EP0768421B1 - Method for continuously dyeing yarns with reactive dyes - Google Patents

Description

The present invention is in the field of textile technology, especially dyeing and particularly the dyeing of textile yarns, and relates to a process for continuous dyeing of yarns from cellulose fibers with reactive dyes.

Various methods and devices for dyeing yarn are already known, see e.g. B. FR-A-2 140 692, WO-A-83/00172 and FR-A-2 064 150.

The preamble of claim 1 is based on FR-A-2 140 612.

For example, a strand dyeing process is known in which the spinning on a spool delivered yarn and wound onto a conical bobbin on a strand reel machine is unwound to keep the yarn in rope form, with further handling takes place under coil transport. Each strand is then manually made at different points attached, and the two ends of each strand are joined together. Subsequently the strands obtained are attached to dyeing trees, hung on a cart and then placed in a dyeing machine. After dyeing the strands washed and the excess water removed from it in a sling before it either in a hot air cabinet or by continuous passage a drying tunnel can be dried. After this drying, the strands are back fed to a winding device so that it can be rewound onto conical bobbins, which can be used in the manufacture of knitted or woven goods.

Such a dyeing process, with regard to the penetration of the interstices of fibers To achieve acceptable results with dye liquor requires a variety of Handling steps, which on the one hand leads to relatively long and material-stressing Process times and high production costs.

Coil dyeing processes are also known, in which one of the spinning on one Spool delivered Gam is rewound on a conical or cylindrical spool, whereby the edges of the coil may be rounded off by pressing so that a better later circulation of a dye liquor into the inside of the bobbin is made possible.

According to this embodiment, a new handling is that one spools perforated columns of the material carrier of a dyeing machine stack and this material carrier then transferred to an autoclave and a dye liquor underneath using a pump Presses pressure into the autoclave. The dye liquor is removed after a predetermined time and washing water is pressed into the autoclave. Then the material carrier from the Autoclave is taken and the coils are used to remove the excess water put in a slingshot.

After this step, the coils are discontinuous or in a drying cabinet continuously dried in a high frequency dryer. After drying, the gam rewound.

The excess water can also be referred to as a quick dryer Devices are removed in which the removal of water from the Material carrier-coil unit takes place by means of a vacuum pump and this in one Air or steam pressure is applied to the autoclave. In such a case you come even without additional drying.

Such a coil dyeing process, like the previous one, requires many Steps on the part of the operator and takes a relatively long time, which makes the The costs of this procedure are relatively high.

On the other hand, there are none of these conventional coil or strand dyeing processes Special yarns, e.g. Chiné yarns, yarns dyed using the space dyeing process, or multi-colored spotted yarns, or yarns with partial impregnation of the fibers, e.g. of washed-out type, ring-dyed denim (ring dyeing method) or mechanically with Stone wash denim grindstones available.

In addition, the known dyeing processes for dyeing cellulose fibers Vegetable fibers such as cotton, linen etc. or chemical fibers such as the acetate or Viscose fibers have a high water consumption, of the order of 200 up to 300 liters per kilogram of dyed yarn.

With such water consumption, not only is the cost of water used, but also that of processing the dye and the remaining chemical Auxiliary materials contaminated water before it is drained, disadvantageous.

With the dyes that are used in cellulose fibers, there are also those conventional reagents to be considered, which are used to prepare the dyebath large amount of added salt, in the order of 80 to 100 g per Liters of dye bath, of which only 60 to 70% of the mixture during the Coloring process are fixed and the remaining 30 to 40% of the mixture during washing removed and represent a high environmental impact, which makes a special thorough wastewater treatment is required.

In addition, in the case of coil coloring and, to a lesser extent, strand coloring the multiple unwinding and rewinding processes of the yarn adversely affect the quality of the manufactured gam affect what results in weight loss on the one hand and on the other hand expresses a loss in strength and elongation of the yarn.

Devices for carrying out continuous processes for dyeing Textile games through continuous impregnation of running yarn, which then be transferred to a means of transport on which the yarns pass through chambers be passed through, the steam or hot air under normal pressure or overpressure included are also known. With one called heat-setting The process succeeds in fixing the dyes on the fibers that make up the yarn.

With such devices, yarns based in particular on polyamide, Polyester, polypropylene and acrylic fibers as well as wool and fiber mixtures at im Comparison to the procedures in which the treatment in coil or strand form staining takes place, greatly reduced energy and water consumption.

In these continuous treatment processes, only acidic, dispersion or basic dyes for use.

The object of the present invention is to limit these disadvantages Providing a process for the continuous dyeing of yarns based on Cellulose fibers, with which a considerable saving in dyes with optimal Fixation as well as fantasy effects, e.g. Chiné fibers, using the space dyeing process dyed fibers, single or multi-colored spotted yarns, or yarns with partial impregnation the fibers, e.g. of the washed-out type, ring-dyed denim (ring-dyeing process) or can be achieved with stone wash denim mechanically.

a) Imprägnierung des von einem oder mehreren Trägern (1) kontinuierlich schnellabgewickelten und auf einen oder mehrere Träger (3) umgewickelten Garns mit mindestens einem faserreaktiven Farbstoff in wäßriger Lösung und mindestens einem alkalisch wirkenden Agens in wäßriger Lösung, wobei die Imprägnierung des Garns nach dem Abwickeln und vor dem Aufwickeln erfolgt, sowie

b) Fixierung des Farbstoffs,

dadurch gekennzeichnet, daß es sich bei den in den Färbeflotten zum Einsatz kommenden Farbstoffen um Reaktivfarbstoffe aus der Gruppe der Monoazo-, Disazo-, Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin-, Formazan- oder Dioxazinfarbstoffe handelt, welche mindestens eine Reaktivgruppe der folgenden Formeln enthalten: -NH-CO-Y -SO₂-Z

-W―alkylen―E―alkylen'―SO₂-Z

worin W eine Gruppe der Formel -SO₂-NR₁-, -CONR₁- oder -NR₁CO- ist,

R₁ Wasserstoff, unsubstituiertes oder durch Hydroxy, Sulfo, Sulfato, Carboxy oder Cyano substituiertes C₁-C₄-Alkyl oder ein Rest der Formel

R Wasserstoff, Hydroxy, Sulfo, Sulfato, Carboxy, Cyano, Halogen, C₁-C₄-Alkoxycarbonyl, C₁-C₄-Alkanoyloxy, Carbamoyl oder die Gruppe -SO₂-Z ist,

Z Vinyl oder einen Rest -CH₂-CH₂-U₁ bedeutet und U₁ eine Abgangsgruppe ist,

Y ein Rest der Formel -CH(Hal)-CH₂-Hal oder -C(Hal)=CH₂ und Hal Halogen bedeutet,

E der Rest -O- oder -N(R₂)- ist,

R₂ Wasserstoff oder C₁-C₄-Alkyl,

alkylen und alkylen' unabhängig voneinander C₁-C₆-Alkylen,

arylen einen unsubstituierten oder durch Sulfo, Carboxy, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituierten Phenylen- oder Naphthylenrest bedeutet,

R₃ Wasserstoff oder unsubstituiertes oder durch Carboxy, Cyano, Hydroxy, Sulfo oder Sulfato substituiertes C₁-C₄-Alkyl,

X Chlor oder Fluor ist,

V ein nicht-reaktiver Substituent, eine als Anion abspaltbare Gruppe oder ein Rest der Formel

oder

ist, wobei R, R₁, R₃, E, W, Z, Y, alkylen, alkylen' und arylen die oben angegebenen Bedeutungen haben und t 0 oder 1 ist,

einer der Reste X₁ eine als Anion abspaltbare Gruppe ist und der andere Rest X₁ ein nicht-reaktiver Substituent, eine als Anion abspaltbare Gruppe oder ein Rest der Formeln (3a) bis (3f) ist,

X₂ ein negativer Substituent ist, wobei

in den Reaktivresten der Formel (2) X Fluor ist und V die oben angegebenen Bedeutungen hat, oder X Chlor ist und V ein Rest der Formeln (3a) bis (3f) ist, und

in den Reaktivresten der Formel (4) mindestens einer der Reste X₁ Fluor oder einen Rest der Formeln (3a) bis (3f) bedeutet, und

die Imprägnierung bei Umgebungstemperatur ausgeführt wird.

The present invention thus relates to a process for the continuous dyeing of yarns based on cellulose fibers by the following steps:

a) Impregnation of one or more carriers (1) continuously unwound and wound onto one or more carriers (3) with at least one fiber-reactive dye in aqueous solution and at least one alkaline agent in aqueous solution, the impregnation of the yarn after the Unwind and done before winding, as well

b) fixation of the dye,

characterized in that the dyes used in the dyeing liquors are reactive dyes from the group of monoazo, disazo, polyazo, metal complexazo, anthraquinone, phthalocyanine, formazan or dioxazine dyes, which have at least one reactive group in the contain the following formulas: -NH-CO-Y -SO ₂ -Z

-W ― alkylene ― E ― alkylene' ― SO ₂ -Z

wherein W is a group of the formula -SO ₂ -NR ₁ -, -CONR ₁ - or -NR ₁ CO-,

R _{1 is} hydrogen, C ₁ -C ₄ alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy or cyano or a radical of the formula

R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkanoyloxy, carbamoyl or the group -SO ₂ -Z,

Z is vinyl or a radical -CH ₂ -CH ₂ -U ₁ and U _{1 is} a leaving group,

Y is a radical of the formula -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ and Hal is halogen,

E is the radical -O- or -N (R ₂ ) -,

R _{2 is} hydrogen or C ₁ -C ₄ alkyl,

alkylene and alkylene 'independently of one another C ₁ -C ₆ alkylene,

arylene is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen phenylene or naphthylene radical,

R ₃ is hydrogen or unsubstituted or substituted by carboxyl, cyano, hydroxyl, sulfo or sulfato, C ₁ -C ₄ alkyl,

X is chlorine or fluorine,

V is a non-reactive substituent, a group which can be split off as an anion or a radical of the formula

or

where R, R ₁ , R ₃ , E, W, Z, Y, alkylene, alkylene 'and arylene have the meanings given above and t is 0 or 1,

one of the radicals X _{1 is} a group which can be split off as an anion and the other radical X _{1 is} a non-reactive substituent, a group which can be split off as an anion or a radical of the formulas (3a) to (3f),

X _{2 is} a negative substituent, wherein

in the reactive radicals of the formula (2) X is fluorine and V has the meanings given above, or X is chlorine and V is a radical of the formulas (3a) to (3f), and

in the reactive radicals of the formula (4) at least one of the radicals X _{1 is} fluorine or a radical of the formulas (3a) to (3f), and

the impregnation is carried out at ambient temperature.

According to a feature of the present invention, the yarn is first with at least a fiber-reactive dye in aqueous solution and then with at least one impregnated alkaline agent in aqueous solution.

According to an embodiment variant of the present invention, the gam is first used at least one alkaline agent in aqueous solution and then with impregnated at least one fiber-reactive dye in aqueous solution.

According to a further embodiment variant of the present invention, the yarn can also with one or more dyes, which are used individually or as a mixture and in the form of one or more dye liquors with at least one fiber-reactive dye and at least one alkaline agent are present, are impregnated.

According to a further feature of the invention, the dye or dyes are fixed by lingering the carrier (s) with the yarn, the one or more dyeing liquors was impregnated.

According to a further embodiment variant of the invention, it is also possible Fixation of the dye or dyes immediately after the impregnation by treatment of the yarn with a hot medium, e.g. a gas, especially air, or by Carry out treatment with saturated or superheated steam.

Figur 1 einen Seitenaufriß einer Vorrichtung zur Durchführung des erfindungsgemäßen Verfahrens,

Figur 2 einen Seitenaufriß einer möglichen Ausführungsvariante der Wasch/Entwässerungs- und Trockenvorgänge zur Durchführung des erfindungsgemäßen Verfahrens,

Figuren 3 bis 9 und 12 Schnittansichten verschiedener Ausführungsvarianten der Imprägniervorrichtung zur Durchführung des erfindungsgemäßen Verfahrens,

Figur 10 eine Schnittansicht in größerem Maßstab einer Ausführungsvariante der mit der Imprägniervorrichtung gemäß Figur 4 (bzw. Figur 12) einsetzbaren Zerstäubungs- und Sprühdüse zur Durchführung des erfindungsgemäßen Verfahrens, sowie

Figur 11 eine stark vergrößerte Schnittansicht eines nach dem erfindungsgemäßen Verfahren behandelten Garns.

The following description, which relates to a preferred embodiment, which is given merely by way of example and is not intended to limit the invention and is explained on the basis of the attached schematic illustrations, is intended to make the invention easier to understand. Show here:

FIG. 1 shows a side elevation of a device for carrying out the method according to the invention,

FIG. 2 shows a side elevation of a possible embodiment variant of the washing / dewatering and drying processes for carrying out the method according to the invention,

FIGS. 3 to 9 and 12 are sectional views of different design variants of the impregnation device for carrying out the method according to the invention,

10 shows a sectional view on a larger scale of an embodiment variant of the atomizing and spray nozzle which can be used with the impregnating device according to FIG. 4 (or FIG. 12) for carrying out the method according to the invention, and

Figure 11 is a greatly enlarged sectional view of a yarn treated by the method according to the invention.

According to the invention, as is also particularly evident from FIG. 1 of the accompanying drawings, the process for the continuous dyeing of games based on cellulose fibers preferably comprises the following steps:
Impregnation of the yarn in an impregnation device 2 with at least one fiber-reactive dye from the above-mentioned group in aqueous solution and with at least one alkaline agent in aqueous solution, continuous rapid unwinding of the yarn from one or more carriers 1 and its wrapping onto one or more other carrier 3 takes place, and fixation of the dye.

The method is carried out by means of a device which consists essentially of a one or more carrier 1 system for continuous Fast handling of games, a device 2 for impregnating the or unwound yarns with one or more dyes, one or more other carrier 3 system for wrapping the yarn or yarns treated, and a means 4 for fixing the dyes.

The unwinding, wrapping and treatment speeds of the game are preferably at least 100 m / min, in particular at least 250 m / min and preferred at least 300 m / min. The upper limits are, for example, 1000 m / min and called in particular 600 m / min.

The unwinding, wrapping and treatment speeds of the or are preferably Game between 100 m / min and 1000 m / min, preferably between 250 m / min and 600 m / min.

The one or more carrier 1 system for unwinding the yarn is on the accompanying drawings are not shown in detail and can be made in a known manner a frame with spindles that serve as a support for the spools of thread or superkops, consist. It is also possible to remove the yarns from a carrier, e.g. a warp beam, reeling off. The system for wrapping can also be from a winding machine multiple spindles or from a single carrier, e.g. a warp beam. For example, the unwinding and winding around the yarn can take place from bobbin to bobbin or from one or more spools to a warp beam, from warp beam to warp beam or from a warp beam on one or more spools.

The dyes used in the dyeing liquors are Reactive dyes, which are suitable for dyeing cellulose materials, from the group the monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, Formazan or dioxazine dyes which contain at least one reactive group. These dyes preferably also contain at least one sulfo group.

Reactive groups are radicals that are reactive towards fibers Are able to deal with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and Mercapto groups of wool or silk or with the amino or optionally the Carboxyl groups of synthetic polyamides to form chemical covalent bonds to react. The reactive groups are usually with the dye residue directly or over linked a bridge element. Suitable reactive groups are those which at least one that can be split off from an aliphatic, aromatic or heterocyclic radical Have substituents, or those in which these residues one to react with the Have suitable radical fiber material, such as a halotriazinyl, halopyrimidinyl or vinyl radical.

-W―alkylen―E―alkylen'―SO₂-Z

worin W eine Gruppe der Formel -SO₂-NR₁-, -CONR₁- oder -NR₁CO- ist,

R₁ Wasserstoff, unsubstituiertes oder durch Hydroxy, Sulfo, Sulfato, Carboxy oder Cyano substituiertes C₁-C₄-Alkyl oder ein Rest der Formel

R Wasserstoff, Hydroxy, Sulfo, Sulfato, Carboxy, Cyano, Halogen, C₁-C₄-Alkoxycarbonyl, C₁-C₄-Alkanoyloxy, Carbamoyl oder die Gruppe -SO₂-Z ist,

Z Vinyl oder einen Rest -CH₂-CH₂-U₁ bedeutet und U₁ eine Abgangsgruppe ist,

Y ein Rest der Formel -CH(Hal)-CH₂-Hal oder -C(Hal)=CH₂ und Hal Halogen bedeutet,

E der Rest -O- oder -N(R₂)- ist,

R₂ Wasserstoff oder C₁-C₄-Alkyl,

alkylen und alkylen' unabhängig voneinander C₁-C₆-Alkylen, und

arylen einen unsubstituierten oder durch Sulfo, Carboxy, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituierten Phenylen- oder Naphthylenrest bedeutet.

Suitable aliphatic reactive groups are those of the following formulas: -NH-CO-Y -SO ₂ -Z

-W ― alkylene ― E ― alkylene' ― SO ₂ -Z

wherein W is a group of the formula -SO ₂ -NR ₁ -, -CONR ₁ - or -NR ₁ CO-,

R _{1 is} hydrogen, C ₁ -C ₄ alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxy or cyano or a radical of the formula

R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkanoyloxy, carbamoyl or the group -SO ₂ -Z,

Z is vinyl or a radical -CH ₂ -CH ₂ -U ₁ and U _{1 is} a leaving group,

Y is a radical of the formula -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ and Hal is halogen,

E is the radical -O- or -N (R ₂ ) -,

R _{2 is} hydrogen or C ₁ -C ₄ alkyl,

alkylene and alkylene 'independently of one another C ₁ -C ₆ alkylene, and

arylene is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen phenylene or naphthylene radical.

As aliphatic reactive groups are those of the formulas (1) and (1a) to (1d), in particular those of the formulas (1), (1a) to (1c) and preferably those of the formulas (1), (1a) and (1b) prefers. Of particular interest are those of the formulas (1) and (1a), in particular those of formula (1a).

in Betracht, worin

R₃ Wasserstoff oder unsubstituiertes oder durch Carboxy, Cyano, Hydroxy, Sulfo oder Sulfato substituiertes C₁-C₄-Alkyl,

X Chlor oder Fluor ist und

V einen Rest der Formel

oder

bedeutet,

worin R, R₁, R₃, E, W, Z, Y, alkylen, alkylen' und arylen die oben angegebenen Bedeutungen haben und t 0 oder 1 ist.

Preferred heterocyclic reactive radicals are 1,3,5-triazine radicals of the formula

considering where

R ₃ is hydrogen or unsubstituted or substituted by carboxyl, cyano, hydroxyl, sulfo or sulfato, C ₁ -C ₄ alkyl,

X is chlorine or fluorine and

V is a radical of the formula

or

means

wherein R, R ₁ , R ₃ , E, W, Z, Y, alkylene, alkylene 'and arylene have the meanings given above and t is 0 or 1.

The leaving group U ₁ is, for example, -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ , - OSO ₂ -C ₁ -C ₄ alkyl or -OSO ₂ -N (C ₁ -C ₄ alkyl) ₂ . U ₁ is preferably a group of the formula -Cl, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OPO ₃ H ₂ , in particular -Cl or -OSO ₃ H and particularly preferred -OSO ₃ H.

Alkylene and alkylene 'are independently of each other e.g. a methylene, Ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or their branched isomers.

Alkylene and alkylene 'preferably represent a C ₁ -C ₄ alkylene radical and particularly preferably an ethylene radical.

R is preferably hydrogen or the group -SO ₂ -Z, where Z has the meanings and preferences given above. R particularly preferably represents hydrogen.

R ₁ is preferably hydrogen, C ₁ -C ₄ alkyl or a group -alkylene-SO ₂ -Z, in which alkylene and Z each have the meanings given above. R ₁ is particularly preferably hydrogen or C ₁ -C ₄ alkyl, in particular hydrogen.

R ₃ is preferably hydrogen or a C ₁ -C ₄ alkyl radical and particularly preferably hydrogen.

Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or e.g. by Sulfo, methyl, methoxy or carboxy is substituted.

E preferably represents -NH- and particularly preferably -O-.

W preferably denotes a group of the formula -NHCO- or in particular -CONH-.

X stands for chlorine or especially fluorine.

Hal is preferably chlorine or bromine, especially bromine.

Other interesting reactive groups are those of the formula (2), in which V is a non-reactive Means substituents or in particular is a group which can be split off as an anion.

If V is a group which can be split off as an anion, this is, for example, fluorine, chlorine, bromine, sulfo, C ₁ -C ₄ -alkylsulfonyl or phenylsulfonyl and preferably chlorine or in particular fluorine.

V stands for a non-reactive substituent, this can be, for example, a hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, amino, NC ₁ -C ₄ alkylamino or N, N -Di-C ₁ -C ₄ alkylamino, where the alkyl is optionally substituted, for example by sulfo, sulfato, hydroxy, carboxy or phenyl, cyclohexylamino, morpholino, or NC ₁ -C ₄ alkyl-N-phenylamino or Phenylamino or naphthylamino radical, where the phenyl or naphthyl is optionally substituted, for example by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxy, sulfo or halogen.

Examples of suitable non-reactive substituents V are amino, methylamino, ethylamino, β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, Morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As a non-reactive substituent, V preferably has the meaning amino, NC ₁ -C ₄ -alkylamino which is unsubstituted in the alkyl part or is substituted by hydroxyl, sulfato or sulfo, morpholino, phenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino, wherein the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy. Particularly preferred are the meanings as phenylamino or NC ₁ -C ₄ alkyl-N-phenylamino, in which the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy.

The residues of the formulas (3a) to (3f) here and below are those of the formulas (3a) to (3d) and (3f), in particular those of the formulas (3c) to (3d) and (3f) and preferably those of the formulas (3c) and (3f) are preferred. Those of particular interest are of particular interest Formula (3c).

Heterocyclic reactive radicals of the formula (2) are those in which X is fluorine and V has the meanings and preferences given above, or
X is chlorine and V represents a radical of the formulas (3a) to (3f).

worin einer der Reste X₁ eine als Anion abspaltbare Gruppe ist und der andere Rest X₁ die für V als nicht-reaktiven Substituenten angegebenen Bedeutungen und Bevorzugungen hat oder ein Rest der Formeln (3a) bis (3f) oder eine als Anion abspaltbare Gruppe ist,

X₂ ein negativer Substituent ist und

R₃ unabhängig die oben angegebene Bedeutung hat.

Also of interest as heterocyclic reactive radicals are those of the formula

wherein one of the radicals X _{1 is} a group which can be split off as an anion and the other radical X _{1 has} the meanings and preferences given for V as non-reactive substituents or is a radical of the formulas (3a) to (3f) or a group which can be split off as an anion .

X _{2 is} a negative substituent and

R ₃ independently has the meaning given above.

The radical X ₁ which can be split off as an anion is preferably chlorine or in particular fluorine. Examples of suitable radicals X ₂ are nitro, cyano, C ₁ -C ₄ -alkylsulfonyl, carboxy, chlorine, hydroxy, C ₁ -C ₄ -alkoxysulfonyl, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -alkoxycarbonyl or C ₂ -C ₄ alkanoyl, where the meanings chlorine, cyano and methylsulfonyl, in particular chlorine, are preferred for X ₂ . At least one of the radicals X ₁ is fluorine or a radical of the formulas (3a) to (3f). One of the radicals X _{1 is} preferably fluorine and the other radical X _{1 is} fluorine or chlorine, X ₂ having the meanings and preferences given above.

Of particular interest for the process according to the invention are those reactive groups which contain a radical of the formula -SO ₂ -Z or -NH-CO-Y, or contain a triazine or pyrimidine radical in which at least one of the substituents is fluorine.

Particularly preferred reactive groups are those of the formulas (1) and (1a) to (1d), in particular those of the formulas (1), (1a) to (1c), and
Reactive residues of the formula (2), and
Reactive radicals of the formula (4), in particular in which X _{1 is} fluorine and the other radical X _{1 is} fluorine or chlorine and X _{2 has} the meanings and preferences given above.

Very particularly preferred as reactive groups are those of the formulas (1), (1a) and (1b), in particular of the formulas (1) and (1a) and preferably those of the formula (1a), and reactive radicals of the formula (2), in which X Is fluorine or chlorine and V represents a radical of the formulas (3a) to (3f), and
Reactive radicals of the formula (4) in which X _{1 is} fluorine and the other radical X _{1 is} fluorine or chlorine and X _{2 has} the meanings and preferences given above.

Of particular interest as reactive groups are those of the formulas (1), (1a) to (1f) and (2), where the meanings and preferences above apply.

The reactive dyes can in addition to the reactive groups on their backbone organic dyes contain conventional substituents bound.

Examples of such substituents for the reactive dyes are:

Alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; Alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy or sulfo; Acylamino groups with 1 to 8 carbon atoms, especially those alkanoylamino groups such as acetylamino or propionylamino; benzoylamino optionally substituted in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo; phenylamino optionally substituted in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo; N, N-di-β-hydroxyethylamino; N, N-di-β-sulfatoethylamino; sulfobenzylamino; N, N-disulfobenzylamino; Alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; Alkylsulfonyl having 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; amino; cyano; Halogen such as fluorine, chlorine or bromine; carbamoyl; N-alkylcarbamoyl with 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono- or N, N-dialkylsulfamoyl each having 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, where the alkyl radicals can be further substituted, for example by hydroxy or sulfo; N- (β-hydroxyethyl) sulfamoyl; N, N-di- (β-hydroxyethyl) sulfamoyl; N-phenylsulfamoyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy or sulfo; ureido; hydroxy; carboxy; Sulfomethyl or sulfo. The reactive dyes preferably contain at least one sulfo or sulfato group, in particular 1 to 6 such groups and preferably 2 to 6 such groups.

Examples of reactive dyes are those of the formula A ₁ -U into consideration, wherein A _{1 is} the residue of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye and U is a reactive residue, here and below for the reactive residues U the meanings given above and favors apply. The radical A ₁ can also contain one or more further, identical or different reactive groups U. The total number of reactive groups in the dyes is preferably 1 to 3, preferably 1 or 2 and in particular 2.

in Betracht, worin

R₄, R₅, R₆ und R₇ unabhängig voneinander Wasserstoff oder gegebenenfalls substituiertes C₁-C₄-Alkyl,

X₁' und X₂' Halogen sind,

B₁ ein aromatisches oder aliphatisches Brückenglied ist oder der Rest der Formel -N(R₅)-B₁-N(R₆)- einen Piperazinrest darstellt, und

A₂ und A₃ unabhängig voneinander die oben für A₁ angegebenen Bedeutungen haben.

Other reactive dyes are, for example, those of the formula

considering where

R ₄ , R ₅ , R ₆ and R ₇ independently of one another are hydrogen or optionally substituted C ₁ -C ₄ -alkyl,

X ₁ 'and X ₂ ' are halogen,

B _{1 is} an aromatic or aliphatic bridge member or the radical of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - represents a piperazine radical, and

A ₂ and A ₃ independently of one another have the meanings given above for A ₁ .

The radicals R ₄ , R ₅ , R ₆ and R ₇ are straight-chain or branched as alkyl radicals. The alkyl radicals can be further substituted, for example by hydroxy, sulfo, sulfato, cyano or carboxy. The following radicals may be mentioned as examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicals substituted by hydroxyl, sulfo, sulfato, cyano or carboxy. Hydroxy, sulfo or sulfato, in particular hydroxy or sulfato and preferably hydroxy, are preferred as substituents.

R ₄ , R ₅ , R ₆ and R ₇ are preferably hydrogen or C ₁ -C ₄ alkyl, in particular hydrogen.

X ₁ 'and X ₂ ' are preferably chlorine or fluorine, in particular fluorine, independently of one another.

As an aliphatic bridge member, B _{1 is,} for example, a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which is composed of 1, 2 or 3 members from the group -NH-, -N (CH ₃ ) - or in particular -O- can be interrupted and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy. Suitable substituents for said B ₁ for alkylene radicals are hydroxyl, sulfo or sulfato, in particular hydroxyl, preferred.

Other suitable aliphatic bridge members for B ₁ are, for example, C ₅ -C ₉ cycloalkylene radicals, such as, in particular, cyclohexylene radicals. The cycloalkylene radicals mentioned can optionally be substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy, in particular by C ₁ -C ₄ alkyl. As aliphatic bridges for B _1, methylene-cyclohexylene-methylene radicals optionally substituted in the cyclohexylene ring by C ₁ -C ₄ -alkyl may also be mentioned.

in Betracht.For the rest of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - the piperazine residue is, for example, a radical of the formula

into consideration.

worin die Benzolringe I und II gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₄-Alkanoylamino, Sulfo, Halogen oder Carboxy substituiert sind und L die direkte Bindung oder ein C₂-C₁₀-Alkylenrest ist, welcher durch 1, 2 oder 3 Sauerstoffatome unterbrochen sein kann, oder L ein Brückenglied der Formel -CH=CH-, -N=N-, -NH-, -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- oder -SO₂- ist. Als aromatisches Brückenglied ist B₁ bevorzugt Phenylen, welches wie oben angegeben substituiert sein kann. Vorzugsweise sind die für B₁ genannten aromatischen Brückenglieder unsubstituiert oder duch Sulfo substituiert.As aromatic bridge member B ₁ is, for example optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy-substituted C ₁ -C ₆ -Alkylenphenylen or phenylene, or Rest of the formula

wherein the benzene rings I and II are optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₁₀ -alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula -CH = CH-, -N = N-, -NH-, -CO-, -NH-CO-, - NH-CO-NH-, -O-, -S- or -SO ₂ - is. As an aromatic bridge member, B _{1 is} preferably phenylene, which can be substituted as indicated above. The aromatic bridge members mentioned for B ₁ are preferably unsubstituted or substituted by sulfo.

B ₁ is preferably a C ₂ -C ₁₂ alkylene radical which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH ₃ ) - or -O- and is unsubstituted or by hydroxyl, sulfo, Sulfato, cyano or carboxy is substituted; or
an optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy C ₅ -C ₉ cycloalkylene radical, C ₁ -C ₆ alkylene phenylene radical or phenylene radical ;
or B ₁ is a radical of the formula (7), in which the benzene rings I and II are optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₁₀ alkylene radical which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula -CH = CH-, -N = N-, -NH- , -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- or -SO ₂ -;
or the radical of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - is a piperazine radical of the formula

B ₁ is particularly preferably a C ₂ -C ₁₂ alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxy, or
a phenylene radical optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy.

B ₁ is very particularly preferably a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy.

Of particular interest as reactive dyes of the formula (6) are those in which at least one of the radicals X ₁ 'and X ₂ ' is fluorine, or X ₁ 'and X ₂ ' is chlorine and at least one of the radicals A ₂ and A _{3 is} a reactive group contains.

The following are preferably suitable as monoazo, polyazo or metal complex azo dye residues for A ₁ , A ₂ and A ₃ :
Mono- or disazo dye residues of the formula DN = N- (MN = N) _u -K- or -DN = N- (MN = N) _u -K wherein D is the remainder of a diazo component of the benzene or naphthalene series, M is the remainder of a middle component of the benzene or naphthalene series, K is the remainder of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series and u is the number 0 or 1, where D, M and K are common substituents in azo dyes, for example C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, halogen, carboxy, sulfo which is further substituted by hydroxy, sulfo or sulfato , Nitro, cyan, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, sulfomethyl, C ₂ -C ₄ alkanoylamino, optionally in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo substituted benzoylamino, optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy or sulfo phenyl, and fiber-reactive radicals. Furthermore, the metal complexes derived from the dyes of the formulas (8) and (9) also come into consideration, these being in particular 1: 1 copper complex azo dyes of the benzene or naphthalene series, in which the copper atom is attached to a metallizable group, such as, for example, a Hydroxy group, bound on both sides in the ortho position to the azo bridge. If the dye radicals of the formula (8) or (9) carry a reactive radical, the meanings and preferences given above apply to them.

worin (R₈)_0-3 für 0 bis 3 gleiche oder verschiedene Substituenten aus der Gruppe C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₄-Alkanoylamino, Ureido, Sulfamoyl, Carbamoyl, Sulfomethyl, Halogen, Nitro, Cyan, Trifluormethyl, Amino, Hydroxy, Carboxy und Sulfo steht,
(R₉)_0-2 für 0 bis 2 gleiche oder verschiedene Substituenten aus der Gruppe Hydroxy, Amino, N-Mono-C₁-C₄-alkylamino, N,N-Di-C₁-C₄-alkylamino, C₂-C₄-Alkanoylamino und Benzoylamino steht und
(U)_0-2 für 0 bis 2 gleiche oder verschiedene Reaktivgruppen steht;

worin (R₉)_0-2 und (U)_0-2 die oben angegebenen Bedeutungen haben;

worin (R₁₀)_0-3 und (R₁₁)_0-3 unabhängig voneinander für 0 bis 3 gleiche oder verschiedene Substituenten aus der Gruppe C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Carboxy und Sulfo stehen und (U)_0-2 die oben angegebenen Bedeutungen hat;

worin R₁₂ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Phenyl, und R₁₃ Wasserstoff, Cyano, Carbamoyl oder Sulfomethyl ist;

worin (R₁₆)_0-3 für 0 bis 3 gleiche oder verschiedene Substituenten aus der Gruppe C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Carboxy und Sulfo steht,
(R₁₅)_0-3 und (R₁₇)_0-3 unabhängig voneinander die oben für (R₈)_0-3 angegebenen Bedeutungen haben, und
(U)_0-2 die oben angegebenen Bedeutungen hat;

worin (R₁₅)_0-3, (R₁₇)_0-3 und (U)_0-2 die oben angegebenen Bedeutungen haben und (R₁₈)_0-2 für 0 bis 2 gleiche oder verschiedene Substituenten aus der Gruppe C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Carboxy, Sulfo, Hydroxy, Amino, N-Mono-C₁-C₄-alkylamino, N,N-Di-C₁-C₄-alkylamino, C₂-C₄-Alkanoylamino und Benzoylamino steht.The dye residues of the formulas (8) and (9) are preferably those of the formulas

wherein (R ₈ ) _0-3 for 0 to 3 identical or different substituents from the group C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl , Halogen, nitro, cyan, trifluoromethyl, amino, hydroxy, carboxy and sulfo,
(R ₉ ) _0-2 for 0 to 2 identical or different substituents from the group hydroxyl, amino, N-mono-C ₁ -C ₄ -alkylamino, N, N-di-C ₁ -C ₄ -alkylamino, C ₂ -C ₄ -alkanoylamino and benzoylamino and
(U) _{0-2 represents} 0 to 2 identical or different reactive groups;

wherein (R ₉ ) _0-2 and (U) _{0-2 have} the meanings given above;

wherein (R ₁₀ ) _0-3 and (R ₁₁ ) _0-3 independently of one another for 0 to 3 identical or different substituents from the group C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy and sulfo stand and (U) _{0-2 has} the meanings given above;

wherein R ₁₂ and R _{14 are} independently hydrogen, C ₁ -C ₄ alkyl or phenyl, and R _{13 is} hydrogen, cyano, carbamoyl or sulfomethyl;

wherein (R ₁₆ ) _{0-3 represents} 0 to 3 identical or different substituents from the group C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy and sulfo,
(R ₁₅ ) _0-3 and (R ₁₇ ) _0-3 independently of one another have the meanings given above for (R ₈ ) _0-3 , and
(U) _{0-2 has} the meanings given above;

in which (R ₁₅ ) _0-3 , (R ₁₇ ) _0-3 and (U) _{0-2 have} the meanings given above and (R ₁₈ ) _0-2 for 0 to 2 identical or different substituents from the group C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy, sulfo, hydroxy, amino, N-mono-C ₁ -C ₄ alkylamino, N, N-di-C ₁ -C ₄ alkylamino, C ₂ -C ₄ alkanoylamino and benzoylamino.

in Betracht, worin (U)_0-2 die oben angegebenen Bedeutungen hat und die Benzolkeme keine weiteren Substituenten enthalten oder durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylsulfonyl, Halogen oder Carboxy weitersubstituiert sind.The radicals of a formazan dye for A ₁ , A ₂ and A _{3 are,} for example, those of the formula

into consideration, in which (U) _{0-2 has} the meanings given above and the benzene cores contain no further substituents or by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylsulfonyl, halogen or Carboxy are further substituted.

in Betracht,

worin Pc der Rest eines Metallphthalocyanins, insbesondere der Rest eines Kupfer- oder Nickelphthalocyanins, ist,

W' -OH und/oder -NR₂₀R₂₀',

R₂₀ und R₂₀' unabhängig voneinander Wasserstoff oder gegebenenfalls durch Hydroxy oder Sulfo substituiertes C₁-C₄-Alkyl,

R₁₉ Wasserstoff oder C₁-C₄-Alkyl,

A ein gegebenenfalls durch C₁-C₄-Alkyl, Halogen, Carboxy oder Sulfo substituierter Phenylenrest oder ein C₂-C₆-Alkylenrest und

k 1 bis 3 ist.

The remainder of a phthalocyanine dye for A ₁ , A ₂ and A _{3 are,} for example, those of the formula

into consideration

where Pc is the rest of a metal phthalocyanine, in particular the rest of a copper or nickel phthalocyanine,

W '-OH and / or -NR ₂₀ R ₂₀ ',

R ₂₀ and R ₂₀ 'independently of one another are hydrogen or C ₁ -C ₄ -alkyl optionally substituted by hydroxy or sulfo,

R _{19 is} hydrogen or C ₁ -C ₄ alkyl,

A is a phenylene radical optionally substituted by C ₁ -C ₄ alkyl, halogen, carboxy or sulfo or a C ₂ -C ₆ alkylene radical and

k is 1 to 3.

in Betracht, worin A' ein gegebenenfalls durch C₁-C₄-Alkyl, Halogen, Carboxy oder Sulfo substituierter Phenylenrest oder ein C₂-C₆-Alkylenrest ist,
r, s, v und v' unabhängig voneinander je die Zahl 0 oder 1 bedeuten und
Z die zuvor angegebene Bedeutung hat.The remainder of a dioxazine dye for A ₁ , A ₂ and A _{3 are,} for example, those of the formula

into consideration, in which A 'is a phenylene radical optionally substituted by C ₁ -C ₄ alkyl, halogen, carboxy or sulfo or a C ₂ -C ₆ alkylene radical,
r, s, v and v 'each independently represent the number 0 or 1 and
Z has the meaning given above.

in Betracht, worin G einen unsubstituierten oder durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Carboxy oder Sulfo substituierten Phenylenrest oder einen Cyclohexylen-, Phenylenmethylen- oder C₂-C₆-Alkylenrest bedeutet.The remainder of an anthraquinone dye is for A ₁ , A ₂ and A _3, for example those of the formula

into consideration, in which G represents an unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy or sulfo phenylene radical or a cyclohexylene, phenylene methylene or C ₂ -C ₆ alkylene radical.

The above dye residues of formulas (10a) to (10f) and (11) to (14) preferably contain in each case at least one sulfo group, in particular 1 to 4 sulfo groups and preferably 1 to 3 sulfo groups.

The reactive radicals mentioned above are suitable as reactive radicals U, the above Preferences apply.

Preferred are dye residues of the formulas (10a) to (10f), (11) and (14), in particular the Formulas (10a) to (10f) and (11) and preferably those of the formulas (10a) to (10f).

The reactive dyes are known or can be made analogously to known ones Manufacturing processes such as diazotization, coupling and condensation reactions, be preserved.

The amount of dye in the dye liquor can vary greatly depending on the depth of color desired fluctuate and is e.g. up to 100 g / l liquor, preferably 10 g / l to 70 g / l, in particular 10 g / l to 50 g / l dyeing liquor.

It is advisable to use dyes with weak to medium fiber affinity. The Dyeing liquors used according to the invention can contain one or more dyes contain.

As an alkaline agent for fixing the reactive dyes, use is made, for example, of alkali carbonates or alkali hydrogen carbonates, in particular Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ or KHCO ₃ , alkali hydroxides, in particular NaOH or KOH, ammonia, organic ammonium salts, such as, for example, ammonium formate and acetate or tartrate, sodium trichloroacetate, borax, phosphates such as trisodium phosphate, polyphosphates or sodium silicate or a mixture of two or more of the above-mentioned alkaline agents. It is advisable to use a mixture of an aqueous sodium hydroxide and sodium silicate solution as an alkaline agent.

In addition to the dye and the alkaline agent, the dyeing liquor can also be used usual additives, e.g. Wetting agents, solubilizers, e.g. ε-caprolactam or Polyethylene glycol, penetration accelerator, electrolyte, e.g. Sodium chloride or Contain sodium sulfate, complexing agents such as urea or glycerin.

After drawing up the dye and the alkaline agent, the dye becomes on the yarn based on cellulose fibers by means of a thermal process or also fixed a cold process.

If the fixation is carried out by exposure to heat, a procedure is included Steam application or holding at elevated temperature or on Thermal insulation process in question.

The cellulose fiber yarn may e.g. around cotton, in particular mercerized and / or bleached cotton, or also unbleached yarn, expediently without prior washing according to the invention Process can be colored. Such a dyeing process is with the previously known Colorants not feasible. Blended yarns based on cellulose, e.g. Cotton / polyamide blended yarns or especially cotton / polyester blended yarns are also possible. Viscose materials such as e.g. Tencel or Lyocell) as well as corresponding mixed fibers with cotton, e.g. Cotton / Lycra (polyurethane elastomer) into consideration.

With the method according to the invention, cellulose yarns with high Color speed, i.e. with high yield. Furthermore, yarns can be used special effects, e.g. Chiné yarn, yarn dyed using the space dyeing process, single or multi-colored spotted yarn, or yarn with partial impregnation of the fibers, e.g. of the washed-out type, ring-dyed denim (ring dyeing method) or mechanically with Make grindstones of washed (stone wash) denim. These different effects could previously only be achieved by mixing several fibers of different colors Spinning, but not using a dyeing process.

The impregnation device 2 (see e.g. FIG. 1) has one or more dye liquors, in which the yarn is impregnated with when passing through the device 2. When they leave diffuse the dyeing liquor (s) on the yarn into the interior of the yarn constructive fibers. The essential components of these dyeing liquors, namely the Reactive dye and the alkaline agent, which are present in aqueous solution, can be presented in separate containers or as a mixture in a single container become. By placing the dye and the agent in separate containers, one ensures high stability of the dye liquor, thereby renewing the latter in regular intervals because of the alkaline agent Hydrolysis is avoided.

If the dye liquor is used as a mixture, i.e. with the reactive dye and the alkaline agent in aqueous solution, the two solutions can be separated Containers are presented and before use in a buffer containing Intermediate containers are mixed. This way, over time, only a small one Amount of the dye liquor attacked hydrolytically and can be removed or if necessary be replaced, especially if the dyeing cycle is not used for a long time.

The impregnation of the yarn with the dyeing liquor (s) is regulated so that the Gams weight gain e.g. 15 to 100%, especially 15 to 80% and preferably about 15 to 50%. With such an impregnation, the dyeing liquor, after the yarn has left the impregnation device 2, diffuse into the interior of the fibers.

The impregnation takes place at ambient temperature, e.g. 15 to 40 ° C so that before and especially during the impregnation step on a heating device entirely can be dispensed with. This corresponds to both the temperature of the impregnating chamois as well as the temperature of the dye liquor when impregnating a the above temperatures. The above conditions preferably also apply to the Step of winding the yarn onto one or more carriers 3.

After winding, the or the diffuse after impregnation in the device 2nd colorant drawn onto the respective yarn while staying in the system 4 in the fibers of the yarn. These are those for the present method preferred cold fixation. With this fixation, the dyes in the fibers are depending on Yarn quality and type and the selected dyes with a degree of fixation in the Order of magnitude of 80 to 95%, based on the coloring material, fixed.

This cold fixation of the dye on the gam by lingering the impregnated and wound yarn takes place, e.g. at ambient temperature, e.g. at a Temperature between 10 and 40 ° C, especially between 15 and 35 ° C. The duration of the Cold treatment may depend on the dye used and will vary within further limits, between 3 and 24 hours, preferably between 4 and 10 hours, are particularly preferably between 6 and 8 hours.

A corresponding fixation at a higher temperature can also be considered, wherein the dye on the cellulose fiber yarn by dwelling in one impregnated and wound yarn-containing storage (4) at one temperature above 40 ° C, in particular up to 70 ° C and preferably up to 60 ° C, is fixed. The Duration of treatment may depend on the dye used and will vary within wide limits. The duration of the treatment is preferably up to 3 Hours, in particular 0.5 to 3 hours and preferably 1 to 3 hours.

The application of the device to carry out the method according to the invention depends on the foreseen need or the foreseen production rate and can be used with single yarn or multiple yarns of any denier or type different forms.

So one or more game from multiple carriers 1 or a single carrier unwound and wrapped on multiple carriers 3 or a single carrier. It However, it is also possible to handle multiple supports 1 and on a single one Wrap carrier 3 and vice versa. In addition, before unwinding from the Carriers 1 preparatory steps are carried out, in particular from a Wrapping can consist of a super cop.

According to a feature of the invention, the yarn or yarns after leaving the Dwell memory 4 dried directly without an intermediate washing process and are especially used directly for woven or knitted fabrics. In such a case is only the textile product obtained after the weaving, knitting or finishing process washed and then dewatered and dried. In such a case, they will not fixed dyes as well as the alkalis, silicates and other auxiliaries by the Washing process removed from the woven, knitted or finished textile product. Of special Such a procedure is of interest for velor fiber materials.

This drying process can also be done in an autoclave using saturated or Hyperbaric steam in a chamber in the form of a channel, the high-frequency or Infrared energy is supplied, or in a duct to which hot air or hot gas is supplied will take place, the fixation then also taking place at the same time.

If the drying is done in an autoclave using steam, this is done with the dye liquor impregnated textile yarn in a treatment chamber, optionally with superheated Steam at an operating temperature between 98 and 210 ° C, advantageously between 100 and 180 ° C, and preferably between 102 ° C and 120 ° C subjected.

If the treatment is carried out by lingering at an elevated temperature, this is not allowed impregnated cellulose-based yarn in wet condition in an autoclave from 1 min to 120 min e.g. stay at a temperature between 80 ° C and 102 ° C.

The dye can be fixed using the thermal insulation process with or without Intermediate drying, e.g. at a temperature between 100 ° C and 210 ° C, expediently between 120 ° C and 200 ° C, and very particularly between 140 ° C and 180 ° C are carried out. Depending on the treatment temperature, the Thermal insulation over a period of between 20s and 5 minutes, preferably between 30s and 60s.

According to a further feature of the invention, the yarn or yarns according to the Leaving the temporary storage 4 also handled by an intermediate gate coil 5 and then at a high running speed of the chamois in a washing and drainage system 6 continuously washed and e.g. centrifuged and then dried in a device 7 be, after which the yarn or yarns are wrapped on new carrier 8 (Figure 1).

The device for performing this method has one of the devices for Unwind the game from the carrier 1 comparable intermediate gate coil 5, the new wrapping carrier 8 can be operated by means of a device that the system for Wrapping the yarn or yarns on one or more carriers 3 is similar.

Figure 2 of the accompanying drawings shows an embodiment of the method according to the invention, in which those coming from the temporary storage 4 Carrier 3 in an autoclave 9 a washing process and in a rapid dryer 9 'one Undergo drying, whereupon the game from the carrier 3 in one Wrapping machine 11 to be wrapped on new carrier 10. In such a case, they can Carrier 3 for later washing in the autoclave 9 by countercurrent circulation perforated columns of a material carrier are attached, whereupon the material carrier in the quick dryer 9 'is transferred, in which the yarns on the carriers Moisture is extracted by the chamber representing the quick dryer 9 ' pressurized and by means of the perforated columns of the material carrier through the on the Carriers 3 located yarn sucks air.

The games rewound onto the carriers 8 or 10 are from excess dyes and yarns freed from other components of the dyeing liquors, which are completely stable in terms of color, i.e. where there is no risk of washing out more exists, and which are suitable for the production of woven and knitted fabrics, one later washing of the fabric or knitted fabric can be omitted.

These cellulose fiber yarns then have a moisture content of e.g. 8 to 12% in an environment common to textiles, i.e. at 22 ° C and a relative Humidity of 65%.

As can be seen from FIG. 3, the impregnation device 2 can be made from a dye liquor trough 12, by means of a feed pump 13, with a containing the dye liquor 14 and optionally connected by means of a heat source 15 heated storage tank is maintained at a constant level, the yarn or yarns to be impregnated in the Dyeing liquor can be unwound by means of a return roller, and from a means 16 to Squeeze excess paint on the yarn (s) with compressed air adjustable pressure exist, the entire device in a chamber 17 Recovery of the squeezed paint is located and openings for passage of the yarn or yarns. Such an embodiment of the impregnation device is suitable is particularly good for a single color using a in the form of a mixture of dye and alkaline dyeing liquor.

The squeezing means 16 consists of a container which is provided with two openings, through which the yarn (s) loaded with dye liquor are passed, and is placed under an air pressure. Through the one in the container through which the yarns throughput, generated excess pressure, becomes a large part of that on the gam remaining dye liquor squeezed out of it and through the openings of the container pushed out. In this way, a game with between can at the output of the device 2 15 and 100% of its weight in dye liquor, which is about that used on average 16 Air pressure is maintained.

FIG. 4 shows an embodiment variant of the impregnation device 2, in which this consists of several means 18 for guiding and holding the respective yarn in the longitudinal direction, from at least one nozzle 19 for atomizing and spraying the dye liquor onto or the running yarn, from a device 20 for squeezing excess dyeing liquor and consists of a device 21 for the continuous supply of dye liquor with the atomizing and spraying nozzles 19 and with a trough 22 for receiving excess atomized and / or squeezed dye liquor is connected, this Trough 22 forms the bottom of the chamber which represents the impregnation device 2. Thereby, that a sequence of atomizing and spray nozzles 19 are provided, can be depending on the desired effect an increased impregnation of the yarn and thus, if necessary an optimization of the penetration of the fibers representing the yarn and their Reach spaces with dye liquor. Another variant is shown in FIG.

When using such a device, one can adjust the spray pressure of the dye liquor the number of rows of nozzles and their distance from the yarn and on the Diameter of the nozzles and their atomization or spray angle with respect to the Running chamois influence, so that the yarn ring or core colored differently can be.

Furthermore, this impregnation device according to FIG. 4 (or according to FIG. 12) enables a differentiated spraying of the reactive dye (s) and the alkaline Agent, the latter being sprayed on before or after the reactive dye. From this it follows that the dye and agent are not previously mixed and a possible one Hydrolysis of the dye by the agent can be avoided. For this purpose it is particularly interesting, the yarn first with an aqueous solution of the reactive dye and then impregnated with the alkaline agent. In such a case the excess flowing back into the trough to absorb the excess Dye is not contaminated by the alkaline agent and does not suffer at all Hydrolysis, so that the stability of the liquor is guaranteed over a long period of time.

Preferably, the device 20 for squeezing excess dye liquor Carrier anvil 23 of the running yarn or formed slightly higher than that horizontal running direction of the yarn or yarns is and on the upstream side of the yarn or yarns with an edge bevel 23 'or rounding and a nozzle 24 is provided for blowing in compressed air with which an air jet is directed onto the game or games becomes. So by slightly changing the forced direction of the yarn Anvil 23 and by blowing compressed air through the nozzle 24 in the amount of change of direction removal or squeezing of the excess dyeing liquor by a Combination of mechanical and pneumatic drainage.

The squeezing device 20 can of course also be used instead of the squeezing means 16 Execution form of the impregnation device according to Figure 3 are used and vice versa.

To support a thorough impregnation of the yarn (s) and subsequent optimal diffusion of the dyeing liquor into the yarn The impregnation device 2 according to FIG. 4 (or according to FIG. 12) is single fiber. expediently equipped with several atomizing and spraying nozzles 19.

According to an embodiment variant of the invention, it is also possible to use the the yarns at right angles to the respective atomizing and spray nozzle 19 one Provide support plate 25 to support the yarn. This embodiment is in FIG. 4 of the accompanying drawings at right angles to a nozzle 19.

As a result, the yarn or yarns is held in place and against a possible Deflection by which they would be moved away from the corresponding nozzles 19, so that their impregnation by the jet and the penetration of the fibers by the Dyeing liquors are better guaranteed.

In fact, the kinetic energy of the dye liquor sprayed onto the gam shows one optimal effect if the gam rests on a solid support and if the Dye jet can hit the gam without it being able to evade.

The guiding and holding means 18 in turn act to avoid any deviation in a horizontal plane lying outside the longitudinal axis of the yarn or yarns prevent.

In Figure 4 (or Figure 12) of the accompanying drawings is also another Embodiment variant of the invention shown, in which at least two atomizing and Spray nozzles 19 with respect to the longitudinal axis of the one or more to be colored treating yarns are arranged diametrically opposite. With such a Embodiment is characterized in that the kinetic energy of the two opposite rays added, an optimization of the impregnation and Penetration of the fibers and their spaces with dye liquor at right angles to the respective nozzle pair 19 reached.

According to a further embodiment variant of the invention, which is shown in the attached Drawings are not shown, it is also possible in the impregnation device 2 to provide a sequence of evaporation nozzles 19, between each one by one Anvil 23 formed squeeze device 20 and an air injection nozzle 24 are connected. With such an embodiment, successive yarns can be made on each running yarn Carry out mechanical impregnation and drainage processes, which makes this better can be impregnated with the dye liquor and thus the impregnation and diffusion of the Dyeing liquor through all fibers and inside all fibers of the yarn depending on the desired effect can be optimized and accelerated.

According to a further feature of the invention, it is also possible to inject the nozzles 19 in Form of piezoelectric nozzles (of the drop on demand type), thermal nozzles (of the type Bubble jet) or high-frequency nozzles with continuous or deflected jet perform. In Figure 10 of the accompanying drawings is an example High-frequency nozzle 19 'shown, in which a high-frequency drop generator 38 drops over a charger 39, a detector 40 and a deflector 41 the drops are directed either onto a yarn 42 or onto a return means 43. In this way, a very precise application of the dye liquor can be achieved.

FIG. 5 of the accompanying drawings shows a further embodiment variant of the Impregnation device 2 shown, in which an ink reservoir 26 via a Supply line and a pump 27 with a pressurized impregnation channel 28 which is formed by a longitudinal tube for each game or for several games, through which the yarn or yarns are passed in the longitudinal direction, the channel 28 is followed by a device 29 for squeezing off excess dye liquor, wherein the emerging from the pressurized channel 28 and from the Squeezing system 29 dye liquor at the bottom of the device 2 representing Chamber collected and returned to the reservoir 26 by means of a line 30 becomes.

According to a feature of the invention, the pressurized channel 28 in especially suitable for dyeing uniform fibers or in the form of a tube rectangular elongated box for coloring bundle or litz-shaped Multiple fibers can be formed. The cross section and the length of these channels can be so be chosen that both the contact time of the chamois with the dye liquor depending of its speed as well as the relative speed of that in the channel circulating dye liquor regarding the speed of the yarn in the same channel can be varied. All of these factors can affect the effect of contact Dyeing liquor with the yarn and its fiber components influence.

An embodiment is also possible in which the pressurized dye liquor in time intervals in the channel 28, so the speed differential between dyeing liquor and yarn to be taken into account since the speeds of the yarn and the pressurized dye liquor upstream with respect to the direction of travel of the Add yarns as they subtract downstream.

According to a further feature of the invention, the pressurized Impregnation channels 28 rough on their inside parallel to the running direction of the yarn Places or internals or surface deformations. The latter lead to a non-laminar flow of the dye liquor, the turbulence thus obtained being favorable to the generation of high local pressures and one which is also favorable for the yarn Impact movement, which results in fast and high-quality impregnation, if this effect is desired.

In the embodiment according to FIG. 5, the squeezing system 29 can either consist of one Pressure vessel, through which the yarn loaded with the dye liquor is passed, or consist of a combination of anvil and air injection nozzle. Also be the fibers representing the game (s) due to the fact that the Yarns are immersed in a pressurized dye liquor during impregnation be surrounded quickly and in intimate contact with dye liquor, causing diffusion of the coloring substances in the fibers starts better during the impregnation. To comes in that the relative speed between the running yarn and the dyeing liquor the tubular or other shaped channel 28, the uniform impregnation of the Gam performing fibers reinforced.

In Figure 6 of the accompanying drawings is a further embodiment of the Impregnation device 2 shown, in which it is in the form of an impregnation pad 31st is present, which consists of two horizontal cylinders that are in with each other along their surface line Are in contact and above which the dye liquor is constantly provided, and an arrangement of side sealing flanges 31 'at the cylinder ends composed, the impregnation of the yarn or yarns by passing through between the cylinders.

According to another embodiment variant of the invention, there is also the possibility of as shown in Figure 9 of the accompanying drawings, the impregnation device 2 in the form of a contact impregnation drum 32, the drum in one Dyeing liquor is moved and the color on the running yarn or yarns due to contact draws up by means of return roller 33 or the like on a part of the drum circumference are guided, the position of these return rollers 33 with respect to the drum 32nd is adjustable.

In this way, the degree of impregnation of the yarns can be modified by the rollers 33 be moved away from the drum 32 or approach it, so that a longer or shorter, stronger or weaker contact of the yarn with the drum, one leads to a certain amount of dye liquor during its rotation. The Degree of impregnation can also be influenced by influencing the speed of rotation Drum 32 and thus the relative speed of the yarn with respect to the drum modify. This effect on the relative speed can be changed by changing the Direction of rotation of the drum 32 are further reinforced. In the case of one to the direction of travel the opposite rotation of the drum 32 exerts the former on that of the Drum carried film from dyeing liquor namely a soaking effect, which causes results in better penetration of the fibers of the Gam with liquor.

Finally, the degree can be adjusted by adjusting the viscosity of the dye liquor Fleet intake can be varied by the running yarn.

The device according to FIG. 9 is particularly well suited for carrying out Partially impregnated yarn of the ring-dyed type (ring dyeing process) or only part of the outer surface of a yarn. In fact, in the case of one only slight contact of the yarn with the drum 32 and a slight covering of the Drum 32 with the dye liquor only a part of the circumference of the chamois on the surface be impregnated.

From Figure 11 of the accompanying drawings, the one on a greatly enlarged scale Gam treated according to the invention in section shows a partial impregnation of the yarn clearly visible on the peripheral fibers of the lower part of this chamois. The on the For this purpose, surface impregnated fibers are drawn with a very border. while the undyed fibers are drawn in thin lines.

In the case of a core staining, such as that which is in particular with the impregnating agent 2 3 to 6 and 12 can be obtained, all fiber components of the yarn impregnated by the dye liquor, which after being drawn onto the outer surface of the fibers diffuses inside.

According to another embodiment variant of the invention, the impregnation device 2, as can be seen in section from Figure 7a of the accompanying drawings a dyeing machine with several applicators, each one different Dyeing liquors are assigned and each in steps of the same or different lengths apply stains of different colors one after the other. With such a Impregnation device can be especially yarns with fancy effects like the one below the designation of single or multi-colored space dyeings, Chiné-type yarns and Make spotted or washed out or denim yarns.

A dyeing machine with several coaters that can be used for this purpose is in particular from FR-A-2 650 311 and FR-A-2 719 058.

In Figure 7a of the accompanying drawings is a possible embodiment of a Coater of such an apparatus. This is done in one with nozzles, each are arranged at right angles to the barrel axis of one or more yarns Atomizing device 34 successively transferred dye liquor from these nozzles sprayed a slot 35 arranged in a disk 36 (FIG. 7b), the disk is between the nozzles and the direction of rotation of the yarn or yarns and thus fastened is that it rotates about a vertical axis 37. This way you can go through Actuation of the disk 36 and the nozzles of the device 34 in more or less periodically and over a predetermined period of time one spots on the or spray on the dye liquor applied. It follows that Use of sequentially arranged, each with different dyeing liquors connected coaters, which are synchronized with each other, with special yarns Monochrome space dyeing, multi-colored space dyeing, type effects Have chiné or spotted or even washed out or denim yarns made.

Such a sequential application process for different dyeing liquors can also be used by spraying the paint on using a rotary turbine or a plate realize. In such a case, the turbine can be constructed as in FR-A-2 650 311, i.e. exist in the form of a cylindrical hollow body, which on its outer surface several openings or nozzles for spraying paint with the same or has different cross sections, this turbine rotating on an axis attached, which runs parallel to the axis of the yarn, and the dyeing liquor through this sprayed through different nozzles. This will keep on walking by Yarn spots of color with a size and spaced apart that match the geometry and correspond to the arrangement of the openings or spray nozzles of the turbine.

In Figure 8 of the accompanying drawings is an embodiment variant of the invention shown, in which the impregnation device 2 in several chambers 2 ' Yarn impregnation is divided. With the help of such an embodiment, a simultaneous treatment of a variety of yarns with different colors, according to Yarn groups are carried out, each corresponding to one or more chambers 2 '. In in fact, in such a case it is possible to have one chamber 2 'or chamber groups 2' each to be treated with various dyeing liquors as required.

When using such a multi-chamber device, the different obtained yarns are necessarily subjected to various washing processes.

The washing and drainage system 6 can be analogous to the impregnation device 2 be constructed, as is the case in the different design variants in FIGS. 3 to 5 is shown, the liquor troughs and atomization and spray nozzles simply with Water or detergent products containing water and the Dewatering process takes place using squeezing agent, through which the water from the yarn Will get removed.

After dyeing, the gam can e.g. at a temperature between 60 and 80 ° C washed, e.g. by treatment with a solution, the soap or one or contains several detergents. Washing can be done continuously with the running yarn or by treating the chamois wound on spools.

The washing and drainage system 6 consists of a sequence of atomization and Spray nozzles, it is useful to wash them in countercurrent Reuse of the wash water carried out at the last wash nozzle, with respect to the direction of the chamois, taken and successively to the first Washer nozzle is reused, whereupon the residual water is discharged and treated becomes. In such an embodiment, it is sufficient to collect the washing water that from the treatment in the last nozzle, with regard to the direction of the game or the game and press it back into the penultimate nozzle and continue until the first Jet. This water is therefore increasingly enriched with dye residues and thus in Connected chemical products and is used for successive Washing processes of the yarn used without affecting the washing quality. hereby there is a considerable saving in washing water. In such a case it works Squeezing agent downstream of the last nozzle as a drainage device for the or the game.

By turning on the squeeze devices 20 between the different ones Washing nozzles can be optimized by the mechanical squeezing effect, which makes the yarn more suitable for rewetting.

The drying device 7 (not shown in detail) is expediently in shape a channel through which the yarn or yarns are passed and which with hot air or a hot gas is pressurized. With the help of this drying device 7 manages to use one or more yarns with those required for later use Obtain properties related to their relative humidity. Is the device 7 in shape formed a channel, this can advantageously with internals or rough Bodies that have a beneficial effect on the formation of turbulence Exert drying air or drying gas as well as vibrations of the yarn, which optimizes the drying effect.

According to a further embodiment variant of the invention, which is shown in the attached Drawings not shown, the drying device 7 can also be in the form of a chamber be trained to concentrate the chamois through education successive strands comes on tension rollers, this chamber one Circulation with hot air or hot gas is subjected.

According to a further embodiment variant of the invention (in the accompanying drawings (not shown), the drying device 7 can also be designed in the form of a channel be through which the yarn or yarns are passed and which with radio frequency or Infrared energy is applied.

According to a further embodiment of the invention, which is shown in the attached Drawings are not shown, it is also possible to dry the treated Yarns either by blowing hot air in during winding or by Passing the coils through a radio frequency or infrared drying channel cause.

Thanks to the invention, one or more textile games made of cellulose fibers can be used high speed, in the order of 600 m / min or more, with Reactive dyes with significant savings in dye, i.e. with greatly reduced Discharge of dye into the wash water, as well as considerable energy savings and color water consumption continuously.

In addition, using the method according to the invention through uniform impregnation of the respective yarn Representative fiber composite and by fixing the dyes on and in the fibers achieve more brilliant colors and higher wash, rub and light fastness etc.

The yarns dyed by the present process are mechanically reduced claims and retains their physical and mechanical qualities, e.g. Regularity, stability and stretch, longer at.

Furthermore, in the method according to the invention, the required ones Handling steps are greatly reduced and the space requirement of the device compared to conventional dyeing machines significantly reduced.

This leads to the total cost of implementing the invention Process compared to the conventional known dyeing processes and already existing equipment is also lower.

It goes without saying that the invention is not based on the described and in the Embodiments shown in the accompanying drawings is limited. They are too still further modifications are possible, in particular with regard to the structure of the different elements or exchanges for equivalent methods without this leaves the scope of the invention.

The following examples serve to illustrate the present invention.

30 g/l des Farbstoffs der Formel:

70 ml/l Natriumsilikat 38° Bé

21 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Example 1: An undyed, bleached mercerized cotton yarn is unwound from a storage tank at a speed of 500 m / min and a dyeing liquor is sprayed onto it by means of a nozzle, the excess dye being sucked off under air pressure, whereupon the yarn is rewound onto a new support. Composition of the dye liquor:

30 g / l of the dye of the formula:

70 ml / l sodium silicate 38 ° Bé

21 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

The wrapped impregnated gam is then at 8 hours Allow ambient temperature to linger, the dye being fixed on the fiber. After washing with hot water and then drying, an in is obtained brilliant red shades of dyed yarn with good properties.

30 g/l des Farbstoffs der Formel:

70 ml/l Natriumsilikat 38° Bé

21 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Example 2: An undyed, bleached mercerized cotton yarn is unwound from a storage device at a speed of 500 m / min and a dyeing liquor is sprayed onto it by means of a nozzle, whereupon the yarn is rewound onto a new carrier. A perforated disk is arranged between the dye nozzle and the running yarn, with the aid of which the dyeing liquor is sprayed onto the yarn only at predetermined and successive intervals. Composition of the dye liquor:

30 g / l of the dye of the formula:

70 ml / l sodium silicate 38 ° Bé

21 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

The wrapped impregnated yarn is then at 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 to 80 ° C) with an aqueous liquor containing 2 g / l Detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l contains a preparation of esterified phosphorus derivatives and water-soluble polymers, washed, and the colored gam is dried. Here you get a gam of Chiné types, on which undyed parts and parts in brilliant yellow tones alternate.

Färbeflotte 1:

30 g/l des roten Farbstoffs der Formel aus Beispiel 1;

70 ml/l Natriumsilikat 38° Bé

21 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Färbeflotte 2:

30 g/l des Farbstoffs der Formel:

70 ml/l Natriumsilikat 38° Bé

21 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Färbeflotte 3:

70 g/l des Farbstoffs der Formel:

70 ml/l Natriumsilikat 38° Bé

34 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Example 3: An undyed, bleached, mercerized cotton yarn is unwound from a storage tank at a speed of 500 m / min, and three dyeing liquors are sprayed thereon by means of nozzles, whereupon the yarn is rewound onto a new carrier. Between the dye nozzles and the running gam a perforated disk is arranged, with the help of which it is achieved that the spraying of the different dyeing liquors onto the gam takes place only at predetermined, synchronized and successive intervals, the synchronization and the angular velocity of the perforated disks on the speed of the running yarn are matched.
Composition of the dyeing liquors:

Dyeing liquor 1:

30 g / l of the red dye of the formula from Example 1;

70 ml / l sodium silicate 38 ° Bé

21 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

Dyeing liquor 2:

30 g / l of the dye of the formula:

70 ml / l sodium silicate 38 ° Bé

21 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

Dyeing liquor 3:

70 g / l of the dye of the formula:

70 ml / l sodium silicate 38 ° Bé

34 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

The wrapped impregnated yarn is then at 6 to 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 to 80 ° C) with an aqueous liquor containing 2 g / l Detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l contains a preparation of esterified phosphorus derivatives and water-soluble polymers, washed, and the colored gam is dried. Here you get a multi-colored Gam, in which red, blue and black colored parts as well as parts with different Alternate color shades from the mixture of the three dyes used.

0,5 g/l des roten Farbstoffs entsprechend der Formel aus Beispiel 1

11 g/l des blauen Formazanfarbstoffs entsprechend der Formel aus Beispiel 3

70 ml/l Natriumsilikat 38° Bé

15 ml/l Natriumhydroxidlösung 36° Bé

3 g/l anionisches Netzmittel

3 g/l Durchdringungsbeschleuniger (wäßrige Lösung mit ethoxylierten linearen C₉-C₁₁-Fettalkoholen mit endständigen Alkylgruppen, Ricinusöl/Polyglykolether, Paraffinöl, Maleinsäure-bis(2-ethylhexyl)-ester, Phosphorsäure-di(2-ethylhexyl)-ester und Natriumhydroxid als Hauptbestandteilen).

Example 4: An undyed, unbleached unwashed cotton yarn is unwound from a storage tank at a speed of 500 m / min and a dyeing liquor is sprayed onto it by means of a nozzle, whereupon the yarn is rewound onto a new carrier. A perforated disk is arranged between the dye nozzle and the running yarn, with the aid of which the dyeing liquor is sprayed onto the yarn only at predetermined and successive intervals. Composition of the dye liquor:

0.5 g / l of the red dye according to the formula from Example 1

11 g / l of the blue formazan dye according to the formula from Example 3

70 ml / l sodium silicate 38 ° Bé

15 ml / l sodium hydroxide solution 36 ° Bé

3 g / l anionic wetting agent

3 g / l penetration accelerator (aqueous solution with ethoxylated linear C ₉ -C ₁₁ fatty alcohols with terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, maleic acid bis (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester and Sodium hydroxide as main components).

The wrapped impregnated yarn is then at 6 to 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 ° C to 100 ° C) with an aqueous liquor 2 g / l detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water-soluble polymers contains, washed, and the dyed yarn is dried. Here you get a blue one Special effects yarn for weaving fabrics for blue jeans of the type Denim dyed using an indigo process. Depending on the pressure of the Impregnation nozzles, which causes a different exposure (i.e. depending on the Flow rate of the nozzles and the exit speed of the dyeing liquor) of the fiber results (% impregnation), it is therefore possible to use differently ring-colored games to produce, which gives the impression that the game is, with different strengths, with Pumice stone washed (stone wash).

Claims (16)

1. Method for continuously dyeing yarns based on cellulose fibres by the following steps:

   a) impregnating the yarn continuously and rapidly unwound from one or more carriers (1) and wound onto one or more carriers (3) with at least one fibre-reactive dye in aqueous solution and at least one alkali-acting agent in aqueous solution, the yarn being impregnated after unwinding and prior to winding, and

   b) fixing of the dye,

   characterised in that the dyes used in the dye liquors are reactive dyes from the group comprising monoazo, disazo, polyazo, metallocomplexazo, anthraquinone, phthalocyanine, formazane or dioxazine dyes, which contain at least one reactive group of the following formulae: -NH-CO-Y -SO₂-Z

   

   -W-alkylene―E―alkylene '―SO₂-Z

   

   

   

   

   

   wherein W is a group of formula -SO₂-NR₁-, -CONR₁- or -NR₁CO-,

   R₁ is hydrogen, unsubstituted C₁ to C₄ alkyl or C₁ to C₄ alkyl substituted by hydroxy, sulpho, sulphato, carboxy or cyano or a radical of formula

   

   R is hydrogen, hydroxy, sulpho, sulphato, carboxy, cyano, halogen, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkanoyloxy, carbamoyl or the group -SO₂-Z,

   Z is vinyl or a radical -CH₂-CH₂-U₁ and U₁ is a leaving group,

   Y is a radical of formula -CH(Hal)-CH₂-Hal or -C(Hal)=CH₂ and

   Hal is halogen,

   E is the radical -O- or -N(R₂)-,

   R₂ is hydrogen or C₁ to C₄ alkyl,

   alkylene and alkylene', independently of one another, are C₁ to C₆ akylene,

   arylene is an unsubstituted phenylene or naphthylene radical or a phenylene or naphthylene radical substituted by sulpho, carboxy, C₁ to C₄ alkyl, C₁ to C₄ alkoxy or halogen,

   R₃ is hydrogen or unsubstituted C₁ to C₄ alkyl or C₁ to C₄ alkyl substituted by carboxy, cyano, hydroxy, sulpho or sulphato,

   X is chlorine or fluorine,

   V is an unreactive substituent, a group which can be split off as an anion or a radical of formula

   

   

   

   

   

   or

   

   wherein R, R₁, R₃, E, W, Z, Y, alkylene, alkylene' and arylene have the meanings given above and t is 0 or 1,

   one of the radicals X₁ is a group which can be split off as an anion and the other radical X₁ is an unreactive substituent, a group which can be split off as an anion or a radical of formula (3a) to (3f),

   X₂ is a negative substituent, wherein

   in the reactive radicals of formula (2) X is fluorine and V has the meanings given above, or X is chlorine and V is a radical of formulae (3a) to (3f), and

   in the reactive radicals of formula (4) at least one of the radicals X₁ is fluorine or a radical of formulae (3a) to (3f), and

   the impregnation is carried out at ambient temperature.
2. Method according to claim 1, characterised in that the yarn is initially impregnated with at least one fibre-reactive dye in aqueous solution and is subsequently impregnated with at least one alkali-acting agent in aqueous solution.
3. Method according to claim 1, characterised in that the yarn is initially impregnated with at least one alkali-acting agent in aqueous solution and is subsequently impregnated with at least one fibre-reactive dye in aqueous solution.
4. Method according to claim 1, characterised in that the yarn is impregnated with one or more dyes which are applied individually or in a mixture and are present in the form of one or more dye liquors which contain at least one fibre-reactive dye and at least one alkali-acting agent.
5. Method according to claim 1, characterised in that the dye or dyes is/are fixed by detention of the carrier or carriers with the yarn which has been impregnated with the dye liquor or liquors.
6. Method according to claim 1, characterised in that the dye or dyes is/are fixed immediately after impregnation by treating the yarn with a hot gas, in particular air, or by treatment with saturated or superheated steam.
7. Method according to claim 1, characterised in that the unwinding, winding and treatment speeds of the yarn or yarns are at least 100 m/min, preferably at least 250 m/min.
8. Method according to any one of claims 1 to 7, characterised in that alkali carbonates or alkali hydrogen carbonates, in particular Na₂CO₃, NaHCO₃, K₂CO₃ or KHCO₃, alkali hydroxides, in particular NaOH or KOH, ammonia, organic ammonium salts, in particular ammonium formiate, acetate or tartrate, sodium trichloroacetate, borax, phosphates, polyphosphates or sodium silicate or a mixture of two or more of the above-mentioned alkali-acting agents are used as alkali-acting agent to fix the reactive dye.
9. Method according to claim 1, characterised in that the dye is fixed on the yarn of cellulose fibres by means of a cold process by detention in a store (4) containing the impregnated and wound yarn at ambient temperature for a duration of 3 to 24 hours, preferably of 4 to 10 hours and particularly preferably of 6 to 8 hours.
10. Method according to claim 1, characterised in that the dye is fixed on the yarn of cellulose fibres by detention in a store (4) containing the impregnated and wound yarn at a temperature above 40°C for a duration of up to 3 hours.
11. Method according to claim 1, characterised in that the dye is fixed to the yarn of cellulose fibres by means of a thermal process in which steam or maintenance at elevated temperature is used, or by means of a heat insulation process.
12. Method according to claim 1, characterised in that the yarn of cellulose fibres is cotton, in particular mercerised or bleached cotton.
13. Method according to any one of claims 1, 9 and 10, characterised in that the yarn or yarns issuing from the detention store (4) are dried without an intermediate washing process.
14. Method according to any one of claims 1, 9 and 10, characterised in that the yarn or yarns issuing from the detention device (4) are unwound from an intermediate creel (5) and are subsequently continuously washed and dewatered, in that the yarn is passed at high speed through a washing and dewatering unit (6) and is subsequently subjected to a drying stage in a device (7), whereupon the yarn or yarns are wound upon leaving onto new carriers (8).
15. Method according to any one of claims 1, 9 and 10, characterised in that the yarn carriers (3) issuing from the detention store (4) are subjected to a washing process in an autoclave (9) and to yarn drying in a rapid dryer (9'), whereupon the yarn from the carriers (3) is wound in a winding unit (11) onto new carriers (10).
16. Method according to claim 1, characterised in that the impregnated yarn is dried in an autoclave on winding carriers (3) by means of saturated steam or steam under excess pressure in a chamber in the form of a duct which is loaded with high frequency or infrared energy, or in a duct which is loaded with hot air or hot gas, fixing taking place at the same time.

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