dyeing pad with an aqueous solution which
40 g / l CI Solubilized Sulfur Red 11
3 g / l wetting agent (ethoxylated nonylphenol)
contains.

In a continuous dyeing steamer, steaming takes place at 102 - 104 ° C for 60 seconds.

After an aftertreatment, which is also customary for reactive dyes, by rinsing, boiling soaping with a surfactant and rinsing again, an uneven, light-dark-stained dyeing of the cotton chains is obtained even without the reducing agent and alkali amounts normally required for dyeing and also without the chemicals required for oxidation with good fastness properties. In addition, the weft yarn that has not been pre-pickled with Solidogen FFL practically becomes white again through this process. A spotty fabric with a denim effect is thus obtained.

Example 3

Cotton warp yarns are treated as follows on a sizing machine in the trough provided:
50 g / l polyvinyl alcohol (PVA)
3 g / l wetting agent (nonylphenol + 10 EO)
20 g / l alkanesulfonate (commercial product: ^(R) Hostapur SAS)
100 g / l polyethyleneimine condensation product according to the example in Table 1, last line of patent application EP 0 133 933.
Fleet absorption 100 - 120%

The yarn runs at a speed of 60 m / min., The temperature of the sizing liquor is 80 - 90 ° C. After leaving the sizing trough, the yarns run over drying cylinders and are dried at approx. 130 ° C.

Then the so-sized cotton chains are woven with raw white cotton weft and the fabric obtained is processed into garments. The items of clothing, eg men's trousers, are washed on a paddle dyeing machine in a 1:40 liquor ratio at 30 ° C for 40 min. treated with an aqueous bath containing 1% by weight of Blue 77 reactive.

After the aftertreatment usual for reactive dyeings by rinsing, soaping and rinsing, a turquoise blue shade with light and dark spots is obtained. The coloring shows good fastness properties.

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
3 g / l of a wetting agent (nonylphenol + 10 EO)
and 14 g / l of degraded starch
contains, cold padded and dried. The 30 ° C warm liquor for this auxiliary block is 30 min. set up before use and kept in motion during this waiting period with a slowly running agitator (approx. 60 rpm) in order to achieve agglomeration of the aids.

After drying, padding with a liquor
30 g / l CI Reactive Yellow 15
and 4 g / l of a wetting agent (nonylphenol + 10 EO)
contains.

The dyeing is lingered and treated according to Example 1. A yellow color is obtained with light and dark spots and good fastness properties.

Claims (6)

1. A process for the uneven dyeing of cellulose fibers without alkali or reducing agent, characterized in that the cellulose fibers are treated with a liquor which contains a wetting agent, an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent and an anionic surfactant, dries and without the addition of Alkali colors. 2. A process for the uneven dyeing of cellulose fibers without alkali or reducing agents to achieve denim special effects, characterized in that a warp yarn made of cellulose fibers is treated with a size liquor containing a wetting agent, an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent and contains an anionic sizing agent, dries, woven with weft yarn and dyes without the addition of alkali. 3. The method according to claim 1 and 2, characterized in that the reaction product is preferably used in an amount of 5 to 100 g / l. 4. The method according to claim 1 and 2, characterized in that the anionic surfactant is used in an amount of 1 to 80 g / l. 5. The method according to claim 1 and 2, characterized in that a reaction product of polyethyleneimine with epichlorohydrin, 1,3-dichloropropan-2-ol or mixtures thereof is used. 6. The method according to claim 1 and 2, 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.