EP0090272A2 - Procédé de teinture égale de fibres de polyester par la méthode d'épuisement - Google Patents

Procédé de teinture égale de fibres de polyester par la méthode d'épuisement Download PDF

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Publication number
EP0090272A2
EP0090272A2 EP83102623A EP83102623A EP0090272A2 EP 0090272 A2 EP0090272 A2 EP 0090272A2 EP 83102623 A EP83102623 A EP 83102623A EP 83102623 A EP83102623 A EP 83102623A EP 0090272 A2 EP0090272 A2 EP 0090272A2
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EP
European Patent Office
Prior art keywords
dye
dyeing
liquor
dyes
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83102623A
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German (de)
English (en)
Other versions
EP0090272A3 (fr
Inventor
Siegfried Dr. Glander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
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Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0090272A2 publication Critical patent/EP0090272A2/fr
Publication of EP0090272A3 publication Critical patent/EP0090272A3/fr
Withdrawn legal-status Critical Current

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34Material containing ester groups
    • D06P3/52Polyesters
    • D06P3/54Polyesters using dispersed dyestuffs
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34Material containing ester groups
    • D06P3/36Material containing ester groups using dispersed dyestuffs
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06BTREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/20Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004General aspects of dyeing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D06P1/92General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
    • D06P1/928Solvents other than hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066Thermic treatments of textile materials
    • D06P5/2072Thermic treatments of textile materials before dyeing

Definitions

  • the present invention relates to a process for the uniform dyeing of textile material from hydrophobic synthetic fibers, preferably polyester (PES) fibers, alone or as a component of mixtures with natural or other synthetic fibers using the exhaust method with heat-fixable colorants in a closed apparatus system under high temperature (HT) conditions at the increasing pressure as well as under atmospheric pressure, at temperatures between 90 ° and 140 ° C. from an aqueous medium by means of a moving liquor which is circulated in the dyeing system until the colorant is present the textile material is pulled up and fixed in it.
  • HT high temperature
  • the entire dyeing liquor, including the dye is heated to a dyeing temperature in a batch container separate from the actual dyeing vessel and then, with the help of relative overpressure, quickly transferred to the connected circulation dyeing machine, in which the fiber material arranged in the packing or slip-on system is located, which is in a preparatory step vented with flowing steam and at the same time had also been heated to about dyeing temperature.
  • the complete condensation of the steam atmosphere is forced and the dyeing tank is completely filled with the pressed liquor.
  • Disperse dyes in particular have proven themselves as colorants for the stated purpose.
  • Disperse dyes which are known to contain no solubilizing groups in the molecule, are organic compounds with limited solubility in water, but with the proportionally low form in water of high affinity for polyester fibers.
  • dyeing synthetic fibers from an aqueous phase takes place over the dispersed dye by adding appropriate additives, such as a relatively high amount of dispersant (to stabilize the Fleet) into a fine distribution, without which a spot-free and level coloring would not be possible.
  • the actual dyeing process takes place through the adsorption of the dissolved monomolecular dye onto the surface of the PES fiber and through the subsequent diffusion into the interior of the fiber.
  • the solution balance in the fleet which is disturbed during this exhaust process, becomes Compensation restored by redissolving dye from the dispersed state.
  • the finish of the commercial dyes therefore has a great influence on the dyeing properties and accounts for about half of the dye production costs. Despite all of this, difficulties arise due to the different leveling behavior of disperse dyes in the PES pull-out dyeing.
  • the present invention is based on the object of making dyes or pigments without a finish or without a binder accessible for all exhaust process variants for dyeing PES fibers from an aqueous bath and in this way to simplify the treatment measures.
  • the focus here is on achieving level dyeings in a short time even with poorly leveling dyes and saving on expensive finishing costs.
  • This object is achieved according to the invention in that dyes and / or pigments which are practically insoluble or sparingly soluble in water, without prior preparation by means of a finish aimed at suitable dyeing properties or in the absence of special binders, in one or more organic solvents which operate under dyeing conditions are sufficiently soluble in water or are miscible with it, and the solution thus obtained is then circulated into the Textile material is introduced, dye-free or dye-depleted aqueous liquor flowing through or around dyeing temperature.
  • the claimed process advantageously makes use of the fact that when a water-insoluble dye dissolved in an organic solvent of the type defined above is introduced into water which is hot at about 130 ° C., surprisingly a higher proportion of dye remains in solution than from the dye dispersion during conventional heating to 130 ° C. goes into solution in the aqueous liquor.
  • the idea of the invention on which the present case is based now consists of using this experimental finding directly for dyeing and metering the dye solution obtained in the above manner in portions into the circuit of a disturbing, aqueous liquor without dyeing at any temperature, so that under A exploitation 'of the increased concentration of the monomolecular dye results in a better levelness of the dyeings.
  • dyestuffs are used as dyestuffs which meet the abovementioned conditions with regard to solubility.
  • Such products are well known and are described in the Color Index, 3rd edition, volume 2 under the class name "Disperse Dyes”. According to their constitution, most disperse dyes belong to the azo, antrachinone or in a few cases to the nitro or quinophthalone compounds.
  • the disperse dyes can advantageously be used in the unfinished state and can be used, for example, as press cakes, ie coming from the manufacture and not yet provided with the finish (unfinished fabrication (raw) goods).
  • the present 'invention also enables those gefinishten disperse dyes, according to the usual exhaust difficult matter to dye are to dye with very good levelness.
  • pigments can also be used, provided they meet the requirements with regard to solubility, especially organic pigments which, in the course of the new process, do not require a binder system as a mediator for their binding to the fiber, and those in the color index, Edition, Volume 3 are divided under the term "Pigments".
  • Solvent Dyes in the Color Index, 3rd edition, volume 3 have also proven to be suitable according to the process.
  • the dyes and / or pigments mentioned are dissolved in a solvent (of the type defined above) alone or in a mixture thereof in as high a concentration as possible and this concentrated dye solution is metered in portions at certain intervals , expediently distributed over several pumping cycles with changing flow direction, pressed into the aqueous dye liquor.
  • a solvent of the type defined above
  • this concentrated dye solution is metered in portions at certain intervals , expediently distributed over several pumping cycles with changing flow direction, pressed into the aqueous dye liquor.
  • the entire amount required for dyeing can be added to the circulating liquor in one batch or in a few portions in the form of a concentrated solution, with less-level or poorly leveling dyes, it can be introduced in several portions certain time intervals or distributed over different circulation cycles.
  • the reductive aftertreatment can be dispensed with and the coloring only needs to be rinsed.
  • the present invention is technically easy to implement, because all existing zirhulation dyeing machines can be used for the new process and a controllable sluice device according to the known state of the art can be easily installed on the fleet circulation system of the dyeing machines.
  • the blind liquor (without dye) can advantageously be heated to the dyeing temperature as quickly as possible.
  • An additional batch container for heating the dyeing liquor, as in the isothermal rapid color process according to DE-PS 23 31 669, is unnecessary according to the invention.
  • the claimed process can be carried out very safely and provides very reproducible dyeings because the dosage or the introduction of the dye solution can easily be controlled automatically, especially since modern dyeing machines already work under program control.
  • the organic solvent in the residual liquor and the associated wastewater pollution appear to be disadvantageous compared to the conventional process for dyeing from aqueous dispersion.
  • concentration of such a solvent in the liquor is very low (for example 0.3% by volume in Example 1), that in most cases no dispersing and leveling agents get into the waste water with the remaining liquor that if necessary, a reductive aftertreatment the dyeings can be dispensed with and therefore no alkali or sodium dithionite can get into the waste water, and that finally biodegradable organic solvents can be used.
  • all HT dyeing machines with circulating liquor e.g. Cross-wound and tree dyeing machines, including those with separate batch tanks, as are otherwise used for isothermal dyeing processes, and also all HT jet dyeing machines are suitable.
  • the dyeing apparatus of the same design working at cooking temperature under atmospheric pressure can also be considered.
  • the concentrated dye solution can be introduced into the liquor circulation in various ways.
  • the dosing is either carried out via a secondary or sample chamber or via a separate vessel. taken.
  • Exemplary embodiments of such metering devices which can be used according to the invention are shown schematically in the drawings given below. This can be done, for example, with the aid of a bypass line which can be locked against the pressurized dyeing system and in which a batch or storage vessel is located Preparation and absorption of the dye solution is located.
  • the distribution of the dye solution in the total dyeing liquor is then carried out by including the bypass in the liquor cycle.
  • This process can be carried out by means of pressure superimposition by, for example, compressed air, water vapor or an inert gas on the liquid surface of the dye solution, which is equipped with a compressed air supply in a heatable and pressure-tight sealable.
  • Batch or storage vessel deposited which is connected to the fleet circuit directly or indirectly via a riser pipe with the interposition of a metering valve.
  • the dosing of the dye solution in predetermined portions can be accomplished by appropriate control, for example a solenoid valve or a pneumatically controllable valve, manually or automatically, after certain times or distributed over a predetermined number of pumping cycles.
  • the injector will then consist of an additional pump which conveys the dye solution into the pressurized dyeing system from a batch or storage vessel under atmospheric pressure.
  • the dyeing described below was carried out in a yarn dyeing apparatus, which essentially consists of a pressure-tight dye container with carriers for the textile material to be dyed, a pipeline connected to form the liquor circuit and a circulation pump for the circulating liquor, the pipeline mentioned ( 1) contains a connection to the metering device shown in Fig. 1 for feeding the dye solution into the liquor circuit.
  • This metering device is itself constructed from a batch or storage vessel (2) for the dye solution (3), which is equipped with a feed (4) for compressed air or a compressed gas, a closable pressure outlet (5) and a liquid emptying pipe (6) and with a Heating jacket (7) for controlling the temperature in the dye solution (3) is equipped.
  • a riser pipe (8) reaching almost to the bottom of the vessel leads after an approximately right-angled bend out of the batch or storage vessel (2) and establishes the connection to the pipeline (1) of the liquor circulation system via a metering valve (9).
  • the riser pipe (8) is provided for the portion-wise removal and transfer of the dye solution (3) from the batch or storage vessel (2) into the pipeline (1), which is achieved by applying relative overpressure to the liquid level of the dye solution (3) is, and expediently at dyeing temperature, ensures the uniform distribution of the dye solution (3) in the total dye liquor pulsating due to pump action with changing flow direction through the pipeline (1), the dyeing tank and the textile material or poor in dye.
  • a blind liquor made of 320 liters of water had been filled into the dyeing container charged with the textile material to be dyed.
  • the switching intervals were 4 minutes each .. from outside to inside and 3 minutes from inside to outside.
  • the dye solution (3) was divided into 3 switching intervals and about 1/3 of the batch amount was added to the cycle of the entire fleet.
  • the dye solution (3) was transferred with the aid of nitrogen, which was pressed into the batch vessel (2) and superimposed on the liquid level at a pressure of 5 bar. As soon as the metering valve (9) was opened, the dye solution rose in this riser pipe due to the increased pressure on the surface of the liquid outside the riser pipe (8) and in this way reached the circulating liquor.
  • the dyeing system was cooled, the textile material was removed from the dyeing tank and only rinsed with water without reductive aftertreatment.
  • a yarn dyeing apparatus similar to the description in Example 1 was used for the subsequent dyeing, but in this case the pipeline (1) used to form the liquor circuit is provided here with a metering device connected as a bypass according to FIG. 2.
  • This metering device consists in that a shunt line (10a, 10b), which is installed between the sections (10a) and (10b) and equipped with a pressure outlet (5) which can be closed by a valve (3) passes through, branches off from the pipeline section (1a) and is fed back to this pipeline in section (1b) after a certain distance.
  • a shunt line (10a, 10b) which is installed between the sections (10a) and (10b) and equipped with a pressure outlet (5) which can be closed by a valve (3) passes through, branches off from the pipeline section (1a) and is fed back to this pipeline in section (1b) after a certain distance.
  • the dosing principle is based on the fact that hot, blind or dye-depleted liquor is removed in the flow direction of the pipelines at (1b) by suitable actuation of three-way cock (11b), over the distance (10b) through the batch or storage vessel (2 ) and is then returned via the line (10a) and the second three-way valve (11a) back into the pipeline at (1a).
  • This measure causes the dye solution (3) to be carried in portions is then distributed evenly in the entire circulating fleet.
  • the blind liquor of 20 l of water was adjusted to pH 5 by acidification and via the pipeline composed of sections (1a), (1c) and (1b) through the PES muff stored in the dyeing tank under the same treatment conditions as in Example 1 brought to circulation.
  • the transfer of the dye solution (3) into the dyeing container was started.
  • the hot fleet circulated 8 times briefly over the route (1b) - (11b) - (10b) - (2) - (10a) - (11a) - (1a) and took from the preparation vessel (2) each time with about 25 cm 3 of dye solution in the circulation stream.
  • This dyeing was also ended after a dyeing time of 20 minutes, the dyed PES material with an aqueous bath with the addition of 3 cm 3 / l NaOH solution of 38 ° Be and 3 g / l sodium dithionite and 1 g / l of a nonionic detergent for 10 minutes after-treated at 85 ° C and then rinsed with water.
  • the dyeing system used comprising the dyeing tank and the textile goods contained therein, was of the same type as in Example 1.
  • a blind 20 liter liquor circulated through a 700 g PES fiber muff. This aqueous, 130 ° C warm liquor was mixed with 1 g / l of a dispersant and adjusted to pH 5.
  • the dye solution was transferred into 8 portions. After the metering had ended, the dyeing operation was continued for a further 20 minutes and then ended.
  • the yarn dyeing apparatus used here corresponds in principle to that of Example 1, but in this case the pipeline (1) provided to form the liquor circuit has a connection to the metering device shown in FIG. 3.
  • This dosing device is composed of a batch or storage vessel (2) for the dye solution (3), containing a feed (4) for compressed air or compressed gas and is surrounded by a heating jacket (7) for controlling the temperature in the dye solution ( 3).
  • a transfer line (12) branching off from the bottom of the vessel and provided with a metering valve (9) serves as a connection between the batch or storage vessel (2) and the pipeline (1) for the liquor circuit.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)
EP83102623A 1982-03-20 1983-03-17 Procédé de teinture égale de fibres de polyester par la méthode d'épuisement Withdrawn EP0090272A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3210380A DE3210380C2 (de) 1982-03-20 1982-03-20 Verfahren zum gleichmäßigen Färben von hydrophoben synthetischen Fasern nach der Ausziehmethode
DE3210380 1982-03-20

Publications (2)

Publication Number Publication Date
EP0090272A2 true EP0090272A2 (fr) 1983-10-05
EP0090272A3 EP0090272A3 (fr) 1984-11-28

Family

ID=6158908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83102623A Withdrawn EP0090272A3 (fr) 1982-03-20 1983-03-17 Procédé de teinture égale de fibres de polyester par la méthode d'épuisement

Country Status (5)

Country Link
US (1) US4491995A (fr)
EP (1) EP0090272A3 (fr)
JP (1) JPS58169583A (fr)
KR (1) KR840004204A (fr)
DE (1) DE3210380C2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0143077A1 (fr) * 1983-11-15 1985-05-29 Ciba-Geigy Ag Procédé de teinture de matière textile hydrophobe
EP0204656A1 (fr) * 1985-05-14 1986-12-10 Ciba-Geigy Ag Procédé de teinture de matiére textile hydrophobe
FR2658210A1 (fr) * 1990-02-13 1991-08-16 Champagne Teinturerie Procede de traitement et de reajustement d'un bain de traitement (teinture) de produits textiles ainsi que dispositif utilise pour la mise en óoeuvre de ce procede.

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61252381A (ja) * 1985-05-01 1986-11-10 株式会社 日阪製作所 低浴比染色における染液の供給方法
DE3720697A1 (de) * 1987-06-23 1989-01-05 Hoechst Ag Verfahren zum faerben von textilen geweben oder gewirken aus polyesterfasern oder mischungen aus polyesterfasern mit anderen fasern in jet-faerbemaschinen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1794193A1 (de) * 1967-09-29 1971-05-06 Ciba Geigy Ag Verfahren zum Faerben von hydrophoben Textilmaterialien
DE2337097A1 (de) * 1972-09-01 1974-03-07 Ciba Geigy Ag Verfahren zum faerben von synthetischem fasermaterial und dessen mischungen mit natuerlichem fasermaterial
LU70654A1 (fr) * 1974-04-13 1974-12-10
DE2331669A1 (de) * 1973-06-22 1975-01-23 Hoechst Ag Verfahren zum faerben von synthesefasern
DE2534562A1 (de) * 1975-08-02 1977-02-03 Hoechst Ag Verfahren zum gleichmaessigen, isothermischen hochtemperaturfaerben von hydrophoben synthetischen fasern mit dispersionsfarbstoffen
DE2456250B2 (de) * 1974-11-28 1979-09-27 Rudolf Then, Faerbereimaschinenfabrik Gmbh, 7172 Schwaebisch Hall Verfahren und Vorrichtung zum Färben von in einem Färbekessel im Pack- oder Aufstecksystem angeordnetem garn- oder faserförmigem Textilgut

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH555939A (fr) * 1972-06-19 1974-11-15
DK514674A (da) * 1974-05-22 1975-11-23 Obermaier & Cie Fremgangsmade til veskebehandling, navnlig til farvning af tekstilfibre, og apparat til gennemforelse af fremgangsmaden
DE2534618C3 (de) * 1975-08-02 1978-03-23 Hoechst Ag, 6000 Frankfurt Verfahren und Vorrichtung zum isothermischen Hochtemperaturfärben
JPS5845519B2 (ja) * 1976-07-16 1983-10-11 三井東圧化学株式会社 合成繊維の染色法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1794193A1 (de) * 1967-09-29 1971-05-06 Ciba Geigy Ag Verfahren zum Faerben von hydrophoben Textilmaterialien
DE2337097A1 (de) * 1972-09-01 1974-03-07 Ciba Geigy Ag Verfahren zum faerben von synthetischem fasermaterial und dessen mischungen mit natuerlichem fasermaterial
DE2331669A1 (de) * 1973-06-22 1975-01-23 Hoechst Ag Verfahren zum faerben von synthesefasern
LU70654A1 (fr) * 1974-04-13 1974-12-10
DE2456250B2 (de) * 1974-11-28 1979-09-27 Rudolf Then, Faerbereimaschinenfabrik Gmbh, 7172 Schwaebisch Hall Verfahren und Vorrichtung zum Färben von in einem Färbekessel im Pack- oder Aufstecksystem angeordnetem garn- oder faserförmigem Textilgut
DE2534562A1 (de) * 1975-08-02 1977-02-03 Hoechst Ag Verfahren zum gleichmaessigen, isothermischen hochtemperaturfaerben von hydrophoben synthetischen fasern mit dispersionsfarbstoffen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0143077A1 (fr) * 1983-11-15 1985-05-29 Ciba-Geigy Ag Procédé de teinture de matière textile hydrophobe
EP0204656A1 (fr) * 1985-05-14 1986-12-10 Ciba-Geigy Ag Procédé de teinture de matiére textile hydrophobe
FR2658210A1 (fr) * 1990-02-13 1991-08-16 Champagne Teinturerie Procede de traitement et de reajustement d'un bain de traitement (teinture) de produits textiles ainsi que dispositif utilise pour la mise en óoeuvre de ce procede.
EP0443281A1 (fr) * 1990-02-13 1991-08-28 Teinturerie De Champagne Procédé de traitement et de réajustement d'un bain de traitement (teinture) de produits textiles ainsi que dispositif utilisé pour la mise en oeuvre de ce procédé

Also Published As

Publication number Publication date
KR840004204A (ko) 1984-10-10
EP0090272A3 (fr) 1984-11-28
JPS58169583A (ja) 1983-10-06
DE3210380A1 (de) 1983-09-29
DE3210380C2 (de) 1986-01-02
US4491995A (en) 1985-01-08

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