MXPA96004752A - Procedure for the continuous staining of filaments with reagent dyes and apparatus to carry out this procedimie - Google Patents

Abstract

The present invention relates to a process for the continuous dyeing of filaments of cellulose fiber, which comprises the steps of: a) impregnating the filament that has been unrolled continuously at high speed from one or more supports (1) and re-wound on one or several supports (3) with at least one dye reactive with the fiber in aqueous solution and at least one alkaline reagent in aqueous solution at room temperature whose impregnation of the filament is carried out after the filament is unwound of one or several supports (3), and wherein the dye reactive with the fiber used as a reactive dye of the group consisting of monoazo, disazo, polyazo, azo dyes of metal complexes, anthraquinone, phthalocyanine, formazan, or dioxacin, the which contain at least one reactive group of the following formulas. (SEE FORMULA

Description

PROCEDURE FOR THE CONTINUOUS STAINING OF FILAMENTS WITH REACTIVE DYES AND APPARATUS TO MAKE THIS PROCEDURE The present invention is in the technical field of textiles, in particular of dyeing and very particularly of dyed textile filaments, and refers to the process for the continuous dyeing of filaments of cellulose fiber with reactive dyes. The invention also provides an apparatus for carrying out this method. Various methods and apparatuses for filament dyeing are already known. It is known, for example, a process for staining in suspension of the skeins in which the filament supplied from the rotary mill on a reel and wound on a conical reel is unwound on a skein spinning machine, in order to obtain the filament in the form of skeins, with additional handling taking place with the transport of the spools. Each skein is then fixed manually at different points and the two ends of each skein are tied together. The resulting skeins are then placed on dye racks, attached to a cart and transferred to a dyeing apparatus. After staining, the skeins are washed, their excess water is removed in a hydroextractor and the skeins are then dried either in a hot-air circulation oven or by passing them continuously through a drying tunnel. After of this drying, the skeins are again placed on a winding device to be rewound on conical reels that are used in the knitted or woven fabric. Such a dyeing process, which gives acceptable results with respect to the penetration between fibers of the dye liquor, necessitates many handling operations, resulting in relatively long process times which are full of stresses for the material and in high cost of processing. production. Coil dyeing processes are also known, in which the filament supplied from the rotary mill on a coil is wound on a conical or cylindrical coil, the edges of the coil being optionally rounded by pressure, to allow the subsequent better circulation. of a dye liquor inside the coil. According to this embodiment, another handling operation consists of stacking coils on perforated columns of the material support of a dyeing apparatus, after which this material support is placed in an autoclave and a pressure dye liquor is injected inside of the autoclave by means of a pump. After a predetermined period, the dyeing liquor is removed and washing water is injected into the autoclave. The material support is removed after the autoclave and the coils are placed in a hydroextractor to remove the excess water.

After this operation, the coils are dried in the form of batches in a drying cabinet or continuously in a high frequency oven. After drying, the filament is rewound. The excess water can also be removed by means of the devices referred to as high speed dryers, in which the unit comprising the material support and the coils is dried by means of a vacuum pump and then pressurized in an autoclave by means of a vacuum pump. medium of air or steam. In this case, additional drying is no longer necessary. Like the above procedure, said coil dyeing procedure requires many operator interventions and extends over a relatively long period, as a result of which the costs of this procedure are relatively high. On the other hand, these methods of traditional hank dyeing and coil dyeing are not capable of producing special filaments, such as chine filaments, "space" filaments, single color or multi-colored dotted filaments, or filaments with partial impregnation of the fibers, for example, those of the washed type, of the annularly dyed denim type or of the stone washed denim type. Furthermore, when cellulose fibers, such as acetate and viscous fibers, are stained, the known dyeing procedures involve a high water consumption, that is in the order of 200 to 300 liters per kilogram of dyed filament.

Such consumption of water not only has the disadvantage of the cost of the water consumed, but also that of the treatment of the water enriched with dyes and the residual chemical auxiliaries before it is discharged. However, in the case of dyes used for cellulose fibers, customary reagents should also be taken into consideration, which, when used to prepare the dye liquor, require a large amount of added salt, namely in the order of 80 to 100 grams per liter of dye liquor, of which only 60% to 70% of the mixture are fixed during the dyeing process and the remaining 30% to 40% of the mixture is discharged during washing and represents an important source of contamination, which requires a particularly careful treatment of waste water. In addition, when dyeing in the coil form and, to a lesser extent, in the form of skeins, the multiple operations of unwinding and rewinding of the filament have adverse effects on the quality of the filament product, which includes, in part, , a loss of weight and, on the other hand, a loss of the tenacity and lengthening of the filament. Devices are also known in which the processes for continuous filament dyeing is carried out by continuous impregnation of moving filaments, which are subsequently transferred to a conveyor means, which carries the filaments through steam containing chambers. I will go hot under atmospheric pressure or high pressure. Such a process called heat setting, allows the dyes to be fixed on the fibers that make up the filament. Such apparatuses make it possible in particular to dye filaments based on polyamide, polyester, polypropylene and acrylic fibers and also wool fiber blends, with a substantially reduced energy and water consumption in comparison with the treatment processes in the form of coils or skeins. These continuous treatment procedures only use acid dyes, dispersion dyes and basic dyes. The object of the present invention is to limit these disadvantages by providing a method and an apparatus for the continuous dyeing of filaments based on cellulose fibers, by means of which a substantial saving of dyes with optimum fixation and preferably effects, such as chine filaments, "space" filaments, dotted filaments of a single color or multiple colors, or filaments with partial impregnation of the fibers, for example of the washed-out type, of the annularly dyed denim type or of the denim type washed in stone. Accordingly, the present invention provides a process for the continuous dyeing of cellulose-based filaments, comprising the steps of: a) impregnating the filament that has been continuously unwound at a high speed from one or more supports and re-wound on one or more more supports with at least one dye reagent with fiber in aqueous solution and at least one alkaline reagent in the aqueous solution, and b) fixing the dye. According to a feature of the present invention, the filament is first impregnated with at least one dye reactive with the fiber in aqueous solution and then with at least one alkaline reagent in aqueous solution. According to one embodiment of the present invention, the filament is first impregnated with at least one alkaline reagent in aqueous solution and then with at least one dye reactive with the fiber in aqueous solution. According to another embodiment of the present invention, the filament can only be impregnated with one or more of the dyes that are used individually or in a mixture in the form of one or more dye liquors containing at least one dye reactive with the fiber and at least one alkaline reagent. According to another characteristic of the present invention, the fixation of the dye (s) is carried out by storing the support (s) comprising the filament impregnated with the dyeing liquor (s). According to another embodiment of the present invention, the fixation of the dye (s) can be carried out directly after the impregnation by treating the filament with a hot gas, in particular with air, or by treating it with saturated or superheated steam.

The invention also provides an apparatus for carrying out this method, which essentially comprises an apparatus for continuous high-speed unwinding of the filament ("fil") from one of the various supports, an apparatus for impregnating the filament (s) unwound with one or more dyes that are used individually or in a mixture in the form of one or more dye liquors, a device for rewinding the treated filaments on one or more supports and an agent for fixing the dyes. The invention will be better understood by virtue of the description given below, which refers to a preferred implementation, which is given only by way of non-limiting example and is explained with reference to the accompanying schematic drawings, in which: Figure 1 is a side elevational view of an apparatus for practicing the method according to the invention, Figure 2 is a side elevational view showing a possible modality of washing / dehydrating and drying operations. Figures 3 to 9 and 12 are sectional views of different embodiments of the impregnation apparatus, Figure 10 is an enlarged sectional view of an embodiment of the atomization and spray nozzle usable with the impregnation apparatus according to the invention. Figure 4 (or Figure 12, respectively), and Figure 11 is a greatly enlarged sectional view of a filament treated by the method according to the invention. According to the invention and as shown especially in Figure 1 of the accompanying drawings, the cellulosic-based filament continuous dyeing process preferably comprises the steps of impregnating the filament in an impregnation apparatus 2 with at least one dye reactive with the fiber in aqueous solution and at least one alkaline reagent in aqueous solution, the filament being continuously unrolled at high speed from one or more supports 1 and re-wound on one or more different supports 3 and fixing the dye. The method is carried out by means of an apparatus essentially comprising a device for unrolling the filaments continuously at high speed comprising one or more supports 1, an apparatus 2 for impregnating the filament unwound with one or more dyes, a device for rewinding the treated filament (s) comprising one or more different supports 3 and an agent for fixing dyes. The uncoiling, rewinding and treatment speeds of the filament (s) are preferably at least 100 m / min, in particular at least 250 m / min and more preferably at least 300 m / min. The upper limits are for example 1000 m / min and in particular 600 m / min.

The speeds of unwinding, re-rolling and treatment of the filament (s) are preferably between 100 m / min and 1000 m / min, preferably between 250 m / min and 600 m / min. The filament unwinding unit comprises one or more supports 1 which are not shown in detail in the accompanying drawings and may consist of a known form of a grid comprising spindles supporting the filament spools or on tapers with conical ends . It is also possible to unwind the filaments from a support such as a warp frame. Similarly, the rewinding device may be composed of a winding machine comprising multiple spindles or of an individual support such as a filament roll. Therefore, the filament may be unwound and rewound for example from coil to coil, from one or more coils on a filament roll, from a filament roll on another filament roll, or from a filament roll on one or more coils The dyes used in the dye liquors are reactive dyes which are suitable for dyeing cellulose materials, such as dyes from the group consisting of mono-, dis or polyazo dyes, azo dyes of metallic complex or anthraquinone, phthalocyanine, formazan or dioxane dyes containing at least one reactive group. In addition, these dyes preferably contain at least one sulfo group. It is understood that reactive groups mean radicals that are reactive with the fibers and are capable of reacting with the fibers. hydroxyl groups of cellulose or with amino, carboxyl, hydroxyl groups and mercapto groups of wool or silk or with amino groups or, if present, carboxyl groups of synthetic polyamides, with the formation of bonds covalent chemicals. In general, the reactive groups are linked to the radical directly or through a bridge element. Examples of suitable reactive groups are those which contain at least one substituent that can be removed from an aliphatic, aromatic or heterocyclic radical or those in which those radicals contain a radical capable of reacting with the fiber material, such as halotriacinyl, halopyrimidyl or vinyl radical. Examples of suitable aliphatic reactive groups are those of the following formulas: -NH-CO-Y (1), -S02-Z d a), -W-alkylene- S02-Z d b), I -W-alkylene-E-alkylene'- S02-Z (1 c), -alkylene-W-alkylene'- S02-ZO d), I R -O-alkylene-W-alkylene 'S02-Z d e), I R -W-arylene-N-alkylene-SO? -Z (1f). wherein W is a group of the formula -S02-R! -, -CONRi or, NR1CO-, R1 is hydrogen, unsubstituted C1-C4 alkyl or hydroxyl, sulfo, sulfate, carboxyl or cyano- or a radical of the formula -alkylene- S02-ZI R is hydrogen, hydroxyl, sulfo, sulfate, carboxyl, cyano, halogen, C? -C alkoxycarbonyl, C? -C4 alkanoyloxycarbamoyl or the group -S02-Z, Z is vinyl or a radical -CH2-CH2-U ? - and U is a group that comes out Y is a radical of the formula -CH (hal) -CH2-hal or -C (hal) = CH2 E is the radical -O- or -N (R2) -, R2 is hydrogen or C1-C4 alkyl, alkylene and alkylene They are, independently of one another, d-C6 alkylene, and arylene is a phenylene or naphthylene radical substituted with a sulfo-, carboxyl-, C1-C4 alkyl, alkoxy CrC4, or halogen or unsubstituted. Preferred 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 (1 B). Of particular interest are those of formulas (1) and (1a), in particular that of formula (1a). The heterocyclic reactive radicals are preferably 1,3,5-triazine radicals of the formula .N. -N- -V (2) X wherein R3 is hydrogen or alkyl unsubstituted or substituted by d-C4, carboxyl, cyano, hydroxyl, sulfo or sulfate X is a group that can be eliminated as an anion, and V is a radical of the formula R I N-alkylene-S02-Z (3a), I -N-alkylene-E-alkylene'-S02-Z (3b), I -N-arylene-S02-Z (3c), I R3 -N-arylene- (alkylene) t-W-alkylene 'S02-Z (3d), I R3 -N N- alkyl? No-S02-Z (3e) or • N-arylene-NH-CO-Y (3f), wherein R, Ri, R3, E, W, Z, Y, alkylene, alkylene, and arylene are as defined above and t is 0 or 1. Examples of the leaving group U ^ include -Cl, -Br, -F . -OS03H, -SO03H, -OCO-CH3, -OP03H2, -OCO-C6H5, -OS02-C-C4 alkyl or-OS02-N (C? -C) alkyl 2. Preferably, is a group of the formula -Cl, -OS03H, -SS03H, -OCO-CH3, -OCO-C6H5 or -OP03H2, in particular -Cl or OS03H and particularly preferably -OS03H. Alkylene and alkylene, independently of one another, are, for example, a methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or branched isomers thereof. Preferably the alkylene and alkylene are an alkylene radical of C, -C and particularly preferably an ethylene radical. R is preferably hydrogen or the group -S02-Z wherein Z has the meanings and preferences mentioned above. Particularly preferably, R is hydrogen. Ri is preferably hydrogen, C1-C4 alkyl or an alkylene-S02-Z group in which the alkylene and Z are each as defined above. Particularly preferably Ri is 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 radical 1, 3- or 1,4-phenylene which is or is not substituted, for example, by sulfo, methyl, methoxy, or carboxyl. E is preferably -NH- and particularly preferably -O, W is preferably a group of the formula -NHCO- or in particular -CONH-. X is, for example, fluorine, chlorine, bromine, sulfo, alkylsulfonyl or phenylsulfonyl of C? -C and preferably chlorine or in particular fluorine. Hal is preferably chlorine or bromine, in particular bromine. In addition, the reactive groups of interest are those of the formula (2) in which (V) is a non-reactive substituent or in particular a group that can be eliminated as an anion. V as a group which can be eliminated as an anion is for example fluorine, chlorine, bromine, sulfo, alkylsulfonyl or phenylsulfonyl of C? -C4 and preferably chlorine and in particular fluorine. V as a non-reactive substituent may be, for example, a hydroxyl radical, Ci-Ct alkoxy, C? -C alkylthio, amino, N-C1-C4 alkylamino or N, N-di-C! C4 wherein the alkyl is unsubstituted, for example, by sulfo, sulfate, hydroxyl, carboxyl or phenyl, or it can be a cyclohexylamino, morpholino or N-C 1 -C 4 -N-phenylamino or phenylamino or naphthylamino radical where the fenium or naphthyl is or is not substituted, for example, by alkyl , C 1 -C 4 alkoxy, carboxyl, sulfo or halogen. Examples of 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, methoxy, ethoxy, n- or isopropoxy and hydroxyl. As a non-reactive substituent, V is preferably amino, NC? -C4-alkylamino which is unsubstituted in the alkyl or substituted by hydroxyl, sulfate or sulfo, or is morpholino, phenylamino or N-Cn-C-alkyl-N-phenylamino wherein each phenyl is or is not substituted by sulfo, carboxyl, methyl or methoxy. Particularly preferred meanings are phenylamino or N-C 1 -C 4 -N-phenylamino alkyl wherein each phenyl is or is not substituted by sulfo, carboxyl, methyl or methoxy. Here and then, the preferred radicals of the formulas (3a) to (3f) 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). Of particular interest are those of the formula (3c). Preferred heterocyclic radicals of the formula (2) are those in which X is fluorine and V has the meanings and preferences mentioned above, or X is chlorine and V is a radical of the formulas (3a) to (3f). The reactive heterocyclic radicals that are of interest are also those of the formula wherein one of the radicals Xi is a group that can be eliminated as an anion and the other radical Xi has the meanings and preferences given for V as a non-reactive substituent or is a radical of the formulas (3a) to (3f) or a g rupe that can be eliminated as an anion, X2 is a negative substituent, and R3 independently is as defined above. The radical Xi which can be eliminated as an anion is preferably chlorine or in particular fluorine. Examples of suitable X2 radicals are nitro, cyano, C?-C, alkylsulfonyl, carboxyl, chloro, hydroxyl, C 1 -C 4 alkoxysulfonyl, C 1 -C 4 alkylsulfonyl, d-C 4 alkoxycarbonyl or C ?C alkanoyl, the preferred meanings being X2 chloro, cyano and methylsulfonyl, in particular chlorine. Of particular preference at least one of the radicals Xt is fluorine or a radical of the formulas (3a) to (3f). Of very particular preference, one of the radicals Xi is fluorine and the other radical Xi is fluorine or chlorine with X2 having the meanings and preferences mentioned above. Of particular interest for the process according to the invention are those reactive groups containing a radical of the formula -S02-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 (1a) to (1d), in particular those of the formulas (1), (1a) to (1c), and the reactive radicals of the formula (2) wherein X is fluorine and V has the meanings and preferences mentioned above or, wherein X is chlorine and V is a radical of formulas (3a) to (3f), and reactive radicals of formula (4) in which one of the radicals Xi is fluorine or a radical of the formulas (3a) to (3f), in particular those in which Xi is fluorine and the other radical Xi is fluorine or chlorine and X2 has the meanings and preferences mentioned above. Very particularly preferred reactive groups are those of formulas (1), (1a) and (1b), in particular those of formulas (1), (1a) and (1b), in particular those of formulas (1) and (1a), and preferably those of the formula (1a), and the reactive radicals of the formula (2) wherein X is fluorine or chlorine and V is a radical of the formulas (3a) to (3f), and the reactive radicals of the formula (4) in which Xi is fluorine and the other radical Xi is fluorine or chlorine and X2 has the meanings and preferences mentioned above. Reactive groups which are of particular interest are those of formulas (1), (1a) to (1f) and (2) wherein the radicals have the meanings and preferences mentioned above.

The reactive dyes may contain, apart from the reactive groups, customary substituents in the organic dyes which are attached to their basic structure. Examples of such substituents of the reactive dyes include: alkyl groups having from 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, or butyl wherein the alkyl radicals may be further substituted, for example, by hydroxyl, sulfo or sulfate; alkoxy groups having 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 sulfate; phenyl which is or is not substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo; acrylamino groups having from 1 to 8 carbon atoms, in particular alkanoylamino groups such as, for example, acetylamino or propionylamino, benzoylamino which is or is not substituted on the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or sulfo; phenylamino which is or is not substituted on the phenyl ring by C 1 -C 4 alkyl, C 1 -C alkoxy, halogen or sulfo; N, N-di-β-hydroxyethylamino; N, N-di-β-sulfoethylamino; N, N-di-β-sulfatoethylamino; sulfobenzylamino; N, N-disulfobenzylamino; alkoxycarbonyl having from 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; alkylsulfonyl having from 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; Not me; cyano; halogen, such as fluorine, chlorine or bromine; carbamoyl; N-alkocarbamoyl having 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono or N, N-di-dialkylsulfamoyl having each of 1 to 4 carbon atoms, such as N-methylsulphamoyl, N-ethylsulphamoyl, N-ethylsulphamoyl, N-propylsulphamoyl, N-isopropylsulphamoyl or N-butylsulphamoyl wherein the alkyl radicals may be further substituted, for example, by hydroxyl or sulfo; N- (β-hydroxyethyl) sulfamoyl; N, N-di- (β-hydroxyethyl) sulfamoyl; N-phenylsulfamoyl which is or is not substituted by C 1 -C 4 alkyl, C 1 -C alkoxy, halogen, carboxyl or sulfo; ureido; hydroxyl; carboxyl; sulfomethyl or sulfo. The reactive dyes preferably contain at least one sulfo group or sulfate, in particular 1 to 6 such groups and preferably 2 to 6 such groups. Examples of suitable reactive dyes include those of the formula wherein A1 is the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye and U is a reactive radical, the radical reagents U here and below have in particular the meanings and preferences above mentioned. In addition, the radical A1 may contain one or more reactive groups U that are identical to or different from each other. The total number of reactive groups in the dyes is preferably from 1 to 3, more preferably from 1 to 2, and more preferably 2. Additional examples of suitable reactive dyes are those of the formula where R. R5 Re and R, independently of one another, are hydrogen or substituted or unsubstituted C 1 -C 4 alkyl, X 1 'and X 2' are halogen, B 1 is an aliphatic or aromatic bridge member or the radical of the formula -N (R 5) -B1-N (Rß) - is a piperazine radical, and A2 and A3, independently of one another, have the meanings given above for Ai. The radicals R, R5, R6 and R7 as alkyl radicals are straight or branched chain. The alkyl radicals can be further substituted, for example, by hydroxyl, sulfo, sulfato, cyano or carboxyl. Examples include the following radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl and the hydroxyl, sulfo, sulfate, cyano or substituted radicals carboxyl. Preferred substituents are hydroxyl, sulfo or sulfate, in particular hydroxyl or sulfate, and preferably hydroxyl. Preferably, R4) R5, Re and R7 are hydrogen or C? -C alkyl, in particular hydrogen. X1 'and X2', independently of one another, are preferably chlorine or fluorine, in particular fluorine. A preferred aliphatic bridge member B1 is, for example, an alkylene radical of C-C12, in particular an alkylene radical of C2-C6 which may be interrupted by 1, 2 or 3 members of the group consisting of -NH-, - N (CH3) - or in particular -O- and whether or not it is substituted by hydroxyl, sulfo, sulfato, cyano or carboxyio. Preferred substituents of the alkylene radicals given for B1 are hydroxyl, sulfo or sulfate, in particular hydroxyl. Additional examples of suitable aliphatic bridge members Bi are C5-C9 cycloalkylene radicals, such as, in particular, cyclohexylene radicals. The aforementioned cycloalkylene radicals can, if desired, be substituted by C 1 -C 4 alkyl, C 1 -C alkoxy, C 2 -C 6 alkanoylamino, sulfo, halogen or carboxyl, in particular C 1 -C 4 alkyl. The aliphatic bridging members further include methylenecyclohexylenemethylene radicals which are or are not substituted in the cyclohexylene ring by C 1 -C 4 alkyl. A piperazine radical as a radical of the formula -N (R5) -B1- N (R6) - is, for example, a radical of the formula / \ N N \ / An aromatic bridging member B i is, for example, a Ci-C 6 alkylenephenylene or phenylene each of which is or is not substituted by C 1 -C 4 alky, C 1 -C alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxyl or is a radical of the formula wherein the benzene rings I and II are or are not substituted by C? -C alkyl, C? -C4 alkoxy, C2-C4 alkanoylamino, sulfo, halogen or carboxyl and L is a direct bond or a C2-C10 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-, -NHCO-, -NH-CO -NH-, -O-, -S- or -S02-. As the aromatic bridge member Bi is preferably phenylene which may be substituted as indicated above. Preferably, the aromatic bridge members given for B i are or are not substituted by sulfo. Preferably, B i is a C 2 -C 12 alkyne radical which can be interrupted by 1, 2 or 3 members from the group consisting of -N H-, -NH (ch 3) - or -O- and is or not its substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl; or is a C5-C9 cycloalkylene, a alkylene phenylene of d-C6 or a phenylene radical each of which is or is not substituted by Ci-C4 alkyl, C? -C alkoxy, C2-C4 alkanoylamino, sulfo, halogen or carboxyl; or B1 is a radical of the formula (7) in which the benzene rings I and II are or are not substituted by C1-C4 alkyl, C? -C4 alkoxy, C2-C alkanoylamino sulfo, halogen or carboxyl and L is a direct bond or a C 2 -C 0 alkylene radical which may be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridging member of the formula -CH = CH-, -N = N-, -NH -, -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- or -S02-. or the radical of the formula - ÍRsJ-Bi-N-ÍRe) - is a piperazine radical of the formula - N N- \ / Particularly preferably, B1 is a C2-C12 alkylene radical which can be inter-mixed by 1, 2 or 3 members -O- and is or is not substituted by hydroxyl, sulfo, sulfate, cyano or carboxyl, or is a phenylene radical which is or not substituted by dd alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxyl. Most particularly, Bi is preferably an alkylene radical C2-C12, in particular a C2-C6 alkylene radical, which can be interrupted by 1, 2 or 3 members -O- and whether or not it is substituted by hydroxyl. The reactive dyes of the formula (6) which are of particular interest are those in which at least one of the radicals Xi ' and X2 'is fluorine or Xi' and X2 'are chlorine and at least one of the radicals A2 and A3 contains a reactive group. The monoazo, polyazo or azo metal complex dye radicals such as Ai, A2 and A3 preferably include the following: Mono or disazo dye radicals of the formula: D-N = N- (M-N = N) U-K- (8) or D-N = N- (M-N = N) U-K (9) where D is the radical of a diazo component from the benzene or naphthalene series, M is the radical of a middle component from the benzene or naphthalene series, K is the radical of a coupling component from the benzene, naphthalene, pyrazolone, 6-hr idroxypyrid-2-one or acetoacetaryl amide series yu is 0 or 1 where D, M and K can carry customary substituents for azo dyes, for example dd alkyl or Ci-d alkoxy which it is desired to be further substituted by hydroxy, sulfo or sulfate, or halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C2-dinoxylamino, benzoylamino which is or is not substituted on the phenyl ring by C 1 -C 4 alkoxy, C 1 -C 4 alkoxy, halogen or its lfo, or phenyl which is or is not substituted by alkoyl dd. alkoxy d-C4, halogen, carboxyl or sulfo, and the radicals reactive with fiber. The metal complexes are also suitable derivatives from dyes of formulas (8) and (9), which are in particular 1: 1 copper complex azo dyes from the benzene and naphatalene series in which the copper atom is attached to a metalatable group each , for example a hydroxyl group, on both sides in the ortho position relative to the azo bridge. If the dye radicals of formula (8) and (9) bear a reactive radical, the latter has the meanings and preferences mentioned above. The dye radicals of formulas (8) and (9) are preferably those of the formulas wherein (Rβ) or -3 represents 0 to 3 identical substituents or different from the group consisting of C?-Calkyl, C?-Calkoxy, C 2 -C 4 -alkylamino, ω-C 4, its l-hamoyl, carbamoyl, sulfomethyl , halogen, nitro, cyano, trifluoromethyl, amino. Hydroxyl, carboxyl and sulfo, (Rg) o-2 represents 0 to 2 identical substituents of the group consisting of hydroxyl, amino, N-mono-alkylamino dd, N, N-di-alkylamino C? -C4, alkanoylamino C2 -C and benzoylamino, and (U) o-2 represents O to 2 identical or different reactive groups; wherein (R9) 0-2 and (U) 0-2 are as defined above; wherein (R? o) o -3 and (Rn) o-3, independently of one another, represent 0-3 identical or different substituents of the group consisting of C? -alkyl, C? -C4 alkoxy, halogen , carboxyl and sulfo, and (U) o-2 is as defined above; wherein R 2 and R 4, independently of one another, are hydrogen, alkyl or C 1 -C 4 phenyl, and R 3 is hydrogen, cyano, carbamoyl or sulfomethyl; wherein (R? 6) or -3 represents 0 to 3 substituents identical or different from the group consisting of dd alkyl, C1-C4 alkoxy, halogen, carboxyl and sulfo, (Rid) o-3 and (i7) o- 3. independently of one another, they have the meanings given above for (R8) or -3, and (U) or -2 is as defined above; wherein (R? 5) or -3, (Ri7) or -3 and (U) 0-2 are as defined above and (R? 8) or-2 represents 02 substituents identical or different from from the group consisting of alkyl d-C, alkoxy d-d. halogen, carboxyl, sulfo, hydroxyl, amino, N-mono-alkylamino C? -C4, N, N-di-C1-C4 alkylamino, C2-C4 alkanoylamino and benzoylamino. Examples of suitable formazan dye radicals are those of the formula wherein (U) 0-2 is as defined above and the benzene rings do not contain any additional substituents or are substituted by C 1 -C 4 alkyl, d-alkoxy, alkylsulfonyl d-d. halogen or carboxyl. Example of suitable phthalocyanine dye radicals Ai A2 and A3 are those of the formula wherein Pe is the radical of a metal phthalocyanine, in particular the phthalocyanine radical of copper or nickel phthalocyanine, W is -OH- and / or -NR20R20R2o and R2o ', independently of one another, are hydrogen, or d-C4 alkyl which is or is not substituted by hydroxyl or sulfo, R19 is hydrogen or C? -C alkyl. A is a phenylene radical that is or is not substituted by C? -C, halogen, carboxyl or sulfo alkyl, or is a C2-C6 alkylene radical, and k is 1 to 3. Examples of suitable dioxane dye radicals Ai, A2 and A3 are those of the formula wherein A 'is a phenylene radical which is or is not substituted by d-C4 alkyl, halogen, carboxyl sulfo or is a C2-C6 alkylene radical, r, s, v and v', independently of each other, are each 0 or 1. And Z is as defined before. Examples of suitable anthraquinone dye radicals A, A2 and A3 are those of the formula wherein G is a phenylene radical that is or is not substituted by d-C4 alkyl, C? -C4 alkoxy, halogen, carboxy or sulfo or is a cyclohexane, phenylenemethylene or C2-C6 alkylene radical. The above dye radicals of formulas (10a) to (1 Of) and (11) to (14) preferably each contain at least one sulfo group, in particular 1 to 4 sulfo groups, and preferably 1 to 3 groups sulfo Suitable reactive radicals U are, in particular, the aforementioned reactive radicals having the previously mentioned preferences. Preference is given to the dye radicals of formulas (10a) to (1 Of), (11) and (14), in particular those of formulas (10a) to (1 Of) and (11), and preferably those of the formulas (10a) to (1 Of) The reactive dyes are known or can be obtained analogously to the known preparation methods, such as diazotization, coupling and condensation reaction. The amount of dye in the dye liquor can vary widely as a function of the desired color depth and is, for example, up to 100 g / l of the liquor, preferably 10 g / l to 70 g / l, in particular 10 g / l. g / l up to 50 g / l of the staining liquor.

The use of dyes that have a low to medium fiber affinity is recommended. The dye liquors used according to the invention may contain one or more dyes. The alkaline reagent used to fix the reactive dyes comprises, for example, alkali metal carbonates or alkali metal bicarbonates, in particular NaCO3, Na HC03, K2C03, or KHC03, alkali metal hydroxides, in particular NaOH or KO H, ammonia, organic ammonium salts, for example ammonium formate, ammonium acetate or ammonium tartrate, sodium trichloroacetate, borax, phosphates such as trisodium phosphate, polyphosphate or sodium silicate or a mixture of two or more of the aforementioned alkaline reagents. It is recommended for use, as an alkaline reagent, a mixture of an aqueous solution of sodium hydroxide and sodium silicate. Apart from the dye and the alkaline reagent, the dye liquor may contain other common additives, for example wetting agents, solubilizing agents, for example, e-caprolactam or polyethylene glycol, penetration accelerators, electrolytes, for example, chlorine sodium or sodium sulfate and, complex formation agents, such as urea and glycerol. After the absorption of the dye and the alkaline reagent, the dye is fixed on the filament based on cellulose fibers by a thermal method or else by a low temperature method.

If fixation takes place through the application of heat, a method involving the application of steam or maintenance at elevated temperature or a method of thermal insulation is possible. Examples of filaments of cellulose fiber include cotton, in particular mercerized and / or white cotton, or else unbleached filament which can be advantageously dyed by the process according to the invention without being previously washed. . Such a staining operation can not be carried out using the staining materials known hitherto. The combined filaments based on cellulose, for example cotton / polyamide combination filaments or especially the cotton / polyester combination filaments, are also suitable. Suitable filaments also include viscous materials, for example "Tencel" or "Lyocell" and, the corresponding combination fibers with cotton, for example cotton / Tycra "(polyurethane elastomer) The process according to the invention makes it possible to dye filaments of cellulose at a high speed, that is to say, at high performance.In addition, it is possible to produce filaments that inhibit special effects, such as the filament of chiné, the filament of "space", the single-color or multi-colored dotted filament , or the filament with partial impregnation of the fibers, for example those of the washed type, of the type of denim dyed anularly or of the type of denim washed in stone.

Until now, different effects could only be obtained by means of a combination of several fibers colored in different ways during spinning, but not by a dyeing process. The impregnation apparatus 2 (see for example Fig. 1) comprises one or more of the dye liquors, in which the filament is impregnated during its passage through the apparatus 2. Upon leaving the latter, the liquor (s) The dyes present in the filament diffuse into the interior of the fibers that make up this filament. The essential components of these dye liquors, specifically the reactive dye and the alkaline reagent, which are in aqueous solution, can be provided in separate containers or as a mixture in a single container. Providing the dye and alkaline reagent in separate containers ensures high stability of the dye liquor and avoids having to replace the latter at regular intervals due to hydrolysis by the alkaline reagent. In the case where the dye liquor is applied as a mixture, ie when the reactive dye and the alkaline reactant are present in aqueous solution, it is possible to provide the two solutions in separate storage tanks and mix them in a tank of intermediate buffer storage before application. In this way, only a small amount of the dye liquor is affected by the hydrolysis over time and It can be removed or replaced when necessary, especially in prolonged detentions of the staining cycle. The impregnation of the filament with the dyeing liquor (s) is regulated in such a way that the collection of the liquor of the filament is between 15 and 100% by weight, preferably about 15 to 80% by weight and more preferably about 15 to 100% by weight. 15 to 50% by weight. To that impregnation, the staining liquor, after the filament has left the impregnation apparatus 2, can diffuse into the interior of the fibers. The impregnation is preferably carried out at a temperature of 5 to 95 ° C, in particular 10 to 80 ° C. Preferably, this temperature is 10 to 70 ° C, in particular 15 to 60 ° C. Particular preference is given to a temperature of 15 to 50 ° C, in particular 15 to 40 ° C. When this treatment is carried out, not only the temperature of the filament to be impregnated but also the temperature of the dye liquor during the impregnation corresponds to one of the above temperatures. It is of particular interest that the impregnation is carried out at room temperature, for example from 15 to 40 ° C, which makes completely unnecessary the use of a heating device before and in particular during the impregnation step. Preferably, the above preferences also apply to the step of winding the filament on one or more supports 3. A variant of the process in which the filament is treated at an elevated temperature prior to the operation is also of interest. of impregnation (impregnation apparatus 2). This treatment can be carried out, for example, before or after the support 1. Preferably the treatment at elevated temperature is carried out continuously. The treatment can be carried out, for example, in a chamber that is fed with hot gas or preferably hot steam. In this chamber you can let the filament circulate. Such a chamber may be present between the support 1 and the impregnation apparatus 2. Said chamber further, or as an alternative, may be present between the impregnation apparatus and the support 3. After being rolled up, each filament is stored in unit 4. During storage, the dyes absorbed onto the filament as a result of impregnation in the apparatus 2 are dispersed within the fibers of the filament. This treatment is known as a low temperature fixation, which is preferred in the current procedure. This type of fixing causes the dyes to be fixed in the fibers, depending on the quality of the filament and the type of selected dyes, at a degree of fixation in the order of 80 to 95%, in relation to the coloring composition. This fixing of the dye at low temperature on the filament, which takes place by storing the impregnated and wound filament, is carried out, for example, at an ambient temperature, for example, at a temperature between 10 and 40 ° C, in particular between 15 and 40 ° C. 35 ° C. The duration of the treatment at low temperature may depend on the dye used and varies within limits broad, which vary from 3 to 24 hours, preferably from 4 to 10 hours, and of particular preference from 6 to 8 hours. A fixing treatment corresponding to high temperature is also possible, in which the dye is fixed on the cellulose fiber filament by storage at a temperature above 40 ° C, in particular up to 70 ° C and preferably from up to 60 ° C, in a storage unit (4) containing the impregnated and rolled filament. The duration of treatment may depend on the dye used and varies within wide limits. Preferably, the duration of the treatment is up to 3 hours, in particular 0.5 to 3 hours, and preferably 1 to 3 hours. The feeding of the apparatus according to the invention depends on the intended requirements or the desired production indices and can be carried out with a single filament or with several filaments of any linear fiber density or type., in different ways. Therefore, one or more filaments can be unrolled from multiple supports 1 or a single support and wound up on multiple supports 3 or a single support. However, before unrolling from the supports 1, preparatory operations can also be carried out, which may consist in particular of re-coiling from tapering ends. According to a feature of the invention, the filament or filaments, after leaving the storage unit 4, are dried directly without an intermediate washing operation and are used directly in particular for braiding or knitting products. In such a case, the resulting textile product is washed, squeezed and dried, next to the braid or knitted fabric or immediately after the making operation. In this case, unfixed dyes and alkalis, silicates and other auxiliaries are removed by the washing operation of the braided fabric, the knitted fabric or the final textile product. Such a procedure is of particular interest for velor fiber materials. This drying operation can be carried out in the same way in an autoclave by means of a saturated or pressurized steam, in a chamber in the form of a tunnel to which high frequency or infrared energy is supplied or in a tunnel provided with hot air or gas hot, taking place at the same time. If the drying is carried out in a steam autoclave, the textile filament impregnated with the dye liquor is subjected to a treatment in a chamber with, if desired, superheated steam at an operating temperature of between 98 and 210 ° C, advantageously between 100 and 180 ° C, preferably between 102 and 120 ° C. If the treatment is carried out by maintaining at elevated temperature, the impregnated cellulose based filament is left in the wet condition in the autoclave for 1 to 120 minutes, for example at a temperature between 80 and 120aC. The fixing of the dye by the thermal insulation method can be carried out with or without intermediate drying, for example at a temperature between 100 and 210 ° C, advantageously between 120 and 200 ° C, and especially between 140 and 180 ° C. Depending on the temperature of the treatment, the thermal insulation is prolonged for a period between 20 seconds and 5 minutes, preferably between 30 and 60 seconds. According to another feature of the invention, the filament (s), after leaving the storage unit 4, can also be unwound from an intermediate grid 5 and then washed, for example, continuously squeezed while moving at high speed in a washing and squeezing unit 6, before being subjected to drying in an apparatus 7 after which the filaments are re-wound on new supports 8 (Figure 1). The apparatus for carrying out this procedure has an intermediate grid 5, which is comparable with the apparatus for unrolling filaments from the supports 1, and the new reinforcement supports 8 are activated by a device similar to the unit for rewinding the filaments on one or more supports 3. Fig. 2 of the attached drawings shows a method of the method according to the invention and of the apparatus according to the invention, in which the supports 3 leaving the storage unit 4 are subjected to the operation of washing in an autoclave 9 and to a drying operation of the filament in a high-speed dryer 9 ', the filament being re-wound from the supports 3 on new supports 10 in a rewinding unit 1 1. In such a case, the supports 3 can be placed on perforated columns of a material support, for the purpose of to be washed by the countercurrent circulation in an autoclave 9, after which the material support is transferred to the high speed dryer 9 ', in which the moisture of the filaments present on the supports is removed by the application of pressure to the chamber forming the high speed dryer 9 'and sucking the air through the filaments on the supports 3 by means of the perforated columns of the material support. The filaments rewound on the supports 8 or 10 are filaments that have been freed from the excess dyes and other components of the dye liquors and are perfectly stable with respect to the dyeing produced thereon, ie there is no longer any risk of dyeing. that the dye is washed out and are suitable for use in braiding fabrics or knitted fabric, without requiring a subsequent washing of the braided fabric or knitted fabric. These filaments of cellulose fiber then have a moisture content of, for example, 8 to 12% in a normal textile environment, ie at 22 ° C and at a relative humidity of 65%. As shown in Figure 3, the impregnation apparatus 2 can be composed of a dye liquor duct 12 which is held at a constant level by a feed pump 13 which is linked to a storage tank containing the dye liquor 14 which, if desired, is heated by a heat source 15, the filament (s) to be impregnated being unwound in the dye liquor by means of return rods and by means 16 for squeezing the excess dye on the filament or filaments with compressed air whose pressure can be regulated, the whole unit being placed in a chamber 17 for the recovery of the squeezed dye and being provided with openings through which the filaments can pass. Such an embodiment of the impregnation apparatus is especially suitable for dyeing combined with a dye liquor in the form of a mixture of dye and alkaline reagent. The squeezing means 16 consists of a container which is provided with two openings through which pass the filaments charged with dye liquor and which are subjected to super-atmospheric pressure. As a result of the super-atmospheric pressure generated in the container through which the filaments pass, a substantial portion of the dye liquor remaining on the filament is squeezed out of the latter and discharged through the openings in the container. This makes it possible to obtain, at the outlet of the apparatus 2, a filament exhibiting a liquor collection in the order of 15 to 100% by weight, which is regulated as a function of the air pressures used in the means 16. Figure 4 shows an embodiment of the impregnation apparatus 2, wherein the latter comprises a plurality of means 18 for gating and supporting each filament longitudinally, in at least one nozzle 19 for atomization and spraying of the dyeing liquor. on the moving filament (s), an apparatus 20 for squeezing excess liquor from staining and, a unit 21 for the continuous supply of the dyeing liquor, which is connected to the atomization and spray nozzles 19 and to a duct 22 to receive the excess atomized dye liquor and / or squeezed spray, this duct 22 forming the bottom of the chamber constituting the impregnation apparatus 2. By providing a succession of atomization and spray nozzles 1 9, depending on the desired effect an improved impetus of the filament can be obtained, as a result of which penetration of the dye liquor into and between the fibers constituting the filament can, if desired, be improved. By using such an apparatus it is possible to modify the spray pressure of the dye liquor, the number of rows of nozzles and their distance from the filament and also, the diameter of the dies and their angle of atomization and spray with respect to the filament that is moves, so that different levels of annular or central staining can be obtained. Further, by means of this impregnation apparatus according to Fig. 4 (or Fig. 12, respectively), the spraying of the reactive dyes and the alkaline reagent can be effected separately, the latter being sprayed before or after the Reactive dye. As a result, the dye and the reagent are not previously mixed, avoiding as much as possible any hydrolysis of the dye by the reagent. For this purpose, it is particularly advantageous to first impregnate the filament with an aqueous solution of reactive dye and then with the alkaline reagent. In this case, the Excess dye return to the duct to receive the excess liquor is not contaminated by the alkaline reagent and does not undergo hydrolysis, thus ensuring the long term stability of the liquor. The apparatus 20 for squeezing the excess dye liquor is preferably in the form of a supporting anvil 23 for the moving filament (s) which is slightly elevated with respect to the horizontal feed direction of the filaments and is equipped , on the upstream side of the filaments, with a groove or rounding and with a nozzle 24 for blowing compressed air, which directs a jet of air over the filaments. Therefore, due to the slightly forced change of direction of the filament by means of the anvil 23 and the blowing of compressed air, it is possible to remove or squeeze the excess dye liquor at the site of this change of direction, from the nozzle 24, by means of a combination of mechanical and pneumatic drying. The squeezing device 20 can, of course, also be used in the embodiment of the impregnation apparatus according to Figure 3, instead of the squeezing means 16 and vice versa. In order to promote the efficient imaging of the filaments and the diffusion of the dye liquor into the individual fibers constituting the filament, the impregnation apparatus 2 according to FIG. 4 is advantageously used with a plurality of dye liquors. spray and atomization nozzles 19.

According to another embodiment of the invention, it is equally possible to provide a support plate 25 under the filaments, at right angles to each atomization and spray nozzle 19, to support the filament. This embodiment is shown in FIG. 4 of the accompanying drawings, at right angles to a nozzle 19. In this way, the filaments are held in place and protected against any deviation that would move them away from the corresponding nozzles. , thus ensuring the best impregnation by the jet and the best penetration of the dye liquor inside the fibers. In fact, the kinetic energy of the dye liquor sprayed on the filament exhibits an optimum effect if the filament rests on a fixed support and if the dye jet can hit the filament without the possibility of the filament moving away. The guide and support means 1 8 in turn prevent any deviation in a horizontal plane away from the longitudinal axis of the filaments. Figure 4 (or Figure 12, respectively) of the accompanying drawings further show another embodiment of the invention, in which at least two atomization and spray nozzles 19 are diametrically opposed to the longitudinal axis of movement of the filaments that they will be dyed or treated. In such an embodiment, the impregnation and penetration of the dye liquor between and within the fibers at right angles for each pair of nozzles 19 was optimized due to the fact that the kinetic energies of the two opposite jets are added. According to another embodiment of the invention, not shown in the accompanying drawings, it is possible to provide, in the impregnation apparatus 2, a succession of vaporization nozzles 19 between each of which is inserted a squeezing apparatus 20 formed by an anvil 23 and an air blowing nozzle 24. Such an arrangement makes it possible to subject each moving filament to the successive operations of mechanical impregnation and drying, giving as a result the best impregnation of the filament with the dyeing liquor and therefore in the optimization and acceleration of the impregnation and diffusion of the dyeing liquor through all the fibers and inside the interior of all the fibers of the filament, depending on the desired effect. According to another characteristic of the invention, the nozzles 19 can also be designed in the form of piezoelectric nozzles (drop-over-order type), thermal nozzles (of the bubble-jet type) or high-frequency nozzles with jet continued or diverted. FIG. 10 of the accompanying drawings shows by way of example a high frequency nozzle 19 'in which a high frequency drip generator 38 supplies droplets through a charging device 39, a detector 40 and a baffle 41. which drops the drops either on a filament 42 or to recycling media. In this way a very precise application of the dyeing liquor can be effected.

Figure 5 of the accompanying drawings shows another embodiment of the impregnation apparatus 2 in which a dye storage tank 26 is connected by means of a feed line and a pump 27 to a pressurized impregnation channel 28 formed, for each filament or for a plurality of filaments, for an inal length tube through which the filaments pass in their longitudinal direction, a unit 29 for squeezing the excess staining liquor which is placed downstream of this channel 28, the dye liquor discharged from the pressurized channel 28 and which comes from the squeeze unit 29 is recovered at the bottom of the chamber forming the apparatus 2 and is returned to the storage tank 26 through a line 30. According to With a feature of the invention, the pressurized channel 28 can be designed in tubular form, which is particularly suitable for the staining of unitary fibers., or in the form of a rectangular elongated box for the staining of multiple fibers in a sheet or core form. The cross section and the length of such channels can be selected such that the contact time of the filament with the dye liquor can be varied as a function of the filament velocity and the relative velocity of the dye liquor circulating in the filament. The channel can be varied with respect to the speed of the filament in the same channel. All these factors can influence the contact effect of the dye liquor with the filament and its constituent fibers.

It is also possible to cause the pressurized dye liquor to reach channel 28 at intervals, in order to take into account the different speeds of the dyeing liquor and of the filament, due to the fact that upstream, with respect to the direction of movement of the dye. filament, the speeds of the filament and the liquor under pressure are added, while downstream they are subtracted. According to another characteristic of the invention, the pressurized impregnation channels 28 can be provided, on their internal surface extending parallel to the direction of movement of the filament, with rough sections or obstacles or surface deformations. The latter generate a non-lamellar flow of the dye liquor and the turbulences thus obtained favor the formation of strong local pressures and the agitation which is also favorable for the filament, resulting in rapid impregnation, if this effect is desired. In the embodiment according to Fig. 5, the squeezing unit 29 may be composed of either a pressurized vessel through which the filament loaded with the dyeing liquor passes or by means of a combination of anvil and blowing nozzle. air. In addition, due to the fact that the filaments are immersed in a dyeing liquor under pressure during impregnation, the fibers constituting the filaments are rapidly and deeply surrounded by the dyeing liquor, with the result that the diffusion of the dyes inside the fibers starts from most efficient way during the im pretion. In addition, the relative velocity between the moving filament and the dye liquor in channel 28, which is in the form of a tube or in a different form, reinforces the uniform impregnation of the fibers constituting the filament. Figure 6 of the attached drawings shows another embodiment of the impregnation apparatus 2, in which the latter is in the form of an impregnation cushion-rolling machine 31 composed of two horizontal cylinders which together with its surface line are in contact between and on which the provision is made for a constant supply of dyeing liquor and, from a disposition of lateral tabs that are leak proof 31 'at the ends of the cylinder, the filaments being impregnated when passing between the cylinders. According to another embodiment of the invention, it is also possible, as shown in Figure 9 of the accompanying drawings, to design the impregnation apparatus 2 in the form of a contact impregnation drum 32 which is immersed in a dyeing liquor and applying the dye by contact to the moving filaments which are guided by means of return rolls 33 or a similar device on a portion of the circumference of the drum, the position of those return rolls 33 being adjustable with respect to the drum 32. In this way it is possible to modify the degree of impregnation of the filaments by moving the rollers 33 away from or near the tam 32, so that more contact is obtained large or shorter, smaller or larger of the filament with the drum, which has entered a certain amount of the dye liquor during the rotation. The degree of impregnation can also be modified by acting on the speed of rotation of the drum 32 and, consequently, on the relative speed of the filament with respect to the drum. This action on the relative speed can be increased by modifying the direction of rotation of the tam 32. The reason for this is that, in the case where the rotation of the drum 32 is opposite to the direction of movement of the filament, the latter exerts on the dye liquor film which is accessed by the drum an impregnation effect, resulting in the best penetration of the liquor in the filament fibers. Finally, by adjusting the viscosity of the dyeing liquor, the degree of collection of liquor by the moving filament can be varied. The apparatus according to Figure 9 is particularly suitable for effecting partial impregnations of the filament, of the ring staining type, or only a portion of the periphery of a filament. If there is only a slight contact of the filament with the drum 32 and the drum 32 is lightly coated with the dyeing liquor, it is possible in fact to impregnate only a portion of the circumference of the filament on its surface. FIGURE 1 1 of the accompanying drawings, which shows a sectional view of a filament treated according to the invention on a greatly enlarged scale, illustrates perfectly the partial impregnation of the filament on the peripheral fibers of the lower portion of the filament. The fibers impregnated in the surface are therefore shown with thick profiles, while the undyed fibers are shown in thin lines. In the case of core staining, since it can be obtained in particular by impregnation 2 according to Figures 3 to 6 and 12, all the fibers constituting the filament are impregnated by the staining liquor which, after If it is absorbed in the periphery of the fibers, it will flow into it. According to another embodiment of the invention, and as shown in the sectional view in Fig. 7a of the accompanying drawings, the impregnation apparatus 2 may also be composed of a dyeing machine equipped with multiple applicators each assigned to a different dyeing liquor and each one supplies in succession, in sequences of identical or unequal lengths, dots of different dyes. An impregnation apparatus of this type allows, in particular, the production of filaments with effects of preference such as those known as "single-color or multi-color filaments of space", filaments of the chiné or dotted type or of the A washed out or denim type A dyeing machine comprising multiple applicators that can be used for this purpose is described in particular FR-A-2, 650.31 1 and FR-A-2, 719,058 Figure 7a attached drawings shows a possidesign of a plicator of said machine, therefore, the staining liquor fed into the atomization apparatus 34 comprising nozzles which are each positioned at right angles to the axis of movement of one or more filaments is sprayed in succession by means of these nozzles through a slot 35 provided in a disk 36 (FIG. 7b) that extends between the nozzles and the path of the filaments and is mounted to rotate about a vertical axis 37. Thus, by activating the disc 36 and the nozzles of the apparatus 34, it is possito spray points of a dye liquor. given on the filaments at more or less regular intervals and during a predetermined period. By using a succession of such applicators each linked to a different staining liquor, the applicators being synchronized with each other, it is therefore possito produce special filaments with effects preferably of the type of space of a single color, of multicolored space, chiné or dotted or any of the washed or denim type. Such successive application of different dye liquors can also be effected by spraying the dye using a rotating turbine or another using a plate. In such a case, the turbine may be of the type described in FR-A-2,650,311; that is, it may be in the form of a hollow cylindrical body equipped on its periphery with a plurality of dyeing or dyeing nozzles of equal or different cross sections, this turbine being mounted to rotate about an axis extending parallel to the axis of movement of the filaments, and spraying the liquor of staining through these different nozzles. This makes possible to produce on the moving filaments colored dots whose sizes and separations correspond to the geometry and the arrangement of the turbine sprinkler openings or nozzles. FIG. 8 of the accompanying drawings shows an embodiment of the invention in which the impregnation apparatus 2 is divided into a plurality of filament impregnation chambers 2 '. By means of such modality a multitude of filaments can be treated simultaneously with different dyes, which takes place with groups of filaments each of which corresponds to one or more chambers 2 '. In such a case, it is in fact possito feed each chamber 2 'or the set of chambers 2' with different dye liquors, depending on the requirements. If such an apparatus comprising multiple cameras is used, the different filaments obtained must of course undergo separate washing operations. The washing and squeezing unit 6 may have a construction analogous to that of the impregnation apparatus 2, as shown in its different embodiments in Figures 3 to 5, where the liquor conduits and the atomization and spray nozzles are simply fed with water or detergent products containing water and, the squeezing operation is effected by the squeezing means that remove the water from the filament. After staining, the filament can be washed, for example by treating it at a temperature between 60 and 80 ° C, with a solution containing soap or one or more detergents. The washing can be carried out continuously on the moving filament or by treating it while it is wound or unrolled on the bobbins. If the washing and squeezing unit 6 is composed of a succession of atomization and spray nozzles, the washing by means of those nozzles is advantageously carried out by means of backwashing by reusing the washing water successively from the last nozzle. illa, as seen in the direction of advance of the filament, to the first washing nozzle, followed by the discharge and treatment of the residual water. In fact, in such an embodiment, it is sufficient to recover the wash water obtained from the treatment in the last nozzle, as seen in the direction of advancement of the filaments and reinject it in the penultimate nozzle and so on until the first nozzle. This water is progressively mixed with the residual dye and the associated chemicals and is used for successive washes of the filament without affecting the quality of the wash. This leads to a substantial saving of the wash water. In this case, the squeezing means placed after the last nozzle performs the squeezing of the filaments. By inserting the squeezing devices 20 between the different spray nozzles, it is possible to optimize the washing by means of the mechanical squeezing action, which makes the filament susceptible to other wetting.

The drying apparatus 7 (not shown in detail) is advantageously in the form of a tunnel through which the filaments pass and to which hot air or hot gas is supplied under pressure. This drying apparatus 7 makes it possible to obtain one or more filaments having the relative humidity content required for the final use. If the apparatus 7 is designed in the form of a tunnel, it can advantageously be equipped with obstacle or rough regions which have a favorable effect on the formation of drying air turbulences or of drying gas and filament vibrations, thus optimizing the drying action. According to another embodiment of the invention, which is not shown in the accompanying drawings, the drying apparatus 7 may also be in the form of a chamber for the concentration of the filament through the formation of successive loops on the rollers of voltage, this chamber being subjected to the circulation of hot air or hot gas. According to another embodiment of the invention (not shown in the accompanying drawings), the drying apparatus 7 may also be in the form of a tunnel through which the filaments pass and to which high frequency or infrared energy is supplied. . According to another embodiment of the invention, not shown in the accompanying drawings, it is also possible to dry the treated filament either by blowing it in hot air during the rolling or passing the coils through a high frequency or infrared drying tunnel. By virtue of the invention, it is possible to carry out the continuous dyeing of one or more textile filaments of cellulose fiber at high speed, that is to say of the order of 600 m / min or more, with reactive dyes while saving is obtained substantial dyeing, that is to say, with an extremely red discharge of the dye in the washing water, as well as with a substantial saving in the consumption of energy and water. Furthermore, by means of the method according to the invention and the apparatus according to the invention, the uniform impregnation of the fiber assembly constituting each filament and the fixing of the dyes on and in the fibers makes it possible to obtain brighter shades and superior washing, friction and light firmness properties and the like. The filaments dyed according to this process are less subject to mechanical stress and retain to a greater degree their physical and mechanical properties, such as regularity, strength and extension. Furthermore, the process according to the invention and the apparatus according to the invention make it possible to reduce the requirements in terms of handling and the space requirements of the apparatus are substantially reduced compared with the existing dyeing apparatus.

As a result, the overall cost of carrying out the process according to the invention is also compared to conventional known dyeing methods and existing apparatuses. It is obvious that the invention is not limited to the embodiments described and shown in the accompanying drawings. The modifications, especially with respect to the design of the different elements or the replacement by equivalent techniques, are possible even without exceeding the scope of protection of the invention. The following examples serve to explain the present invention. Example 1: A filament of mercerized, bleached and undyed cotton was unrolled from a storage supply at a speed of 500 m / min and sprayed with a dye liquor by means of a nozzle, after which pneumatically removed the excess dye and, the filament was then re-rolled on a new support. Staining liquor composition: 30 g / l of the dye of the formula: 70 ml / l of sodium silicate 38 ° Bé 21 ml / l of sodium hydroxide solution 36 ° Bé 3 g / l of anionic wetting agent 3 g / l penetration accelerator (aqueous solution containing linear ethoxylated C9-C11 fatty alcohols having terminal alkyl groups, castor oil / polyol ether, paraffin oil, bis ( 2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as main components). The rewetted impregnated filament is then stored at room temperature for 8 hours, which results in fixing the dye on the fiber. Washing with hot water and subsequent drying give a filament dyed in a bright red shade that exhibits good properties. Example 2: A filament of mercerized, whitened and unstained cotton was unrolled from a storage supply at a speed of 500 m / min and sprayed with a dye liquor by means of a nozzle, and the filament was re-rolled then on a new support. A perforated disk is placed between the dye nozzle and the moving filament, the function of which is to allow the spraying of the dye liquor onto the filament only at previously defined and successive intervals.

Staining liquor composition: 30 g / l of the dye of the formula: 70 ml / l of sodium silicate 38 ° Bé 21 ml / l of sodium hydroxide solution 36 ° C 3 g / l of anionic wetting agent 3 g / l penetration accelerator (aqueous solution containing C9-fatty alcohols) Linear ethoxylates having terminal alkyl groups, castor oil / polyol ether, paraffin oil, bis (2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as main components). The rewetted impregnated filament is then stored at room temperature for 8 hours, which results in fixing the dye on the fiber. The filament is then washed at elevated temperature (approximately 60 to 80 ° C) with an aqueous liquor containing 2 g / l of a detergent containing a copolymer of acrylic acid and a surfactant and 1 g / l of a preparation of derivatives of esterified phosphorus and water-soluble polymers and the dyed filament is dried. This provides a filament of the chiné type on which the unstained portions and the portions in a bright yellow shadow alternate with each other.

Example 3: A bleached and unbleached mercerized cotton filament was unrolled from a storage supply at a speed of 500 m / min and sprayed with three dye liquors by means of nozzles, and the filament was wound up then on a new support. A perforated disk is placed between each dye nozzle and the moving filament, the function of which is to allow the sprinkling of the different dye liquors on the filament only at previously defined, synchronized and successive intervals, the synchronization and the angular velocity of the filaments. perforated discs being correlated to the speed of the filament in motion. Composition of the staining liquors: Staining liquor 1: 30 g / l of the red dye of the formula of Example 1; 70 ml / l of sodium silicate 38 ° Bé 21 ml / l of sodium hydroxide solution 36 ° Bé 3 g / l of anionic wetting agent 3 g / l of penetration accelerator (aqueous solution containing alcohols linear ethoxylated C8-Cn fatty acids which have terminal alkyl radicals, castor oil / polyglycol ether, paraffin oil, bs (2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as components main).

Staining liquor 2: 30 g / l of the dye of the formula: 70 ml / l of sodium silicate 38 ° Bé 21 ml / l of sodium hydroxide solution 36 ° Bé 3 g / l of anionic wetting agent 3 g / l of penetration accelerator (aqueous solution containing C9-fatty alcohols) C11 linear ethoxylates having terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, bis (2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as main components). Staining liquor 3: 70 g / l of the dye of the formula: 70 ml / l of sodium silicate 38 ° Bé 34 ml / l of sodium hydroxide solution 36 ° Bé 3 g / l of anionic wetting agent 3 g / l of penetration accelerator (aqueous solution containing fatty alcohols C9-C11 linear ethoxylates having terminal alkyl groups, castor oil / polyglycol ether, paraffin oil, bis (2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as main components). The rewetted impregnated filament is then stored at room temperature for 6 to 8 hours, which results in the fixation of the dye on the fiber. The filament is then washed at elevated temperature (approximately 60 to 80 ° C) with an aqueous liquor containing 2 g / l of a detergent containing a copolymer of acrylic acid and a nonionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water soluble polymers and the dyed filament is dried. This provides a multicolored filament in whose portions dyed red, blue and black and also the portions with different shades of the mixture of the three dyes used alternate with each other. Example 4: A filament of mercerized, undyed mercerized cotton was unrolled from a storage supply at a speed of 500 m / min and sprayed with a dye liquor by means of a nozzle, and the filament was re-rolled then on a new support. A perforated disc is placed between the dye nozzle and the moving filament, the function of which is to allow the Spraying the dye liquor onto the filament only at previously defined and successive intervals. Staining liquor composition: 0.5 g / l of the red dye of the formula of Example 1 1 g / l of the blue formazan dye of the formula of Example 3 70 ml / l of sodium silicate 38 ° Bé 15 ml / l of sodium hydroxide solution 36 ° Bé 3 g / l of anionic wetting agent 3 g / l penetration accelerator (aqueous solution containing linear ethoxylated Cg-Cn fatty alcohols having terminal alkyl groups, castor oil / polyglycol ether , paraffin oil, bis (2-ethylhexyl) maleate, di (2-ethylhexyl) phosphate and sodium hydroxide as main components). The rewetted impregnated filament is then stored at ambient temperature for 6 to 8 hours, which results in the fixing of the dye on the fiber. The filament is then washed at elevated temperature (approximately 60 to 80 ° C) with an aqueous liquor containing 2 g / l of a detergent containing a copolymer of acrylic acid and a nonionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water soluble polymers and the dyed filament is dried. This provides a blue filament with special effects, which is suitable for use on braided fabrics for jeans of the denim type as dyed by the indigo blue method. Depending on the pressure supplied to the nozzles impregnation, which results in different loads (depending on the performance of the nozzles and the speed at which the staining liquor leaves the bath) on the filament (% impregnation), different levels of annular staining can be obtained, which give the impression that the filaments have been washed to a different degree.

Claims (1)

1. CLAIMS 1. A process for the continuous dyeing of filaments based on cellulose fibers, which comprises the steps of a) impregnating the filament that has been unrolled continuously at high speed from one or more supports (1) and re-wound on one or more supports (3) with at least one dye reactive with the fiber in aqueous solution and at least one alkaline reagent in aqueous solution, and b) fixing the dye 2. A process according to claim 1, wherein the filament is impregnated first with at least one dye reactive with the fiber in aqueous solution and then with at least one alkaline reagent in aqueous solution. 3. A process according to claim 1, wherein the filament is first impregnated with at least one alkaline reagent in aqueous solution and then with a dye reactive with the fiber in aqueous solution. 4. A process according to claim 1, wherein the filament is impregnated with one or more dyes that are employed individually or in a mixture in the form of one or more dye liquors containing at least one reactive dye. with fiber and at least one alkaline reative. 5. A method according to claim 1, wherein the fixation of the dye (s) is carried out by storing the (the) support (s) comprising (n) the filament impregnated with the dye liquor (s). 6. A method according to claim 1, wherein the fixing of the dye is carried out directly after impregnation by treating the filament with a hot gas, in particular with air, or by treating it with saturated or superheated steam. 7. A process according to claim 1, wherein the speeds of unwinding, re-rolling and treatment of the filament (s) are at least 100 m / min, preferably at least 250 m / min. 8. A process according to claim 1, wherein the dyes used in the dye liquors are reactive dyes of the group comprising monoazo, disazo, polyazo, azo metal complex, anthraquinone, phthalocyanine, formazan or dioxacin dyes, which they contain at least one reactive group of the following formulas -NH-CO-Y (1), -S02-Z (1a), -W-alkylene- S02-Z (1b), I R -W-alkylene-E-alkylene'- S02-Z (1c), -alkylene-W-alkylene'- S02-Z (1d), I R -O-alkylene-W-alkylene 'S02-Z (1e), I R -W-arylene-N-alkylene-S02- (1f). wherein W is a group of the formula -SO2-NR1-, -CONRi or, NR1CO-, R1 is hydrogen, unsubstituted dC4 alkyl or hydroxyl, sulfo, sulfate, carboxyl or cyano- or a radical of the Formula -alkylene- S02-ZI R R is hydrogen, hydroxyl, sulfo, sulfate, carboxyl, cyano, halogen, C1-C4 alkoxycarbonyl, C? -C4 alkanoyloxy, carbamoyl or the group -S02-Z, Z is vinyl or a radical -CH2-CH2-U ? - and U1 is a group that comes out Y is a radical of the formula -CH (hal) -CH2-hal or -C (hal) = CH2 and hal is a halogen E is the radical -O- or -N (R2) -, R2 is hydrogen or alkyl d -C4 alkylene and alkylene are, independently or not of the other, C6-C6 alkylene, and arylene is a phenylene or naphthylene radical substituted with a sulfo-, carboxyl-, dd-alkyl, d-alkoxy. or halogen or unsubstituted R 3 is hydrogen or alky not substituted or substituted by C 1 -C 4 alkyl, carboxyl, cyano, hydroxyl, sulfo or sulfate X is a group that can be eliminated as an anion, and V is a non-substituted substituent. reactive, a group that can be eliminated as an anion or a radical of the formula R N-alkylene-S02-Z (3a), I N-alkylene-E-alkylene'-S 02- (3b), I R3 • N-arylene-S02-Z (3c), I R3 -N-a ri leno- (alq u ileno) t-W-a Iq u ileno 'S02-Z (3d), I R3 N-alkyl-S02-Z (3ß)? -N-arylene-N H-CO-Y (3f), I R3 wherein R, Ri, R3, E, W, Z, Y, alkylene, alkylene, and arylene are as defined above and t is 0 or 1. one of the radicals Xi is a group that can be eliminated as an anion and the other radical Xi is a non-reactive substituent, a group which can be eliminated as an anion or a radical of the formulas (3a) to (3f), and X2 is a negative substituent 9. A process according to claim 8, wherein in the reactive radicals of formula (2) X is fluorine and V is as defined in claim 8, or X is chlorine and V is a radical of formulas (3a) to (3f), and in the reactive radicals of the formula (4) at least one of the radicals Xi is fluorine or a radical of the formulas (3a) to (3f). A process according to any one of claims 1 to 9, wherein the alkaline reagent used to fix the reactive dyes comprises alkali metal carbonate, alkali metal bicarbonate, alkali metal hydroxide, ammonia, an ammonium salt organic, sodium trichloroacetate, borax, a phosphate, a polyphosphate or sodium silicate, or a mixture of two or more of the aforementioned alkaline reagents. eleven . A process according to claim 1, wherein the dye is fixed on the cellulose fiber filament by means of a low temperature method by storage at room temperature for a period of 3 to 24 hours, preferably 4 to 10 hours, and particularly preferably from 6 to 8 hours, in a storage unit (4) containing the impregnated and wound filament. 12. A process according to claim 1, wherein the dye is fixed onto the cellulose fiber filament by means of storage at a temperature of plus 40 ° C for a period of up to 3 hours in a storage unit (4). ) containing the impregnated and rolled filament. 13. A process according to claim 1, wherein the dye is fixed on the cellulose fiber filament by a thermal method using steam or maintenance at an elevated temperature or by a thermal insulation method. 14. A process according to claim 1, wherein the cellulose fiber filament is cotton, in particular mercerized or bleached cotton. 5. A method according to any one of claims 1, 11 and 12, wherein the filament (s) leaving the storage unit (4) are dried directly without a washing operation. intermediate. 16. A method according to any one of claims 1, 11 and 12, wherein the filament (s) leaving the storage unit (4) are unwound from an intermediate grid (5) and then washed and drained continuously while the filament passes at high speed through a washing and dripping unit (6) before undergoing drying in an apparatus (7) after allowing the filament (s) to be re-wound onto new ones supports (8). 17. A method according to any of claims 1, 11 and 12, wherein the filament supports (3) leaving the storage unit (4) are subjected to a washing operation in an autoclave (9) and a drying the filament in a high speed dryer (9 '), the filament being then re-wound from the supports (3) on new supports (10) in a rewinding unit (11). A method according to claim 1, wherein the impregnated filament is dried on the rewinding means (3) in an autoclave by means of saturated or pressurized steam, in a chamber in the form of a tunnel which is provided with high frequency or infrared energy or in a tunnel provided with hot air or hot gas, the fixing taking place at the same time. 19. A process according to claim 1, wherein the impregnation is carried out at a temperature of 5 to 95 ° C, in particular 10 to 80 ° C. 20. An apparatus for implementing the method according to claim 1, which essentially comprises the following: a device for unrolling at the continuous continuous speed of the filament from one or more supports (1), an apparatus (2) for impregnating the ( the filament (s) unwinding (s) with one or more dyes which are used individually or in a mixture in the form of one or more dye liquors, a device for reworking the treated filament (s) on one or more of the supports (3), and an agent (4) for fixing the dyes.