DE3320629A1 - Process for dyeing textile materials made of hydrophilic fibres - Google Patents

Abstract

Process for dyeing textile materials made of cellulose fibres or wool, optionally in a blend with synthetic fibres, by first producing on the textile materials a firmly adherent film by applying thereto (a) water-soluble compounds containing primary and/or secondary basic amino groups and (b) water-soluble compounds which contain propylene chlorohydrin groups, the water-soluble condensates which are obtained therefrom and which contain epoxides, N-methylol or N-methylol ether groups, then drying the textile material and dyeing in a conventional manner with reactive or acid dyes in an aqueous medium at a pH from 6 to 12.

Description

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Process for dyeing textile materials made from hydrophilic fibers

Dyed denim fabrics made from cellulosic fibers are widely used in the Technique made by having the warp yarn before weaving, for example dyes blue with indigo and leaves the weft threads of the fabrics undyed or dyed differently. The denim fabrics are mainly used to make Jeans and work clothes. A special feature of denim fabrics compared to other fabrics is their behavior when washing. The chain of the denim fabric dyed with indigo becomes after several Wash lighter and get a more brilliant tone. Just this effect is desired by consumers. The application of indigo takes place on special, relatively expensive dyeing machines, which are not in everyone Operation are encountered.

The object of the invention is to provide a method for dyeing textile materials made of cellulose fibers or wool, optionally mixed with synthetic fibers, with reactive dyes or acid dyes in aqueous To provide medium at pH values of 6 to 12, which can be carried out on systems that are widely used in textile finishing companies are, and the dyed goods that show a washout behavior, as is known from denim fabrics that are dyed with indigo.

The object is achieved according to the invention that one on the textile Materials first created a firmly-adhering film by placing on it 25th

a) containing polyfunctional primary and / or secondary basic amino groups water soluble compounds and

b) water soluble containing two or more propylene chlorohydrin groups Compounds, the epoxides or N-methylol- or water-soluble condensates of urea, melamine, acrylamide and formaldehyde containing N-methylol ether groups

then applies the textile material in the form of an aqueous solution dries and stains in the usual way.

Textile materials dyed by the process of the invention are, for example, threads, yarns, woven, knitted or non-woven fabrics. They consist of hydrophilic fibers such as cellulose fibers, cellulose ester -Fibers or wool as well as from mixtures of cellulose fibers with synthetic fibers, preferably polyester fibers, or from fiber mixtures of Wool and polyester fibers. It is preferred to dye threads and yarns

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Cellulose fibers. With the use of suitable wetting agents, raw cotton can also be used so colored.

The dyes are water-soluble reactive dyes and acid dyes into consideration. These dyes are fully described in the Color Index; they are commercially available. Essential feature The reactive dye is the reactive group through which the chromophoric part of the dye molecule is bound to the substrate to be colored will. Examples of reactive groups are vinyl sulfone, ß-sulfatoethyl sulfone, ß-chloroethyl sulfone and ß-dialkylaminoethyl sulfone groups or heterocycles substituted by 1 to 3 halogen atoms, such as triazine, pyridazine, pyridazone, quinoxaline and pyrimidine. The reactive dyes can contain one or more reactive groups. The chromophoric part of the reactive dye molecule derives first Line of azo compounds, diazo compounds, metal complexes of azo dyes, Anthraquinone derivatives and phthalocyanino compounds.

The acid dyes, like the reactive dyes, are water-soluble making substituents, such as one or more sulfonic acid groups or Carboxyl groups and belong to the azo, anthraquinone, phthalcyanine, diazo and metal complex dyes. For the method according to the invention reactive dyes are preferably used. The dye liquor contains the specified dyes in the usual amounts, e.g. 0.5 to 100 g / l and can also use the auxiliaries commonly used in dyeing, such as wetting agents, leveling agents, anti-migration agents, complexing agents, surfactants, foam suppressors, Contain oxidizing agents, salts and dispersants.

First of all, the textile materials that are to be colored a tightly adhering, water-insoluble film made of two different ones Groups of compounds (a) and (b) which react with one another are formed. These compounds are known substances. The connections of group (a) contain primary and / or secondary amino groups. They are soluble in water. Connections of this type are for example Polyalkylenepolyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Dipropylenetriamine and tripropylenetetramine. Polyethyleneimines also belong to this class of compounds. Commercial products of this type contain, for example, 5 to 500 ethyleneimine units. In addition to the polyalkylenepolyamines and polyethyleneimines, derivatives thereof are also suitable, for example partially protonated, acylated, partially alkylated products. Protonated products are obtained by partial neutralization of the compounds mentioned with acids such as hydrochloric acid, Sulfuric acid, phosphoric acid, formic acid or acetic acid, while partially acylated derivatives by conversion of the polyalkylene poly-

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amines or the polyethyleneimines, e.g. with acetic anhydride or urea can be obtained. Suitable alkylating agents are alkyl halides, such as methyl chloride, ethyl chloride, lauryl chloride, benzyl chloride or alkyl sulfates such as dimethyl sulfate and diethyl sulfate.

Polyamidoamines, which are also suitable as compounds of group (a) come, are obtained, for example, by reacting dicarboxylic acids having 4 to 10 carbon atoms with polyalkylenepolyamines which have 3 to Have 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, Glutaric acid, suberic acid, sebacic acid or terephthalic acid. For the production of the polyamides it is also possible to use mixtures of dicarboxylic acids to use, e.g. mixtures of adipic acid and maleic acid. Adipic acid is preferably used. The dicarboxylic acids are made with polyalkylene polyamines or mixtures thereof condensed which contain 3 to 10 basic nitrogen atoms in the molecule, e.g. diethylenetriamine, triethylenetetramine, Tetraethylene pentamine, dipropylene triamine, tripropylene tetramine or dihexamethylene triamine. The amines can optionally contain up to 10% by weight of a diamine, such as ethylenediamine or hexamethylenediamine. The condensation of the dicarboxylic acids with the polyalkylene polyamines is preferably carried out in bulk, but can also be carried out in one solvents inert to these substances are made. The condensation takes place in the temperature range from 80 to 200 "C. That at water resulting from the reaction is distilled off from the system. The condensation can also take place in the presence of lactones or lactams of carboxylic acids can be made with 5 to 12 carbon atoms. These products are condensed into the polyamidoamine. Per mole of dicarboxylic acid it is preferred to use 0.8 to 1.4 moles of a polyalkylenepolyatin. The condensation reaction is carried out so far that water-soluble polyamidoamines are formed.

The polyamidoamines can also be modified cationically by Ethylenimine or propylenimine grafted on. The easiest way to do this is to react to the polyamidoamines in the presence of acids or Lewis acids such as boron trifluoride addition compounds, sulfuric acid or alkylbenzenesulfonic acids, ethyleneimine or propyleneimine can act. This grafting reaction is used based on 100 parts by weight a polyamidoamine, 10 to 400, preferably 50 to 300 parts by weight of ethyleneimine or propyleneimine.

Homo- and copolymers are also suitable as compounds of group (a) of N-vinylamine or 2-vinylimidazoline. Method of manufacture of polymers containing polymerized N-vinylamine units,

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are for example from GB-PS 1 044 956, GB-PS 1 094 794, the DE-OS 17 20 671 and EP-A-71 050 are known. Homo- and copolymers of 2-vinylimidazolines can be prepared as described in U.S. Patent No. 4,006,247 will. In order to get to compounds containing NH groups, one starts from 2-vinylimidazolines, which are in the 3-position as a substituent have a hydrogen atom.

Another class of compounds of group (a) is obtained by hydrolysis of homo- and copolymers of 1-vinylimidazolines in the alkaline pH range. Polymers of l-vinyl-2-imidazolines are for example in U.S. Patent 3,473,901. These polymers can also thereby be obtained by the corresponding l-vinyl-2-imidazolinium salts subjected to homopolymerization or copolymerization. In the treatment of the water-soluble polymers containing l-vinyl-2-imidazoline units with bases, e.g. in the pH range from 7 to 13, one obtains with opening of the imidazoline ring containing NH or N ^ groups.

Water-soluble compounds are also suitable as compounds of group (a) Resins that are formed during the reaction of ammonia or amines, such as ethylene diamine, with epichlorohydrin or ethylene chloride and which do not contain epoxy or contain chlorohydrin groups. Another class of compounds are water-soluble homo- or copolymers of di (C2-Co) -alkylamino (C2-Cg-alkyl) acrylates or the corresponding ones which are grafted with ethyleneimine Methacrylates or di (C2-C3) -alkylamino (C2-Cg-alkyl) amides of the acrylic or methacrylic acid, e.g., dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl acrylamide, diethylaminoethyl acrylamide and dimethylaminoneopentyl acrylate or methacrylate. These polymers, as well as those containing carboxyl groups other polymers, e.g. copolymers of acrylic acid and styrene or saponified copolymers of maleic anhydride and styrene or copolymers of Vinylimidazole or methyldiallylamine with ethyleneimine or propyleneimine grafted as described above for the polyamidoamines.

The compounds of group (a) contain 20 to 400 mg nitrogen per gram as primary or secondary basic amino groups. This content can be determined by titrating a compound of group (a) in glacial acetic acid with perchloric acid initially the total nitrogen content determined (sum of primary, secondary and tertiary amino groups) and with the help of a second titration of another sample of the to The compound being investigated determines the content of tertiary amino groups by treating the primary and secondary amino groups with acetic anhydride acylated and then determined by titration in glacial acetic acid with perchloric acid, the content of tertiary amino groups. The difference between the two

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The values obtained from the two titrations then give the content of primary and secondary basic amino groups of the compound of group (a).

Compounds of group (b) are those containing propylene chlorohydrin groups water-soluble compounds and the epoxides resulting therefrom in the alkaline pH range are considered. The connections of this group contain at least 2 propylene chlorohydrin groups

- CRj - CH - CH ₉

OH Cl

These products are, for example, cationic thermosetting Resins obtained by reacting polyamidoamines with epichlorohydrin in an aqueous medium. Such products are for example used for wetting paper (see U.S. Patent No. 2,926,116). Per 100 parts by weight of a polyamidoamine, 80 to 250 parts by weight are used, preferably 100 to 200 parts by weight of epichlorohydrin. Other suitable connections of group (b) are polymers quaternized with epichlorohydrin Allylamines, as described for example in DE-AS 21 03 .617. In addition, water-soluble polymers are suitable as polymers of group (b) Cationic thermosetting resins obtained by reacting epichlorohydrin with polymers containing amino groups. Such products are for example in EP-A-16 623, pages 15 to 18 described.

Further compounds of group (b) are the addition products of epichorohydrin to water-soluble polyalkylene oxides or to alcohols with 2 to 6 OH groups. Suitable polyalkylene oxides are, for example, the addition products of ethylene oxide on glycol or on polyol with more than 2 alcoholic hydroxyl groups, water, per mole of polyol or Glycol adds 2 to 100 moles of ethylene oxide. Block copolymers of ethylene oxide and propylene oxide are also suitable. The content of propylene oxide is adjusted so that water-soluble polymers are still obtained in each case. Water-soluble ones can also be used as polyalkylene oxides Use homopolymers of propylene oxide, which can be obtained, for example, by adding propylene oxide to water, propylene glycol, glycol or other alcohols. Alcohols with 2 to 6 OH groups that are reacted with epichlorohydrin are, for example, ethylene glycol, propylene glycol, Glycerol, sorbitol and pentaerythritol. The implementation with epichlorohydrin is carried out in such a way that at least 2 OH groups of the polyalkylene oxides or of the polyhydric alcohols mentioned are treated with epichlorohydrin

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are set. The reaction products are preferably used as component (b) the reaction of epichlorohydrin with polyethylene glycol having a molecular weight of 200 to 1000, with optionally ethoxylated Trimethylolpropane, with ethoxylated sorbitol or pentaerythritol. If the ethoxylated compounds are used, has 1 to 50 mol of ethylene oxide are added to each OH group of the ethoxylated compound.

Compounds of group (b) also include N-methylol or N-methylol ether groups containing water-soluble condensates of urea, melamine, acrylamide and formaldehyde into consideration. Connections of this kind will be produced by condensing urea with formaldehyde and the N-methylol ether groups of the resulting resins with alcohols, if appropriate etherified. It is preferred to use condensation products from this class of substances, the condensation of urea with formaldehyde in a molar ratio of 1:10 to 20 initially in the alkaline and then possibly in the acidic range and neutralization of the resin. Other suitable methylol compounds are derived from melamine, ethylene urea, Propylene urea, l, 3-diaza-5-oxa-diazinon (2), bis-hydroxyethylene urea, Acetylene urea and others.

The chlorohydrin group content of the compounds (b) is determined by Saponification of the chlorohydrin-chlorine with adjusted alcoholic caustic soda and back titration of the caustic consumption. The methylol group content and the amount of free formaldehyde can be determined according to H. Petersen, Melliand Textilberichte 54, 415, 529, 669 (1973) and Textilveredlung 3_, 629 (1968) and 8_ (1973), 412.

The content of propylene chlorohydrin groups or of epoxy groups formed therefrom -Groups in the compounds of component (b) is 0.4 to 8 meq / g of compound (b).

The compounds of group (a) and (b) are in the form of an aqueous Solution applied to the textile material either separately from one another or in a mixture. The textile materials are preferably impregnated with aqueous solutions containing mixtures of components (a) and (b). The concentration of the two different groups of compounds in the aqueous solution is in each case 1 to 50 g / l (100% product). Regarding the use of the connections of the two different ones There are numerous possibilities for groups. Some of these are explained in more detail in the following examples. You can do both Mixtures of compounds of group (a), e.g. a water-soluble polyamidoamine and polyethyleneimine or mixtures of polyethyleneimines

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of different molecular weights, optionally together with polyalkylene polyamines and / or polymers containing N-vinylamine units. It is also possible to use mixtures of compounds (b), for example mixtures of a polyethylene glycol of molecular weight 300, reacted with 2 epichlorohydrin in a mixture with a polyamidoamine which contains propylene chlorohydrin groups. The pH of the liquors is set between 6 and 12, preferably between 8 and 10. When using acidic crosslinking products (for example the methylol compounds, the pH can also be lowered to 4. The liquor pick-up when the compounds in groups (a) and (b) are applied is 70 to 120, preferably 80 to 100 7 Compounds of groups (a) and (b) are used in such a ratio that when the compounds condense on the textile materials, a water-insoluble resin is formed which adheres firmly to the textile materials Group (a) at least 0.1 part by weight of the compounds of group (b), preferably 1 to 10 parts by weight of compounds (b) based on 1 part by weight of the compounds (a) To apply an aqueous solution of the compounds (a) and (b) to the textile material, the devices customary in textile dyeing, for example a padder or padding device, are used.

The textile material impregnated with the compounds (a) and (b) is dried, specifically at temperatures of 80 to 200, preferably from 120 to 140 ^° C. In general, drying times of about 1 to 2 minutes at a temperature of 120 "are sufficient. are C in order for the compounds (a) and (b) If react. lower temperatures for the drying process selected ₅ must extend the drying time accordingly. the provided with a film text lien materials are then placed in an aqueous medium with the above-described reactive dyes or Dyed with acid dyes, dyeing can be carried out either by an exhaust process or by the padding process. The pH value during dyeing is between 6 and 12, preferably between 7 and 10.

Together with the compounds of groups (a) and (b) one can in the case of warp yarns also apply the sizing agent required for the weaving process to the warp yarn at the same time. After that the warp threads dyed or warp yarns and woven into fabrics that are then washed. In this way, fabrics are obtained whose chains are colored and whose weft threads remain undyed (Deniüi fabrics). The warp threads and warp yarns can also be dyed using this method in the absence of a sizing agent, then sized and then processed into a fabric will. Denira fabrics are then also obtained. Another possibility consists of the warp threads together with the connections of the

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Groups (a) and (b) to size, to weave, and then finally to to dye. Here, too, one obtains dyed textile materials in which only the chain is dyed because it was previously with the connections of the Groups (a) and (b) was treated. The dyes used here do not affect the untreated textiles under the dyeing conditions Materials on.

If, however, a fabric is treated with the compounds (a) and (b), dried and dyed, the warp and weft threads are evenly dyed. The dyeing is carried out in the usual way, for example by padding the dye onto the impregnated and dried fabric and then drying the fabric at higher temperatures, for example 120 ^° C., and then washing it. However, dyeing can also be carried out using the so-called cold batch process, by letting the treated textile material padded with the dye liquor remain for 1 to 3 hours and then washing it. If the exhaust process is used for dyeing, dyeing times of about 60 minutes at room temperature are sufficient. The depth of color of the dyed textile materials depends essentially on the amount of compounds (a) and (b) used, ie on the thickness of the firmly adhering film formed on the textile material, and on the dye concentration in the dye liquor. The process according to the invention gives very high fixation yields and very good depths of color. The textile materials dyed according to the invention also have very good dry rub fastness, good behavior in multiple washes and satisfactory light fastnesses. The properties mentioned correspond to the indigo color or are better. This means that denim articles in all colors can be produced by the process according to the invention. Compared to dyeing with indigo, the process according to the invention means a simplification and a cheaper price, with lower energy costs and lower wastewater pollution in particular.

The parts given in the examples are parts by weight, the data in percent relate to the weight of the fabrics. The content of primary and secondary amino groups was determined according to that given on page 4 Method determined. The chlorohydrin groups were determined according to the information on page 6.

The viscosities reported in the examples were measured in a Brookfield viscometer at a temperature of 20 ⁰ C, spindle 1 at 20 rpm.

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Compounds of groups (a) and (b) used in the examples became:

Compounds of group (a)
05

Amino compound 1 :

50% aqueous solution of a polyethyleneimine, the 50 ethyleneimine-one. contains units.

Amino compound 2 :

50% aqueous solution of a polyethyleneimine containing 500 ethyleneimine units contains.

Amino compound 3

A polyamidoamine was first prepared by adding 2800 g (19.2 mol of adipic acid with 2440 g of aminopropylethylenediamine in the presence of 1044 g of water condensed under nitrogen. The water was distilled off within 5 hours and the reaction temperature was increased to 170.degree increased. The condensation was continued at this temperature until the resin had an acid number of 7 mg KOH per gram. The amine number of the 100% resin was 4.08 mg, the viscosity of a 33% aqueous Resin solution was 80 mPas.

400 g of a 50% strength aqueous solution of the polyamidoamine from adipic acid and aminopropylethylenediamine was mixed with 4.5 g of concentrated sulfuric acid and at 80 ° C. within 5 hours with 200 g of 50% strength aqueous Ethylenimine implemented. After about 3 hours of post-condensation at 80 ° C., no more ethyleneimine could be found in the reaction mixture with p-nitrobenzylpyridine be detected. The viscosity of a 45% aqueous solution of the Resin was 390 mPas, the content of primary and secondary amino groups in the resin was 2.6 mmol per gram.

Compounds of group (b)

Chlorohydrin compound 1 :

A polyamidoamine was first prepared by adding 2150 g (21 mol) of diethylenetriamine and 2800 g (19.2 mol) of adipic acid in the presence of 1044 g of water under a nitrogen atmosphere and with distilling off the Water condensed within 5 hours. The temperature in the reaction mixture was raised to 170 ° C and maintained until the resin had an acid number of less than 10 mg KOH per gram. This was the case after about 8 to 10 hours. The reaction mixture was then left cool to a temperature of 130 ° C and added the melt to

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then with 3100 g of water. An aqueous approximately 60% solids was obtained Resin solution containing a polyamidoamine with an acid number of 5.7 mg KOH per gram The viscosity of a 45% strength aqueous solution was 202 mPas.

100 g of the approximately 60% strength aqueous solution of the polyamidoamine were diluted with 135 g of water and ^{32 g of epichlorohydrin were added at a temperature of 40 to 50 °} C. over the course of 20 minutes. The reaction mixture was held for 2 hours at a temperature of 50 ⁰ C and then warmed to 65 to 70 ⁰ C until a viscosity of 800 mPas (measured at 20 ° C) had been reached. 100 g of water were then added and the mixture was heated to 70.degree. The viscosity increased in the process. The condensation was continued until a sample had a viscosity at 20 ° C. of 700 to 800 taPas. The reaction mixture was then ^{cooled to 30 °} C., adjusted to a pH value in the range from 4.0 to 4.5 with concentrated hydrochloric acid and diluted with water to a solids content of 20%. A clear aqueous solution of a resin containing propylene hydrin groups with a viscosity of the 20% strength aqueous solution at 20 ^° C. of 130 mPas was obtained. The acid number of the resin was 0.21 mmol per gram, the total chlorine content 1.15 mmol per gram and the chloride content 0.76 mmol per gram.

Chlorohydrin compound 2 :

300 g of polyethylene glycol with an average molecular weight of 300 were placed in a flask, heated to 70 ° C. and 0.9 g of boron fluoride hydrate were added ⁰ to 75 C. Within 2 hours, at a temperature of 75 "C the Epoxidtiter fell below 0.05 mmol per gram. the cooled to room temperature, clear, viscous resin had a chlorohydrin content of 4.6 mmol per gram (Hexaglykol- to Propylenchlorhydrinether ).

example 1

A boiled cotton yarn was immersed in an aqueous liquor which

50 parts of polyvinyl alcohol which was completely saponified, 15 parts of the amino compound 1 and 60 parts of the chlorohydrin compound 1 contained. The pH of the liquor was 8.5. The cotton yarn was squeezed off to a liquor pick-up of about 90 % and dried at a temperature of 120 ^° C. for 2 minutes. The yarn treated in this way was then immersed at room temperature in an aqueous liquor containing 20 parts of the yellow reactive dye of CINr. Contained 13 245 per 1000 parts of liquor. The pH of the liquor was 8.5. The textile material was then squeezed off so that

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the liquor pick-up was 90%. It was then dried for 2 minutes at a temperature of 120 ^° C. A dyed warp yarn was obtained which was woven into a fabric and then soaped in a wide washing machine using 1 part per 1000 parts of liquor of a commercial detergent at boiling temperature. A yellow fabric corresponding to the denim article was obtained with properties which are desired from denim articles, ie sufficient resistance to light and gradual lightening without clouding of the coloration with repeated washing.

Example 2

A boiled cotton yarn was immersed in a liquor which contained 50 parts of a commercially available starch ether, 30 parts of the amino compound 2 and 120 parts of the chlorohydrin compound 2 per 1000 parts. The pH of the liquor was adjusted to 8.5. The cotton yarn was then squeezed off to a liquor pick-up of about 90% and ^{dried at a temperature of 120 °} C. for 2 minutes. The cotton warp yarn, coated in this way with a firmly adhering film, was then dyed by immersing it in a liquor adjusted to pH 8.5 containing 50 parts of the blue reactive dye of CINr per 1000 parts. 61 205: 1. The yarn was squeezed off to 90% liquor pick-up and dried at a temperature of 120 ° C. for 2 minutes. The warp yarn was then woven, and the fabric was then soaped in a wide washing machine using one part per 1000 parts of liquor of a commercially available detergent at boiling temperature. A dark blue fabric was obtained in which only the warp threads were colored. This fabric corresponds in its properties to a denim article dyed with indigo.

Example 3

A pre-cleaned cotton fabric was impregnated with a solution containing the in 1000 parts 10 parts of the amino compound 3 and 30 parts of the chlorohydrin compound 2 contained. The pH of the liquor was 9.5 and the liquor uptake of the fabric was 90%. The tissue was then at 1 minute a temperature of 12O ° C and then dried with a dye liquor impregnated, the 20 parts per 1000 parts of liquor of the blue reactive dye from C.I.No. 61,200 contained. The pH of the liquor was 9.5, the liquor uptake 90%. The cotton fabric was then rolled up Stored for 3 hours and then washed. After a boil wash with one part per 1000 parts of water of a commercially available detergent a blue dyeing with good fastness properties was obtained.

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The fabric provided with a firmly adhering film could also be used for a long time Liquor can be colored by, for example, on a reel vat in a liquor ratio of 1:25 with 2% of the dye mentioned at room temperature treated. The dye was largely absorbed onto the fabric within 1 hour at room temperature, and with a firmly adhering water-insoluble Film was provided.

In Examples 4 to 7, dyes became as follows Constitution used:

Example A:

NH

SO ₃ Na

SO ₃ Na

Example 5:

25 SO ₃ Na

N = N-CH-CO-NK- / \> COCH.

Cobalt (1: 2) complex (II

Example 6:

0 NH

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Example 7:

CuPc-

Cl

NH,

- (SO ₃ Na)

(IV)

Example 4

A pre-cleaned cotton fabric was impregnated with a solution containing the in 1000 parts 15 parts of the amino compound 1 and 60 parts of the chlorohydrin compound 1 contains. The pH of the liquor was 8.5 and the liquor absorption of the fabric was 80%. The tissue was then at 1 minute dried at a temperature of 120 * C and then with a dye Impregnated solution containing 30 parts per 1000 parts of liquor of the blue reactive dye of the formula I. The pH of the liquor was 8.5 the liquor pick-up 80%. The material was dried at 120 ° C. for 2 minutes and then washed at the boil for 5 minutes with a commercially available detergent. A clear reddish blue coloration was obtained with regard to the fastness properties to the desired goal. Without the treatment with the amino compound 1 and the chlorohydrin compound 1 was that Material not stained after washing. The same was the case when treating with the chlorohydrin compound without the amino compound carried out. Treated with the amino compound in the absence of Before the chlorohydrin compound, a blue coloration was obtained after washing, but the wet fastness properties were inadequate.

Example 5

Example 2 was repeated, but used instead of there described dye the same amount of dye II. An ocher-colored fabric was obtained, the properties of a denir - Item resembles.

You can also proceed in such a way that on the yarn as in Example 2 amino compound and applying chlorohydrin compound together with the size, drying, producing the fabric and impregnating it with it the dye liquor and a hot air drying dye. After a boil wash the untreated weft thread remains undyed, so that a denim article is also produced in this way.

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Example 6

Example 4 was repeated and a well pre-cleaned and substrate absorbent wool fabric is used, but the dye of formula III used. A deep blue coloration with satisfactory properties was obtained.

Similar results were obtained if a fabric was used as the substrate a regenerated cellulose fiber or a fabric made of cellulose acetate fiber or a fabric made of polyester / cotton (50:50) used.

■ Example 7

A pre-cleaned cotton fabric was impregnated with a solution which contained, in 1000 parts, 15 parts of the amino compound 2 and 25 parts of diraethylol-ethyleneurea (50%). The pH of the liquor was 8.0, the liquor uptake was 80%. The fabric was then dried for 1 minute at 120 ° C. and then impregnated with a dye solution which contained 40 parts per 1000 parts of liquor of the blue dye of the formula IV. The pH of the liquor was 8.5, the liquor uptake was 80 % Dried for 2 minutes at 130 ° C. and soaped at the boil as in Example 4. A clear turquoise coloration with very good lightfastness and good wet fastness was obtained.

The same result was obtained when the treatment with the amino compound and the crosslinker was made with a liquor, the pH of which was set to 4.

The same result was obtained if, instead of the diraethylol -ethylene urea the same amount of partially etherified dimethylol- -dihydroxyethylene urea or tetramethylolacetylenediurea or Used trimethoxymethyl melamine.

Claims (6)

BASF Aktiengesellschaft O.Z. 0050/36550 claims 1. Process for dyeing textile materials made of hydrophilic fibers, optionally mixed with synthetic fibers, with reactive dyes. or acid dyes in an aqueous medium at pH values of 6 to 12, characterized in that a firmly adhering film is first produced on the textile materials by placing on it a) polyfunctional primary and / or secondary basic amino groups containing water-soluble compounds and b) water-soluble ones containing two or more propylene chlorohydrin groups Compounds, the epoxides formed therefrom, N-methylol- or water-soluble condensates containing N-methylol ether groups of urea, melamine, acrylamide and formaldehyde then applies the textile material in the form of an aqueous solution dries and stains in the usual way. 2. The method according to claim 1, characterized in that the compounds of group (a) used are polyalkylenepolyamines, polyethyleneimines, polyamidoamines, homo- and copolymers of N-vinylamine, 1- or 2-vinylimidazoline or polymers grafted with ethyleneimine. 3. The method according to claim 1, characterized in that the compounds of group (b) used are reaction products which are obtained by reacting 1 mole of an alcohol or polyetherol containing 2 to 6 OH groups with at least 2 moles of epichlorohydrin. 4. The method according to claim 1, characterized in that thermosetting cationic resins are used as compounds of group (b). 5. Process according to claims 1 to 4, characterized in that the concentration of the compounds (a) and (b) in the aqueous solution is in each case 1 to 50 g / l. 6. Process according to Claims 1 to 5, characterized in that the textile materials impregnated with compounds (a) and (b) are dried at temperatures of 80 to 220 ° C. ²²² JfI ^{Ks / r} ° ⁷ - ⁰⁶ · ¹⁹⁸³ 'copy]