EP0580091B1 - Process for the manufacturing of a modified fibrous material and process for dyeing this modified fibrous material with anionic dyestuffs - Google Patents

Abstract

Fibre materials can be modified by treating them at a temperature between 60 and 230 DEG C with an aqueous, alkaline solution of hetero-cycloaliphatic compounds which contain at least one primary, secondary or tertiary amino group or quaternary ammonium group and in which the hetero moiety in the cycle is a carbonic ester radical of the formula -O-CO-O- or a carbamic acid radical of the formula -O-CO-NH-. The modified fibre material has the property of being dyeable using low-electrolyte or completely electrolyte-free and/or low-alkali or completely alkali-free solutions of water-soluble, anionic textile dyes. A dyeing process carried out in that way has the advantage, in particular for fibre-reactive dyes, that there is no need to fix the dyes under alkaline conditions.

Description

Textile materials such as woven fabrics, knitted fabrics or yarns containing cellulose fibers can be dyed with anionic dyes by known processes. All processes have in common that for the fixation of the dye on the fiber, in particular when dyeing with reactive dyes, alkali and to achieve acceptable depths of salt are necessary. In particular when dyeing with fiber-reactive dyes, the salt-containing dye liquor is additionally contaminated with inactive dye hydrolyzates which arise in the course of the dyeing process in the strongly alkaline dye solution. The fixing process is therefore no longer complete, and the waste water from the dyeing process is enriched with hydrolyzates and colored accordingly. For the reasons listed above, dyeings obtained by conventional processes are subject to complex washing processes, on the one hand to remove excess alkali and on the other hand to free the fiber material from dye hydrolyzates.

It was therefore an object of the present invention to find a process for dyeing (including printing) textile fiber materials that only with the smallest possible amount of electrolyte salts or entirely without electrolyte salts and at the same time with only a small amount of an alkaline agent or can be carried out entirely without such an alkaline agent.

It has now been found with the present invention that, in a surprising manner, level and strongly colored with anionic dyes, in particular those with fiber-reactive groups, without or only with a slight use of an alkaline agent and electrolyte salts Dyes with good fastness properties are obtained if the textile material used is a fiber material which has been pretreated and modified by a compound which is a heterocycloaliphatic compound which contains at least one primary, secondary or tertiary amino group or quaternary ammonium group, these amino groups also being a component of Cycle can be and the hetero portion in the cycle is a carbonic acid ester residue of the formula -O-CO-O- or a carbamic acid residue of the formula -O-CO-NH-.

in welcher bedeuten:

R^A

ist Wasserstoff oder Alkyl von 1 bis 3 C-Atomen, das durch Hydroxy oder eine Gruppe der Formel (2) oder (3)

substituiert sein kann, in welchen

R¹

Wasserstoff, Methyl oder Ethyl ist,

R²

Wasserstoff, Methyl oder Ethyl ist und

R³

Wasserstoff, Methyl oder Ethyl ist oder

R¹ und R²

zusammen mit dem N-Atom einen aus einem Alkylenrest von 5 bis 8 C-Atomen oder zwei Alkylenresten von 1 bis 4 C-Atomen und einem Sauerstoffatom oder einer Aminogruppe der Formel -NH- gebildeten gesättigten heterocyclischen Rest darstellen, wie beispielsweise den N-Piperazino-, N-Piperidino- oder N-Morpholino-Rest, und

Z^(-)

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

R^B

hat eine der für R^A angegebenen Bedeutungen;

W

ist eine direkte Bindung oder eine Gruppe der Formel -CHR^C-, in welcher R^C eine der für R^A angegebene Bedeutungen besitzt;

X

ist eine Gruppe -O- oder -NH- .

Such compounds which can be used according to the invention for modifying fiber materials are, for example, compounds corresponding to the general formula (1)

in which mean:

R ^A

is hydrogen or alkyl of 1 to 3 carbon atoms, which is substituted by hydroxyl or a group of the formula (2) or (3)

can be substituted in which

R¹

Is hydrogen, methyl or ethyl,

R²

Is hydrogen, methyl or ethyl and

R³

Is hydrogen, methyl or ethyl or

R1 and R2

together with the N atom one of an alkylene radical of 5 to 8 carbon atoms or two alkylene radicals of 1 to 4 carbon atoms and an oxygen atom or an amino group of the formula -NH- formed saturated heterocyclic radical, such as the N-piperazino, N-piperidino or N-morpholino radical, and

Z ^(-)

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

R ^B

has one of the meanings given for R ^A ;

W

is a direct bond or a group of the formula -CHR ^C -, in which R ^{C has} one of the meanings given for R ^A ;

X

is a group -O- or -NH-.

Preferably only one of the radicals R ^A , R ^B and R ^{C represents} an alkyl group with a group of the formula (2) or (3).

Such hetero-cycloaliphatic compounds which can be used according to the invention are, for example, 2-oxo-1,3-oxazolidine, 4-aminomethyl-2-oxo-1,3-oxazolidine, 5-aminomethyl-2-oxo-1,3-oxazolidine, 4- ( Trimethylammonium methyl) -2-oxo-1,3-oxazolidine chloride, 5- (trimethylammonium methyl) -2-oxo-1,3-oxazolidine chloride and 1- (trimethylammonium methyl) ethylene carbonate chloride.

The compounds which can be used according to the invention can be prepared in accordance with known procedures, as are described in large numbers in the literature (see Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E4, pages 82-88 and 192ff.), For example by reacting an alkanediol which has a latent nitrogen-containing functional group in the side chain with phosgene in aqueous solution at a pH between 7 and 9 to produce the heterocycloaliphatic carbonates or, for example, by reacting aminoalkanols with phosgene in aqueous solution heterocycloaliphatic carbamic acid compounds (2-oxo-1,3-oxazolidines).

The present invention thus relates to a process for dyeing fiber materials containing hydroxyl and / or carbonamide groups with water-soluble, anionic dyes, preferably with fiber-reactive dyes, which is characterized in that the dyeing using an electrolyte-poor or completely electrolyte-free and / or alkali-free or completely alkali-free dye solution (dye liquor, printing paste) and using a fiber material pretreated and modified with one of the hetero-cycloaliphatic compounds described above carries out.

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, and also synthetic polyamide 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 method for modifying a fiber material, which is characterized in that a heterocycloaliphatic compound of the type mentioned above in aqueous, alkaline solution at a temperature between 60 and 230 ° C, preferably between 90 and 190 ° C, can act on a fiber material.

Furthermore, the invention relates to the use of such heterocycloaliphatic compounds, which are defined in more detail 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 process according to the invention for modifying the fiber material can be carried out, for example, by contacting the fiber material with a heterocycloaliphatic compound which can be used according to the invention in an alkaline aqueous solution. The concentration of this compound in the alkaline aqueous solution is generally between 0.1 and 20% by weight, preferably between 5 and 10% by weight. The alkaline agent, such as sodium hydroxide, sodium carbonate and potassium carbonate, is dissolved in a concentration between 0.1 and 20% by weight, preferably between 5 and 10% by weight. As a rule, the alkaline, aqueous solution containing the heterocycloaliphatic 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 be present in all processing states, such as yarn, flake, sliver and piece goods (fabric), and also in a mixture with other fiber materials, as in Form of blended fabrics, for example in the form of cotton / polyester fiber materials.

The heterocycloaliphatic compounds 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 dyeing agent). Exhaust process) at a temperature between 15 and 100 ° C, the modification of the Fiber material already done. 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 heterocycloaliphatic compound which 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 the aqueous alkali-impregnated material is optionally squeezed to a required liquid content and the alkaline-impregnated material is 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.

After impregnation of the fiber material in one of the various ways specified above, except for the pretreatment according to a pull-out procedure, the impregnated material is dried; as a rule, the drying of the fiber-modifying compound is carried out at the same time as the drying, a drying and fixing being carried out Temperature between 100 and 230 ° C, preferably between 120 and 190 ° C, chooses. As a rule, drying and simultaneous fixing take place by treatment with hot air for 1 to 5 minutes. The heterocycloaliphatic compound modifying the fiber can 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 the dyebaths, padding liquors and printing pastes of the dyeing process according to the invention contain alkaline compounds, such as are usually used for fixing fiber-reactive dyes, such as sodium carbonate, potassium carbonate, sodium hydroxide solution and water glass, not at all or in an insignificant amount, and that, moreover, the usual amount Addition of electrolyte salts, which should increase the migration of the dye on the fiber in particular, not or only to a small extent, ie up to a maximum of 10 gp ro liter of dye bath or dye liquor, is required. 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 pad-cold residence method 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. As a rule, the modified fiber material according to the invention can only be dyed using a pure aqueous dye solution in which only an extremely small amount of electrolyte salts (such as sodium chloride and sodium sulfate), which are contained in the dye powders as adjusting agents, are dissolved.

The present invention can also advantageously be used for single-bath dyeing processes for dyeing mixtures of cellulose and polyester fibers if, in addition, a disperse dye which is suitable for dyeing polyester fiber materials is used in the common dye bath with a reactive dye. 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 the 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, for example 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, still the range of anthraquinone dyes, Copper and cobalt phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine 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, for example, a group of 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-sulfatoethylsulfonyl) -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-chlorine -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-methylsulfonyl-acryloyl, propionyl, chloroacetyl, bromoacetyl, 4- (β-chloroethylsulfonyl) butyryl, 4-vinylsulfonylbutyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- ( β-Chl orethyl-sulfonyl) -caproyl, 6-vinylsulfonyl-caproyl, 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl, 2-fluorine -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-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-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-chloro-methyl-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-c hlor-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-bis- (methylsulfonyl) pyrimidinyl-4, 2,5-bis (methylsulfonyl) -5-chloro-pyrimidinyl-4, 2-methylsulfonyl-pyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-5- chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4, 2-methylsulfone yl-5-chloro-6-ethyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4, 2,5,6- Tris-methylsulfonylpyrimidinyl-4, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-6-chloropyrimidinyl-4, 2, 6-bis- (methylsulfonyl) -5-chloropyrimidinyl-4, 2-methylsulfonyl-6-carboxypyrimidinyl-4, 2-methylsulfonyl-5-sulfopyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxypyrimidinyl-4, 2-methylsulfonyl-5-carboxypyrimidinyl-4, 2-methylsulfonyl-5-cyano-6-methoxypyrimidinyl-4, 2-methylsulfonyl-5-chloropyrimidinyl-4, 2-sulfoethylsulfonyl-6-methylpyrimidinyl-4, 2- Methylsulfonyl-5-bromopyrimidinyl-4, 2-phenylsulfonyl-5-chloro-pyrimidinyl-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-bis (methylsulfonyl) pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl- 6-chloropyrimidine-5-carbonyl, 2,4-bis (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-dichlorophthalazin-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'-dichloropyridazinon-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-ethylsulfonyl-benzothiazole-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-ode containing sulfo groups in the fused-on benzene ring r -6-carbonyl- or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -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) -aminotriazinyl-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, which in 2-position containing the 1,4-bis-aza-bicyclo [2,2,2] octane or the 1,2-bis-aza-bicyclo- [0,3,3] octane bound via a nitrogen bond, 2-pyridinium-4-phenylamino- or 4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6 and corresponding 2-oniumtriazinyl-6 radicals which are 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 (4)

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 radicals are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and Benzoxazole residues. Suitable amino groups, in which the amino nitrogen atom is a member of an N-heterocyclic ring, are preferably residues of six-membered N-heterocyclic compounds 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, tolinoino, toluene , 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 that by 1 or 2 substituents from the group methoxy, ethoxy, methyl, ethyl, chlorine, carboxy and may be substituted by sulfo, or R11 is alkyl of 2 to 4 carbon atoms, such as ethyl or n-propyl, which is substituted by a fiber-reactive group of the vinylsulfone series, or alkylenephenyl having an alkylene radical of 1 to 4 carbon atoms, the Phenyl is substituted by a fiber-reactive radical of the vinyl sulfone series, or in which R¹⁰ and R¹¹ are both alkyl of 2 to 4 carbon atoms, such as ethyl and n-propyl, which are substituted by a fiber-reactive group of the vinylsulfone series, or in which R¹⁰ and R¹¹ both mean alkylene of 3 to 8 carbon atoms, which are interrupted by 1 or 2 oxi and / or amino groups 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 the manner according to 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 complicated aftertreatment process including washing. As a rule, it is sufficient to rinse the colored substrate once or several times with warm or hot and, if appropriate, cold water, which may optionally contain a nonionic wetting agent. A final boiling treatment of the dyed 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 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 2-oxo-1,3-oxazolidine in 1000 parts of water with a liquor absorption of 75%. The material is then treated with hot air at 180 ° C. for 45 seconds, with both the drying and the fixing of the oxazolidinone compound taking place on the tissue. The material is then treated in cold and hot 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 added to 2000 parts by volume of an aqueous dye solution, the 2 parts of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the known dye of the formula
  
  (ie 1 part of this dye and 1 part of the electrolyte) contains dissolved; 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 red color is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 2

100 Teile Harnstoff 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 vier Stunden bei 40 bis 50°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 in accordance with Example 1a) according to the invention is dyed by a conventional pad-dying dyeing process. For this purpose, an aqueous dye solution containing 20 parts of the known dye of the formula in 1000 parts by volume

Contains 100 parts of urea and 3 parts of a commercially available nonionic wetting agent dissolved, by means of a foulard 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 wrap and left at 40 to 50 ° C for four 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 yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 3

• a) A mercerized and bleached cotton fabric is washed with an aqueous solution of 37.5 parts of sodium hydroxide and 75 parts of 2-oxo-1,3-oxazolidine in 1000 parts of water at a temperature between 25 and 30 ° C impregnated with a liquor absorption of 85% and then treated to fix the oxazolidinone compound on the fiber material for about 2.5 minutes with hot air at 150 ° C, while the impregnated fabric is dried at the same time. The modified material is then freed from excess alkali by treatment with cold water at 60 ° C.
• b) The modified, dried fabric 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 the dye of the formula
  
  (known from Color Index under CI No. 51 320) contains dissolved. The dyeing takes place at 80 ° C. for 60 minutes. The dyed fabric is then rinsed with cold and hot water, which may optionally contain a commercially available nonionic surfactant, then washed again with cold water and dried if necessary.

A deep blue color is obtained with the good fastness properties customary for this dye.

Example 4

• a) 10 parts of a polyester / cotton blend are with an aqueous solution, the 75 parts of 2-oxo-1,3-oxazolidine and 37.5 parts Contains 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 60 ° C 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 from Example 1 of 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 5

und unter Verwendung des aus Beispiel 3 der deutschen Auslegeschrift Nr. 28 35 035 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 4 is followed to produce a dyeing of a polyester / cotton blend, but using the disperse dye of the formula known from Japanese Patent Application Publication Sho-54-69139

and using the fiber-reactive copper phthalocyanine dye of the formula known from Example 3 of German Patent Application No. 28 35 035

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

Examples 6 to 17

To produce further dyeings, one can 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 according to 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 known dyes specified in the following table examples in the manner according to the invention, ie without using an alkali and without or only with very little use of an electrolyte, the material used also being a modified cellulose fiber material in a mixture with a polyester fiber material can. Based on the cellulose fiber material, clear dyeings and prints with the hue given in the respective table example and the good fastness properties for the respective dye.

Claims (9)

1. A process for the dyeing of hydroxyl - and/or carboxamido - containing fiber materials with water-soluble, anionic dyes, which comprises carrying out the dyeing with the use of dye solutions (dye liquors, printing pastes) which are low in electrolytes or are entirely free of electrolytes and/or low in alkali or entirely free of alkali and with the use of a fiber material which has been pre-treated and modified by means of a compound which is a heterocycloaliphatic compound containing at least one primary, secondary or tertiary amino group or quaternary ammonium group, it being possible for these amino groups also to form part of the ring and the hetero portion in the ring being a carbonic ester radical of the formula -O-CO-O- or a carbamic acid radical of the formula -O-CO-NH-.
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 (1)

   

   in which

   R^A   is hydrogen or alkyl of 1 to 3 carbon atoms, which can be substituted by hydroxyl or a group of the formula (2) or (3)

   

   in which

   R¹   is hydrogen, methyl or ethyl,

   R²   is hydrogen, methyl or ethyl, and

   R³   is hydrogen, methyl or ethyl, or

   R¹ and R²   together with the nitrogen atom are a saturated heterocyclic radical formed by an alkylene radical of 5 to 8 carbon atoms or two alkylene radicals of 1 to 4 carbon atoms and an oxygen atom or an amino group of the formula -NH-, and

   Z^⊖   is an anion;

   R^B   has one of the meanings given for R^A;

   W   is a direct bond or a group of the formula -CHR^C-, in which R^C has one of the meanings given for R^A;

   X   is a group -O- or -NH-.
4. A process for the modification of a fiber material, which comprises exposing the fiber material to a heterocycloaliphatic compound containing at least one primary, secondary or tertiary amino group or quaternary ammonium group, the hetero portion of which in the ring is a carbonic ester radical of the formula -O-CO-O- or a carbamic acid radical of the formula -O-CO-NH-, in aqueous, alkaline solution at a temperature of between 60 and 230°C.
5. The process as claimed in claim 4, wherein the fiber material is exposed to the heterocycloaliphatic compound in aqueous, alkaline solution at a temperature of between 120 and 190°C.
6. The process as claimed in claim 4 or 5, wherein the heterocycloaliphatic compound is a compound of the formula (1)

   

   in which

   R^A   is hydrogen or alkyl of 1 to 3 carbon atoms, which can be substituted by hydroxyl or a group of the formula (2) or (3)

   

   in which

   R¹   is hydrogen, methyl or ethyl,

   R²   is hydrogen, methyl or ethyl, and

   R³   is hydrogen, methyl or ethyl, or

   R¹ and R²   together with the nitrogen atom are a saturated heterocyclic radical formed by an alkylene radical of 5 to 8 carbon atoms or two alkylene radicals of 1 to 4 carbon atoms and an oxygen atom or an amino group of the formula -NH-, and

   Z^⊖   is an anion;

   R^B   has one of the meanings given for R^A;

   W   is a direct bond or a group of the formula -CHR^C-, in which R^C has one of the meanings given for R^A;

   X   is a group -O- or -NH-.
7. Use of a heterocycloaliphatic compound containing at least one primary, secondary or tertiary amino group or quaternary ammonium group, the hetero portion of which in the ring is a carbonic ester radical of the formula -O-CO-O- or a carbamic acid radical of the formula -O-CO-NH-, for the modification of a hydroxyl - and/or carboxamido - containing fiber material.
8. A hydroxyl - and/or carboxamido - containing fiber material modified by means of a heterocycloaliphatic compound containing at least one primary, secondary or tertiary amino group or quaternary ammonium group, the hetero portion of which in the ring is a carbonic ester radical of the formula -O-CO-O- or a carbamic acid radical of the formula -O-CO-NH-.
9. A process for the single-bath dyeing of cellulose/polyester blend fiber materials, which comprises dyeing a fiber material modified as claimed in claim 4 in an aqueous, alkali-free dye liquor containing at least one fiber-reactive dye and at least one disperse dye.