EP0768421A1 - Procédé de teinture en continu de fils avec des colorants réactifs et dispositif pour la mise en oeuvre de ce procédé - Google Patents

Procédé de teinture en continu de fils avec des colorants réactifs et dispositif pour la mise en oeuvre de ce procédé Download PDF

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Publication number
EP0768421A1
EP0768421A1 EP96810665A EP96810665A EP0768421A1 EP 0768421 A1 EP0768421 A1 EP 0768421A1 EP 96810665 A EP96810665 A EP 96810665A EP 96810665 A EP96810665 A EP 96810665A EP 0768421 A1 EP0768421 A1 EP 0768421A1
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EP
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Prior art keywords
yarn
dye
yarns
radical
reactive
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EP96810665A
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German (de)
English (en)
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EP0768421B1 (fr
Inventor
Robert Enderlin
Mickael Mheidle
Didier Thibault
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Superba SAS
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
Superba SAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
    • D06B11/002—Treatment of selected parts of textile materials, e.g. partial dyeing of moving yarns
    • D06B11/0023—Treatment of selected parts of textile materials, e.g. partial dyeing of moving yarns by spraying or pouring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B19/00—Treatment of textile materials by liquids, gases or vapours, not provided for in groups D06B1/00 - D06B17/00
    • D06B19/0005—Fixing of chemicals, e.g. dyestuffs, on textile materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/932—Specific manipulative continuous dyeing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/934—High temperature and pressure dyeing

Definitions

  • the present invention is in the field of textile technology, especially dyeing and especially dyeing textile yarns, and relates to a process for the continuous dyeing of yarns made of cellulose fibers with reactive dyes.
  • the invention further relates to a device for performing this method.
  • a strand dyeing process in which the yarn delivered by the spinning mill on a spool and wound around a conical spool is unwound via a strand reel machine in order to obtain the thread in strand form, the further handling being carried out with bobbin transport.
  • Each strand is then manually attached at different locations and the two ends of each strand are joined together.
  • the strands obtained are then attached to dyeing trees, hung on a trolley and then placed in a dyeing machine. After dyeing, the strands are washed and the excess water removed from them in a centrifuge before being dried either in a hot air cabinet or by continuous passage through a drying tunnel. After this drying, the strands are again fed to a winding device so that they can be rewound onto conical bobbins which can be used in the manufacture of knitted or woven goods.
  • Spool dyeing processes are also known in which a yarn delivered by the spinning mill on a spool is rewound onto a conical or cylindrical spool, wherein the edges of the bobbin 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.
  • a new handling consists in stacking bobbins on perforated columns of the material carrier of a dyeing apparatus and then transferring this material carrier into an autoclave and pressing a dyeing liquor under pressure into the autoclave using a pump. After a predetermined time, the dye liquor is removed and wash water is pressed into the autoclave. The material carrier is then removed from the autoclave and the coils are placed in a centrifuge to remove the excess water.
  • the coils are dried discontinuously in a drying cabinet or continuously in a high-frequency dryer. After drying, the yarn is wound back.
  • the excess water can also be removed using devices called rapid dryers, in which the water is removed from the material carrier-coil unit by means of a vacuum pump and this is then pressurized with air or steam pressure in an autoclave. In such a case, you can do without additional drying.
  • Such a bobbin dyeing process like the previous one, requires numerous operations by the operator and takes a relatively long time, which makes the costs of this process relatively high.
  • the known dyeing methods for dyeing cellulose fibers, vegetable fibers such as cotton, linen etc. or chemical fibers such as acetate or Viscose fibers have a high water consumption, which is in the order of 200 to 300 liters per kilogram of dyed yarn.
  • the conventional reagents must also be taken into account, which require a large amount of added salt to produce the dyebath, in the order of 80 to 100 g per liter of dyebath, of which only 60 to 70% of the mixture are fixed during the dyeing process and the remaining 30 to 40% of the mixture are removed during washing and represent a high environmental impact, which means that the waste water has to be treated particularly thoroughly.
  • the multiple unwinding and rewinding processes of the yarn have an adverse effect on the quality of the yarn produced, which manifests itself on the one hand in a weight loss and on the other hand in a loss of strength and elongation of the yarn .
  • Devices for carrying out continuous processes for dyeing textile yarns by continuously impregnating running yarns, which are subsequently transferred to a transport means, on which the yarns are passed through chambers which contain steam or hot air under normal pressure or overpressure, are also known. With such a process, known as heat setting, the dyes can be fixed on the fibers that make up the yarn.
  • Such devices can be used, in particular, for yarns based on polyamide, polyester, polypropylene and acrylic fibers, as well as wool and fiber mixtures, with a greatly reduced energy and water consumption compared to the processes in which the treatment takes place in bobbin or strand form to dye.
  • the object of the present invention is to limit these disadvantages by providing a method and a device for the continuous dyeing of yarns based on cellulose fibers, with which a considerable saving in dyes with optimal fixation and imagination effects, such as e.g. Chiné fibers, fibers dyed by the space dyeing process, single or multi-colored spotted yarns, or yarns with partial impregnation of the fibers, e.g. of the washed type, ring-dyed denim (ring dyeing method) or mechanically washed with grindstones (stone wash) denim.
  • a method and a device for the continuous dyeing of yarns based on cellulose fibers with which a considerable saving in dyes with optimal fixation and imagination effects, such as e.g. Chiné fibers, fibers dyed by the space dyeing process, single or multi-colored spotted yarns, or yarns with partial impregnation of the fibers, e.g. of the washed type, ring-dyed denim
  • the yarn is first impregnated with at least one fiber-reactive dye in aqueous solution and then with at least one alkaline agent in aqueous solution.
  • the yarn is first impregnated with at least one alkaline agent in aqueous solution and then with at least one fiber-reactive dye in aqueous solution.
  • the yarn can also be impregnated with one or more dyes which are used individually or as a mixture and are in the form of one or more dye liquors with at least one fiber-reactive dye and at least one alkaline agent.
  • the dye or dyes are fixed by lingering the carrier or carriers with the yarn which has been impregnated with the dyeing liquor (s).
  • a hot medium such as e.g. a gas, especially air, or by treatment with saturated or superheated steam.
  • Another object of the invention is an apparatus for carrying out this method, which is characterized in that it essentially comprises the following: an installation for the continuous rapid unwinding of yarn (fil) from one or more carriers, an apparatus for impregnating the unwound one or more Yarns with one or more dyes, which are used individually or in a mixture and are in the form of one or more dye liquors, a system for wrapping the treated yarn or yarns on one or more other carriers, and a means for fixing the dyes.
  • the process for the continuous dyeing of yarns 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 in aqueous solution and with at least one alkaline agent in aqueous solution, the yarn being continuously unwound from one or more supports 1 and being wrapped around one or more other supports 3, and fixation of the dye.
  • the method is carried out by means of a device which essentially comprises a system for continuous rapid unwinding of yarns having one or more carriers 1, a device 2 for impregnating the unwound yarn or yarns with one or more dyes, one or more other carriers 3 having system for wrapping the treated yarn or yarns, and a means 4 for fixing the dyes.
  • the unwinding, winding and treatment speeds of the yarn or yarns are preferably at least 100 m / min, in particular at least 250 m / min and preferably at least 300 m / min.
  • the upper limits are, for example, 1000 m / min and in particular 600 m / min.
  • the unwinding, winding and treatment speeds of the yarn or yarns are preferably 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 not shown in detail in the accompanying drawings and can be made in a known manner a frame with spindles that serve as a support for the spools of thread or superkops. It is also possible to unwind the yarns from a carrier, such as a warp beam.
  • the system for wrapping can also consist of a winding machine with several spindles or of a single carrier, such as a warp beam.
  • the yarn can be unwound and wrapped from bobbin to bobbin or from one or more bobbins to a warp beam, from warp beam to warp beam or from a warp beam to one or more bobbins.
  • the dyes used in the dyeing liquors are reactive dyes that are suitable for dyeing cellulose materials, such as Dyes from the group of 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 which are reactive to fibers and which are capable of reacting 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 to react covalent bonds.
  • the reactive groups are usually linked to the dye residue directly or via a bridge element.
  • reactive groups e.g. suitable are those which have at least one substituent which can be removed from an aliphatic, aromatic or heterocyclic radical, or those in which these radicals have a radical which is suitable for reaction with the fiber material, such as e.g. a halotriazinyl, halopyrimidinyl or vinyl radical.
  • 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.
  • those of the formulas (1) and (1a) in particular those of the formula (1a).
  • the leaving group U 1 is, for example, -Cl, -Br, -F, -OSO 3 H, -SSOH 3, -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. is substituted by sulfo, methyl, methoxy or carboxy.
  • E preferably represents -NH- and particularly preferably -O-.
  • W preferably denotes a group of the formula -NHCO- or in particular -CONH-.
  • X stands for example for fluorine, chlorine, bromine, sulfo, C 1 -C 4 alkylsulfonyl or phenylsulfonyl and preferably for chlorine or in particular fluorine.
  • Hal is preferably chlorine or bromine, especially bromine.
  • 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.
  • non-reactive substituents V are amino, methylamino, ethylamino, ⁇ -hydroxyethylamino, N, N-di- ⁇ -hydroxyethylamino, ⁇ -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-methyl-
  • 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.
  • 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.
  • Preferred 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 is a radical of the formulas (3a) to (3f).
  • the radical X 1 which can be split off as an anion is preferably chlorine or in particular fluorine.
  • 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 particularly preferably fluorine or a radical of the formulas (3a) to (3f).
  • One of the radicals X 1 is very particularly preferably fluorine and the other radical X 1 is fluorine or chlorine, X 2 having the meanings and preferences given above.
  • the reactive dyes can contain the substituents customary in organic dyes bound to their backbone.
  • substituents for the reactive dyes are: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, where the alkyl radicals can 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
  • Examples of reactive dyes are those of the formula A 1 -U (5) into consideration, in which A 1 is the residue of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane or dioxazine dye and U is a reactive residue, here and below for the reactive residues U in particular those given above Meanings and preferences 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.
  • 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.
  • 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.
  • 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 -ASkanoykamino, sulfo, halogen or carboxy, in particular by C 1 -C 4 -alkyl.
  • aliphatic bridge members for B 1 methylene-cyclohexylene-methylene radicals optionally substituted in the cyclohexylene ring by C 1 -C 4 -alkyl may also be mentioned.
  • the piperazine residue is, for example, a radical of the formula into consideration.
  • 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.
  • 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.
  • a 1 , A 2 and A 3 are preferably suitable as monoazo, polyazo or metal complex azo dye residues for A 1 , A 2 and A 3 :
  • the metal complexes derived from the dyes of the formulas (8) and (9) are also suitable, 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 hydroxyl 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.
  • 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 nuclei 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.
  • an anthraquinone dye for A 1 , A 2 and A 3 are, 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 the formulas (10a) to (10f) and (11) to (14) each preferably contain at least one sulfo group, in particular 1 to 4 sulfo groups and preferably 1 to 3 sulfo groups.
  • reactive residues are particularly suitable as reactive residues U, the above preferences applying.
  • the reactive dyes are known or can be obtained analogously to known production processes, such as diazotization, coupling and condensation reactions.
  • the amount of dye in the dye liquor can vary widely depending on the desired depth of color 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.
  • the dyeing liquors used according to the invention can contain one or more dyes.
  • 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.
  • the dye liquor can also contain other conventional additives, such as Wetting agents, solubilizers, e.g. ⁇ -caprolactam or polyethylene glycol, penetration accelerator, electrolyte, e.g. Contain sodium chloride or sodium sulfate, complexing agents such as urea or glycerin.
  • Wetting agents e.g. ⁇ -caprolactam or polyethylene glycol
  • solubilizers e.g. ⁇ -caprolactam or polyethylene glycol
  • penetration accelerator e.g. Contain sodium chloride or sodium sulfate
  • complexing agents such as urea or glycerin.
  • the dye is fixed on the yarn based on cellulose fibers by means of a thermal process or else a cold process.
  • fixation is carried out by the action of heat
  • a method using steam or holding at elevated temperature or a heat insulation method are suitable.
  • the cellulose fiber yarn may e.g. are cotton, in particular mercerized and / or bleached cotton, or else unbleached yarn, which can advantageously be dyed without prior washing by the process according to the invention. Such a dyeing process cannot be carried out with the previously known colorants.
  • Blended yarns based on cellulose e.g. Cotton / polyamide blended yarns or very particularly 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.
  • cellulose yarns can be dyed at high speed, ie with high yield.
  • yarns can be used special effects, such as 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 type, ring-dyed denim (ring dyeing process) or mechanically washed with grindstones (stone wash) Make denim.
  • the impregnation device 2 (see e.g. FIG. 1) has one or more dyeing liquors in which the yarn is impregnated as it passes through the device 2. When they leave, the dyeing liquor (s) on the yarn diffuse into the interior of the fibers forming the yarn.
  • the essential constituents of these dye 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. By placing the dye and the agent in separate containers, a high stability of the dye liquor is ensured, whereby renewal of the latter is avoided at regular intervals due to the hydrolysis caused by the alkaline agent.
  • the two solutions can be placed in separate containers and mixed before use in an intermediate container containing a buffer. In this way, only a small amount of the dye liquor is attacked hydrolytically over time and can be removed or replaced, if necessary, in particular 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 weight gain of the yarn e.g. 15 to 100%, in particular 15 to 80% and preferably about 15 to 50%, increases. With such an impregnation, the dyeing liquor can diffuse into the interior of the fibers after the yarn has left the impregnation device 2.
  • the impregnation is preferably carried out at a temperature of 5 to 95 ° C., in particular 10 to 80 ° C.
  • a temperature of 15 to 50 ° C. is very particularly preferred, in particular 15 to 40 ° C.
  • both the temperature of the yarn to be impregnated and the temperature of the dyeing liquor during impregnation correspond to one of the above temperatures.
  • It is of particular interest to carry out the impregnation at ambient temperature, for example 15 to 40 ° C., so that a heating device can be dispensed with completely before and in particular during the impregnation step.
  • the above preferences preferably also apply to the step of winding the yarn onto one or more carriers 3.
  • the yarn is thermally treated before the impregnation process (impregnation device 2).
  • This treatment can e.g. before or after the carrier 1.
  • the thermal treatment is preferably carried out continuously.
  • a means for the thermal treatment comes e.g. a container is considered which is filled with hot gas or in particular hot steam and in which the yarn e.g. circulates.
  • such a means would be e.g. between impregnation device 2 and carrier 3.
  • the colorant (s) applied to the respective yarn after impregnation in the device 2 diffuse into the fibers of the yarn while it is in the system 4.
  • the dyes are fixed in the fibers depending on the yarn quality and type and the chosen dyes with a degree of fixation in the order of 80 to 95%, based on the coloring material.
  • This calf fixation of the dye on the yarn which takes place by dwelling 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 can depend on the dye used and varies within wide limits which are between 3 and 24 hours, preferably between 4 and 10 hours, particularly preferably between 6 and 8 hours.
  • the duration of the treatment can depend on the dye used and varies 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 according to the invention depends on the foreseen need or the foreseen production rate and can take place with single yarn or multiple yarns of any titer or of any kind in various forms.
  • one or more yarns from multiple carriers 1 or a single carrier can be unwound and wound onto multiple carriers 3 or a single carrier.
  • preparatory steps can be carried out before unwinding from the carriers 1, which steps can in particular consist of a super-scope being wrapped around.
  • the yarn or yarns are dried directly after leaving the temporary store 4 without an intermediate washing process and are used in particular directly for woven or knitted fabrics.
  • the textile product obtained after the weaving, knitting or finishing process is washed and then dewatered and dried.
  • the unfixed dyes as well as the alkalis, silicates and other auxiliaries are removed from the woven, knitted or finished textile product by the washing process.
  • Such a procedure is of particular interest for velor fiber materials.
  • This drying process can also be carried out in an autoclave by means of saturated or excess pressure steam in a chamber in the form of a channel to which high-frequency or infrared energy is supplied, or in a channel to which hot air or hot gas is supplied, the fixing then also taking place at the same time.
  • the textile yarn impregnated with the dyeing liquor is subjected to a superheated treatment in a treatment chamber Steam subjected to an operating temperature between 98 and 210 ° C, advantageously between 100 and 180 ° C, and preferably between 102 ° C and 120 ° C.
  • the impregnated cellulose-based yarn is left wet in an autoclave for 1 min to 120 min e.g. stay at a temperature between 80 ° C and 102 ° C.
  • the dye can be fixed by the thermal insulation process with or without intermediate drying, e.g. at a temperature between 100 ° C and 210 ° C, advantageously between 120 ° C and 200 ° C, and very particularly between 140 ° C and 180 ° C.
  • the thermal insulation extends over a period of between 20s and 5 minutes, preferably between 30s and 60s.
  • the yarn or yarns can also be unwound from an intermediate creel 5 after leaving the temporary store 4 and then washed continuously in a washing and dewatering system 6 at a high running speed of the yarn and e.g. are spun and then dried in a device 7, after which the yarn or yarns are wound onto new carriers 8 (FIG. 1).
  • the device for carrying out this method has an intermediate creel 5 comparable to the device for unwinding the yarns from the carriers 1, the new wrapping carriers 8 being actuated by means of a device which the system for wrapping the yarn or yarns onto one or more carriers 3 resembles.
  • FIG. 2 of the accompanying drawings shows an embodiment variant of the method and the device according to the invention, in which the carriers 3 coming from the temporary store 4 are subjected to a washing process in an autoclave 9 and a yarn drying in a rapid dryer 9 ', whereupon the yarns from the carriers 3 be wrapped on new carriers 10 in a wrapping system 11.
  • the carriers 3 can be attached to perforated columns of a material carrier for later washing in the autoclave 9 by countercurrent circulation , whereupon the material carrier is transferred to the quick dryer 9 ', in which the moisture from the yarns on the carriers is removed by pressurizing the chamber which represents the quick dryer 9' and by means of the perforated columns of the material carrier by means of those on the carriers 3 yarns sucks air.
  • the yarns rewound onto the carriers 8 or 10 are yarns freed from excess dyes and from other constituents of the dyeing liquors and are completely stable with regard to their dyeing, i.e. in which there is no longer a risk of washing out, and which are suitable for the production of woven and knitted fabrics, a later washing of the woven or knitted fabric being unnecessary.
  • These cellulose fiber yarns then have a moisture content of e.g. 8 to 12% in an environment typical for textiles, i.e. at 22 ° C and a relative humidity of 65%.
  • the impregnation device 2 can be kept at a constant level from a dyeing liquor trough 12 which is kept at a constant level by means of a feed pump 13 which is connected to a storage tank containing the dyeing liquor 14 and possibly heated by a heat source 15, the or the yarns to be impregnated in the dyeing liquor are unwound by means of a return roller and consist of a means 16 for squeezing off excess paint on the yarn (s) by compressed air with adjustable pressure, the entire device being in a chamber 17 for recovering the squeezed-off paint and Has openings for the passage of the yarn or yarns.
  • Such an embodiment of the impregnation device is particularly well suited for uniform dyeing by means of a dye liquor in the form of a mixture of dye and alkaline agent.
  • 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 excess air pressure. Due to the excess pressure generated in the container through which the yarns are passed, a large part of the dye liquor remaining on the yarn is squeezed out of it and pressed out through the openings of the container. This allows a yarn with between at the exit of the device 2 15 and 100% of its weight in dye liquor, which is regulated by the air pressures used in the average 16, received.
  • FIG. 4 shows an embodiment variant of the impregnation device 2, in which it consists of several means 18 for guiding and holding the respective yarn in the longitudinal direction, of at least one nozzle 19 for atomizing and spraying the dyeing liquor onto the running yarn or yarns, from a device 20 for Squeezing excess dye liquor and consists of a device 21 for the continuous supply of dye liquor, which is connected to the atomizing and spraying nozzles 19 and to a trough 22 for receiving excess atomized and / or squeezed dye liquor, this trough 22 being the bottom of the Forming impregnation device 2 chamber.
  • this impregnation device enables a differentiated spraying of the reactive dye (s) and the alkaline agent, the latter being sprayed on before or after the reactive dye. It follows from this that the dye and the agent are not previously mixed and possible hydrolysis of the dye by the agent can be avoided.
  • the device 20 for squeezing off excess dyeing liquor is designed as a carrier anvil 23 of the running yarn or yarns, which is somewhat higher than the horizontal running direction of the yarn or yarns and on the upstream side of the yarn or yarns with an edge bevel 23 'or Rounding and a nozzle 24 for blowing compressed air is provided with which an air jet is directed onto the yarn or yarns.
  • a carrier anvil 23 of the running yarn or yarns which is somewhat higher than the horizontal running direction of the yarn or yarns and on the upstream side of the yarn or yarns with an edge bevel 23 'or Rounding
  • a nozzle 24 for blowing compressed air is provided with which an air jet is directed onto the yarn or yarns.
  • the squeezing device 20 can of course also be used instead of the squeezing means 16 in the embodiment of the impregnation device according to FIG. 3 and vice versa.
  • the impregnation device 2 according to FIG. 4 (or according to FIG. 12) is expediently equipped with several atomizing and spray nozzles 19.
  • a support plate 25 for supporting the yarn under the yarn or yarns at right angles to the respective atomizing and spray nozzle 19. This embodiment is shown in Figure 4 of the accompanying drawings at right angles to a nozzle 19.
  • the yarn or yarns are held in place and protected against any 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 liquor are better guaranteed.
  • the kinetic energy of the dye liquor sprayed on the yarn shows an optimal effect when the yarn rests on a solid support and when the dye jet can hit the yarn without it being able to escape.
  • the guiding and holding means 18 in turn act to prevent any deviation in a horizontal plane lying outside the longitudinal axis of the yarn or yarns.
  • FIG. 4 (or FIG. 12) of the accompanying drawings also shows a further embodiment variant of the invention, in which at least two atomizing and spray nozzles 19 are arranged diametrically opposite with respect to the longitudinal axis of the yarn or yarns to be dyed or treated.
  • the fact that the kinetic energy of the two opposite jets is added optimizes the impregnation and penetration of the fibers and their spaces with dye liquor at right angles to the respective pair of nozzles 19.
  • FIG. 10 of the accompanying drawings shows an example of a high-frequency nozzle 19 'in which a high-frequency drop generator 38 supplies drops via a charging device 39, a detector 40 and a deflection device 41, through which the drops are directed either onto a yarn 42 or onto a return means 43 .
  • 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, in which an ink reservoir 26 is connected via a feed line and a pump 27 to a pressurized impregnation channel 28, which is formed by a longitudinal tube for each yarn or for several yarns , through which the yarn or yarns are passed in the longitudinal direction, with the channel 28 being followed by a device 29 for squeezing off excess dyeing liquor, the dyeing liquor emerging from the pressurized channel 28 and coming from the squeezing system 29 at the bottom of the device 2 representing chamber collected and returned to the reservoir 26 by means of a line 30.
  • a pressurized impregnation channel 28 which is formed by a longitudinal tube for each yarn or for several yarns , through which the yarn or yarns are passed in the longitudinal direction, with the channel 28 being followed by a device 29 for squeezing off excess dyeing liquor, the dyeing liquor emerging from the pressurized channel 28 and coming from the squeezing system 29 at the bottom of the
  • the pressurized channel 28 can be formed in a tube shape particularly suitable for dyeing uniform fibers or in the form of a rectangular elongated box for dyeing bundle-shaped or litz-shaped multiple fibers.
  • the cross section and the length of these channels can be chosen so that both the contact time of the yarn with the dyeing liquor depending on its speed and the relative speed of the dyeing liquor circulating in the channel can be varied with respect to the speed of the yarn in the same channel. All these factors can influence the effect of the dye liquor's contact with the yarn and its fiber components.
  • pressurized dyeing liquor enters channel 28 at intervals so as to take into account the speed differential between the dyeing liquor and the yarn, since the speeds of the yarn and the pressurized dyeing liquor are upstream with respect to the direction of travel add the yarn as they subtract downstream.
  • the impregnation channels 28 under pressure can have rough spots or internals or surface deformations on their inner side parallel to the running direction of the yarn. The latter lead to a non-laminar flow of the dyeing liquor, the turbulence obtained in this way having a favorable effect on the generation of high local pressures and a movement which is likewise favorable for the yarn, whereby a quick and high-quality impregnation is achieved if this effect is desired.
  • the squeezing system 29 can either consist of a pressure vessel through which the yarn loaded with the dyeing liquor is passed, or of a combination of anvil and air injection nozzle.
  • the fibers constituting the yarns are quickly and in intimate contact with the dyeing liquor, thereby causing the diffusion of the colorants into the fibers starts better during impregnation.
  • the relative speed between the running yarn and the dyeing liquor in the tubular or other shaped channel 28 reinforces the uniform impregnation of the fibers representing the yarn.
  • FIG. 6 of the accompanying drawings shows a further embodiment variant of the impregnation device 2, in which it is in the form of an impregnation pad 31, which consists of two horizontal cylinders that are in contact with one another along their surface line and above which the dye liquor is constantly present and is composed of an arrangement of lateral sealing flanges 31 'at the cylinder ends, the impregnation of the yarn or yarns being carried out by passing them between the cylinders.
  • an impregnation pad 31 which consists of two horizontal cylinders that are in contact with one another along their surface line and above which the dye liquor is constantly present and is composed of an arrangement of lateral sealing flanges 31 'at the cylinder ends, the impregnation of the yarn or yarns being carried out by passing them between the cylinders.
  • FIG. 9 of the accompanying drawings there is also the possibility, as shown in FIG. 9 of the accompanying drawings, to design the impregnation device 2 in the form of a contact impregnation drum 32, the drum being moved in a dyeing liquor and the color being applied to the current one
  • the drum being moved in a dyeing liquor and the color being applied to the current one
  • yarns are drawn up which are guided on part of the drum circumference by means of return roller 33 or the like, the position of these return rollers 33 with respect to drum 32 being adjustable.
  • the degree of impregnation of the yarns can be modified by moving the rollers 33 away from the drum 32 or approaching it, so that a longer or shorter, stronger or weaker contact of the yarn with the drum during a certain amount of dyeing liquor their rotation with them is achieved.
  • the degree of impregnation can also be influenced by influencing the rotational speed of the drum 32 and thus the relative speed of the yarn with respect to the drum modify. This effect on the relative speed can be increased by changing the direction of rotation of the drum 32. In the case of a rotation of the drum 32 opposite to the running direction of the yarn, the former exerts a soaking effect on the film of dyeing liquor carried by the drum, which results in better penetration of the fibers of the yarn with liquor.
  • the degree of liquor absorption by the running yarn can be varied by adjusting the viscosity of the dyeing liquor.
  • the device according to FIG. 9 is particularly well suited for carrying out partial impregnations of the ring-dyed type yarn (ring dyeing method) or only part of the outer surface of a yarn.
  • ring dyeing method ring dyeing method
  • only part of the circumference of the yarn can be impregnated on the surface.
  • FIG. 11 of the accompanying drawings shows a section of a yarn treated according to the invention on a greatly enlarged scale.
  • the fibers impregnated on the surface are drawn with a large border, while the non-dyed fibers are drawn in thin lines.
  • the impregnation device 2 can likewise consist of a dyeing machine with a plurality of application devices, each of which is assigned to a different dyeing liquor and each with different spots in steps of the same or different length Apply colors, pass.
  • an impregnation device in particular yarns with fancy effects like the one below producing single or multi-colored space dyeings, Chiné-type yarns as well as spotted or washed-out or denim yarns.
  • a dyeing apparatus which can be used for this purpose and has a plurality of coaters is known in particular from FR-A-2 650 311 and FR-A-2 719 058.
  • Figure 7a of the accompanying drawings shows a possible embodiment of a coater of such an apparatus.
  • the dyeing liquor transferred into a atomizing device 34 equipped with nozzles, which are each arranged at right angles to the running axis of one or more yarns is successively sprayed by these nozzles through a slot 35 arranged in a disk 36 (FIG. 7b), the disk itself is located between the nozzles and the direction of travel of the yarn or yarns and is fixed so that it rotates about a vertical axis 37.
  • spots of a dyeing liquor applied to the yarn or yarns can be sprayed on at more or less regular intervals and for a predetermined period of time.
  • Such a sequential application process of different dyeing liquors can also be achieved by spraying the paint on using a rotary turbine or also using a plate.
  • the turbine can be constructed as described in FR-A-2 650 311, ie in the form of a cylindrical hollow body which has on its outer surface a plurality of openings or nozzles for spraying paint with the same or different cross sections has, wherein this turbine is rotatably mounted on an axis that runs parallel to the running axis of the yarns, and sprayed the dyeing liquor through these different nozzles.
  • FIG. 8 of the accompanying drawings shows an embodiment variant of the invention in which the impregnation device 2 is divided into several chambers 2 'for impregnating the yarn.
  • a simultaneous treatment of a plurality of yarns with different colors can be carried out according to yarn groups, each of which corresponds to one or more chambers 2 '.
  • yarn groups each of which corresponds to one or more chambers 2 '.
  • the washing and drainage system 6 can be constructed analogously to the impregnation device 2, as is shown in the various design variants in FIGS. 3 to 5, the liquor troughs and atomizing and spraying nozzles simply being charged with water or detergent products and the drainage process by means of Squeezing agent is used to remove the water from the yarn.
  • the yarn can e.g. washed at a temperature between 60 and 80 ° C, e.g. by treatment with a solution containing soap or one or more detergents. Washing can be done continuously with the running yarn or by treating the yarn wound on bobbins.
  • the washing and dewatering system 6 consists of a sequence of atomizing and spray nozzles, these are expediently carried out in countercurrent washing with reuse of the washing water, which is removed from the last washing nozzle with respect to the running direction of the yarn and successively up to the first washing nozzle is reused, whereupon the residual water is discharged and treated.
  • it is sufficient to collect the washing water that comes from the treatment in the last nozzle, with respect to the direction of the yarn or yarns, and to press it back into the penultimate nozzle and continue so to the first nozzle.
  • This water is therefore increasingly enriched with dye residues and related chemical products and is used for consecutive washings of the yarn are used without affecting the wash quality. This results in a considerable saving in washing water.
  • the squeezing agent downstream of the last nozzle acts as a drainage device for the yarn or yarns.
  • the washing can be optimized by the mechanical squeezing action, as a result of which the yarn is more suitable for rewetting.
  • the drying device 7 (not shown in detail) is expediently in the form of a channel through which the yarn or yarns are passed and which is pressurized with hot air or a hot gas. With the help of this drying device 7 it is possible to obtain one or more yarns with the properties required for later use with regard to their relative humidity. If the device 7 is designed in the form of a channel, it can advantageously be equipped with internals or rough spots which have a favorable effect on the formation of turbulence in the drying air or drying gas and on vibrations of the yarn, as a result of which the drying effect is optimized.
  • the drying device 7 can also be designed in the form of a chamber in which the yarn is concentrated by the formation of successive strands on tensioning rollers, this chamber having a circulation Hot air or hot gas is subjected.
  • the drying device 7 can also be designed in the form of a channel through which the yarn or yarns are passed and to which high-frequency or infrared energy is applied.
  • one or more textile yarns made of cellulose fibers can be reacted at high speed, in the order of magnitude of 600 m / min or more, with reactive dyes with considerable savings in dye, i.e. dye continuously with greatly reduced discharge of dye into the wash water and with considerable savings in energy and water consumption.
  • more uniform dyeing and higher washing, rubbing and light fastness etc. can be achieved by uniformly impregnating the fiber composite representing the respective yarn and by fixing the dyes on and in the fibers.
  • the yarns dyed according to the present process are subjected to less mechanical stress and retain their physical and mechanical qualities, such as Regularity, stability and stretch, longer at.
  • the required handling steps are greatly reduced in the method and the device according to the invention and the space requirement of the device is significantly reduced compared to the conventional dyeing apparatus.
  • the wrapped impregnated yarn is then left at ambient temperature for 8 hours, with the dye being fixed on the fiber. After washing with hot water and then drying, a yarn dyed in brilliant red tones with good properties is obtained.
  • the wrapped impregnated yarn is then left at ambient temperature for 8 hours, whereby the dye is fixed on the fiber.
  • the mixture is then washed at elevated temperature (about 60 to 80 ° C.) with an aqueous liquor which contains 2 g / l of detergent which contains an acrylic acid copolymer and a nonionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water-soluble polymers, and the dyed yarn is dried.
  • the result is a chiné-type yarn on which undyed parts and parts in brilliant yellow tones alternate.
  • the wrapped impregnated yarn is then left at ambient temperature for 6 to 8 hours, thereby fixing the dye to the fiber.
  • the mixture is then washed at elevated temperature (about 60 to 80 ° C.) with an aqueous liquor which contains 2 g / l of detergent which contains an acrylic acid copolymer and a nonionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water-soluble polymers, and the dyed yarn is dried.
  • the result is a multicolored yarn in which red, blue and black colored parts and parts with different shades of color alternate from the mixture of the three dyes used.
  • the wrapped impregnated yarn is then left at ambient temperature for 6 to 8 hours, thereby fixing the dye to the fiber. Then at elevated temperature (about 60 ° C to 100 ° C) with an aqueous liquor containing 2 g / l detergent, which contains an acrylic acid copolymer and a nonionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water-soluble polymers, washed, and the dyed yarn is dried. This gives a blue yarn with special effects, which is suitable for weaving fabrics for blue jeans of the type dyed using an indigo process.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)
EP96810665A 1995-10-13 1996-10-04 Procédé de teinture en continu de fils avec des colorants réactifs Expired - Lifetime EP0768421B1 (fr)

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FR9512193A FR2739880B1 (fr) 1995-10-13 1995-10-13 Procede de teinture en continu de fils, en particulier a base de fibres cellulosiques avec des colorants reactifs, et dispositif pour la mise en oeuvre de ce procede
FR9512193 1995-10-13

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DE (1) DE59608552D1 (fr)
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FR2693486B1 (fr) * 1992-07-08 1994-09-02 Superba Sa Procédé et machine pour teindre en continu des fils textiles.
FR2719058B1 (fr) * 1994-04-22 1996-07-12 Superba Sa Machine pour teindre en continu des fils textiles.

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FR2140692A1 (fr) * 1971-06-14 1973-01-19 Unitika Ltd
WO1983000172A1 (fr) * 1981-07-01 1983-01-20 Sloan, Frederick, Richard, Wilfred Teinture de materiaux fibreux

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005016928A1 (de) * 2005-04-13 2006-10-19 Saurer Gmbh & Co. Kg Paraffiniereinrichtung
WO2008056396A1 (fr) * 2006-11-10 2008-05-15 Maino International S.R.L. Appareil de traitement de marchandises en morceaux
WO2014202223A2 (fr) * 2013-06-21 2014-12-24 Rototech Urban Ltda. Procédé de dépôt contrôlé d'un bain de teinture sur un fil, un assemblage de fils ou une bande textile
WO2014202223A3 (fr) * 2013-06-21 2015-03-12 Rototech Urban Ltda. Procédé de dépôt contrôlé d'un bain de teinture sur un fil, un assemblage de fils ou une bande textile
EP3346053A3 (fr) * 2016-08-26 2018-08-22 Brauns-Heitmann GmbH & Co. KG Système de coloration pour matériaux textiles
CN108179574A (zh) * 2018-03-21 2018-06-19 陶守江 一种段染设备及工艺

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DE59608552D1 (de) 2002-02-14
EP0768421B1 (fr) 2002-01-09
BR9605105A (pt) 1998-11-10
ES2171218T3 (es) 2002-09-01
US5983678A (en) 1999-11-16
FR2739880B1 (fr) 1997-12-05
US5891201A (en) 1999-04-06
US6134924A (en) 2000-10-24
TR199600810A2 (tr) 1997-04-22
PT768421E (pt) 2002-07-31
MX9604752A (es) 1997-09-30
KR970021426A (ko) 1997-05-28
JPH09119075A (ja) 1997-05-06
FR2739880A1 (fr) 1997-04-18

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