EP0768421B1 - Verfahren zum kontinuierlichen Färben von Garnen mit Reaktivfarbstoffen - Google Patents

Verfahren zum kontinuierlichen Färben von Garnen mit Reaktivfarbstoffen Download PDF

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Publication number
EP0768421B1
EP0768421B1 EP96810665A EP96810665A EP0768421B1 EP 0768421 B1 EP0768421 B1 EP 0768421B1 EP 96810665 A EP96810665 A EP 96810665A EP 96810665 A EP96810665 A EP 96810665A EP 0768421 B1 EP0768421 B1 EP 0768421B1
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Prior art keywords
yarn
dye
radical
reactive
alkyl
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EP96810665A
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German (de)
English (en)
French (fr)
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EP0768421A1 (de
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Robert Enderlin
Mickael Mheidle
Didier Thibault
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Superba SAS
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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 particularly the dyeing of textile yarns, and relates to a process for continuous dyeing of yarns from cellulose fibers with reactive dyes.
  • the preamble of claim 1 is based on FR-A-2 140 612.
  • a strand dyeing process in which the spinning on a spool delivered yarn and wound onto a conical bobbin on a strand reel machine is unwound to keep the yarn in rope form, with further handling takes place under coil transport.
  • Each strand is then manually made at different points attached, and the two ends of each strand are joined together.
  • the strands obtained are attached to dyeing trees, hung on a cart and then placed in a dyeing machine. After dyeing the strands washed and the excess water removed from it in a sling before it either in a hot air cabinet or by continuous passage a drying tunnel can be dried. After this drying, the strands are back fed to a winding device so that it can be rewound onto conical bobbins, which can be used in the manufacture of knitted or woven goods.
  • Coil dyeing processes are also known, in which one of the spinning on one Spool delivered Gam is rewound on a conical or cylindrical spool, whereby the edges of the coil may be rounded off by pressing so that a better later circulation of a dye liquor into the inside of the bobbin is made possible.
  • a new handling is that one spools perforated columns of the material carrier of a dyeing machine stack and this material carrier then transferred to an autoclave and a dye liquor underneath using a pump Presses pressure into the autoclave. The dye liquor is removed after a predetermined time and washing water is pressed into the autoclave. Then the material carrier from the Autoclave is taken and the coils are used to remove the excess water put in a slingshot.
  • the coils are discontinuous or in a drying cabinet continuously dried in a high frequency dryer. After drying, the gam rewound.
  • the excess water can also be referred to as a quick dryer Devices are removed in which the removal of water from the Material carrier-coil unit takes place by means of a vacuum pump and this in one Air or steam pressure is applied to the autoclave. In such a case you come even without additional drying.
  • the known dyeing processes for dyeing cellulose fibers Vegetable fibers such as cotton, linen etc. or chemical fibers such as the acetate or Viscose fibers have a high water consumption, of the order of 200 up to 300 liters per kilogram of dyed yarn.
  • the object of the present invention is to limit these disadvantages Providing a process for the continuous dyeing of yarns based on Cellulose fibers, with which a considerable saving in dyes with optimal Fixation as well as fantasy effects, e.g. Chiné fibers, using the space dyeing process dyed fibers, single or multi-colored spotted yarns, or yarns with partial impregnation the fibers, e.g. of the washed-out type, ring-dyed denim (ring-dyeing process) or can be achieved with stone wash denim mechanically.
  • the yarn is first with at least a fiber-reactive dye in aqueous solution and then with at least one impregnated alkaline agent in aqueous solution.
  • the gam is first used at least one alkaline agent in aqueous solution and then with impregnated at least one fiber-reactive dye in aqueous solution.
  • the yarn can also with one or more dyes, which are used individually or as a mixture and in the form of one or more dye liquors with at least one fiber-reactive dye and at least one alkaline agent are present, are impregnated.
  • the dye or dyes are fixed by lingering the carrier (s) with the yarn, the one or more dyeing liquors was impregnated.
  • the process for the continuous dyeing of games based on cellulose fibers preferably comprises the following steps: Impregnation of the yarn in an impregnation device 2 with at least one fiber-reactive dye from the above-mentioned group in aqueous solution and with at least one alkaline agent in aqueous solution, continuous rapid unwinding of the yarn from one or more carriers 1 and its wrapping onto one or more other carrier 3 takes place, and fixation of the dye.
  • the method is carried out by means of a device which consists essentially of a one or more carrier 1 system for continuous Fast handling of games, a device 2 for impregnating the or unwound yarns with one or more dyes, one or more other carrier 3 system for wrapping the yarn or yarns treated, and a means 4 for fixing the dyes.
  • the unwinding, wrapping and treatment speeds of the game are preferably at least 100 m / min, in particular at least 250 m / min and preferred at least 300 m / min.
  • the upper limits are, for example, 1000 m / min and called in particular 600 m / min.
  • the unwinding, wrapping and treatment speeds of the or are preferably Game between 100 m / min and 1000 m / min, preferably between 250 m / min and 600 m / min.
  • the one or more carrier 1 system for unwinding the yarn is on the accompanying drawings are not shown in detail and can be made in a known manner a frame with spindles that serve as a support for the spools of thread or superkops, consist. It is also possible to remove the yarns from a carrier, e.g. a warp beam, reeling off.
  • the system for wrapping can also be from a winding machine multiple spindles or from a single carrier, e.g. a warp beam.
  • the unwinding and winding around the yarn can take place from bobbin to bobbin or from one or more spools to a warp beam, from warp beam to warp beam or from a warp beam on one or more spools.
  • the dyes used in the dyeing liquors are Reactive dyes, which are suitable for dyeing cellulose materials, from the group the monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, Formazan or dioxazine dyes which contain at least one reactive group. These dyes preferably also contain at least one sulfo group.
  • Reactive groups are radicals that are reactive towards fibers Are able to deal with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and Mercapto groups of wool or silk or with the amino or optionally the Carboxyl groups of synthetic polyamides to form chemical covalent bonds to react.
  • the reactive groups are usually with the dye residue directly or over linked a bridge element.
  • Suitable reactive groups are those which at least one that can be split off from an aliphatic, aromatic or heterocyclic radical Have substituents, or those in which these residues one to react with the Have suitable radical fiber material, such as a halotriazinyl, halopyrimidinyl or vinyl radical.
  • 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 formula (1a).
  • the leaving group U 1 is, for example, -Cl, -Br, -F, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OPO 3 H 2 , -OCO-C 6 H 5 , - OSO 2 -C 1 -C 4 alkyl or -OSO 2 -N (C 1 -C 4 alkyl) 2 .
  • U 1 is preferably a group of the formula -Cl, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OCO-C 6 H 5 or -OPO 3 H 2 , in particular -Cl or -OSO 3 H and particularly preferred -OSO 3 H.
  • Alkylene and alkylene ' are independently of each other e.g. a methylene, Ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or their branched isomers.
  • Alkylene and alkylene ' preferably represent a C 1 -C 4 alkylene radical and particularly preferably an ethylene radical.
  • R is preferably hydrogen or the group -SO 2 -Z, where Z has the meanings and preferences given above. R particularly preferably represents hydrogen.
  • R 1 is preferably hydrogen, C 1 -C 4 alkyl or a group -alkylene-SO 2 -Z, in which alkylene and Z each have the meanings given above.
  • R 1 is particularly preferably hydrogen or C 1 -C 4 alkyl, in particular hydrogen.
  • R 3 is preferably hydrogen or a C 1 -C 4 alkyl radical and particularly preferably hydrogen.
  • Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or e.g. by Sulfo, methyl, methoxy or carboxy is substituted.
  • E preferably represents -NH- and particularly preferably -O-.
  • W preferably denotes a group of the formula -NHCO- or in particular -CONH-.
  • X stands for chlorine or especially fluorine.
  • Hal is preferably chlorine or bromine, especially bromine.
  • V is a non-reactive Means substituents or in particular is a group which can be split off as an anion.
  • 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
  • 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.
  • Heterocyclic reactive radicals of the formula (2) are those in which X is fluorine and V has the meanings and preferences given above, or X is chlorine and V represents a radical of the formulas (3a) to (3f).
  • 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 fluorine or a radical of the formulas (3a) to (3f).
  • One of the radicals X 1 is preferably fluorine and the other radical X 1 is fluorine or chlorine, X 2 having the meanings and preferences given above.
  • Particularly preferred reactive groups are those of the formulas (1) and (1a) to (1d), in particular those of the formulas (1), (1a) to (1c), and Reactive residues of the formula (2), and Reactive radicals of the formula (4), in particular in which X 1 is fluorine and the other radical X 1 is fluorine or chlorine and X 2 has the meanings and preferences given above.
  • reactive groups are those of the formulas (1), (1a) and (1b), in particular of the formulas (1) and (1a) and preferably those of the formula (1a), and reactive radicals of the formula (2), in which X Is fluorine or chlorine and V represents a radical of the formulas (3a) to (3f), and Reactive radicals of the formula (4) in which X 1 is fluorine and the other radical X 1 is fluorine or chlorine and X 2 has the meanings and preferences given above.
  • the reactive dyes can in addition to the reactive groups on their backbone organic dyes contain conventional substituents bound.
  • Alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; Alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; phenyl optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or sulfo; Acylamino groups with 1 to 8 carbon atoms, especially those alkanoylamino groups such as acetylamino or propionylamino; benzoylamino optionally substituted in the phenyl ring by C 1 -C 4 alkyl
  • reactive dyes are those of the formula A 1 -U into consideration, wherein A 1 is the residue of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye and U is a reactive residue, here and below for the reactive residues U the meanings given above and favors apply.
  • the radical A 1 can also contain one or more further, identical or different reactive groups U.
  • the total number of reactive groups in the dyes is preferably 1 to 3, preferably 1 or 2 and in particular 2.
  • 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 alkanoylamino, sulfo, halogen or carboxy, in particular by C 1 -C 4 alkyl.
  • aliphatic bridges for B 1 methylene-cyclohexylene-methylene radicals optionally substituted in the cyclohexylene ring by C 1 -C 4 -alkyl may also be mentioned.
  • the piperazine residue is, for example, a radical of the formula into consideration.
  • B 1 is preferably a C 2 -C 12 alkylene radical which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH 3 ) - or -O- and is unsubstituted or by hydroxyl, sulfo, Sulfato, cyano or carboxy is substituted; or an optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy C 5 -C 9 cycloalkylene radical, C 1 -C 6 alkylene phenylene radical or phenylene radical ; or B 1 is a radical of the formula (7), in which the benzene rings I and II are optionally substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, sulfo, halogen or carboxy and L is the
  • 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.
  • the metal complexes derived from the dyes of the formulas (8) and (9) also come into consideration, these being in particular 1: 1 copper complex azo dyes of the benzene or naphthalene series, in which the copper atom is attached to a metallizable group, such as, for example, a Hydroxy group, bound on both sides in the ortho position to the azo bridge. If the dye radicals of the formula (8) or (9) carry a reactive radical, the meanings and preferences given above apply to them.
  • the dye residues of the formulas (8) and (9) are preferably those of the formulas wherein (R 8 ) 0-3 for 0 to 3 identical or different substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl , Halogen, nitro, cyan, trifluoromethyl, amino, hydroxy, carboxy and sulfo, (R 9 ) 0-2 for 0 to 2 identical or different substituents from the group hydroxyl, amino, N-mono-C 1 -C 4 -alkylamino, N, N-di-C 1 -C 4 -alkylamino, C 2 -C 4 -alkanoylamino and benzoylamino and (U) 0-2 represents 0 to 2 identical or different reactive groups; wherein (R 9 ) 0
  • the radicals of a formazan dye for A 1 , A 2 and A 3 are, for example, those of the formula into consideration, in which (U) 0-2 has the meanings given above and the benzene cores contain no further substituents or by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, halogen or Carboxy are further substituted.
  • a ' is a phenylene radical optionally substituted by C 1 -C 4 alkyl, halogen, carboxy or sulfo or a C 2 -C 6 alkylene radical, r, s, v and v 'each independently represent the number 0 or 1 and Z has the meaning given above.
  • an anthraquinone dye is for A 1 , A 2 and A 3, for example those of the formula into consideration, in which G represents an unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or sulfo phenylene radical or a cyclohexylene, phenylene methylene or C 2 -C 6 alkylene radical.
  • the above dye residues of formulas (10a) to (10f) and (11) to (14) preferably contain in each case at least one sulfo group, in particular 1 to 4 sulfo groups and preferably 1 to 3 sulfo groups.
  • reactive radicals mentioned above are suitable as reactive radicals U, the above Preferences apply.
  • the reactive dyes are known or can be made analogously to known ones Manufacturing processes such as diazotization, coupling and condensation reactions, be preserved.
  • the amount of dye in the dye liquor can vary greatly depending on the depth of color desired fluctuate and is e.g. up to 100 g / l liquor, preferably 10 g / l to 70 g / l, in particular 10 g / l to 50 g / l dyeing liquor.
  • the Dyeing liquors used according to the invention can contain one or more dyes contain.
  • 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 dyeing liquor can also be used usual additives, e.g. Wetting agents, solubilizers, e.g. ⁇ -caprolactam or Polyethylene glycol, penetration accelerator, electrolyte, e.g. Sodium chloride or Contain sodium sulfate, complexing agents such as urea or glycerin.
  • wetting agents e.g. Wetting agents, solubilizers, e.g. ⁇ -caprolactam or Polyethylene glycol
  • penetration accelerator e.g. Sodium chloride or Contain sodium sulfate
  • electrolyte e.g. Sodium chloride or Contain sodium sulfate
  • complexing agents such as urea or glycerin.
  • the dye After drawing up the dye and the alkaline agent, the dye becomes on the yarn based on cellulose fibers by means of a thermal process or also fixed a cold process.
  • fixation is carried out by exposure to heat, a procedure is included Steam application or holding at elevated temperature or on Thermal insulation process in question.
  • the cellulose fiber yarn may e.g. around cotton, in particular mercerized and / or bleached cotton, or also unbleached yarn, expediently without prior washing according to the invention Process can be colored. Such a dyeing process is with the previously known Colorants not feasible.
  • Blended yarns based on cellulose e.g. Cotton / polyamide blended yarns or especially cotton / polyester blended yarns are also possible.
  • Viscose materials such as e.g. Tencel or Lyocell) as well as corresponding mixed fibers with cotton, e.g. Cotton / Lycra (polyurethane elastomer) into consideration.
  • cellulose yarns with high Color speed i.e. with high yield.
  • yarns can be used special effects, e.g. Chiné yarn, yarn dyed using the space dyeing process, single or multi-colored spotted yarn, or yarn with partial impregnation of the fibers, e.g. of the washed-out type, ring-dyed denim (ring dyeing method) or mechanically with Make grindstones of washed (stone wash) denim.
  • the impregnation device 2 (see e.g. FIG. 1) has one or more dye liquors, in which the yarn is impregnated with when passing through the device 2. When they leave diffuse the dyeing liquor (s) on the yarn into the interior of the yarn constructive fibers.
  • the essential components of these dyeing liquors namely the Reactive dye and the alkaline agent, which are present in aqueous solution, can be presented in separate containers or as a mixture in a single container become. By placing the dye and the agent in separate containers, one ensures high stability of the dye liquor, thereby renewing the latter in regular intervals because of the alkaline agent Hydrolysis is avoided.
  • the two solutions can be separated Containers are presented and before use in a buffer containing Intermediate containers are mixed. This way, over time, only a small one Amount of the dye liquor attacked hydrolytically and can be removed or if necessary be replaced, especially if the dyeing cycle is not used for a long time.
  • the impregnation of the yarn with the dyeing liquor (s) is regulated so that the Gams weight gain e.g. 15 to 100%, especially 15 to 80% and preferably about 15 to 50%.
  • the dyeing liquor after the yarn has left the impregnation device 2, diffuse into the interior of the fibers.
  • the impregnation takes place at ambient temperature, e.g. 15 to 40 ° C so that before and especially during the impregnation step on a heating device entirely can be dispensed with. This corresponds to both the temperature of the impregnating chamois as well as the temperature of the dye liquor when impregnating a the above temperatures.
  • the above conditions preferably also apply to the Step of winding the yarn onto one or more carriers 3.
  • These are those for the present method preferred cold fixation.
  • the dyes in the fibers are depending on Yarn quality and type and the selected dyes with a degree of fixation in the Order of magnitude of 80 to 95%, based on the coloring material, fixed.
  • This cold fixation of the dye on the gam by lingering the impregnated and wound yarn takes place, e.g. at ambient temperature, e.g. at a Temperature between 10 and 40 ° C, especially between 15 and 35 ° C.
  • the duration of the Cold treatment may depend on the dye used and will vary within further limits, between 3 and 24 hours, preferably between 4 and 10 hours, are particularly preferably between 6 and 8 hours.
  • a corresponding fixation at a higher temperature can also be considered, wherein the dye on the cellulose fiber yarn by dwelling in one impregnated and wound yarn-containing storage (4) at one temperature above 40 ° C, in particular up to 70 ° C and preferably up to 60 ° C, is fixed.
  • the Duration of treatment may depend on the dye used and will vary within wide limits. The duration of the treatment is preferably up to 3 Hours, in particular 0.5 to 3 hours and preferably 1 to 3 hours.
  • the application of the device to carry out the method according to the invention depends on the foreseen need or the foreseen production rate and can be used with single yarn or multiple yarns of any denier or type different forms.
  • Such a procedure is of interest for velor fiber materials.
  • This drying process can also be done in an autoclave using saturated or Hyperbaric steam in a chamber in the form of a channel, the high-frequency or Infrared energy is supplied, or in a duct to which hot air or hot gas is supplied will take place, the fixation then also taking place at the same time.
  • drying is done in an autoclave using steam, this is done with the dye liquor impregnated textile yarn in a treatment chamber, optionally with superheated Steam at an operating temperature between 98 and 210 ° C, advantageously between 100 and 180 ° C, and preferably between 102 ° C and 120 ° C subjected.
  • the dye can be fixed using the thermal insulation process with or without Intermediate drying, e.g. at a temperature between 100 ° C and 210 ° C, expediently between 120 ° C and 200 ° C, and very particularly between 140 ° C and 180 ° C are carried out.
  • the Thermal insulation over a period of between 20s and 5 minutes, preferably between 30s and 60s.
  • the yarn or yarns according to the Leaving the temporary storage 4 also handled by an intermediate gate coil 5 and then at a high running speed of the chamois in a washing and drainage system 6 continuously washed and e.g. centrifuged and then dried in a device 7 be, after which the yarn or yarns are wrapped on new carrier 8 ( Figure 1).
  • the device for performing this method has one of the devices for Unwind the game from the carrier 1 comparable intermediate gate coil 5, the new wrapping carrier 8 can be operated by means of a device that the system for Wrapping the yarn or yarns on one or more carriers 3 is similar.
  • FIG. 2 of the accompanying drawings shows an embodiment of the method according to the invention, in which those coming from the temporary storage 4 Carrier 3 in an autoclave 9 a washing process and in a rapid dryer 9 'one Undergo drying, whereupon the game from the carrier 3 in one Wrapping machine 11 to be wrapped on new carrier 10.
  • they can Carrier 3 for later washing in the autoclave 9 by countercurrent circulation perforated columns of a material carrier are attached, whereupon the material carrier in the quick dryer 9 'is transferred, in which the yarns on the carriers Moisture is extracted by the chamber representing the quick dryer 9 ' pressurized and by means of the perforated columns of the material carrier through the on the Carriers 3 located yarn sucks air.
  • the games rewound onto the carriers 8 or 10 are from excess dyes and yarns freed from other components of the dyeing liquors, which are completely stable in terms of color, i.e. where there is no risk of washing out more exists, and which are suitable for the production of woven and knitted fabrics, one later washing of the fabric or knitted fabric can be omitted.
  • These cellulose fiber yarns then have a moisture content of e.g. 8 to 12% in an environment common to textiles, i.e. at 22 ° C and a relative Humidity of 65%.
  • the impregnation device 2 can be made from a dye liquor trough 12, by means of a feed pump 13, with a containing the dye liquor 14 and optionally connected by means of a heat source 15 heated storage tank is maintained at a constant level, the yarn or yarns to be impregnated in the Dyeing liquor can be unwound by means of a return roller, and from a means 16 to Squeeze excess paint on the yarn (s) with compressed air adjustable pressure exist, the entire device in a chamber 17 Recovery of the squeezed paint is located and openings for passage of the yarn or yarns.
  • Such an embodiment of the impregnation device is suitable is particularly good for a single color using a in the form of a mixture of dye and alkaline dyeing liquor.
  • the squeezing means 16 consists of a container which is provided with two openings, through which the yarn (s) loaded with dye liquor are passed, and is placed under an air pressure. Through the one in the container through which the yarns throughput, generated excess pressure, becomes a large part of that on the gam remaining dye liquor squeezed out of it and through the openings of the container pushed out. In this way, a game with between can at the output of the device 2 15 and 100% of its weight in dye liquor, which is about that used on average 16 Air pressure is maintained.
  • FIG. 4 shows an embodiment variant of the impregnation device 2, in which this consists of several means 18 for guiding and holding the respective yarn in the longitudinal direction, from at least one nozzle 19 for atomizing and spraying the dye liquor onto or the running yarn, from a device 20 for squeezing excess dyeing liquor and consists of a device 21 for the continuous supply of dye liquor with the atomizing and spraying nozzles 19 and with a trough 22 for receiving excess atomized and / or squeezed dye liquor is connected, this Trough 22 forms the bottom of the chamber which represents the impregnation device 2.
  • 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. From this it follows that the dye and agent are not previously mixed and a possible one Hydrolysis of the dye by the agent can be avoided.
  • the yarn first with an aqueous solution of the reactive dye and then impregnated with the alkaline agent. In such a case the excess flowing back into the trough to absorb the excess Dye is not contaminated by the alkaline agent and does not suffer at all Hydrolysis, so that the stability of the liquor is guaranteed over a long period of time.
  • the device 20 for squeezing excess dye liquor Carrier anvil 23 of the running yarn or formed slightly higher than that horizontal running direction of the yarn or yarns is and on the upstream side of the yarn or yarns with an edge bevel 23 'or rounding and a nozzle 24 is provided for blowing in compressed air with which an air jet is directed onto the game or games becomes. So by slightly changing the forced direction of the yarn Anvil 23 and by blowing compressed air through the nozzle 24 in the amount of change of direction removal or squeezing of the excess dyeing liquor by a Combination of mechanical and pneumatic drainage.
  • the squeezing device 20 can of course also be used instead of the squeezing means 16 Execution form of the impregnation device according to Figure 3 are used and vice versa.
  • the impregnation device 2 according to FIG. 4 (or according to FIG. 12) is single fiber. expediently equipped with several atomizing and spraying nozzles 19.
  • the yarn or yarns is held in place and against a possible Deflection by which they would be moved away from the corresponding nozzles 19, so that their impregnation by the jet and the penetration of the fibers by the Dyeing liquors are better guaranteed.
  • the kinetic energy of the dye liquor sprayed onto the gam shows one optimal effect if the gam rests on a solid support and if the Dye jet can hit the gam without it being able to evade.
  • the guiding and holding means 18 in turn act to avoid any deviation in a horizontal plane lying outside the longitudinal axis of the yarn or yarns prevent.
  • the impregnation device 2 it is also possible in the impregnation device 2 to provide a sequence of evaporation nozzles 19, between each one by one Anvil 23 formed squeeze device 20 and an air injection nozzle 24 are connected.
  • successive yarns can be made on each running yarn Carry out mechanical impregnation and drainage processes, which makes this better can be impregnated with the dye liquor and thus the impregnation and diffusion of the Dyeing liquor through all fibers and inside all fibers of the yarn depending on the desired effect can be optimized and accelerated.
  • nozzles 19 in Form of piezoelectric nozzles (of the drop on demand type), thermal nozzles (of the type Bubble jet) or high-frequency nozzles with continuous or deflected jet perform.
  • Figure 10 of the accompanying drawings is an example High-frequency nozzle 19 'shown, in which a high-frequency drop generator 38 drops over a charger 39, a detector 40 and a deflector 41 the drops are directed either onto a yarn 42 or onto a return means 43. In this way, a very precise application of the dye liquor can be achieved.
  • FIG. 5 of the accompanying drawings shows a further embodiment variant of the Impregnation device 2 shown, in which an ink reservoir 26 via a Supply line and a pump 27 with a pressurized impregnation channel 28 which is formed by a longitudinal tube for each game or for several games, through which the yarn or yarns are passed in the longitudinal direction, the channel 28 is followed by a device 29 for squeezing off excess dye liquor, wherein the emerging from the pressurized channel 28 and from the Squeezing system 29 dye liquor at the bottom of the device 2 representing Chamber collected and returned to the reservoir 26 by means of a line 30 becomes.
  • the pressurized channel 28 in especially suitable for dyeing uniform fibers or in the form of a tube rectangular elongated box for coloring bundle or litz-shaped Multiple fibers can be formed.
  • the cross section and the length of these channels can be so be chosen that both the contact time of the chamois with the dye liquor depending of its speed as well as the relative speed of that in the channel circulating dye liquor regarding the speed of the yarn in the same channel can be varied. All of these factors can affect the effect of contact Dyeing liquor with the yarn and its fiber components influence.
  • An embodiment is also possible in which the pressurized dye liquor in time intervals in the channel 28, so the speed differential between dyeing liquor and yarn to be taken into account since the speeds of the yarn and the pressurized dye liquor upstream with respect to the direction of travel of the Add yarns as they subtract downstream.
  • the pressurized Impregnation channels 28 rough on their inside parallel to the running direction of the yarn Places or internals or surface deformations. The latter lead to a non-laminar flow of the dye liquor, the turbulence thus obtained being favorable to the generation of high local pressures and one which is also favorable for the yarn Impact movement, which results in fast and high-quality impregnation, if this effect is desired.
  • the squeezing system 29 can either consist of one Pressure vessel, through which the yarn loaded with the dye liquor is passed, or consist of a combination of anvil and air injection nozzle.
  • the fibers representing the game (s) due to the fact that the Yarns are immersed in a pressurized dye liquor during impregnation be surrounded quickly and in intimate contact with dye liquor, causing diffusion of the coloring substances in the fibers starts better during the impregnation.
  • the tubular or other shaped channel 28 the uniform impregnation of the Gam performing fibers reinforced.
  • Impregnation device 2 shown, in which it is in the form of an impregnation pad 31st is present, which consists of two horizontal cylinders that are in with each other along their surface line Are in contact and above which the dye liquor is constantly provided, and an arrangement of side sealing flanges 31 'at the cylinder ends composed, the impregnation of the yarn or yarns by passing through between the cylinders.
  • the impregnation device 2 in the form of a contact impregnation drum 32 the drum in one Dyeing liquor is moved and the color on the running yarn or yarns due to contact draws up by means of return roller 33 or the like on a part of the drum circumference are guided, the position of these return rollers 33 with respect to the drum 32nd is adjustable.
  • the degree of impregnation of the yarns can be modified by the rollers 33 be moved away from the drum 32 or approach it, so that a longer or shorter, stronger or weaker contact of the yarn with the drum, one leads to a certain amount of dye liquor during its rotation.
  • the Degree of impregnation can also be influenced by influencing the speed of rotation Drum 32 and thus the relative speed of the yarn with respect to the drum modify. This effect on the relative speed can be changed by changing the Direction of rotation of the drum 32 are further reinforced. In the case of one to the direction of travel the opposite rotation of the drum 32 exerts the former on that of the Drum carried film from dyeing liquor namely a soaking effect, which causes results in better penetration of the fibers of the Gam with liquor.
  • the degree can be adjusted by adjusting the viscosity of the dye liquor Fleet intake can be varied by the running yarn.
  • the device according to FIG. 9 is particularly well suited for carrying out Partially impregnated yarn of the ring-dyed type (ring dyeing process) or only part of the outer surface of a yarn.
  • ring dyeing process ring dyeing process
  • the impregnation device 2 as can be seen in section from Figure 7a of the accompanying drawings a dyeing machine with several applicators, each one different Dyeing liquors are assigned and each in steps of the same or different lengths apply stains of different colors one after the other.
  • Impregnation device can be especially yarns with fancy effects like the one below the designation of single or multi-colored space dyeings, Chiné-type yarns and Make spotted or washed out or denim yarns.
  • a dyeing machine with several coaters that can be used for this purpose is in particular from FR-A-2 650 311 and FR-A-2 719 058.
  • FIG. 7a of the accompanying drawings is a possible embodiment of a Coater of such an apparatus. This is done in one with nozzles, each are arranged at right angles to the barrel axis of one or more yarns Atomizing device 34 successively transferred dye liquor from these nozzles sprayed a slot 35 arranged in a disk 36 (FIG. 7b), the disk is between the nozzles and the direction of rotation of the yarn or yarns and thus fastened is that it rotates about a vertical axis 37. This way you can go through Actuation of the disk 36 and the nozzles of the device 34 in more or less periodically and over a predetermined period of time one spots on the or spray on the dye liquor applied.
  • Such a sequential application process for different dyeing liquors can also be used by spraying the paint on using a rotary turbine or a plate realize.
  • the turbine can be constructed as in FR-A-2 650 311, i.e. exist in the form of a cylindrical hollow body, which on its outer surface several openings or nozzles for spraying paint with the same or has different cross sections, this turbine rotating on an axis attached, which runs parallel to the axis of the yarn, and the dyeing liquor through this sprayed through different nozzles. This will keep on walking by Yarn spots of color with a size and spaced apart that match the geometry and correspond to the arrangement of the openings or spray nozzles of the turbine.
  • FIG 8 of the accompanying drawings is an embodiment variant of the invention shown, in which the impregnation device 2 in several chambers 2 ' Yarn impregnation is divided.
  • a simultaneous treatment of a variety of yarns with different colors, according to Yarn groups are carried out, each corresponding to one or more chambers 2 '.
  • one chamber 2 'or chamber groups 2' each to be treated with various dyeing liquors as required.
  • the washing and drainage system 6 can be analogous to the impregnation device 2 be constructed, as is the case in the different design variants in FIGS. 3 to 5 is shown, the liquor troughs and atomization and spray nozzles simply with Water or detergent products containing water and the Dewatering process takes place using squeezing agent, through which the water from the yarn Will get removed.
  • the gam can e.g. at a temperature between 60 and 80 ° C washed, e.g. by treatment with a solution, the soap or one or contains several detergents. Washing can be done continuously with the running yarn or by treating the chamois wound on spools.
  • the washing and drainage system 6 consists of a sequence of atomization and Spray nozzles, it is useful to wash them in countercurrent Reuse of the wash water carried out at the last wash nozzle, with respect to the direction of the chamois, taken and successively to the first Washer nozzle is reused, whereupon the residual water is discharged and treated becomes.
  • it is sufficient to collect the washing water that from the treatment in the last nozzle, with regard to the direction of the game or the game and press it back into the penultimate nozzle and continue until the first Jet.
  • This water is therefore increasingly enriched with dye residues and thus in Connected chemical products and is used for successive Washing processes of the yarn used without affecting the washing quality. hereby there is a considerable saving in washing water. In such a case it works Squeezing agent downstream of the last nozzle as a drainage device for the or the game.
  • washing nozzles By turning on the squeeze devices 20 between the different ones Washing nozzles can be optimized by the mechanical squeezing effect, which makes the yarn more suitable for rewetting.
  • the drying device 7 (not shown in detail) is expediently in shape a channel through which the yarn or yarns are passed and which with hot air or a hot gas is pressurized. With the help of this drying device 7 manages to use one or more yarns with those required for later use Obtain properties related to their relative humidity. Is the device 7 in shape formed a channel, this can advantageously with internals or rough Bodies that have a beneficial effect on the formation of turbulence Exert drying air or drying gas as well as vibrations of the yarn, which optimizes the drying effect.
  • the drying device 7 can also be in the form of a chamber be trained to concentrate the chamois through education successive strands comes on tension rollers, this chamber one Circulation with hot air or hot gas is subjected.
  • the drying device 7 can also be designed in the form of a channel be through which the yarn or yarns are passed and which with radio frequency or Infrared energy is applied.
  • one or more textile games made of cellulose fibers can be used high speed, in the order of 600 m / min or more, with Reactive dyes with significant savings in dye, i.e. with greatly reduced Discharge of dye into the wash water, as well as considerable energy savings and color water consumption continuously.
  • the yarns dyed by the present process are mechanically reduced claims and retains their physical and mechanical qualities, e.g. Regularity, stability and stretch, longer at.
  • the required ones Handling steps are greatly reduced and the space requirement of the device compared to conventional dyeing machines significantly reduced.
  • the wrapped impregnated gam is then at 8 hours Allow ambient temperature to linger, the dye being fixed on the fiber. After washing with hot water and then drying, an in is obtained brilliant red shades of dyed yarn with good properties.
  • the wrapped impregnated yarn is then at 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 to 80 ° C) with an aqueous liquor containing 2 g / l Detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l contains a preparation of esterified phosphorus derivatives and water-soluble polymers, washed, and the colored gam is dried. Here you get a gam of Chiné types, on which undyed parts and parts in brilliant yellow tones alternate.
  • the wrapped impregnated yarn is then at 6 to 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 to 80 ° C) with an aqueous liquor containing 2 g / l Detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l contains a preparation of esterified phosphorus derivatives and water-soluble polymers, washed, and the colored gam is dried.
  • you get a multi-colored Gam in which red, blue and black colored parts as well as parts with different Alternate color shades from the mixture of the three dyes used.
  • the wrapped impregnated yarn is then at 6 to 8 hours Allow ambient temperature to remain, whereby the dye is fixed on the fiber. Then at an elevated temperature (about 60 ° C to 100 ° C) with an aqueous liquor 2 g / l detergent containing an acrylic acid copolymer and a non-ionic surfactant and 1 g / l of a preparation of esterified phosphorus derivatives and water-soluble polymers contains, washed, and the dyed yarn is dried.
  • the pressure of the Impregnation nozzles which causes a different exposure (i.e.

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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)
  • Treatment Of Fiber Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP96810665A 1995-10-13 1996-10-04 Verfahren zum kontinuierlichen Färben von Garnen mit Reaktivfarbstoffen Expired - Lifetime EP0768421B1 (de)

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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 (ja)
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MX9604752A (es) 1997-09-30
JPH09119075A (ja) 1997-05-06
DE59608552D1 (de) 2002-02-14
KR970021426A (ko) 1997-05-28
ES2171218T3 (es) 2002-09-01
TR199600810A2 (tr) 1997-04-22
PT768421E (pt) 2002-07-31
US5983678A (en) 1999-11-16
FR2739880B1 (fr) 1997-12-05
FR2739880A1 (fr) 1997-04-18
BR9605105A (pt) 1998-11-10
US6134924A (en) 2000-10-24
US5891201A (en) 1999-04-06
EP0768421A1 (de) 1997-04-16

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