CH689135GA3 - Coloring process and aids for it. - Google Patents

Description

When dyeing cellulosic substrates with reactive dyes, in particular exhaust dyeing, generally in the presence of a certain amount of salt, e.g. Sodium sulfate or sodium chloride, because the salt promotes the absorption of the reactive dye on the fiber; Alkali is then also added for fixation. The way in which salt and alkali are added has a significant influence on the levelness and reproducibility of the dyeings. Usually the required amount of salt is added to the dyebath before the dye is added, but in many cases this causes the dye to adsorb too quickly on the substrate and leads to unevenness of the dye. An optimal dye distribution can e.g. can be achieved by dosed addition of salt to the dye-containing dye bath. The difficulty with such a process is that when the necessary amount of salt is added in dissolved form, even if the solution is very concentrated, the dyebath is too diluted. The addition of the salt in solid form is very time-consuming and stressful for staff. It was therefore proposed in DE-A 4 118 367 to use certain, optionally substituted, sulfo group-containing diphenyl ether oligosulfones, in particular sulfo group-containing ditolyl ether oligosulfones, as leveling agents in the presence of a salt, primarily sodium sulfate. Very level dyeings can be achieved with these oligosulfones. Nowadays there is a tendency to use sodium chloride instead of sodium sulfate, which has been mostly used up to now, when dyeing with reactive dyes, either for economic reasons or because of the irregular solubility behavior of sodium sulfate depending on the degree of hydration and temperature increase. It has been shown that at higher sodium chloride concentrations, such as occur when dyeing with reactive dyes, e.g. 60 g / l or more, the oligosulfones mentioned tend to destabilize, especially at elevated temperatures, which can lead to malfunctions (e.g. precipitation and / or deposits in parts of the apparatus and a corresponding loss of active substance and consequently the appearance of the dyed material) in such dyeing processes.

It has now been found that the products (E) defined below from the condensation of sulfonation products of defined aprotic aromatics with formaldehyde to form -CH2 bridges and optionally salt formation, when dyeing with reactive dyes, have a surprisingly good stability at high sodium chloride concentrations, as defined below, and have an excellent leveling effect even at elevated dyeing temperatures.

The invention relates to the corresponding dyeing process using the defined auxiliaries (E), the new condensation products and their production and use, as well as certain (E) -containing leveling agent preparations.

A first object of the invention is therefore a process for dyeing cellulose-containing substrates with reactive dyes (R) in aqueous liquor in the presence of sodium chloride, which is characterized in that dyeing in the presence of an auxiliary (E) which is a sulfonation of

(a) at least one aromatic hydrocarbon compound having 9 to 18 carbon atoms, introducing an average of at least 1.1 sulfo groups per molecule (a), and

(b) at least one optionally alkyl-substituted diphenyl (thio) ether, for introducing an average of at least 1.1 sulfo groups per molecule (b), and condensation of the sulfonation products of (a) and (b) with

(c) formaldehyde or a formaldehyde-releasing compound in an acidic medium, and possibly salt formation, is an available methylene bridge-containing and sulfo-containing aromatic product or product mixture, and the sodium chloride content of the liquor is> / = 20 g / l.

Primarily monocyclic or bicyclic compounds come into consideration as (a), preferably those of the benzene or naphthalene series, which optionally carry one or more low molecular weight alkyl radicals as substituents.

The following are particularly suitable as (a):

(a1) compounds of the formula

wherein R1 is hydrogen or C1-4-alkyl and R2 is hydrogen or C1-4-alkyl, and (A2) alkyl-substituted benzenes and / or benzenes bearing a fused homocyclic ring, in which the sum of the total carbon atoms of the molecule is in the range from 9 to 14 and wherein the ring fused to the benzene ring contains at least one carbon not bonded by double bonds.

The individual alkyl groups occurring in (a2) preferably contain 1 to 4 carbon atoms. Suitable (a2) are advantageously mono-, di-, tri- and / or tetraalkyl-substituted benzenes or bicyclic compounds; the sum of the total carbon atoms of the molecule (a2) is preferably in the range from 9 to 12.

The preferred among the compounds (a2) can be represented by the following average formula

wherein x is a number from 1 to 4 and R3 in each case, independently of one another, C1-4-alkyl or, if x = 2-4, also two vicinal R3 together the divalent, saturated or monoethylenically unsaturated C3-8 hydrocarbon radical required to form a fused 5- or 6-membered homocycle mean, with the proviso that the sum of the number of carbon atoms in all of the x radicals R3 is 3 to 8, preferably 3 to 6.

Compounds of the formula are particularly suitable as (b)

wherein X oxygen or sulfur, R4 and R5 each, independently of one another, C1-4-alkyl and p and q each represent 0, 1 or 2 independently of one another.

As alkyl groups with 1 to 4 carbon atoms in (a) and (b), in particular with the meaning of R1, R2, R3, R4 and R5, all possible representatives come into consideration, namely methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, sec-butyl and t-butyl.

The symbols R1 and R2 can have the same or different meanings. The alkyl radicals R1 and / or R2 can be in any of the respective positions alpha and beta. Among the dialkyl-substituted naphthalenes of the formula (Ia1) (for example diisopropylnaphthalenes), all possible positional isomers come into consideration, in particular the corresponding 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2, 6- and 2,7-dialkyl-substituted naphthalenes. Individual compounds or mixtures can be used. According to a preferred variant, both R1 and R2 are hydrogen, i. Among the compounds of the formula (Ia1), a preferred compound is unsubstituted naphthalene. Technical naphthalenes can also be used, in particular in the form of aromatic hydrocarbon mixtures which contain naphthalene and / or methylnaphthalenes as the main component and are essentially free from C5-6 hydrocarbons.

If x = 2 to 4 in the formula (Ia2), the respective x radicals R3 can have the same or different meanings with one another. If two vicinal R3 are linked together with the two carbons of the benzene ring to which they are bonded to form a condensed homocycle, the respective compounds are advantageously indanes, indenes, dialyne or tetralin, in particular optionally methyl- or ethyl-substituted indanes or indenes . Uniform alkyl-substituted benzenes can be used as (a2) or technical mixtures, e.g. those in which the hydrocarbons contain an average of 10 to 11 carbon atoms, in particular corresponding distillation fractions as are commercially available, e.g. Containing di-, tri- or / and tetramethylbenzenes, ethylmethylbenzenes, ethyldimethylbenzenes, n- or iso-propylbenzenes, methyl-n- or -iso-propylbenzenes, diethylbenzenes, indanes, indenes, methyl- or ethyl-indanes or -indenes or / and C11 aromatics (alkylbenzenes, diaromatics), e.g. "SHELLSOL AB".

In the compounds of the formula (Ib), X is preferably oxygen.

Among the alkyl radicals in the meaning of R4 and R5, the lower molecular weight representatives are preferred, especially ethyl and especially methyl. If p and / or q are 1 or 2, the respective alkyl groups can be in any of the positions ortho, meta and para to X, in particular to the oxygen atom. As monosubstituted diphenyl (thio) ethers, in which only one of p and q is 1, while the other is 0, the corresponding 2-, 3- or 4-alkyldiphenyl (thio) ethers, primarily the 2-, 3- or 4-th -Methyldiphenyl (thio) ethers are mentioned, as well as technical mixtures of these compounds. Of the compounds in which p and q are each 1, both the individual positional isomers 2.2 min, 2.3 min, 2.4, 3.3 min, 3.4 min and 4.4 min and also mixtures, in particular technical mixtures of such isomers are mentioned; among these, ditolyl ether and ditolyl ether mixtures, in particular technical ditolyl ether mixtures, are preferred. If p or q are 2, the two alkyl radicals can have different or preferably the same meanings and can be in any two positions of the phenyl radical (2.3; 2.4; 2.5; 2.6; 3.4; 3, 5). Particularly noteworthy are the respective dixylyl ethers and dixylyl ether mixtures, especially technical dixylyl ether mixtures. Also worth mentioning are the mixed ethers, especially phenyl tolyl ether, phenyl xylyl ether and tolyl xylyl ether. Among the ethers mentioned, those with p = 0 or 1 and q = 0 or 1, in particular p = 1 and q = 1, are preferred, especially ditolyl ethers.

The compounds to be sulfonated are advantageous

at least one compound (a1) and at least one compound (b), or at least one compound (a2) and at least one compound (b), or at least one compound (a1), at least one compound (a2) and at least one compound (b).

The components to be sulfonated can each be sulfonated separately or as a mixture with one another or in stages (beginning with the more inert component and with the addition of the more reactive component at a point in time suitable for the desired degree of sulfonation). The sulfonation of the compounds (a) and (b) can take place under conventional sulfonation conditions, e.g. using oleum, 100% sulfuric acid, concentrated sulfuric acid or chlorosulfonic acid. The sulfonation can be carried out, for example, in the temperature range from room temperature (= 20 ° C.) to 160 ° C., preferably 70 to 160 ° C., optionally under nitrogen. When sulfonating with 100% or concentrated sulfuric acid (e.g. with H2SO4 to H2SO4. H2O), sulfonation is advantageously carried out under nitrogen. The sulfonation is expediently carried out under such conditions that per molecule (a) or (b), in particular of the formula (Ia1), (Ia2) or (Ib), an average of 1.1 to 2, advantageously 1.2 to 2, particularly preferably 1.4 to 1.8 sulfo groups are introduced, using the appropriate amount of sulfonating agent. It is advantageous to use 1.2 to 2.5 mol, preferably 1.4 to 2.3 mol, particularly preferably 1.5 to 2.2 mol of the sulphonating agent per mol of starting product (a) or (b) or mixture of the respective compounds.

Specifically, the sulfonation products of (a1) can be represented by the following average formula

wherein m 1.1 to 2, preferably 1.2 to 2, and M represent hydrogen or a cation.

Specifically, the sulfonation products of (a2) can be represented by the following average formula

wherein y is 1.1 to 2, preferably 1.2 to 2.

Specifically, the sulfonation products of (b) can be represented by the following average formula

wherein n is 1.1 to 2, preferably 1.2 to 2.

The indices m, y and n represent the above degree of sulfonation and are advantageously each in the range from 1.4 to 1.8.

If desired, the sulphonation mixture can be allowed to stand at high temperature for a period of time, e.g. allowed to react further at 140 to 160 ° C, so that some of the sulfonic acid groups (e.g. 5 to 30 eq%, especially 5 to 25 eq%) are condensed to sulfone bridges, and consequently in addition to the compounds of the formulas (IIa1), (IIa2) and / or (IIb) sulfones containing sulfo groups are also present. 1 val sulfonic acid = 1 mole sulfonic acid divided by the average number of sulfo groups per molecule.

The sulfonation products of (a) and (b), in particular the compounds of the formulas (IIa1), (IIa2) and (IIb) and optionally sulfones thereof containing sulfo groups, are preferably used in the form of the free acids (ie where M is hydrogen), since the Reaction with (c) takes place under acidic conditions.

For the preparation of (E), the products (a) and (b) are advantageously used in the molar ratio (a) / (b) in the range from 10:90 to 90:10, preferably from 30:70 to 80:20, in particular 40:60 used until 65:35.

If products (a1) and (a2) are used as (a), these are advantageously in the molar ratio (a1) / (a2) in the range from 2:98 to 98: 2, preferably 5:95 to 95: 5, in particular 5 : 95 to 80:20 used.

If unsubstituted naphthalene and alkyl-substituted naphthalene are used as products (a1), the molar ratio of naphthalene to alkyl-substituted naphthalene is e.g. in the range from 2:98 to 98: 2, advantageously 10:90 to 90:10, preferably 30:70 to 80:20, in particular 40:60 to 65:35.

Free formaldehyde or a formaldehyde-releasing compound can be used as component (c), e.g. Melamine or, preferably, paraformaldehyde. The molar ratio of the total components [(a) + (b)] to (c) is advantageously chosen so that simple to oligomeric condensation products of the sulfonation products can arise. In these condensation products, the respective residues of the sulfonation products of (a) and / or (b), in particular those of the compounds of the formulas (IIa1), (IIa2) or (IIb) and optionally sulfones thereof, are essentially with one another via aromatically bound methylene bridges connected.

The auxiliaries (E) originating from the compounds of the formulas (Ia1), (Ia2) or (Ib) can essentially be represented as products which contain one or more recurring units of the respective average formula

and optionally corresponding sulfone radicals.

In the formulas (IIIa1), (IIIa2) and (IIIb) the free bond shown without a substituent and starting from the aromatic nucleus is either bonded to a further aromatic radical (IIIa1), (IIIa2) or (IIIb) via the methylene bridge or [ when (IIIa1), (IIIa2) or (IIIb) represents an end group] bonded directly to a hydrogen atom. The bond starting from the methylene group is bonded to an aromatic nucleus of a further radical of the formula (IIIa1), (IIIa2) or (IIIb).

The molar ratio of the sulfonation products to (c) is advantageously chosen such that, per mol of the total starting compounds (a) and (b), 0.35 to 0.9, preferably 0.45 to 0.7 mol, especially 0.5 to 0 , 6 mol, formaldehyde, or the corresponding amount of a formaldehyde-releasing compound can be used.

The reaction with (c) is advantageously carried out at temperatures in the range from 50 to 110 ° C. in a strongly acidic medium, for example at pH values <3, preferably below 1. The reaction is particularly advantageous following the sulfonation in a sulfuric acid medium. The reaction with (c) is preferably carried out in an aqueous-acidic medium, where component (c) can be added in a form diluted with water and / or the sulfuric acid reaction mixture resulting from the sulfonation with water up to a water content of advantageously 10 to 50 wt .-% can be diluted.

After the reaction has taken place, the sulfonic acids obtained [in particular those in which in the formulas (IIIa1), (IIIa2) or (IIIb) M is hydrogen] can be converted into a corresponding salt form by reaction with a suitable base or the salt of a strong base with a weak acid are converted [in particular in which in the formulas (IIIa1), (IIIa2) and (IIIb) M is a cation]. The cations M are mainly colorless cations, preferably alkali metal cations (especially lithium, sodium, potassium), alkaline earth metal cations (especially magnesium) and / or ammonium cations (especially unsubstituted ammonium, morpholinium or by, for example, C1-2-alkyl and / or C2-3-hydroxyalkyl substituted ammonium, for example mono-, di- or triethanolammonium or mono-, di- or triisopropanolammonium) into consideration, which by treating the sulfonic acids with appropriate bases or their salts of weak acids, eg with alkali metal hydroxides, carbonates or bicarbonates, magnesium hydroxide, ammonia or corresponding amines can be introduced. Among the cations mentioned, the alkali metal cations and especially the ammonium cations, especially unsubstituted ammonium, are preferred. It is advantageous to use enough base until the pH of a 10% aqueous preparation is in the range from 7 to 10, preferably 7.5 to 9.

The products (E) obtained are readily soluble in water, especially in salt form, and can, as they have been prepared, optionally after adjusting the water content to the desired dry matter content, e.g. in the range from 10 to 70% by weight, can be handled directly or, if desired, they can be dried to give dry preparations, for example by spray drying or granulation (optionally with the addition of granulating aids).

A particular object of the invention is provided by those products (E), i. (E1), which have been prepared starting from (a1) and (b) and in which in at least some of the components (a1) used, R1 and R2 are both hydrogen, i.e. in which at least some of the starting materials of the formula (Ia1) used are naphthalene, e.g. at least 10 mol% of the compounds of the formula (Ia1), preferably at least 50 mol% thereof, particularly preferably in which the starting product of the formula (Ia1) used is exclusively naphthalene.

Another particular object of the invention is provided by those products (E), i. (E2), in which the sulfonation products of (a) and optionally (b) used for the condensation with (c) are partially condensed to sulfones containing sulfo groups.

The products (E) defined above serve as auxiliaries, in particular as leveling agents, for dyeing cellulose-containing substrates with reactive dyes in an aqueous liquor which contains at least 20 g / l NaCl. At least one sequestering agent (Q) and / or at least one hydrotropic agent (H) is advantageously used in such dyeing processes.

Products known as sequestering agents can be used as sequestering agents (Q); the following are primarily considered:

(Q1) alkali metal tetraborates, (Q2) (Co) poly (meth) acrylic acids, optionally in salt form, (Q3) N-methylene-phosphonic or carboxylic acids, optionally in salt form, or (Q4) polyhydroxycarboxylic acids, optionally in salt form, or Mixtures of two or more of these compounds.

For salt formation of the acids mentioned under (Q2), (Q3) and (Q4), mainly alkali metal cations come into consideration (primarily lithium, sodium and / or potassium, of which potassium and especially sodium is preferred).

Sodium tetraborate (e.g. borax or kernite) is the main alkali metal tetraborate (Q1).

Primarily simple polyacrylic acids in sodium salt form come into consideration as (Q2), in particular those with an average molecular weight (weight average) in the range from 1000 to 500,000, advantageously from 2000 to 100,000, of which the lower molecular ones, especially those with an average molecular weight in the range of 2000 to 20,000, are particularly preferred.

As (Q3) are primarily N-methylenephosphonic acids and N-methylenecarboxylic acids, in which the N is a nitrogen of a low molecular weight aliphatic polyamine, in particular an alkylenediamine (e.g. ethylenediamine or propylenediamine) or a polyalkylenepolyamine (e.g. diethylenetriamine, dipropylenetriamine or triethylenetetramine), e.g. Ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acid, or nitrilotriacetic acid, which are preferably in the form of sodium salts.

Saccharide derivatives, for example, are suitable as (Q4), e.g. low molecular weight polyol carboxylic acids, in particular gluconic acid or glucoheptonic acid, and carboxymethylation products of oligosaccharides or poly-alpha-hydroxyacrylic acids (the latter, as sodium salts, preferably in the molecular weight range from 2000 to 140,000, preferably 2000 to 30,000).

(Q) can be a uniform product, preferably (Q1), or also, advantageously, a mixture of several of the products (Q1) to (Q4). Mixtures of two or more of the abovementioned sequestering agents (Q) are advantageously used, primarily of (Q1) with at least one of the components (Q2), (Q3) and (Q4).

5 to 100, preferably 8 to 60 parts by weight (Q) are advantageously used per 100 parts by weight (E). If (Q) is a mixture of (Q1) with one or more of the other components (Q2), (Q3) and (Q4), the weight ratio of (Q1) to the other components (Q) is advantageously in the range of 10: 90 to 80:20, preferably in the range of 20:80 to 70:30.

Advantageously, especially if (Q) is used, especially if (Q1) is used, a hydrotropic agent (H) is also added.

Products known per se can be used as hydrotropic agents (H), primarily the following:

(H1) (thio) urea, (H2) aliphatic C3-6 polyols with at least three hydroxyl groups, or acetic acid partial esters thereof, (H3) mono- or oligo- (C2-4-alkylene) -glycols or mono- (C1-4-alkyl) -ethers thereof, (H4) dicyandiamide or (H5) aliphatic lactones or N-alkyl-lactams or Mixtures of two or more of these compounds.

The easiest to use (H1) is urea.

Examples of (H2) that can be mentioned are glycerol and sorbitol, as well as their acetates (especially partial acetates).

As (H3) e.g. Mono-, di- or triethylene glycol and the respective methyl, ethyl, propyl and butyl monoethers can be used.

As (H5) e.g. Compounds with 4 to 8 carbon atoms are mentioned. Butyrolactone, valerolactone and caprolactone can in particular be mentioned as lactones. The corresponding N-alkyl-substituted pyrrolidones in which alkyl contains 1 to 4 carbon atoms and is preferably methyl can be mentioned as N-alkyl-lactams.

The auxiliaries (E) are expediently used in an effective amount, i.e. in such an amount that their effect, in particular their leveling effect, comes into play. Depending on the dye used, the substrate to be dyed and the dyeing conditions chosen, the effective and the optimal concentration of (E) can vary; in general the concentration (E) is e.g. in the range from 0.05 to 5 g per liter of liquor, preferably 0.1 to 2 g per liter of liquor. The addition can take place before or after the addition of the salt, but preferably before the addition of the dye.

The amount of sequestering agent (0) used can vary widely (partly also depending on the hardness of the water used). (Q) is advantageously used in concentrations of 0.005 to 5 g per liter of liquor, preferably 0.01 to 2 g per liter of liquor; the weight ratio of (Q) to (E) is advantageously in the range from 5 to 100, preferably 8 to 60 parts by weight of (Q) per 100 parts by weight of (E).

The products (E) and (Q) can be added separately to the dyebath or, according to a preferred variant, (E) and (Q) can also be formulated together in the form of a stable, preferably aqueous, concentrated preparation. The hydrotropic agents (H) are advantageously used to formulate such preparations. It is advantageous to use from 2 to 100, preferably from 5 to 60, parts by weight of (H) per 100 parts by weight (Q). In the case of the preferred preparations in which (Q1) is combined with further components (Q2) and / or (Q3) and / or (Q4), correspondingly smaller amounts of (H) can be used, e.g. 1 to 20, preferably 2 to 14% by weight based on (E).

The preparations containing (E) and (Q) and optionally (H) are advantageously formulated in the form of aqueous concentrated compositions, the dry matter content of which is advantageously in the range from 10 to 80, preferably 20 to 70, in particular 25 to 65% by weight.

Reactive dyes (R) that can be used are generally any reactive dyes known in the art under this name and e.g. are defined and also described in the "Color Index" under the designation "Reactive Dyes" and, in particular, are enumerated. Suitable reactive dyes (R) are the dyes containing at least one fiber-reactive group, e.g. the azo, anthraquinone, oxazine, (azo or / and azomethine) metal complex, formazan and phthalocyanine series, especially water-soluble dyes which are in the temperature range from 20 to 100 ° C., at pH values in the range 8 to 12.5 can be fixed using the extraction process. The reactive dyes preferred here contain at least one mono- or dichlorotriazinyl, monofluorotriazinyl, mono- or difluoropyrimidine, fluorochloropyrimidine, dichloroquinoxaline, methylsulfonylchloromethylpyrimidine or sulfatoethylsulfonyl group, e.g. as they are known from the "Color Index".

Suitable substrates for the process according to the invention are generally any fiber materials which may contain modified cellulose such as can be dyed with reactive dyes by the exhaust process, in particular cellulose (e.g. cotton, linen, hemp, sisal), modified cellulose (e.g. viscose rayon and cellulose acetates) and fiber blends containing such fibers. The fibers can be in any processing form, such as are usually used for dyeing processes with reactive dyes by the exhaust process, e.g. as threads, filaments, strands of yarn, bobbins, woven fabrics, knitted fabrics, felts, tufts or even semi-finished and finished goods.

The dyeing process can be exhaust processes and analogous processes in which dyeing is carried out in the presence of an effective amount of added sodium chloride corresponding to an NaCl content of at least 20 g / l in the liquor, essentially exhaust processes and impregnation processes. Above all, exhaust processes come into consideration; these can be carried out from a short or long liquor, e.g. in the case of liquor ratios, liquor: goods in the range from 120: 1 to 2: 1, primarily 60: 1 to 4: 1; in the case of processes from a longer liquor, the liquor length is liquor: goods advantageously values in the range from 60: 1 to 10: 1, preferably 40: 1 to 12: 1; Shorter liquor lengths, in particular in the range from 12: 1 to 2: 1, occur primarily in reel skids and jet dyeing machines. The impregnation process used e.g. those in which the impregnated goods, after soaking with the liquor, are left to stay docked, e.g. at temperatures in the range from 20 to 80 ° C.

The liquors contain an amount of sodium chloride suitable for the respective dyeing process of at least 20 g / l, preferably> / = 50 g / l, in particular> / = 60 g / l, in particular in the range from 50 to 200 g / l, especially 60 to 150 g / l, preferably 70 to 140 g / l. The sodium chloride is advantageously introduced in the form of brine (aqueous almost to fully saturated sodium chloride solution) and then brought to the desired liquor length with water or added to the water initially introduced; the auxiliary (E) is advantageously added to the prepared salt-containing liquor before the addition of the dye and preferably also before the addition of the substrate to be colored. Accidentally premature addition of the auxiliary (E) to the not yet diluted brine has no negative consequences because of the high sodium chloride resistance of (E), since the subsequent addition of water also results in a perfect liquor.

For exhaust dyeing, the goods to be dyed are expediently added to the liquor before the dye is added. After preparing the liquor, adding the substrate and finally the reactive dyes, exhaust dyeing can be carried out in the usual manner. If desired, further dyeing auxiliaries can be added to the liquor, as they correspond to the respectively chosen processes and substrates, e.g. Wetting agents, dispersants, sequestering agents and / or process-related auxiliaries (e.g. lubricants or defoamers). The dyeing can be carried out under conventional conditions, e.g. in the temperature range from 10.degree. C. to the boiling point, advantageously from 20.degree. to 100.degree. C., and is expediently carried out in two stages or "phases": first an absorption phase and then a fixing phase. According to one process variant, the process is carried out at an elevated temperature, in particular at temperatures> / = 60 ° C., primarily in the range from 70 to 100 ° C. The pH of the liquor can fluctuate at the beginning (i.e. in the dye absorption phase) in the almost neutral to slightly alkaline range, e.g. in the range from pH 6 to 9, preferably 6.5 to 8.5, in particular 6.5 to 8; to fix the dye on the fiber, it is expedient to take place at the end of the absorption phase [i.e. when the dye has been absorbed onto the substrate to the desired degree, or after the absorption phase is (almost) complete] a suitable base is added, primarily alkali metal hydroxide or carbonate, particularly preferably sodium hydroxide, sodium carbonate or potassium hydroxide, and it is e.g. fixed at pH values in the range from 8 to 12.5, preferably 9 to 12. The draw-up phase can be carried out in the usual time ranges, as they are suitable for the respective process and substrate, as well as dye and dyeing parameters, in the case of exhaust processes under non-forced conditions (e.g. in the jigger, in the dyeing drum, below level or in the reel vat or according to other exhaust methods preferably with the exception of nozzle dyeing processes) e.g. in the range of 15 minutes to 2 hours, most preferably 20 minutes to 1 hour; In the jet (nozzle dyeing machine) shorter times may also be sufficient, e.g. 5 to 40 minutes, mostly 7 to 25 minutes. The addition of alkali for the dye fixation is advantageously carried out in portions and then the process can be continued for some time, e.g. 5 to 60 minutes. For highly reactive dyes - so-called "cold dyes" - fixation can also take place at low temperature, primarily in the temperature range from 10 to 60 ° C., preferably from 15 to 50 ° C. In this case, the absorption phase and the fixation phase are particularly advantageously carried out at the same temperature. According to another variant of the process, which is suitable for less substantive and less reactive dyes, the alkali, preferably sodium carbonate, can also be added at the beginning, the dyeing process being controlled by temperature; In this case, the absorption phase takes place primarily at temperatures below 80 ° C. and the fixation is then carried out by heating to temperatures> / = 80 ° C., preferably in the temperature range from 90 to 100 ° C. The colored substrate can then be finished in the usual way (Soaping, rinsing, drying). Mixtures of fibers can also be colored, e.g. Mixtures with synthetic fibers that can be treated with disperse dyes in the same liquor.

In the case of impregnation processes, the goods can be impregnated with the salt-containing and dye-containing liquor, then left docked and then subjected to a fixing alkali treatment and finished as usual.

The process according to the invention allows very level dyeings to be produced with reactive dyes (R) u.zw. also using very high sodium chloride concentrations, which also enables the highest possible dye extraction from the liquor. As explained above, incorrect manipulations when setting up the fleet have no negative consequences.

The auxiliaries (E1) and (E2) according to the invention can also be used in dyeing processes for dyeing with reactive dyes in which sodium sulphate or other salts (e.g. sodium silicate or sodium phosphate) are used.

The auxiliaries (E) may have a proportion of sulfates as a by-product from their preparation, e.g. in the form of ammonium sulfate or alkali metal sulfate (depending on the base used). The proportion of these salts is, however, small in relation to the liquor used and not disruptive; he can e.g. up to 20% by weight of (E), preferably 1 to 10% by weight of (E), depending on the synthesis process used.

In the following examples, the parts are parts by weight and the percentages are percentages by weight; the temperatures are given in degrees Celsius. The dyes used in the application examples are used in commercially available form, which is couped with sodium sulfate and sodium carbonate; the amounts of the dyes are based on pure dye. "C.I." stands for "Color Index". The diisopropylnaphthalene used is a commercially available mixture of isomers (KMC from RÜTGERS'S WERKE AG., DUISBURG, Germany); the ditolyl ether is a commercially available mixture of isomers which contains the positional isomers 2.2 min, 2.3 min, 2.4 min, 3.4 min and 4.4 min; "SHELLSOL AB" is a commercially available technical C9-11 aromatic mixture consisting of approx. 20% by weight of C9 aromatics (alkylbenzenes and indane) and approx. 70% by weight of C10 aromatics (alkylbenzenes, methylindanes and naphthalene ) and consists of about 10% by weight of C11 aromatics, the naphthalene making up about 5.37% by weight.

example 1

64 g of naphthalene and 99 g of ditolyl ether are stirred in a five-necked sulphonation flask with a capacity of 1500 ml and provided with a reflux condenser, and the mixture is heated to an internal temperature of 75 ° C. under a nitrogen atmosphere. With thorough stirring, 176.4 g of 100% strength sulfuric acid are added dropwise within one hour. After the addition of sulfuric acid is complete, the mixture is heated to an internal temperature of 143-145 ° C. and stirring is continued for 7 hours at this temperature. After this time, the resulting product has an acid content of 645 to 660 meq / 100 g. It is then cooled to 60 ° C. and 20 parts of demineralized water are added dropwise over the course of 15 minutes. 40.5 parts of 35% strength aqueous formaldehyde are then added dropwise over the course of 25 to 30 minutes in such a way that the internal temperature does not exceed 85.degree. After the addition has ended, the internal temperature is increased to 91-92 ° C. and the mixture is stirred for 1 to 11/4 hours at this temperature. It is then cooled to 80-85 ° C. and diluted with a mixture of 120 ml of demineralized water and 120 g of ice, as a result of which the temperature drops to 40-45 ° C. The resulting clear, light brown solution is then added dropwise with 179 g of 25% strength ammonia water and the pH is adjusted to 7.5-8.2, the temperature being kept between 40 and 25 ° C. After further dilution with 109.1 g of demineralized water, 928 g of aqueous product with approx. 42% dry matter content are obtained.

Example 2

The procedure described in Example 1 is repeated, with the difference that 85 g of naphthalene are used instead of 64 g of naphthalene.

Example 3

The procedure is as described in Example 1, with the difference that 196 g of 100% sulfuric acid are used instead of 176.4 g of 100% sulfuric acid.

Example 4

The procedure is as described in Example 1, with the difference that 205.8 g of 100% sulfuric acid are used instead of 176.4 g of 100% strength sulfuric acid.

Example 5

The procedure is as described in Example 1, with the difference that 71 g of a technical grade methylnaphthalene (mixture of the 1- and 2-position isomers) are used instead of 64 g of naphthalene.

Example 6

The procedure is as described in Example 1, with the difference that 67 g of “SHELLSOL AB” are used instead of the 64 g of naphthalene.

Example 7

The procedure is as described in Example 6, with the difference that 196 g of 100% sulfuric acid are used instead of 176.4 g of 100% sulfuric acid.

Example 8

The procedure is as described in Example 6, with the difference that 147 g of 100% sulfuric acid are used instead of 176.4 g of 100% sulfuric acid and 0.4 mol of formaldehyde is used instead of 0.53 mol of formaldehyde.

Example 9

The procedure is as described in Example 3, with the difference that first the naphthalene alone is sulfonated with 98 g of 100% sulfuric acid and after three hours of sulfonation, the temperature is reduced to 80 ° C. and at this temperature the ditolyl ether and the remaining 98 g of 100% sulfuric acid are added, after which the temperature is increased again to 143-145 ° C. and the mixture is further sulfonated until the same acid content as in Example 3 is reached.

Example 10

The procedure is as described in Example 3, with the difference that only the naphthalene is initially charged and, after 2 hours of sulfonation, it is cooled to 80 ° C., the ditolyl ether is added, after which the temperature is increased again to 143-145 ° C. and until the same acid content as in Example 3 is reached.

Example 11

The procedure is as described in Example 1, with the difference that 0.35 mol of formaldehyde is used instead of 0.53 mol of formaldehyde.

Example 12

The procedure is as described in Example 1, with the difference that 0.45 mol of formaldehyde is used instead of 0.53 mol of formaldehyde.

Example 13

96.5 g of diisopropylnaphthalene and 90 g of ditolyl ether are loaded into a five-necked sulphurizing flask with a capacity of 1500 ml and equipped with a reflux condenser. 133.6 g of 100% strength sulfuric acid are then added over the course of 30 minutes under a nitrogen atmosphere with thorough stirring so that the temperature rises to 85-90 ° C. The mixture is then heated to 110 ° C. within 30 minutes and stirred for 2.5 hours. After cooling to 95 ° C., 74 g of water and 38.9 g of an aqueous 37% strength formaldehyde solution are added in such a way that the temperature does not rise above 90 ° C. After the addition has ended and after stirring for 2 hours at 85-90 ° C., 148.5 g of water are added; 146 g of aqueous 25% strength ammonia solution and 110 g of water are then added at 50 ° C. A pH of 7.5-7.7 is established. 837.5 g of a solution with approx. 40% dry matter content are obtained.

Example 14

147 parts of 100% sulfuric acid are added to a mixture of 106 parts of diisopropylnaphthalene and 99 parts of ditolyl ether at 75 ° C. under a nitrogen atmosphere in the course of 25 minutes, the temperature rising to 80 ° -85 ° C. The mixture is then heated to 105 ° C. and stirring is continued until a sample is water-soluble, which takes about two hours. It is then cooled to 80 ° C. and 43 parts of aqueous 37% formaldehyde are added over the course of 15 minutes, the temperature being kept at 25 ° C. by external cooling. After the addition is complete, 25 parts of water are added and the mixture is heated to an internal temperature of 95-97 ° C. and stirring is continued until the formaldehyde has reacted, which takes about 2 hours. It is then cooled to 80 ° C. and 275 parts of a water / ice mixture are added and the mixture is cooled to 30 ° C. At this temperature, 157 parts of 25% aqueous ammonia are slowly added (pH = 7.5-8) and finally 231 parts of demineralized water are stirred in. 1083 parts of solution with 34.53% dry matter content are obtained.

Preparation I.

The following components are stirred in one after the other to the aqueous product obtained according to Example 1 (928 g): 26.8 g urea, after 30 minutes 15.2 g sodium polyacrylate (average molecular weight 5000) followed by 24.8 g diethylenetriaminepentamethylphosphonic acid sodium salt and after one hour 40.4 g of borax, after which stirring is continued for another hour. 1035.2 g of a stable, perfectly dilutable preparation are obtained.

Preparations II to XIV

The procedure is as described for preparation I, with the difference that, instead of the product of example 1, the products of examples 2 to 14 are used in each case.

Examples 1bis to 14bis

The procedure described in Example 1 is followed, after which the product obtained is dried in an atomizer dryer. The dry product obtained can be perfectly diluted with water.

The products of Examples 2-14 are dried in an analogous manner.

Application example A

100 parts of cotton fabric are introduced into 1800 parts of an aqueous liquor which contains 2 parts of preparation I and 140 parts of common salt (sodium chloride) and which has been heated to 80 ° C. A solution of 1 part C.I. is added to the bath. Reactive Blue 52 in 100 parts of water and heats the liquor to 90 ° C. After 30 minutes at this temperature, five 10 parts of a 3% sodium hydroxide solution are added at intervals of 5 minutes, followed by a further 40 minutes 90 ° C is further colored. It is then cooled and the dyeing is completed in a conventional manner (soaped, rinsed and dried). A very level, pure, reproducible blue coloration is obtained in high yield.

Application example B

Proceed as described in application example A, with the difference that instead of 1 part C.I. Reactive Blue 52 the same amount of C.I. Reactive Yellow 165 is used. A perfectly level and reproducible yellow coloration is obtained in high purity and yield.

Application example C

100 parts of pre-wetted, bleached cotton knitwear are introduced into 1500 parts of an aqueous liquor which contains 120 parts of common salt, 30 parts of calcined soda, 1.5 parts of sodium nitrobenzenesulfonate and 2 parts of preparation I. After the liquor has been heated to 60 ° C., 3 parts of C.I. Reactive Blue 214 in 100 parts of water was added. The liquor is heated to 90-98 ° C. within 30 minutes, after which it is left at this temperature for a further 60 minutes. The staining is completed according to common methods. A very level dark blue dyeing and a uniform, calm appearance of the fabric are obtained.

Application example D

100 parts of pre-wetted, bleached regenerated cellulose fibers are introduced into 1500 parts of an aqueous liquor which contains 150 parts of common salt, 1.5 parts of sodium nitrobenzenesulfonate and 2 parts of preparation I. The liquor is heated to 85 ° C. and 2.5 parts of C.I. Reactive Violet 33 in 50 parts of water was added. After 30 minutes, 10 parts, 30 parts and finally 200 parts of a 10% sodium carbonate solution are added at intervals of 10 minutes, and dyeing is continued for 45 minutes at this temperature. The staining is completed according to common methods. A very level, reproducible violet coloration is obtained.

Application example E

250 parts of bleached, mercerized cotton fabric are introduced into 2000 parts of an aqueous liquor containing 140 parts of common salt and 3 parts of preparation I at 30.degree. C. and wet for 10 minutes. After 10 minutes, 5.6 parts of C.I. Reactive Red 159 dissolved in 150 parts of water was added. At the same temperature, 4 parts of calcined soda are added after 15 minutes. 3 parts of 30% strength sodium hydroxide solution in 30 parts of water, 1 part of 30% strength sodium hydroxide solution twice in 10 parts of water and finally 3 parts of 30% strength sodium hydroxide solution in 30 parts of water are then added at intervals of 10 minutes. The dyeing is then continued for 40 minutes and the dyeing is completed in the usual manner. A very level, readily reproducible, brilliant red coloration is obtained.

Application example F

100 parts of pre-wetted, bleached cotton tricot are introduced into 1500 parts of an aqueous liquor which contains 100 parts of common salt, 3 parts of calcined soda and 2 parts of preparation I. At 20 ° C., 3.15 parts of C.I. Reactive Blue 116 in 50 parts of water was added. The liquor is heated to 50 ° C. within 30 minutes. After 20 minutes, 3 parts of 30% strength sodium hydroxide solution in 30 parts of water are added and the mixture is fixed at the same temperature for 60 minutes. The staining is completed according to common methods. A very level turquoise-blue dyeing and a uniform, calm appearance of the goods are obtained.

Analogously to the preparation I, each of the preparations II to XIV is used in each of the above application examples A to F.

Instead of preparations I to XIV, in the above application examples A to F, the products of the respective examples 1 to 14 can be added to the dye liquor, the remaining components of preparations I to XIV (urea, sodium polyacrylate, diethylenetriaminepentamethylphosphonic acid sodium salt and borax) each individually or together in the form of a concentrated aqueous preparation (dry matter content 35 Z) are added to the liquor before the cotton is added.

Claims (10)

1. A process for dyeing cellulose-containing substrates with reactive dyes (R) in aqueous liquor, in the presence of sodium chloride, characterized in that dyeing in the presence of an auxiliary (E) which is a sulfonation of (a) at least one aromatic hydrocarbon compound having 9 to 18 carbon atoms, introducing an average of at least 1.1 sulfo groups per molecule (a), and (b) at least one optionally alkyl-substituted diphenyl ether or diphenyl thioether, for introducing an average of at least 1.1 sulfo groups per molecule (b), and Condensation of the sulfonation products of (a) and (b) with (c) formaldehyde or a formaldehyde-releasing compound in an acidic medium, and possibly salt formation, is an available methylene bridge-containing and sulfo-containing aromatic product or product mixture, and the sodium chloride content of the liquor is> / = 20 g / l. 2. The method according to claim 1, characterized in that as (a) (a1) at least one compound of the formula wherein R1 is hydrogen or C1-4-alkyl and R2 is hydrogen or C1-4-alkyl, or and (a2) at least one alkyl-substituted benzene and / or one fused-on homocyclic ring, in which the sum of the total carbon atoms in the molecule is in the range from 9 to 14 and wherein the fused-on ring contains at least one carbon not bonded by double bonds, and as (b) at least one compound of the formula wherein X oxygen or sulfur, R4 and R5 each C1-4 alkyl and p and q each represent 0, 1 or 2, can be used. 3. The method according to claim 1 or 2, characterized in that the salt-forming cations in the condensates (E) are alkali metal cations or ammonium cations. 4. The method according to any one of claims 1 to 3, characterized in that one proceeds in the presence of at least one sequestering agent (Q) and / or one hydrotropic agent (H). 5. The method according to any one of claims 1 to 4 with alkaline fixation of the dye, characterized in that (E) is added to the liquor prior to the addition of alkali. 6. The method according to claim 5, characterized in that (E) is added to the liquor before the reactive dye addition. 7. Dyeing auxiliary preparation for dyeing cellulosic substrates with reactive dyes in aqueous liquor containing sodium chloride, characterized by a content of an auxiliary (E) which is a sulfonation of (a) at least one aromatic hydrocarbon compound having 9 to 18 carbon atoms, introducing an average of at least 1.1 sulfo groups per molecule (a), and (b) at least one optionally alkyl-substituted diphenyl ether or diphenylthioether, for introducing an average of at least 1.1 sulfo groups per molecule (b), and condensation of the sulfonation products of (a) and (b) with (c) formaldehyde or a formaldehyde-releasing compound in an acidic medium, and optionally salt formation, is an available methylene bridge-containing and sulfo-containing aromatic product or product mixture, and a sequestering agent (Q) and optionally a hydrotroping agent (H). 8. Condensation product (E1) of (c) formaldehyde or a formaldehyde-releasing compound with a sulfonation product of (a1) at least one compound of the formula wherein R1 and R2 both mean hydrogen, with an average of at least 1.1 sulfo groups per molecule, and a sulfonation product of (b) at least one optionally alkyl-substituted diphenyl ether or diphenylthioether, with an average of 1.1 sulfo groups per molecule (b), optionally in salt form. 9. Condensation product (E2) of (c) formaldehyde or a formaldehyde-releasing compound with a sulfonation product of (a) at least one aromatic hydrocarbon compound having 9 to 18 carbon atoms, with an average of at least 1.1 sulfo groups per molecule (a), and a sulfonation product of (b) at least one optionally alkyl-substituted diphenyl ether or diphenylthioether, with an average of 1.1 sulfo groups per molecule (b), optionally in salt form, characterized in that the sulfonation product is partially condensed to a sulfone containing sulfo groups. 10. Use of the condensation product according to claim 8 or 9 as an aid in dyeing cellulose-containing substrates with reactive dyes.