EP0546476B1 - Process for making a modified fiber material and process for dyeing the modified fiber material with anionic dyestuffs - Google Patents

Abstract

A process for dyeing fibre materials with water-soluble, anionic dyes, in particular those containing a fibre-reactive group, is described, according to which the dyeing is carried out using low-electrolyte or completely electrolyte-free and/or low-alkali or completely alkali-free dye solutions (dye liquors, printing pastes) and in which a fibre material is employed which has been modified with a saturated straight-chain or branched aliphatic or cycloaliphatic compound which is optionally substituted by one or more hydroxy groups and which contains at least one primary, secondary or tertiary amino group or quaternary ammonium group and at least one hydrolysable ester group, it being possible for the aliphatic radical in this compound to be also interrupted by one or more hetero groups. The fibre material is modified by applying the aliphatic compound containing amino and ester groups to the fibre material in aqueous solution and subjecting the impregnated material to a heat treatment. In addition, some novel aliphatic compounds containing amino and ester groups are described which can be employed for the modification of the fibre material.

Description

In the current state of the art, it is essential to use electrolyte salts and urea and alkalis in the dyeing and printing processes for dyeing textile materials with anionic dyes, in order to ensure satisfactory migration and adsorption of the dye on the fiber and its fixing. The large amounts of such auxiliary chemicals released after the end of the dyeing process are often no longer justifiable for ecological reasons. It was therefore an object of the present invention to find a process for dyeing (including printing) textile fiber materials which uses only the smallest possible amounts of electrolyte salts, such as sodium chloride and sodium sulfate, or completely without electrolyte salts and at the same time only uses small amounts of one alkaline agent, such as sodium carbonate, sodium hydroxide or water glass, or can be carried out entirely without such an alkaline agent. The use of alkaline agents is particularly necessary to fix the technically important reactive dyes on the fiber. A dyeing process which can be carried out with little or no salt and at the same time only with the use of small amounts of an alkaline agent or entirely without such an alkaline auxiliary is therefore particularly advantageous in the dyeing process using fiber-reactive dyes. Because in addition to the fixing process of the fiber-reactive dye in the aqueous, often strongly alkaline dye liquor, hydrolysis reactions of the fiber-reactive dye can also take place, which is why the fixing on the fiber material is not complete. For this reason, extensive and time-consuming washing and rinsing processes, such as multiple rinsing with cold and hot water and one, must be carried out after the dyeing process intermediate neutralization treatment to remove excess alkali on the dyed material and further, for example, a boil wash with a nonionic detergent to ensure the good fastness of the dyeing.

It is already known (see text. Res. J. 17 , 625 (1947); loc. Cit. 23 , 522 (1953) and 39 , 686 (1969)) that cellulose can be modified with aminoethylsulfuric acid via the ethyleneimine stage and then dye with direct dyes. Further work later showed (see Melliand Textilber. 45 , 641 (1964)) that fibers modified in this way can also be dyed with monochlorotriazine dyes. However, the alkaline active substance solutions used in these known processes for the treatment of cotton were 25% sodium hydroxide in all cases, and the liquor absorption of the impregnated fabric was more than 100% by weight. After a long pre-drying, the fixation was carried out for several minutes at temperatures above 100 ° C. This procedure for modifying cotton is extremely uneconomical; moreover, it is not possible to dye the textile fabric treated in this way in any way and to produce uniform product images.

With the present invention, it has now been found that, with anionic textile dyes, in particular those with fiber-reactive groups, without or only with little use of alkaline agents and electrolyte salts, level and strong dyeings with good fastness properties are obtained if a fiber material is used as the textile material used which has been pretreated and modified by a compound which is a saturated aliphatic compound of 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, optionally substituted by 1 or 2 or more, such as 3 to 5, hydroxyl groups which contains at least one primary, secondary or tertiary amino group or quaternary ammonium group and at least one hydrolysable ester group, the aliphatic radical (s) being (s) being straight-chain, branched and / or cyclic and optionally by one or more , such as two or three, hetero groups, such as amino groups and d Oxygen atoms, which can be interrupted and the amino group (s) can also be part of a saturated heterocyclic radical, with the exception of compounds of the general formula (A) specified and defined below.

The amino and ester group-containing compounds used according to the invention, in particular those containing sulfuric acid ester groups, cannot form an ethyleneimine structure because of their constitution; they are able to react with the cellulose fiber according to a nucleophilic substitution. Compared to the known methods of modifying cotton mentioned above, the amount of alkali used can be reduced by 75%; the fixing times can also be drastically reduced. Since in the process according to the invention the application can be carried out analogously to conventional dyeing processes, the process according to the invention can be integrated into a continuous process for the general pretreatment of fiber materials where the alkali necessary for fixing is already present. Furthermore, the process according to the invention for dyeing fiber materials modified according to the invention, in particular in the exhaust process, permits the one-off dyeing of polyester / cotton blended fabrics with reactive and disperse dyes without damage to the disperse dye, precisely because alkali is not present in this single-bath dyeing process.

The compounds which can be used according to the invention for modifying fiber materials contain as ester groups at least one hydrolyzable ester group, such as the esters of sulfuric acid, phosphoric acid, a lower alkane carboxylic acid (the term "lower" here and hereinafter means that the groups are alkyl radicals of 1 to 4 C) -Atoms contain or are), such as acetic acid, benzenesulfonic acid and their derivatives substituted on the benzene nucleus by substituents from the group of sulfo, carboxy, lower alkyl, lower alkoxy and nitro, such as p-toluenesulfonic acid and mesitylsulfonic acid (the acidic esters of sulfuric acid and phosphoric acid are also known as sulfato and phosphato groups, respectively, and correspond to general formula -OSO₃M or -OPO₃M₂, in which M represents a hydrogen atom or an alkali metal, such as sodium, potassium or lithium).

The fiber-modifying compounds preferably contain only one ester group. If the fiber-modifying compounds do not contain an azacyclic radical, they preferably have at least one hydroxyl group.

The compounds which cannot be used according to the invention have the general formula (A)



(H₂N) _p - ALK - ER (A)



in which p is the number 1 or 2, ER is an ester group and ALK is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which is optionally interrupted by 1 or more hetero groups and is not substituted by a hydroxyl group.

The present invention thus relates to a process for dyeing fiber materials with water-soluble, anionic dyes, preferably with fiber-reactive dyes, which is characterized in that the dyeing is carried out using low-electrolyte or completely electrolyte-free and / or low-alkali or completely alkali-free dye solutions (dye liquors, printing pastes) and using a fiber material pretreated and modified with the above-mentioned compounds containing ester and amino groups.

entsprechen, in welchen bedeuten:

ER

ist eine Estergruppe;

A und N

bilden zusammen mit 1 oder 2 Alkylengruppen von 1 bis 4 C-Atomen den bivalenten Rest eines heterocyclischen Ringes, bevorzugt eines 5- oder 6-gliedrigen heterocyclischen Ringes, wie beispielsweise des Piperazin-, Piperidin- oder Morpholinringes, worin

A

ein Sauerstoffatom oder eine Gruppe der allgemeinen Formel (a), (b) oder (c)

ist, in welchen

R

ein Wasserstoffatom oder eine Aminogruppe ist oder eine Alkylgruppe von 1 bis 6 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, bedeutet, die durch 1 oder 2 Substituenten aus der Gruppe Amino, Sulfo, Hydroxy, Sulfato, Phosphato und Carboxy substituiert sein kann, oder eine Alkylgruppe von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, ist, die durch 1 oder 2 Heterogruppen, die aus den Gruppen -O- und -NH- ausgewählt sind, unterbrochen ist und durch eine Amino-, Sulfo-, Hydroxy-, Sulfato- oder Carboxygruppe substituiert sein kann,

R¹

Wasserstoff, Methyl oder Ethyl ist,

R²

Wasserstoff, Methyl oder Ethyl ist und

Z^(-)

ein Anion bedeutet, wie beispielsweise das Chlorid-, Hydrogensulfat- oder Sulfatanion;

B

ist die Aminogruppe der Formel H₂N- oder eine Amino- bzw. Ammoniumgruppe der allgemeinen Formel (d) oder (e)

in welchen

R¹, R² und Z^(-)

eine der obengenannten Bedeutungen besitzt und

R³

Methyl oder Ethyl ist und

R⁴

Wasserstoff, Methyl oder Ethyl bedeutet;

p

ist die Zahl 1 oder 2, bevorzugt 1;
   alkylen ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen, der durch 1 oder 2 Hydroxygruppen substituiert sein kann, oder ist ein geradkettiger oder verzweigter, bevorzugt geradkettiger, Alkylenrest von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, der durch 1 oder 2 Heterogruppen, die aus den Gruppen -O-und -NH- ausgewählt sind, unterbrochen ist;
   alk ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen, oder ist ein geradkettiger oder verzweigter, bevorzugt geradkettiger, Alkylenrest von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, der durch 1 oder 2 Heterogruppen, die aus den Gruppen -O- und -NH- ausgewählt sind, unterbrochen ist, und ist bevorzugt ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen;

m

ist die Zahl 1 oder 2, bevorzugt 1;

n

ist eine Zahl von 1 bis 4, bevorzugt 1 oder 2;
   die Amino-, Hydroxy- und Estergruppen können sowohl an einem primären, sekundären oder tertiären C-Atom des Alkylenrestes gebunden sein.

Aliphatic compounds containing amino and ester groups which can be used according to the invention are, for example, compounds which have the general formulas (1a) and (1b)

correspond in which mean:

HE

is an ester group;

A and N

together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the divalent radical of a heterocyclic ring, preferably a 5- or 6-membered heterocyclic ring, such as the piperazine, piperidine or morpholine ring, in which

A

an oxygen atom or a group of the general formula (a), (b) or (c)

is in which

R

is a hydrogen atom or an amino group or an alkyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which are substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy may, or is an alkyl group of 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms, which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and by one Amino, Sulfo, hydroxyl, sulfato or carboxy group can be substituted,

R¹

Is hydrogen, methyl or ethyl,

R²

Is hydrogen, methyl or ethyl and

Z ^(-)

represents an anion, such as the chloride, hydrogen sulfate or sulfate anion;

B

is the amino group of the formula H₂N or an amino or ammonium group of the general formula (d) or (e)

in which

R¹, R² and Z ^(-)

has one of the meanings mentioned above and

R³

Is methyl or ethyl and

R⁴

Represents hydrogen, methyl or ethyl;

p

is the number 1 or 2, preferably 1;
alkylene is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched, preferably straight-chain, alkylene radical of 3 to 8 carbon atoms -Atoms, preferably from 3 to 5 carbon atoms, which is interrupted by 1 or 2 hetero groups selected from the groups -O-and -NH-;
alk is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, or is a straight-chain or branched, preferably straight-chain, alkylene radical of 3 to 8 carbon atoms, preferably of 3 to 5 carbon atoms Atoms, which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH-, and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms ;

m

is the number 1 or 2, preferably 1;

n

is a number from 1 to 4, preferably 1 or 2;
the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom of the alkylene radical.

Such compounds containing ester and amino groups which can be used according to the invention are, for example, N- (β-sulfatoethyl) piperazine, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) -piperidine, N- (γ-sulfato-β-hydroxy-propyl) -pyrrolidine, N- (β-sulfatoethyl) -piperidine, the salts of 3-sulfato-2-hydroxy-1- (trimethylammonium) propane, such as 3 -Sulfato-2-hydroxy-1- (trimethylammonium) propane sulfate, 2-sulfato-3-hydroxy-1-amino propane, 3-sulfato-2-hydroxy-1-amino propane, 1-sulfato-3 -hydroxy-2-amino-propane, 3-hydroxy-1-sulfato-2-amino-propane, 2,3-disulfato-1-amino-propane and 1,3-disulfato-2-amino-propane and derivatives of these compounds with another ester group instead of the sulfato group, such as with the phosphato group, an alkanoyloxy group of 2 to 5 carbon atoms, such as the acetyloxy group, or one optionally substituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and nitro substituted phenylsulfonyloxy group pe, such as the p-tosyloxy and 3,4,5-trimethylphenylsulfonyloxy group.

To prepare the compounds which can be used according to the invention, it is possible to start from the corresponding compounds containing hydroxyl groups and to esterify the hydroxyl groups in a customary manner by reaction with the acids or the corresponding acylating agents, where, if one starts from compounds containing amino groups with more than one hydroxyl group, preferably only one of these hydroxy groups esterified. Such procedures are known in the literature; the compounds which can be used according to the invention can be prepared analogously to such known procedures. For example, the esterification of amino alcohols to their sulfuric acid esters is described in Houben-Weyl, Methods of Organic Chemistry, Volume VI / 2, pages 452-457, and Volume E11, pages 997 ff. Other common modifications of such procedures are based on the fact that, for example the amino alcohol is stirred in a large excess of fuming sulfuric acid (see Cham. Ber. 51 , 1160) or on the use of indifferent solvents which serve as the reaction medium in the esterification, the use of equimolar amounts of concentrated sulfuric acid being possible (see DE -PS 825 841). Esterification and acylating agents which can be used to prepare the compounds containing ester and amino groups that can be used according to the invention from starting compounds are, for example, sulfuric acid, phosphoric acid, polyphosphoric acid, alkane carboxylic acids of 2 to 5 carbon atoms and their chlorides or anhydrides, such as acetic acid (glacial acetic acid ) and acetic anhydride, benzenesulfonic acid and those substituted on the benzene nucleus by substituents from the group consisting of sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and nitro or benzenesulfonic acids or their sulfochlorides. For example, the sulfato compound can be prepared from the corresponding hydroxy compounds by adding the hydroxy compounds in the required amount, ie preferably an equimolar amount, of concentrated sulfuric acid and stirring them at a temperature between 5 and 30 ° C for some time until the solution is complete. They are isolated from the sulfuric acid solution by pouring the solution onto ice and neutralization, by precipitating the sulfate ions using calcium carbonate as calcium sulfate and then filtering and evaporating the aqueous solution. For example, the sulfato compounds can be obtained as crystalline or semi-crystalline substances which can be used directly in the process of modifying the fiber material.

Fiber materials are understood to mean natural and synthetic fiber materials which contain hydroxyl and / or carbonamide groups, such as silk, wool and other animal hair, as well as synthetic polyemide fiber materials and polyurethane fiber materials, for example polyamide-4, polyamide-6 and polyamide-11, and in particular fiber materials which Base bodies of α, β-glucose contain, such as cellulose fiber materials, for example cotton, hemp, jute and linen, and their regenerated derivatives, such as viscose silk and rayon, or mixtures of such fiber materials.

The printing processes and prints are included under the names "dyeing", "dyeing process" and "dyeing".

By "anionic dyes" are meant those which are anionic, i.e. contain acidic groups, such as sulfo and carboxy groups, or their salts, such as alkali metal salts, and are accordingly water-soluble. In particular, these are understood to mean those anionic dyes which have a fiber-reactive group, i.e. a group that is usually able to react with the carbonamide or hydroxy groups of the fiber material and to be able to form a connection with them.

The invention further relates to a process for modifying a fiber material, which is characterized in that a saturated aliphatic compound of 3 to 15 carbon atoms containing ester and amino groups and optionally substituted by 1 or 2 or more, such as 3 to 5, hydroxyl groups , preferably from 3 to 12 carbon atoms, with at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group in which the aliphatic radical (s) is straight-chain, branched and / or cyclic ( are) and may optionally be interrupted by one or more, such as two or three, hetero groups, such as amino groups and oxygen atoms, and the amino group (s) can also be part of a saturated heterocyclic radical, with the exception of compounds of general formula (A), in aqueous, alkaline solution at a temperature between 60 and 230 ° C, preferably between n 90 and 190 ° C, can act on a fiber material.

Furthermore, the invention relates to the use of such ester and amino group-containing compounds as defined above for modifying fiber materials, in particular with the aim of being able to use them for dyeing with water-soluble, anionic dyes without or only with small amounts of electrolyte salts and alkaline agents.

The inventive method of modifying the fiber material can be carried out, for example, by contacting the fiber material with the aliphatic compound containing amino and ester groups in an alkaline aqueous solution. The concentration of this compound in the alkaline aqueous solution is generally between 1 and 20% by weight, preferably between 5 and 10% by weight. The alkaline agent, such as sodium hydroxide, sodium carbonate and potassium carbonate, can be present in a concentration between 1 and 20% by weight; the alkaline agent is preferably used in a concentration between 1.5 and 10% by weight, the amount depending both on the amount of use of the amino and ester group-containing aliphatic compound and on the material to be pretreated. This will avoid high alkali concentrations in polyester materials. As a rule, the alkaline, aqueous solution containing the amino and ester group-containing aliphatic compound has a pH between 10 and 14.

The fiber material, which is both modified according to the invention and used in the modified form in the dyeing process according to the invention, can in all processing states, such as yarn, flake, sliver and piece goods (fabric), and also in a mixture with other fiber materials, such as in Form of cotton / polyester fiber materials and in the form of blended fabrics with other fiber materials.

Some of the compounds containing ester and amino groups which can be used according to the invention have not yet been described and are therefore new. The present invention accordingly also relates to these new compounds. New compounds which can be used according to the invention are, for example, N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (β-sulfatoethyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) piperidine, N - (γ-sulfato-β-hydroxypropyl) pyrrolidine, 3-sulfato-2-hydroxy-1-aminopropane, 2-sulfato-3-hydroxy-1-aminopropane, the salts of 2-sulfato- 3-hydroxy and 3-sulfato-2-hydroxy-1- (trimethylammonium) propane and their derivatives with an ester group other than the sulfato group.

The aliphatic compounds containing ester and amino groups which can be used according to the invention can be brought into contact with the fiber material in a variety of ways in an alkaline aqueous solution, for example by treating the fiber material in an alkaline, aqueous solution of the compound containing ester and amino groups (analogous to a Dye-drawing process) at a temperature between 15 and 100 ° C, the modification of the fiber material already taking place, in particular at the higher temperatures, such as above 80 ° C. Other possibilities are to pad the fiber material with the aqueous, alkaline solution, to splash or to spray the solution onto the fiber material. If the fiber material is impregnated with this alkaline, aqueous solution by introducing the fiber material into this solution or by padding (padding), the impregnated material is then squeezed off by excess liquor, so that the absorption of this aqueous, alkaline solution is between 50 and 120 % By weight, preferably between 70 and 100% by weight, based on the fiber material. As a rule, the impregnation (by padding, splashing or treatment in the solution itself) takes place at a temperature between 10 and 60 ° C., preferably at a temperature between 15 and 30 ° C. When the solution is sprayed onto the fiber material, which generally takes place at a temperature between 10 and 40 ° C., a liquid absorption of preferably between 10 and 50% by weight is selected.

If the fiber material is a mercerized cellulose fiber material, the compound containing amino and ester groups that can be used according to the invention can also advantageously be applied to the cellulose fiber material to be modified directly after the mercerization process, in which the mercerized material still contains the alkali, for example by using the one obtainable after the mercerization process. material impregnated with the aqueous alkali, if necessary, squeezed to a required liquid content and the alkaline impregnated material impregnated with the aqueous solution of the compound containing amino and ester groups which can be used according to the invention, the impregnation being carried out by padding, spraying and similar process steps which are customary and known in the art can be.

After impregnation of the fiber material in one of the various ways specified above, except for the drawing-out procedure, the impregnated material is dried; the drying of the fiber-modifying amino group-containing compound is carried out at the same time, a temperature between 100 and 230 ° C., preferably between 130 and 190 ° C., being chosen for the drying and fixing. As a rule, drying and simultaneous fixing take place by treatment with hot air for 0.5 to 3 minutes. The fiber-modifying compound containing amino groups can also be fixed on the fiber material by simple drying at higher temperatures; it can be hung up in drying cabinets to dry and fix the modifying compound on the fiber material and exposed to the required higher temperatures, such as 80 to 105 ° C.

The modified fiber material is aftertreated by rinsing with cold and hot water and optionally by treatment in an aqueous bath containing a small amount of an acid, such as acetic acid, to remove the alkali from the fiber material and then drying. A neutral-reacting fiber material should be used in the dyeing process if possible.

The dyeing of fiber materials modified in this way is carried out analogously to known dyeing methods and printing processes for dyeing or printing fiber materials with water-soluble textile dyes, such as anionic dyes, in particular fiber-reactive dyes, and using the temperature ranges and customary amounts of dye known for this purpose, but with the exception according to the invention, that for the dyebaths, padding liquors and printing pastes of the dyeing process according to the invention, an addition of alkaline compounds, such as are usually used for fixing fiber-reactive dyes, such as sodium carbonate, potassium carbonate, sodium hydroxide solution and water glass, can be largely or completely excluded and that further the usual addition Electrolyte salts, which are intended in particular to increase the migration of the dye on the fiber, are not required or only to a small extent, for example up to a maximum of 10 g per liter of dye bath or dye liquor. The dyeing process according to the invention is accordingly carried out within a pH range between 4 and 8, preferably between 4.5 and 7.

Dyeing processes which can be used according to the invention are, for example, the various extraction processes, such as dyeing on the jigger and on the reel runner or dyeing from a long or short liquor, dyeing in jet dyeing machines, dyeing using the pad-cold-dwell method or after a block-hot steam fixing process. With the pull-out process you can work in the usual liquor ratio of 1: 3 to 1:20. The dyeing temperature can be between 30 and 90 ° C, preferably it is at a temperature below 60 ° C; As can be seen from the above-mentioned application of the block-cold retention process according to the invention, dyeing is also advantageously possible at room temperature (10 to 30 ° C.).

In the dyeing process according to the invention, the use of the customary, often necessary dyeing aids, such as surfactants (wetting agents), thiourea, thiodiethylene glycol, thickeners, leveling aids, auxiliaries which improve the solubility of dyes in the concentrated padding liquors, such as condensation products of formaldehyde and optionally alkyl-substituted Naphthalenesulfonic acids, and especially urea, can be omitted entirely or to a considerable extent. In general, the modified fiber material according to the invention can be dyed using a purely aqueous dye solution, in which only extremely small amounts of electrolyte salts (such as sodium chloride and sodium sulfate), which are contained in the dye powders as adjusting agents, are additionally dissolved.

The present invention can also be used advantageously for single-bath dyeing processes for dyeing mixtures of cellulose and polyester fibers, if in addition a disperse dye used for dyeing Polyester fiber materials is suitable, is used with a reactive dye in the common dye bath. Since many disperse dyes are sensitive to alkali, especially when using higher temperatures, they cannot be used in single-bath dyeing of cellulose / polyester mixed fiber materials, since the use of high temperatures in the alkali-containing bath in the dyeing of the polyester fiber by the disperse dye leads to damage to the disperse dye. However, the present invention makes it possible to dye free of alkali, so that in the aqueous, alkali-free dye liquor, the reactive dye can be fixed first at low temperature, for example at a dyeing temperature between 30 and 80 ° C., and then the polyester fiber with the disperse dye in the usual way at temperatures above 100 ° C, such as between 110 and 140 ° C, colored.

All water-soluble, preferably anionic dyes, which preferably have one or more sulfo and / or carboxy groups and which can optionally contain fiber-reactive groups, are suitable for the dyeing methods according to the invention. In addition to the class of fiber-reactive dyes, they can belong to the class of azo development dyes, direct dyes, vat dyes and acid dyes, which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan - And triphendioxazine dyes. Such dyes have been described in numerous literature and are well known to those skilled in the art.

Of the above-mentioned dyes which can be used for the dyeing process according to the invention, the fiber-reactive dyes are preferably used. Fiber-reactive dyes are organic dyes which contain 1, 2, 3 or 4 fiber-reactive radicals from the aliphatic, aromatic or heterocyclic series. Such dyes have been extensively described in the literature. The dyes can belong to a wide variety of dye classes, such as the class of monoazo, disazo, polyazo, metal complex azo, such as 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex monoazo and disazo dyes, also the range of anthraquinone dyes, copper and cobalt phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine , Triphendioxazin, phenazin and stilbene dyes. Fiber-reactive dyes are understood to mean those which have a “fiber-reactive” group, ie a group which contains the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups of wool and silk or the amino and possibly carboxy groups of synthetic polyamides are able to react to form covalent chemical bonds. The fiber-reactive residue can be bound to the dye residue directly or via a bridge member; preferably it is directly or via an optionally monoalkylated amino group, such as a group represented by the formula -NH-, -N (CH₃) -, -N (C₂H₅) - or -N (C₃H₇) -, or via an aliphatic radical, such as one Methylene, ethylene or propylene radical or an alkylene radical of 2 to 8 carbon atoms, which can be interrupted by one or two oxi and / or amino groups, or via a bridge member containing an amino group, such as a phenylamino group, to the Dye residue bound. Fiber-reactive radicals are, for example: vinylsulfonyl, β-chloroethylsulfonyl, β-sulfatoethylsulfonyl, β-acetoxy-ethylsulfonyl, β-phosphatoethylsulfonyl, β-thiosulfatoethylsulfonyl, N-methyl-N- (β-sulfatoethyl-sulfonyl) -amino, acryloyl, -CO- CCl = CH₂, -CO-CH = CH-Cl, -CO-CCl = CHCl, -CO-CCl = CH-CH₃, -CO-CBr = CH₂, -CO-CH = CH-Br, -CO-CBr = CH-CH₃, -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, -CO-CBr = CH-COOH, -CO-CH = CBr-COOH, -CO-CCl = CCl-COOH, - CO-CBr = CBr-COOH, β-chloro- or β-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloropropionyl, 2,3-dibromopropionyl, 2-fluoro-2 -chloro-3,3-difluorocyclobutane-2-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, β- (2,2,3,3-tetrafluorocyclobutyl-1) acryloyl, α - or β-methylsulfonylacryloyl, propionyl, chloroacetyl, bromoacetyl, 4- (β-chloroethylsulfonyl) butyryl, 4-vinylsulfonylbutyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- (β-chloroethylsulfonyl) caproyl , 6-vinylsulfonyl-caproyl, 4-fluoro-3-nitrobenzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methyl-sulfonylbenzoyl, 4-fluoro-3-cyano-benzoyl, 2-fluoro-5-methylsulfonyl-benzoyl, 2,4-dichlorotriazinyl-6, 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6, 2,4-dichloro-5-nitro- or -5- methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di or trichloromethyl- or -5-methylsulfonyl -pyrimidinyl-6, 2,5-dichloro-4-methylsulfonyl-pyrimidinyl-6, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl , 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl -6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidnyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyan-4-pyrimidinyl, 2 -Fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4 -pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2 -Fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6- methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl 2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5- phenyl or -5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl , 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyan-4-pyrimidinyl, 2 , 6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-trifluoromethyl -4-pyrimidinyl, 2,4-di- (methylsulfonyl) pyrimidinyl-4, 2,5-di- (methylsulfonyl) -5-chloropyrimidinyl-4, 2-methylsulfonylpyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl -4, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl pyrimidnyl-4, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4, 2,5,6-tri-methylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4, 2-ethylsulfonyl-5-chloro-6-methylpyrimidinyl-4, 2-methylsulfonyl-6-chloropyrimidinyl- 4, 2,6-di- (methylsulfonyl) -5-chloropyrimidinyl-4, 2-methylsulfonyl-6-carboxypyrimidinyl-4, 2-methylsulfonyl-5-sulfopyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxy- pyrimidinyl-4, 2-methylsulfonyl-5-carboxypyrimidinyl-4, 2, -methylsulfonyl-5-cyano-6-methoxy-pyrimidinyl-4, 2-methylsulfonyl-5-chloropyrimidinyl-4, 2-sulfoethylsulfonyl-6-methylpyrimidinyl-4, 2-methylsulfonyl-5-bromo-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-pyrimdinyl-4, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2,4-dichloropyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine- 5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5- sulfonyl, 2,4-dichloro-6-methyl-pyrimidine-5-carbonyl or -5-sulfonyl, 2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl, 2,6-di- (methylsulfonyl) pyrimidine -4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-di (methylsulfonyl) pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5 -sulfonyl- or -5-carbonyl, 2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5 or -6- carbonyl, 2,3- Dichloroquinoxaline-5- or -6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline- 7- or -8-sulfonyl, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6-yl-1') phenylsulfonyl or carbonyl, β- (4 ', 5'-dichloropyridazinone -6'-yl-1 ') propionyl, 3,6-dichloropyridazin-4-carbonyl or -4-sulfonyl, 2-chlorobenzthiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2- Arylsulfonyl- or 2-alkylsulfonylbenzthiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5- or -6-sulfonyl or -carbonyl, 2-phenylsulfonyl-benzothiazole -5- or -6-sulfonyl or -carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl- or -sulfonyl derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl or - containing sulfo groups in the fused benzene ring sulfonyl, 2-chlorobenzimidazole-5- or - 6-carbonyl or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl o the - sulfonyl, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl or -4- or -5-sulfonyl; triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino and -4- (o-, m- or p-sulfophenyl) -amino-triazine-6-, 2- (1,1-dimethylhydrazinium) -4 phenylamino- and -4 - (o-, m- or p-sulfophenyl) aminotriazinyl-6, 2- (2-isopropyl-1,1-dimethyl-hydrazinium) -4-phenylamino ^- and -4- (o-, m- or p- sulfophenyl) aminotriazinyl-6, 2-N-aminopyrrolidinium-, 2-N-aminopiperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6, 4-phenylamino- or 4- (Sulfophenylamino) -triazinyl-6, the 1,4-bis-aza-bicyclo [2,2,2] octane or 1,2-bis-aza-bicyclo- [0 , 3,3] octane quaternary bound, 2-pyridinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6 and corresponding 2-oniumtriazinyl-6 radicals, the in the 4-position by alkylamino, such as methylamino, ethylamino or β-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy or sulfophenoxy.

in welcher Hal Chlor oder Fluor ist und Q eine Amino-, Alkylamino-, N,N-Dialkylamino-, Cycloalkylamino-, N,N-Dicycloalkylamino-, Aralkylamino-, Arylamino-, N-Alkyl-N-cyclohexylamino-, N-Alkyl-N-arylaminogruppe oder eine Aminogruppe bedeutet, die einen heterocyclischen Rest enthält, welcher einen weiteren ankondensierten carbocyclischen Ring aufweisen kann, oder Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, der gegebenenfalls weitere Heteroatome enthält, sowie Hydrazino- und Semicarbazidogruppen, wobei die genannten Alkylreste geradkettig oder verzweigt und niedrigmolekular und höhermolekular sein können, bevorzugt solche mit 1 bis 6 Kohlenstoffatomen sind. Als Cycloalkyl-, Aralkyl- und Arylreste kommen insbesondere Cyclohexyl-, Benzyl-, Phenethyl-, Phenyl- und Naphthylreste in Frage; heterocyclische Reste sind vor allem Furan-, Thiophen-, Pyrazol-, Pyridin-, Pyrimidin-, Chinolin-, Benzimidazol-, Benzthiazol- und Benzoxazolreste. Als Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, kommen vorzugsweise Reste von sechsgliedrigen N-heterocyclischen Verbindungen in Betracht, die als weitere Heteroatome Stickstoff, Sauerstoff oder Schwefel enthalten können. Die oben genannten Alkyl-, Cycloalkyl-, Aralkyl- und Arylreste, die heterocyclischen Reste sowie die N-heterocyclischen Ringe können zusätzlich substituiert sein, z.B. durch Halogen, wie Fluor, Chlor und Brom, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Acylaminogruppen, wie Acetylamino oder Benzoylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo. Als Beispiele für derartige Aminogruppen seien genannt: - NH₂, Methylamino, Ethylamino, Propylamino, Isopropylamino, Butylamino, Hexylamino, β-Methoxyethylamino, γ-Methoxypropylamino, β-Ethoxyethylamino, N,N-Dimethylamino, N,N-Diethylamino, β-Chlorethylamino, β-Cyanethylamino, γ-Cyanpropylamino, β-Carboxyethylamino, Sulfomethylamino, β-Sulfoethylamino, β-Hydroxyethylamino, N,N-Di-β-hydroxyethylamino, γ-Hydroxypropylamino, Benzylamino, Phenethylamino, Cyclohexylamino, Phenylamino, Toluidino, Xylidino, Chloranilino, Anisidino, Phenetidino, N-Methyl-N-phenylamino, N-Ethyl-N-phenylamino, N-β-Hydroxyethyl-N-phenylamino, 2-, 3- oder 4-Sulfoanilino, 2,5-Disulfoanilino, 4-Sulfomethylanilino, N-Sulfomethylanilino, 2-, 3- oder 4-Carboxyphenylamino, 2-Carboxy-5-sulfophenylamino, 2-Carboxy-4-sulfophenylamino, 4-Sulfonaphthyl-(1)-amino, 3,6-Disulfonaphthyl-(1)-amino, 3,6,8-Trisulfonaphthyl-(1)-amino, 4,6,8-Trisulfonaphthyl-(1)-amino, 1-Sulfonaphthyl-(2)-amino, 1,5-Disulfonaphthyl-(2)-amino, 6-Sulfonaphthyl-(2)-amino, Morpholino, Piperidino, Piperazino, Hydrazino und Semicarbazido.Particularly interesting fiber-reactive radicals are fluorine and chloro-1,3,5-triazine radicals of the formula (2)

in which Hal is chlorine or fluorine and Q is an amino, alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino, N-alkyl-N-cyclohexylamino, N- Alkyl-N-arylamino group or an amino group which contains a heterocyclic radical which may have a further fused-on carbocyclic ring, or amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms, and hydrazino and semicarbazido groups , where the alkyl radicals mentioned can be straight-chain or branched and low molecular weight and higher molecular weight, preferably those having 1 to 6 carbon atoms. Suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; Heterocyclic residues are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole residues. The amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring are preferably residues of six-membered N-heterocyclic rings Compounds into consideration which may contain nitrogen, oxygen or sulfur as further heteroatoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, the heterocyclic radicals and the N-heterocyclic rings can additionally be substituted, for example by halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ -C₄-alkyl, C₁-C₄-alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo. Examples of such amino groups are: - NH₂, methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, β-methoxyethylamino, γ-methoxypropylamino, β-ethoxyethylamino, N, N-dimethylamino, N, N-diethylamino, β-chloroethylamino , β-cyanoethylamino, γ-cyanopropylamino, β-carboxyethylamino, sulfomethylamino, β-sulfoethylamino, β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, γ-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, phenylamino, xinoilinoino, toluid , Anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-β-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5-disulfoanilino, 4-sulfomethylanilino , N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino, 3,6-disulfonaphthyl- (1) -amino, 3,6,8-trisulfonaphthyl- (1) -amino, 4,6,8-trisulfonaphthyl- (1) -amino, 1-sulfonaphthyl- (2) -amino, 1,5-disulfonaphthyl- (2) -amino, 6-sulfonaphthyl- (2) -amino, morpholino, piperidino, piperazino, hydrazino and semicarbazido.

Furthermore, Q can be an amino radical of the general formula -NR¹⁰R¹¹, in which R¹⁰ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, and R¹¹ is phenyl which is formed by a fiber-reactive radical of the vinylsulfone series directly or via a methylamino , Ethylamino, methylene, ethylene or propylene group is substituted and which can also be substituted by 1 or 2 substituents from the group methoxy, ethoxy, methyl, ethyl, chlorine, carboxy and sulfo, or R¹¹ alkyl of 2 to 4 C- Atoms is, such as ethyl or n-propyl, which is substituted by a fiber-reactive group of the vinylsulfone series, or alkylenephenyl with an alkylene radical of 1 to 4 carbon atoms, the phenyl of which is substituted by a fiber-reactive radical of the vinylsulfone series, or in which R¹⁰ and R¹¹ both are alkyl of 2 to 4 carbon atoms, such as ethyl and n-propyl, which are substituted by a fiber-reactive group of the vinyl sulfone series, or in which R¹⁰ and R¹¹ both represent alkylene of 3 to 8 carbon atoms, which are replaced by 1 or 2 oxi and / or amino groups are interrupted and to which a fiber-reactive group of the vinyl sulfone series is bonded. Fiber-reactive groups of the vinyl sulfone series are those of the general formula -SO₂-Y, in which Y is vinyl or ethyl which is substituted in the β-position by an alkaline eliminable substituent, such as, for example, chlorine, sulfato, phosphato, thiosulfato, acetyloxy, sulfobenzoyloxy and dimethylamino.

The dyeings of the modified cellulose fiber materials obtainable in accordance with the invention require no further aftertreatment after removal from the dyebath or after completion of the fixation of the dye on the substrate, in particular no complex posttreatment process including washing. As a rule, it is sufficient to rinse the colored substrate once or several times with warm or hot and optionally cold water, which may optionally contain a nonionic wetting agent or a fiber-reactive aftertreatment agent, such as, for example, condensation products from one mole of cyanuric chloride and two moles of 4- (β- Sulfatoethylsulfonyl) aniline, from equivalent amounts of cyanuric chloride, 4- (β-sulfatoethylsulfoanyl) aniline and 4,8-disulfo-2-amino-naphthalene or from equivalent amounts of cyanuric chloride, 4-sulfo-aniline and 4,8-disulfo -2-aminonaphthalene. The use of a fiber-reactive aftertreatment agent is advisable if the fiber material modified according to the invention has been dyed only in slight depths of shade or if a dye has been used which does not have satisfactory fiber reactivity. In these cases, there are still sufficient dye-reactive spots on the modified fiber, which, for example, can react with other dyes in rinsing baths contaminated with these dyes. This aftertreatment deactivates the still active areas of the fiber modified according to the invention, and one also obtains one contaminated with dyes in a technical process Rinse water the originally desired clear color. In addition, a final boiling treatment of the colored substrate with a washing solution to improve the fastness properties is not necessary.

The following examples serve to illustrate the invention. The parts mentioned are parts by weight, the percentages are percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

Example A

To a mixture of 750 parts by volume of a 100% sulfuric acid and 75 parts by volume of a sulfuric acid (20% oleum) containing 20% sulfur trioxide at 10 ° C., 500 parts by volume of N- (β -Hydroxyethyl) -piperidin added, while keeping the reaction temperature between 20 and 25 ° C with constant cooling. After the reaction has ended, the reaction mixture is stirred into 1000 parts of ice water, the pH is adjusted to 4 with calcium carbonate, the batch is briefly heated to 50 ° C. and the calcium sulfate formed is then filtered off. Calcium ions still present are precipitated from the filtrate with sodium oxalate. After the calcium oxalate has been separated off, the aqueous solution of the N- (β-sulfatoethyl) piperidine is evaporated to dryness under reduced pressure. A yellow, oily product is obtained which crystallizes and melts at 124 ° C. with decomposition.
1 H-NMR analysis (in hexadeutero-dimethyl sulfoxide; 300 Hz):
1.5 ppm (d, br, 2H); 1.7 ppm (t, 4H); 3.15 ppm (s, 4H); 3.25 ppm (t, 2H); 4.15 ppm (t, 2H).

Example B

To produce a mixture of the compounds 3-sulfato-2-hydroxy-1-aminopropane and 2-sulfato-3-hydroxy-1-aminopropane, 92.9 parts of 2,3-dihydroxy-1-amino are added with stirring -propane in 98 parts of 96% sulfuric acid, the reaction temperature being kept at 20 to 25 ° C. by external cooling. The reaction mixture is worked up and the sulfato-hydroxy-1-aminopropane compounds are isolated in the same manner as described in Example A.

Example C

100 parts of 2,3-dihydroxy-1- (trimethylammonium) propane chloride are slowly introduced into 110 parts of 100% strength sulfuric acid at a temperature of 20.degree. C., the mixture is stirred for a few hours and the reaction is ended isolates the ester compound formed in the example A specified way. An oily product is obtained as a mixture of 3-sulfato-2-hydroxy-1- (trimethylammonium) propane and 2-sulfato-3-hydroxy-1- (trimethylammonium) propane sulfate.
1 H-NMR analysis (in hexadeutero-dimethyl sulfoxide; 300 Hz):
3.68 and 3.8 ppm (2dd, 2H); 2.94 and 2.7 ppm (2dd, 2H); 4.3 ppm (m, 1H).

Example D

To prepare N- (γ-sulfato-β-hydroxy-propyl) piperidine, 100 parts of N- (β, γ-dihydroxy-propyl) piperidine are slowly added to 67 parts of 100% sulfuric acid with stirring at 20 ° C. . The mixture is stirred for a further hour and the piperidine compound according to the invention is isolated in the manner described in Example A. It is initially obtained as an oily product which crystallizes after some time. It melts at 170 to 175 ° C with decomposition.
1 H-NMR analysis (in hexadeutero-dimethyl sulfoxide; 300 Hz):
1.5 ppm (s, br, 2H); 3.1-3.3 ppm (m, 8H); 3.0 / 3.15 ppm (2dd, 2H); 3.68 / 3.8 ppm (2dd, 2H); 4.1 ppm (m, 2H).

Example E

To prepare N- (γ-sulfato-β-hydroxy-propyl) pyrrolidine, 50 parts of N- (β, γ-dihydroxy-propyl) pyrrolidine in 98 parts of 100% sulfuric acid are slowly added with stirring at 20 ° C. . The batch is stirred for a further hour and the compound formed is then isolated as an oily product in the manner given in Example A.
1 H-NMR analysis (in D₆-dimethyl sulfoxide):
4.0 ppm (m, 1H); 3.76 / 3.68 ppm (2dd, 2H); 3.0 ppm (m, 2H); 1.95 ppm (s, br, 4H); 3.1 ppm (s, br, 4H).

example 1

• a) A fabric of mercerized and bleached cotton is impregnated with a 20 to 25 ° C aqueous solution of 50 parts of sodium hydroxide and 50 parts of 1-N- (β-sulfatoethyl) piperazine in 1000 parts of water with a liquor absorption of 90%. The material is then treated with hot air at 150 ° C. for 2.5 minutes, with both the drying and the fixing of the piperazine compound taking place on the tissue. The material thus obtained is then treated in cold water at 60 ° C. and, if appropriate, in an aqueous bath containing acetic acid until residual alkali has been removed from the tissue.
• b) The modified cotton fabric is dyed analogously to a conventional exhaust dyeing process: 100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution, the 2 parts of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder, for example from the European patent application. Publication No. 0 061 151 known dye of the formula
  
  contains dissolved in the form of the alkali metal salt (ie 1 part of this dye and 1 part of the electrolyte), the dyebath is heated to 60 ° C within 30 minutes, and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then rinsed with cold and hot water, where the hot water can contain a commercially available wetting agent, optionally rinsed again with cold water and dried.

A strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 2

• a) A mercerized and bleached cotton fabric with an aqueous solution of 50 parts of sodium hydroxide and 50 parts of 1-N- (β-sulfatoethyl) piperazine in 1000 parts of water at a temperature of 25 to 30 ° C with a liquor absorption of 85% padded a foulard. The fabric treated in this way is then treated with hot air at 150 ° C. for about 3 minutes to fix the piperazine compound on the cellulose fiber and to simultaneously dry the padded fabric. The modified fabric is then treated with cold and 60 ° C. hot water in baths to remove the alkali and dried.
• b) The modified cotton fabric is then dyed according to a block-cold-dyeing process. For this purpose, an aqueous dye solution which contains 20 parts of the dye powder described in Example 1, 100 parts of urea and 3 parts of a commercially available nonionic wetting agent dissolved in 1000 parts by volume, using a padder with a liquor absorption of 80%, based on the weight of the Fabric, applied to the fabric at 25 ° C. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and then again if necessary cold water rinsed and dried.

A strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 3

• a) A fabric made of mercerized and bleached cotton with a 20 to 25 ° C warm aqueous solution of 50 parts of sodium hydroxide and 50 parts of the monosulfate of 2,3-dihydroxy-1-aminopropane in 1000 parts of water with a liquor absorption of 90%. The impregnated material is then treated with hot air at 150 ° C. for 2.5 minutes to fix the aminopropane compound on the material with simultaneous drying and then washed in cold and 60 ° C. hot water until the excess alkali has been completely removed and then dried.
• b) The fabric modified in this way is dyed according to a conventional padding process, for example analogously to the procedure of Example 2. For this purpose, an aqueous dye liquor containing 28 parts of 1000 parts by volume of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the dye of the formula known, for example, from Belgian Patent No. 715,420
  
  and contains 3 parts of a commercially available nonionic wetting agent dissolved, by means of a padder with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 20 ° C. The padded fabric is then wound onto a dock, wrapped in a plastic sheet and left at 20 ° C for 16 hours and then washed with cold and hot water, which may or may not contain a commercially available nonionic surfactant, and optionally again with cold water and dried.

A strong, uniformly colored yellow color with the usual good fastness properties is obtained.

Example 4

A mercerized and bleached cotton fabric is impregnated with an aqueous solution of 50 parts of sodium hydroxide and 100 parts of the monosulfate of 2,3-dihydroxy-1-aminopropane in 1000 parts of water at a temperature between 25 and 30 ° C with a liquor absorption of 85% and then treated to fix the aminopropane compound on the fiber material for about 3 minutes with hot air at 150 ° C., the impregnated fabric drying at the same time. The modified material is then freed from excess alkali by treatment with cold water at 60 ° C.

gelöst enthält. Die Färbung erfolgt während 60 Minuten bei 60°C. Das gefärbte Gewebe wird anschließend mit kaltem und mit warmem Wasser von 30 bis 35°C, das gegebenenfalls ein handelsübliches nichtionogenes Tensid enthalten kann, gespült, danach gegebenenfalls nochmals mit kaltem Wasser gewaschen und getrocknet.The modified, dried material is dyed in a conventional exhaust process. For this purpose, 10 parts of this material in 200 parts by volume of an aqueous dye solution, the 0.2 parts of a 50% electrolyte-containing dye powder of the dye of the formula known from German Offenlegungsschrift No. 24 12 964

contains dissolved. The dyeing takes place at 60 ° C. for 60 minutes. The dyed fabric is then rinsed with cold and warm water at 30 to 35 ° C, which may optionally contain a commercially available nonionic surfactant, then washed again with cold water and dried if necessary.

A strong blue dyeing is obtained which, in terms of fastness properties and its other qualities, is similar to dyeings which are obtained using the customary dyeing methods of the prior art.

Example 5

und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eines Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Das mit der Farbstofflösung geklotzte Gewebe wird auf eine Docke aufgewickelt, in eine Plastikfolie gehüllt und während 16 Stunden bei 20 bis 25°C liegen lassen und danach mit kaltem und mit heißem Wasser, das gegebenenfalls ein handelsübliches Netzmittel enthalten kann, und gegebenenfalls anschließend nochmals mit kaltem Wasser gespült und getrocknet.A cotton fabric modified according to the information in Example 3a) is dyed in accordance with a pad-cold-dyed dyeing process. For this purpose, an aqueous dye solution containing 20 parts of 1000 parts by volume of a 50% electrolyte-containing dye powder of, for example, copper phthalocyanine dye of the formula known from German Patent No. 1,179,317

and contains 3 parts of a commercially available nonionic wetting agent dissolved, by means of a padder with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 25 ° C. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and then again if necessary cold water rinsed and dried.

A strong, uniformly colored turquoise coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 6

(bekannt aus Beispiel 258 der deutschen Offenlegungsschrift Nr. 1 644 204) und 400 Teile einer etwa 4 %igen wäßrigen Natriumalginat-Verdickung enthält. Das bedruckte Baumwollgewebe wird zunächst bei 60 bis 80°C getrocknet und anschließend 5 Minuten mit Heißdampf von 101 bis 103°C gedämpft, danach durch Spülen mit kaltem und mit heißem Wasser, durch kochende Behandlung in einem ein neutrales, nichtionogenes Waschmittel enthaltenden Bad behandelt, wiederum mit kaltem und heißem Wasser gespült und getrocknet. Es wird ein gleichmäßiger, scharlachfarbener Druck erhalten, der gute Gebrauchsechtheiten aufweist.A cotton fabric modified as described in Example 1 a) is printed with an aqueous printing paste containing 20 parts of the dye of the formula in 1000 parts

(known from Example 258 of German Offenlegungsschrift No. 1 644 204) and contains 400 parts of an approximately 4% aqueous sodium alginate thickener. The printed cotton fabric is first dried at 60 to 80 ° C and then steamed for 5 minutes with superheated steam from 101 to 103 ° C, then treated by rinsing with cold and hot water, by boiling treatment in a bath containing a neutral, nonionic detergent, again rinsed with cold and hot water and dried. A uniform, scarlet-colored print is obtained which has good fastness properties.

Example 7

(bekannt aus Beispiel 3 der deutschen Offenlegungsschrift Nr. 2 557 141) und 400 Teile einer wäßrigen, 4 %igen Natriumalginat-Verdickung enthält. Das bedruckte Gewebe wird zunächst bei etwa 60 bis 80°C getrocknet und sodann 5 Minuten mit Heißdampf von 101 bis 103°C gedämpft. Dar erhaltene Druck, der gemäß den Angaben des Beispieles 6 fertiggestellt wird, zeigt ein brillantes, blaues Druckmuster, das gute Allgemeinechtheiten, insbesondere gute Reib- und Lichtechtheiten, aufweist.A cotton fabric modified as described in Example 1 a) is printed with an aqueous printing paste containing 20 parts of the dye of the formula in 1000 parts

(known from Example 3 of German Offenlegungsschrift No. 2 557 141) and contains 400 parts of an aqueous, 4% strength sodium alginate thickener. The printed fabric is first dried at about 60 to 80 ° C and then steamed for 5 minutes with superheated steam at 101 to 103 ° C. The print obtained, which is completed according to the information in Example 6, shows a brilliant, blue print pattern which has good general fastness properties, in particular good fastness to rubbing and light.

Example 8

(bekannt aus Colour Index unter C.I. Nr. 51320) gegeben. Man färbt das Baumwollgewebe in dieser Farbstofflösung während 60 Minuten bei 60°C. Die Nachbehandlung der erhaltenen Färbung erfolgt in üblicher Weise, wie beispielsweise analog den Angaben des Beispieles 6. Es wird eine farbstarke blaue Färbung erhalten, die sehr gute Gebrauchsechtheiten, wie insbesondere eine gute Waschechtheit, aufweist.10 parts of a cotton fabric modified according to the information in Example 1 a) is represented by 200 parts of an aqueous solution of 0.2 part of the dye

(known from Color Index under CI No. 51320). The cotton fabric is dyed in this dye solution for 60 minutes at 60 ° C. The aftertreatment of the dyeing obtained is carried out in a customary manner, for example analogously to the instructions in Example 6. A strong blue dyeing is obtained which has very good fastness to use, in particular good fastness to washing.

Example 9

gegeben und während 60 Minuten bei einer Färbetemperatur von 80°C gefärbt. Die erhaltene Färbung wird danach mit kaltem und warmen Wasser von 30 bis 35°C, das ein handelsübliches nichtionogenes Tensid enthalten kann, und anschließend nochmals mit kaltem Wasser gespült und getrocknet. Man erhält eine hochwertige türkisfarbene Färbung mit guten Echtheiten.10 parts of a cotton fabric modified as described in Example 1a) is dissolved in 200 parts of an aqueous solution of 0.2 part of the copper phthalocyanine dye of the formula known, for example, from British Patent No. 1,046,520

given and dyed for 60 minutes at a dyeing temperature of 80 ° C. The dyeing obtained is then rinsed with cold and warm water at 30 to 35 ° C., which may contain a commercially available nonionic surfactant, and then rinsed again with cold water and dried. You get a high quality turquoise color with good fastness properties.

Example 10

• a) A fabric of mercerized and bleached cotton is at 20 to 25 ° C with a solution of 50 parts of N- (β-sulfatoethyl) piperidine and 50 parts of sodium hydroxide in 1000 parts of water with a liquor absorption of 75%, based on the weight of the fabric, padded. The padded fabric is then subjected to a treatment of 180 ° C. hot air for 45 seconds, the fabric being dried and the piperidine compound being simultaneously fixed on the material. The material thus modified is washed with cold and hot water at 60 ° C. to remove excess alkali.
• b) The modified cotton fabric is dyed analogously to a conventional exhaust dyeing process: 100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution which contains 2 parts of the dye powder used in Example 1; the dye bath is heated to 60 ° C. within 30 minutes and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then rinsed with cold and hot water, where the hot water can contain a commercially available wetting agent, optionally rinsed again with cold water and dried.

A strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 11

• a) A mercerized and bleached cotton fabric is with an aqueous solution of 50 parts of 3-sulfato-2-hydroxy-1 (trimethylammonium) propane sulfate or 50 parts of a mixture of 3-sulfato-2-hydroxy-1- (trimethylammonium ) -propane sulfate and 2-sulfato-3-hydroxy-1- (trimethylammonium) propane sulfate and 25 parts of sodium hydroxide in 1000 parts at a temperature of 25 to 30 ° C. with a liquor absorption of 85%. The sulfato compound (s) are fixed on the cotton fiber and the padded fabric is dried at the same time by treating the padded fabric with hot air at 150 ° C. for 150 to 180 seconds. The modified fabric is then subjected to a washing process with cold and hot water at 60 ° C.
• b) The modified cotton fabric is then dyed according to a block-cold-dyeing process. For this purpose, an aqueous dye solution which contains 20 parts of the dye powder described in Example 1, 100 parts of urea and 3 parts of a commercially available nonionic wetting agent dissolved in 1000 parts by volume, using a padder with a liquor absorption of 80%, based on the weight of the Fabric, applied to the fabric at 25 ° C. The fabric padded with the dye solution is wound onto a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and then again if necessary cold water rinsed and dried.

A strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 12

• a) A fabric of mercerized and bleached cotton with a liquor absorption of 75%, based on the weight of the fabric, with a 20 to 25 ° C warm solution of 50 parts of N- (γ-sulfato-β-hydroxy-propyl) - piperidine and 50 parts of sodium hydroxide in 1000 parts of water. The impregnated material is then dried with hot air at 150 ° C. for about 2.5 minutes, the piperidine compound being simultaneously fixed on the fiber material. The modified material is then washed with cold and hot water and dried.
• b) The fabric modified in this way is dyed according to a conventional padding process, for example analogously to the procedure of Example 11. For this purpose, an aqueous dye liquor which contains 28 parts of the dye powder described in Example 3 and 3 parts of a commercially available nonionic wetting agent dissolved in 1000 parts by volume, using a padder with a liquor absorption of 80%, based on the weight of the fabric, at 20 ° C applied to the fabric. The padded fabric is then wound up on a dock, wrapped in a plastic film and left at 30 to 40 ° C for eight hours and then with cold and with hot water, which may or may not contain a commercially available non-ionic surfactant, and optionally again washed cold water and dried.

A strong, uniformly colored yellow color with the usual good fastness properties is obtained.

Example 13

• a) A mercierized and bleached cotton fabric is impregnated with a solution of 100 parts of N- (γ-sulfato-β-hydroxypropyl) pyrrolidine and 100 parts of sodium hydroxide in 1000 parts of water at 20 to 25 ° C with a liquor absorption of 85% . The pyrrolidine compound is fixed on the fiber material and the padded fabric is dried at the same time by treatment with air at 180 ° C. for 45 seconds. The modified material is then subjected to a washing process with cold and hot water.
• b) The modified fabric is dyed in a conventional pull-out process. For this purpose, 10 parts of the fabric are added in 200 parts by volume of an aqueous dye solution which contains 0.2 part of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder of the dye known from Example 1 of European Patent No. 0 032 187. The dyeing takes place at 60 ° C. for 60 minutes. The dyed fabric is then rinsed with cold and warm water at 30 to 40 ° C., which may contain a commercially available non-ionic surfactant, then washed again with cold water and dried if necessary.

A strongly colored red dyeing is obtained which, in terms of fastness properties and its qualities, is similar to dyeings which are obtained using the customary dyeing methods of the prior art.

Example 14

A fabric made of cotton tricot is treated with a solution of 50 parts of N- (β-sulfatoethyl) piperidine and 50 parts of sodium hydroxide in 1000 parts of water for 30 minutes at 130 ° C. in a liquor ratio of 1:20. Then the modified material with cold and 60 ° C washed with hot water to remove excess alkali and dried.

The modified cotton fabric obtained is dyed analogously to a conventional pull-out dyeing process:
100 parts of the fabric are placed in 2000 parts by volume of an aqueous dye solution which contains 2 parts of the 50% electrolyte-containing dye powder described in Example 1 dissolved. The fabric is moved therein and the dyebath is heated to 60 ° C. within 30 minutes and the dyeing is then continued at 60 ° C. for 60 minutes. The dyed material is removed from the bath and rinsed with cold and hot water, if appropriate with the addition of a commercially available wetting agent, if necessary then rinsed again with cold water and dried.

A strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 15

während 60 Minuten bei 60°C gefärbt. Die erhaltene Färbung wird danach mit kaltem und warmen Wasser von 30 bis 35°C, das ein handelsübliches nichtionogenes Tensid enthalten kann, und anschließend nochmals mit kaltem Wasser gespült und getrocknet. Man erhält eine hochwertige rote Färbung mit guten Echtheiten.10 parts of a cotton jersey are treated in 200 parts of an aqueous solution of 10 parts of 3-sulfato-2-hydroxy-1- (trimethylammonium) propane sulfate and 5 parts of sodium hydroxide in a pressure vessel at 130 ° C. for 30 minutes. The modified material is then washed intensively and dried. 10 parts of this modified cotton fabric are in 200 parts of an aqueous solution of 0.2 parts of the dye of the formula known, for example, from German Offenlegungsschrift No. 19 43 904

dyed at 60 ° C for 60 minutes. The dyeing obtained is then rinsed with cold and warm water at 30 to 35 ° C., which may contain a commercially available nonionic surfactant, and then rinsed again with cold water and dried. A high-quality red coloring with good fastness properties is obtained.

Example 16

• a) A fabric of mercerized and bleached cotton is impregnated with a 20 to 25 ° C aqueous solution of 60 parts of N- (β-sulfatoethyl) piperidine and 50 parts of sodium hydroxide in 1000 parts of water with a liquor absorption of 90% and then one Subject to hot air treatment at 170 ° C for 60 seconds. The fabric is dried and the piperidine compound is simultaneously fixed on the fiber material. The material treated in this way is then washed thoroughly with cold and hot water and dried.
• b) The modified fabric is then printed with a printing paste which contains 20 parts of the dye known from Example 1 of European Patent Application Publication No. 0 228 348 and 400 parts of a neutral sodium alginate thickener in 1000 parts. The printed fabric is steamed with superheated steam at 101 to 103 ° C for 5 minutes. The modified fabric is finished analogously as described in the previous examples. A brilliant blue print pattern is obtained with good general fastness properties, such as in particular good fastness to rubbing and light.

Example 17

A fabric made of mercerized and bleached cotton with a liquor absorption of 90% with a 20 to 25 ° C warm aqueous solution of 50 parts of N- (γ-sulfato-β-hydroxypropyl) piperidine and 50 parts of sodium hydroxide in 1000 parts of water impregnated and then exposed to hot air treatment at 150 ° C for 2.5 minutes, then rinsed thoroughly with cold and hot water and dried.

The modified cotton fabric obtained is dyed analogously to a conventional pull-out process:

10 parts of the material are placed in 200 parts by volume of an aqueous dye solution with 0.2 part of the dye known from Example 1 of European Patent No. 0 032 187, the dyeing liquor is heated to 60 ° C. and the dyeing at this temperature is still 60 Minutes continued. The dyed fabric is then rinsed with cold and hot water, which may contain a commercially available wetting agent, if necessary rinsed again with cold water and dried.
A color-intensive red color is obtained which has very good fastness properties.

Example 18

• a) 100 parts of a cotton jersey are treated in a jet apparatus with continuous guidance with 1500 parts of an aqueous liquor of 75 parts of N- (β-sulfatoethyl) piperazine and 45 parts of sodium hydroxide by heating the apparatus to 130 ° C and the Let the liquor act on the material at this temperature for 30 minutes. The liquor is then cooled to 80 ° C., drained from the apparatus and the material modified in this way is first rinsed in the apparatus with cold, then with hot water, to which a commercial wetting agent can be added, and then again thoroughly rinsed with cold water.
• b) 2000 parts of water are then introduced into the jet dyeing apparatus and heated to 60.degree. A total of 20 parts of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder of the azo dye described in Example 15 are metered in over a period of 60 minutes, the dyeing is then continued for about 5 minutes more and the colorless residual liquor is then discharged from the apparatus. The colored jersey is washed by rinsing with cold and hot water, by boiling in a bath containing a non-ionic detergent, by rinsing again with hot and cold water and drying completed in the usual way. A deep red color with very good fastness properties is obtained.

Example 19

• a) 10 Teile eines Polyester/Baumwoll-Mischgewebes werden nach einem üblichen Ausziehverfahren in einem Flottenverhältnis von 1:10 mit einer wäßrigen Lösung, die 50 Teile N-(β-Sulfatoethyl)-piperazin und 20 Teile Natriumhydroxid auf 1000 Teile Wasser enthält, während 15 Minuten bei 95°C behandelt. Das modifizierte Gewebe wurde anschließend mit kaltem und heißem Wasser, dem ein handelsübliches nicht-ionogenes Tensid zugesetzt werden kann, und nochmals mit kaltem Wasser gründlich gespült.
• b) Die modifizierte Ware kann in nassem Zustand einem einbadigen Färbeprozeß in einer Jet-Färbeapparatur zugeführt werden. Hierzu werden 10 Teile des modifizierten Mischgewebes in der Apparatur mit 0,1 Teilen eines 50%igen elektrolythaltigen, im Beispiel 1 der Europäischen Patentschrift 0 032 187 beschriebenen faserreaktiven Azofarbstoffes und 0,1 Teilen des bspw. aus der deutschen Offenlegungsschrift Nr. 23 63 376 bekannten Dispersionfarbstoffes der Formel
  

in 200 Teilen Wasser auf 60°C erwärmt, während 15 Minuten bei dieser Temperatur gehalten und anschließend auf 130°C erhitzt. Man färbt 30 Minuten bei 130°C, kühlt auf 60°C ab, läßt die nunmehr farblose Färbeflotte ab und wäscht das gefärbte Material in üblicher Weise, beispielsweise durch Spülen mit kaltem und heißem Wasser, durch kochende Behandlung in einem nicht-ionogenes Waschmittel enthaltenden Bad, durch erneutes Spülen mit Wasser und Trocknen.

• a) 10 parts of a polyester / cotton blend are by a conventional exhaust process in a liquor ratio of 1:10 with an aqueous solution containing 50 parts of N- (β-sulfatoethyl) piperazine and 20 parts of sodium hydroxide per 1000 parts of water, while Treated at 95 ° C for 15 minutes. The modified fabric was then rinsed thoroughly with cold and hot water, to which a commercially available nonionic surfactant can be added, and again with cold water.
• b) The modified goods can be fed in the wet state to a single-bath dyeing process in a jet dyeing machine. For this purpose, 10 parts of the modified blended fabric in the apparatus with 0.1 part of a 50% electrolyte-containing fiber-reactive azo dye described in Example 1 of European Patent 0 032 187 and 0.1 part of, for example, from German Offenlegungsschrift No. 23 63 376 known disperse dye of the formula
  

in 200 parts of water heated to 60 ° C, held at this temperature for 15 minutes and then heated to 130 ° C. It is dyed for 30 minutes at 130 ° C., cooled to 60 ° C., the now colorless dyeing liquor is removed and the dyed material is washed in a conventional manner, for example by rinsing with cold and hot water, by boiling treatment in a nonionic detergent Bath, by rinsing again with water and drying.

A strong, level, level red dyeing is obtained, the fastness properties of which are equivalent to the fastness of the dyeings obtainable by the methods of the prior art.

Example 20

und 1,5 % des im Beispiel 1 beschriebenen faserreaktiven Azofarbstoffes enthält. Man färbt zunächst bei 60°C während 30 Minuten und anschließend nach Erhöhung auf 130°C weitere 30 Minuten bei dieser Temperatur. Anschließend wird die erhaltene Färbung in der im Beispiel 19b) angegebenen Weise fertiggestellt. Man erhält eine lebhafte Orangefärbung auf beiden Faseranteilen.A polyester / cotton blend fabric modified according to Example 19a) is treated in an HT dyeing machine with an aqueous dye liquor which, based on the weight of the dry fabric, contains 1.5% of the disperse dye known, for example, from German Laid-Open Specification No. 1 131 639 of the formula

and contains 1.5% of the fiber-reactive azo dye described in Example 1. First dye at 60 ° C for 30 minutes and then after increasing to 130 ° C for a further 30 minutes at this temperature. The dyeing obtained is then completed in the manner given in Example 19b). A vivid orange color is obtained on both fiber parts.

Example 21

und unter Verwendung des bspw. aus der deutschen Auslegeschrift Nr.1 283 997 bekannten faserreaktiven Kupferphthalocyaninfarbstoffes der Formel

und erhält nach der üblichen Fertigstellung ein lebhaft blau gefärbtes Mischgewebe von hoher Egalität der Färbung und mit hohen Gebrauchsechtheiten.The procedure of Example 20 is followed to produce a dyeing of a polyester / cotton blend, but using the disperse dye of the formula known, for example, from Japanese Patent Application Publication Sho-54-069139

and using the fiber-reactive copper phthalocyanine dye of the formula known, for example, from German Patent Application No. 1,283,997

and after the usual completion receives a lively blue-colored blended fabric with high level of coloration and with high fastness to use.

Example 22

• a) A package with 30 parts of bleached cotton yarn is in a yarn dyeing apparatus in 450 parts of an aqueous solution of 50 parts of N- (β-sulfatoethyl) piperazine and 30 parts of sodium hydroxide in 1000 parts of water while pumping around the liquor through the package at a temperature treated at 130 ° C for 30 minutes. The liquor is then cooled, drained and the coil thoroughly rinsed with cold and hot water, to which a non-ionic surfactant can be added.
• b) After a new rinse with cold water, the yarn is directly subjected to a dyeing process on the package:
  The dyeing machine is mixed with 450 parts of an aqueous dye solution with 0.6 parts of the fiber-reactive azo dye of the formula known, for example, from German Offenlegungsschrift No. 28 40 380
  
  loaded and heated to 60 ° C. The dyeing is carried out at 60 ° C for 30 minutes by pumping the liquor through the cheese. The yarn on the bobbin is then finished in the same way by rinsing with cold and hot water, to which a nonionic detergent can be added, and by rinsing again with cold water. An irrespective yellow colored fiber is obtained with good fastness properties for the dye.

Example 23

• a) 10 parts of a polyester / cotton blend with an aqueous solution containing 50 parts of N- (β-sulfatoethyl) piperazine and 30 parts of sodium hydroxide dissolved in 1000 parts of water, with a liquor absorption of 80%, based on the weight of the fabric, padded. The impregnated fabric is then subjected to heat setting at 180 ° C for 30 seconds, then washed thoroughly with cold and hot water, to which a non-ionic wetting agent can be added, and rinsed again with cold water.
• b) The modified material is placed in an HT dyeing machine and at a liquor ratio of 1:20 with an aqueous dye liquor which, based on the weight of the dry goods, contains 0.1 part of that from Example 1 of European Patent No. 0 028 788 known fiber-reactive copper formazan dye and 0.1 part of the disperse dye of the formula known, for example, from German Patent Application No. 2,833,854
  
  contains, first treated at 60 ° C for 30 minutes and then again at 130 ° C for 30 minutes. The dyed fabric is then finished in the usual way. A deep blue color is obtained on both fiber portions with good fastness properties.

Example 24

während 30 Minuten bei 60°C unterworfen. Die erhaltene Färbung wird in üblicher Weise nachbehandelt und fertiggestellt. Es wird eine farbstarke rote Färbung mit guten Allgemeinechtheiten erhalten.100 parts of a bleached cotton fabric are impregnated in a jigger with 1000 parts of an aqueous solution of 50 parts of N- (β-sulfatoethyl) piperazine and 25 parts of sodium hydroxide at 95 ° C. for 30 minutes. The liquor is then drained off and the textile material in the same apparatus first in a conventional washing process, then in a dyeing process using 1500 parts of an aqueous solution with 2 parts of an approximately 50% electrolyte-containing dye powder, for example from example 106 of the European patent application. Publication No. 0 457 715 known fiber-reactive azo dye of the formula

Subjected at 60 ° C for 30 minutes. The dyeing obtained is aftertreated and finished in the usual way. A strong red color with good general fastness properties is obtained.

Examples 25 to 36

To produce further dyeings, it is possible to start from a cellulose fiber material modified according to the invention, such as, for example, from a cellulose fiber material modified according to the above exemplary embodiments, and this using one of the customary dyeing methods, such as printing processes, exhausting methods or padding methods, for example analogously to one of the dyeing methods described in the above exemplary embodiments, subject to a dyeing process using one of the dyes specified in the following table examples, for example known from German specification No. 2,835,035 in the manner according to the invention, ie without the use of an alkali and without or only with very little use of an electrolyte, the dyeing process used Material can also be a modified cellulose fiber material in a mixture with a polyester fiber material. Based on the cellulose fiber material, strong, clear dyeings and prints are obtained with the hue given in the respective table example and the fastness properties good for the respective dye.

Claims (15)

1. A process for the dyeing of fiber materials with water-soluble, anionic dyes, which comprises carrying out the dyeing using low-electrolyte or entirely electrolyte-free and/or low-alkali or entirely alkali-free dye solutions (dye liquors, printing pastes) and using a fiber material modified by means of a compound which is a saturated aliphatic compound of 3 to 15 carbon atoms which is unsubstituted or substituted by 1 or 2 or more hydroxyl groups and contains at least one primary, secondary or tertiary amino group or quaternary ammonium group and at least one hydrolyzable ester group, the saturated radical(s) being straight-chain, branched and/or cyclic and, if desired, interrupted by one or more hetero groups, with the exception of compounds of the formula (A)
   
   
   
           (H₂N)_p-ALK-ER    (A)
   
   
   
   in which p is the number 1 or 2, ER is an ester group and ALK is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be interrupted by 1 or more hetero groups and is not substituted by a hydroxyl group.
2. The process as claimed in claim 1, wherein the dye contains a fiber-reactive group.
3. The process as claimed in claim 1 or 2, wherein the compound by means of which the fiber was modified is a compound of the formula (1a) or (1b)

   

   in which the symbols have the following meanings:

   ER   is an ester group;

   A and N,   together with 1 or 2 alkylene groups of 1 to 4 carbon atoms, form the bivalent radical of a heterocyclic ring, in which

   A   is an oxygen atom or a group of the formula (a), (b) or (c)

   

   in which

   R   is a hydrogen atom or an amino group or an alkyl group of 1 to 6 carbon atoms, which may be substituted by 1 or 2 substituents from the group consisting of amino, sulfo, hydroxyl, sulfato, phosphato and carboxyl, or is an alkyl group of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxyl group,

   R¹   is hydrogen, methyl or ethyl,

   R²   is hydrogen, methyl or ethyl, and

   Z^(-)   is an anion;

   B   is an amino group of the formula H₂N- or an amino or ammonium group of the formula (d) or (e)

   

   in which

   R¹, R² and Z^(-)   have one of the abovementioned meanings,

   R³   is methyl or ethyl, and

   R⁴   is hydrogen, methyl or ethyl;

   p   is the number 1 or 2;
      alkylen is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH-;
      alk is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O-and -NH-, and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms;

   m   is the number 1 or 2;

   n   is a number from 1 to 4;
      and the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom on the alkylene radical.
4. The process as claimed in at least one of claims 1 to 3, wherein the ester group of the compound by means of which the fiber was modified is a sulfato or phosphato group or a lower alkanoyloxy group, phenylsulfonyloxy or a phenylsulfonyloxy group substituted on the benzene ring by substituents from the group consisting of carboxyl, lower alkyl, lower alkoxy and nitro.
5. The process as claimed in at least one of claims 1 to 4, wherein the modified fiber material is a modified polyester/cellulose fiber blend material and dyeing is carried out by a single-bath dyeing process using at least one reactive dye and at least one disperse dye.
6. A process for the modification of a fiber material, which comprises causing a fiber material to come under the action of a saturated aliphatic compound of 3 to 15 carbon atoms which contains ester and amino groups and is unsubstituted or substituted by 1 or 2 or more hydroxyl groups and contains at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group, in which the saturated radical(s) is (are) straight-chain, branched and/or cyclic and can, if desired, be interrupted by one or more hetero groups, with the exception of compounds of the formula (A)
   
   
   
           (H₂N)_p-ALK-ER    (A)
   
   
   
   in which p is the number 1 or 2, ER is an ester group and ALK is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be interrupted by 1 or more hetero groups and is not substituted by a hydroxyl group, in aqueous, alkaline solution at a temperature of between 60 and 230°C.
7. The process as claimed in claim 6, wherein a fiber material is caused to come under the action of the compound containing ester and amino groups in aqueous, alkaline solution at a temperature of between 130 and 190°C.
8. The process as claimed in claim 6 or 7, wherein the compound containing ester and amino groups is a compound of the formula (1a) or (1b)

   

   in which the symbols have the following meanings:

   ER   is an ester group;

   A and N,   together with 1 or 2 alkylene groups of 1 to 4 carbon atoms, form the bivalent radical of a heterocyclic ring, in which

   A   is an oxygen atom or a group of the formula (a), (b) or (c)

   

   in which

   R   is a hydrogen atom or an amino group or an alkyl group of 1 to 6 carbon atoms, which may be substituted by 1 or 2 substituents from the group consisting of amino, sulfo, hydroxyl, sulfato, phosphato and carboxyl, or is an alkyl group of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxyl group,

   R¹   is hydrogen, methyl or ethyl,

   R²   is hydrogen, methyl or ethyl, and

   Z^(-)   is an anion;

   B   is an amino group of the formula H₂N- or an amino or ammonium group of the formula (d) or (e)

   

   in which

   R¹, R² and Z^(-)   have one of the abovementioned meanings,

   R³   is methyl or ethyl, and

   R⁴   is hydrogen, methyl or ethyl;

   p   is the number 1 or 2;
      alkylen is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O-and -NH-;
      alk is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O-and -NH-, and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms;

   m   is the number 1 or 2;

   n   is a number from 1 to 4;
      and the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom on the alkylene radical.
9. The process as claimed in at least one of claims 6 to 8, wherein the ester group in the fiber-modifying compounds containing ester and amino groups is a sulfato or phosphato group or a lower alkanoyloxy group, phenylsulfonyloxy or a phenylsulfonyloxy group substituted on the benzene ring by substituents from the group consisting of carboxyl, lower alkyl, lower alkoxy and nitro.
10. The process as claimed in claim 6 or 7, wherein the compound modifying the fiber material is the compound N-(β-sulfatoethyl)piperazine, N-[β-(β'-sulfatoethoxy)ethyl]piperazine, N-(γ-sulfato-β-hydroxypropyl)piperidine, N-(γ-sulfato-β-hydroxypropyl)pyrrolidine, N-(β-sulfatoethyl)piperidine, a 3-sulfato-2-hydroxy-propyltrimethylammonium salt or a 2-sulfato-3-hydroxypropyltrimethylammonium salt, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3-disulfato-2-aminopropane or a derivative of these compounds with an ester group other than the sulfato group.
11. One or more compounds of the following constitution: N-(β-sulfatoethyl)piperidine, N-(γ-sulfato-β-hydroxypropyl)piperidine, N-(γ-sulfato-β-hydroxy-propyl)pyrrolidine, 3-sulfato-2-hydroxy-1-aminopropane, 2-sulfato-3-hydroxy-1-aminopropane, a 3-sulfato-2-hydroxypropyltrimethylammonium salt, a 2-sulfato-3-hydroxypropyltrimethylammonium salt or a derivative of these compounds with an ester group other than the sulfato group.
12. Use of a saturated aliphatic compound of 3 to 15 carbon atoms which contains ester and amino groups and is unsubstituted or substituted by 1 or 2 or more hydroxyl groups and contains at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group, in which the saturated radical(s) is (are) straight-chain, branched and/or cyclic and can, if desired, be interrupted by one or more hetero groups, with the exception of compounds of the formula (A)
    
    
    
            (H₂N)_p-ALK-ER    (A)
    
    
    
    in which p is the number 1 or 2, ER is an ester group and ALK is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be interrupted by 1 or more hetero groups and is not substituted by a hydroxyl group for the modification of a fiber material.
13. Use as claimed in claim 12, wherein the compound containing ester and amino groups is the compound N-(β-sulfatoethyl)piperazine, N-[β-(β'-sulfatoethoxy)ethyl]piperazine, N-(γ-sulfato-β-hydroxypropyl)-piperidine, N-(γ-sulfato-β-hydroxypropyl)-pyrrolidine, N-(β-sulfatoethyl)piperidine, a 3-sulfato-2-hydroxypropyltrimethylammonium salt or a 2-sulfato-3-hydroxypropyltrimethylammonium salt, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3-disulfato-2-aminopropane or a derivative of these compounds with an ester group other than the sulfato group.
14. Use as claimed in claim 12, wherein the compound containing ester and amino groups is the compound N-(β-sulfatoethyl)piperidine, N-(γ-sulfato-β-hydroxypropyl)piperidine, N-(γ-sulfato-β-hydroxypropyl)pyrrolidine, 3-sulfato-2-hydroxy-1-aminopropane, 2-sulfato-3-hydroxy-1-aminopropane, a 3-sulfato-2-hydroxypropyltrimethylammonium salt, a 2-sulfato-3-hydroxypropyltrimethylammonium salt or a derivative of these compounds with an ester group other than the sulfato group.
15. A fiber material modified by means of a saturated aliphatic compound of 3 to 15 carbon atoms which contains ester and amino groups and is unsubstituted or substituted by 1 or 2 or more hydroxyl groups and contains at least one primary, secondary, tertiary or quaternary amino group and at least one hydrolyzable ester group, in which the saturated radical(s) is (are) straight-chain, branched and/or cyclic and can, if desired, be interrupted by one or more hetero groups, with the exception of compounds of the formula (A)
    
    
    
            (H₂N)_p-ALK-ER    (A)
    
    
    
    in which p is the number 1 or 2, ER is an ester group and ALK is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be interrupted by 1 or more hetero groups and is not substituted by a hydroxyl group.