Classifications

• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65168—Sulfur-containing compounds
• • 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
  • D06P1/00—General 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
  • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
• • 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
  • D06P1/00—General 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
  • D06P1/30—General 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 sulfur dyes
• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65106—Oxygen-containing compounds
  • D06P1/65112—Compounds containing aldehyde or ketone groups
• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65106—Oxygen-containing compounds
  • D06P1/65118—Compounds containing hydroxyl groups
• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65168—Sulfur-containing compounds
  • D06P1/65175—Compounds containing thioaldehyde or thiocetone groups
• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General 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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65168—Sulfur-containing compounds
  • D06P1/65181—Compounds containing thiol groups
• • 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
  • D06P1/00—General 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
  • D06P1/44—General 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 insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides
  • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
• • 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
  • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes
• • 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
  • D06P5/2022—Textile treatments at reduced pression, i.e. lower than 1 atm
  • D06P5/2033—Textile treatments at reduced pression, i.e. lower than 1 atm during 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
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/918—Cellulose textile

Definitions

• the invention relates to exhaust dyeing processes for dyeing cellulosic fiber material.
• sulfur dyes are advantageous for dyeing and / or printing of cellulose fiber material and / or cellulose-containing textile fiber mixtures used.
• the dyeing process uses the sulfur dyes in a water-soluble (pre) reduced form, i.e. in leuco form applied and applied to the cellulose fiber in a variety of methods and then oxidizes to a color development and / or a fastness level of the colored cellulose substrate achieve.
• DE-A-4215678 describes an exhaust dyeing in a liquor which has a reducing effect Contains sugar (glucose, dextrose) as a reducing agent, and wherein the dye in leuco form is added.
• US-A-4917706 discloses liquid, concentrated, low-salt leucosulfur dye preparations described that have been reduced with a reducing sugar (mostly glucose).
• Reducing agents that are usually used to apply sulfur dyes are used in particular: sodium bisulfide, sodium sulfide and sodium polysulfide. So are e.g.
• sulfide-free reducing agents which are known for the reduction of sulfur dyes, include: sodium borohydride, formamidine sulfinic acid, glyceraldehyde, hydroxyacetone, hydroxylamine sulfate, Lignin sulfonates, sodium formaldehyde sulfoxylate, sodium hydrosulfite, thioglycolic acid and various reducing sugars. Although they are effective, these reducing agents known disadvantages. For example, although sulfides are known to be effective reducing agents, who are quite insensitive to air oxidation, they can smell bad in terms of safety and waste disposal.
• sulfide-free reducing agents offer on the other hand the advantage that they are not the same environmental concerns and appropriate Waste disposal like sulfide-containing reducing agents cause, but they are usable largely limited due to the inconsistency of their corresponding reduction fleets Oxidation in the presence of atmospheric oxygen. This is particularly the case for other sulfur dyes as black sulfur dyes.
• special dyeing machines especially reel runners and jet dyeing equipment, in which due to the type of transport of the The textile material to be dyed therein, which entrains adhering air (and consequently oxygen), is the The use of such sulfide-free reducing agents is mostly unsuccessful except in a certain one Extent when the dye used is a black sulfur dye.
• an improved process for dyeing cellulose fiber materials and to provide cellulosic fiber materials in which one or more Sulfur dyes are used and one or more sulfide-free reducing agents are used especially when using non-black sulfur dyes.
• the invention thus relates to a process for dyeing cellulosic fiber material a sulfur dye by the exhaust method according to claim 1.
• An atmosphere with a reduced oxygen content is here an atmosphere in which the oxygen content not more than 12 Volume% oxygen, preferably not more than 10 volume%.
• a cellulose-containing fiber material means a substrate that contains cellulose fibers and optionally contain fibers other than cellulose fibers, which with the cellulose fibers can be mixed, and is preferably textile material.
• fibers other than cellulose fibers semi-synthetic and fully synthetic polymeric fiber materials come into consideration, in particular Cellulose acetates, polyamides (also aramids), polyesters, polyolefins, polyacrylonitriles and others which are known in the art as being suitable for forming fiber mixtures with cellulose fibers.
• the Fibers can be in any conventional processing form, especially as loose fibers, Threads, yarns or semi-finished products, primarily in the form of twisted yarn or fiber strands or docks, spools of thread, knitted or woven fabrics, or also finished products such as clothing.
• the Fiber material in particular the textile material, advantageously contains at least 15% by weight Cellulose fibers, primarily at least 40% by weight, i.e. 40-100% by weight cellulose fibers.
• Suitable sulfur dyes (S) which can be used according to the invention are those which are used either in non-reduced form (S 1 ) for subsequent reduction by sulfide-free reducing agents for sulfur dyes in the dyebath, or (pre) reduced sulfur dyes (S 2 ) especially as liquid concentrated preparations, which are usually aqueous alkaline solutions containing alkali-soluble leucosulfur dye thiolates, or as dry dye preparations.
• reduced sulfur dyes are particularly (pre) reduced sulfur dyes (S 2 '), which are present in a partially reduced form, which is sufficient for them to be readily soluble in alkaline solution and, if desired, to be further reduced for application can, as well as further or fully reduced sulfur dyes (S 2 "), which are readily soluble in alkaline solutions and can be used directly for application. Both (S 2 ') and (S 2 ") are included in the term "leuco sulfur dyes”. Thiosulfonate sulfur dyes (colored salts) (S 3 ) can also be used according to the invention.
• the dyes (S A ), which are at least partially dissolved in the alkaline dye liquor, are alkali-soluble forms of sulfur dyes, such as colored salts (S 3 ), pre-reduced sulfur dyes (S 2 '), further reduced sulfur dyes (S 2 ") or alkali-soluble thionation products ( S 1 "). If the dye is in insoluble form (S 1 '), a soluble form is formed in the (R) -containing dye bath; in the dyebath the dissolved dyes (S A ) are reduced, if necessary or desired, to a reduced form (S A ') which is suitable for dyeing and which in particular (S 2 ) and at least partially reduced forms of (S 3 ), ie (S 3 ').
• sulfur dye for which the process according to the invention is particularly suitable, include shades of yellow, orange, red, purple, blue, green, and brown, and combinations thereof, blue (also navy blue) dyes are particularly preferred.
• a sulfur-free reducing agent (R) is used in the dye liquor; it can be used to reduce a sulfur dye (S 1 ) or (S 3 ) or a pre-reduced dye (S 2 ') present in the dye liquor or to reduce the reduced state (leuco form) of a (pre) reduced dye (S 2 ) receive.
• the dyes (S) can be used in a commercially available form: the soluble, reduced or pre-reduced dyes, ie leucosulfur dyes (S 2 ), can be used in particular in commercially available forms, which may contain other reducing agents from their production and, especially in liquid form, if necessary or desired may contain additional reducing agent to stabilize the reduced form against the oxidizing influence of the ambient air.
• the sulfide content of (S) is so low as possible, preferably ⁇ 3%, particularly preferably ⁇ 0.1%, based on the dry weight of the dye.
• Suitable sulfide-free reducing agents come reducing sugar, hydroxyacetone or glyceraklehyd according to the invention Particularly preferred are reducing sugars.
• the reducing sugars to reduce the sulfur dyes include: a safer one Chemical system because of the reduced likelihood of dangerous Hydrogen sulfide gas when the dye liquor is acidified compared to sulfide reducing agent; reduced environmental concerns related to waste disposal because of the sulfide-free reducing agents (R), and especially the preferred ones, especially the reducing sugars that are easily biodegradable, and the elimination of the formation of nasty ones Odors from the aqueous sulfur dye liquor.
• a preferred group of sulfide-free reducing agents thus contains reducing sugars which are particularly effective in the process according to the invention for reducing sulfur dyes (S 1 ) and also (S 3 ) or (S 2 ') to their reduced forms, and consequently for dyeing cellulose fiber material or Cellulose fiber mixtures are particularly suitable.
• effective reducing sugars are meant those that are able to reduce the Fehling's solution and include a variety of carbohydrates, especially mono- and oligosaccharides, some of which are already known in the art.
• Useful reducing sugars are in particular those which are referred to as aldo- and / or keto-triose, -tetrose, -pentose and -hexose, but are not limited thereto.
• reducing sugars examples include fructose, galactose, glucose, mannose, maltose and lactose; other reducing sugars that are able to reduce the Fehling's solution and consequently also a sulfur dye to its (pre) reduced form can also be used.
• Sodium hydrosulfite also known as sodium dithionite
• Vat Dyes vat dyes
• the use thereof in usual sulfur dye fleets leads to the observed difficulties in the control of the Degree of reduction of the sulfur dye, so that this method is not a general inclusion in the Experts find.
• Over-reduction of some sulfur dyes leads to the destruction of the Dye chromophores, while under-reduction the reduced dye bath against air oxidation makes inconsistent, which can lead to "bronzed” staining; both of these drawbacks lead to Variations in nuances and deviations in the ultimately colored product compared to the expected pattern can be observed.
• Thiourea dioxide also called formamidine sulfinic acid
• Thiourea dioxide is also a well-known in the art usable reducing agent for vat dyes, but also does not find a general decrease in use for the application of sulfur dyes because of the same difficulties which are mentioned above for sodium hydrosulfite etc. the uneven reduction of sulfur dyes.
• the dyeing is expediently carried out under alkaline conditions, advantageously at pH values 10 10, in particular in the range from 10 to 14, preferably 10.5 to 13, particularly preferably 11 to 12.5.
• the liquor length can fluctuate in any range as is suitable for dyeing processes in closed vessels, in particular in reel runners or jet dyeing machines, and is advantageously in the range from 1: 4 to 1:20, preferably 1: 6 to 1:12, particularly preferably 1: 8 to 1:10.
• the concentration of (R) can be selected depending on the type, amount and concentration of the dye used and the type of (R) and can also vary depending on the type of substrate and the particular dyeing method.
• the reducing agent (R) is expediently used in an amount which is suitable for a sulfur dye, in particular (S 1 ) and also (S 3 ) or (S 2 '), in a suitable manner to its reduced form under the dyeing conditions used reduce and / or to obtain the reduced state of a (pre) reduced sulfur dye, in particular (S 2 ).
• the concentration of the reducing agent (R) is advantageously in the range from 0.5 to 15% by weight, preferably 1 to 10% by weight, particularly preferably 2 to 6% by weight, in particular 3 to 5% by weight, based on the dry weight of the substrate.
• the dyeing temperature may also vary depending on the dyeing method and the dyeing apparatus and is advantageously in the range from 35 to 130.degree. C., primarily 45 to 105.degree. C., preferably 60 to 100.degree.
• the Sulfur dye is present in such a concentration, as determined by the dyeing conditions and the desired depth and shade of color is required.
• the suitable or preferred amount of (R) depends essentially on the type and amount of (S) and is, for example, in the range from 0.5 to 10 g / l, based on the volume of the dyeing liquor. Even if the dye (S) is used in (pre) reduced form (S 2 ), a certain amount of (R) must be present in the liquor, preferably 0.5 to 5 g / l, also depending on the type of substrate and the amount of trapped air carried through and in the substrate and to maintain unoxidized conditions during dyeing.
• the amount of reducing agent (R) which may be present in a commercial form of (S 2 ) can also be included in the calculation.
• the process can be used for any dyeing process in which dyeing is carried out using sulfur dyes using sulfide-free reducing agents or, if the dye already contains a reducing agent (R), even in the absence of added reducing agent.
• a sulfide-free reducing agent (R) is used, while in the case of a (pre) reduced form of a sulfur dye (S 2 ), as stated above, the Presence of an added reducing agent (R) is not absolutely necessary.
• the reducing agent (R) is used in the presence of a chelating agent (C), in particular an exhaustively carboxymethylated derivative of a low amino compound, such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid or nitrilotriacetic acid, preferably in alkali metal salt form, for example in a concentration in the range from 0 , 1 to 2 wt .-% (C) based on the dry weight of the substrate, for example in the range of 1 to 20 wt .-% (C) based on the weight of (R).
• C chelating agent
• a leucosulfur dye (S 2 ) is used in the form of a concentrated (R) -containing preparation
• a. chelating agent (C) may already be contained in such a preparation, which is preferably alkaline, for example in a concentration of 3 to 40 parts by weight (C) per 100 parts by weight (S 2 ).
• the content of (S 2 ) in these concentrated preparations is preferably 8 8.5% by weight, predominantly 12 12% by weight; they can be aqueous or dry and are preferably alkaline
• the first stage of the invention Process characterized in that the cellulose fiber with a sulfur dye dyeing liquor in the presence of a sulfide-free reducing agent (R) and in the presence of an inert gas in Brings into contact, the inert gas to form an inert gas atmosphere and / or to purge the atmosphere that is in contact with the dye liquor can be used.
• the inert gas is used to maintain the inert gas atmosphere above or in contact with the Dyeing liquor is used so that an inert atmosphere is obtained within the dyeing apparatus.
• the first stage is under vacuum or reduced pressure method.
• the first stage of the dyeing process is carried out after or then purging the atmosphere with steam and introducing another inert gas carried out, which then to maintain the inert gas atmosphere within the dyeing apparatus is used.
• the process described here is particularly useful in reel runners and jet dyeing machines advantageous.
• Inert gases which are suitable for the process according to the invention include in particular one or more of the following: noble gases (preferably argon), nitrogen or water vapor and optionally carbon dioxide.
• Inert gases are understood in particular to be those which do not tend in the dye liquor that is contained in the dyeing machine with the reduced sulfur dye to react, especially to oxidize him, and who are able to increase the amount of oxygen, which is contained in the atmosphere captured in the vessel at the values given above to effectively reduce.
• the inert gas nitrogen, an inert gas or carbon dioxide is advantageous. preferably nitrogen or an inert gas, particularly preferably nitrogen.
• the substrate to be colored is loaded in a conventional coloring apparatus, in which the internal volume which is not filled with liquid, ie the "trapped atmosphere” or simply “atmosphere", is first flushed out with an inert gas reduce the amount of oxygen contained in the captured atmosphere to no more than 12% by volume, preferably no more than 10% by volume, especially no more than 7% by volume.
• the oxygen content is preferably in the range from 0.5 to 7.0% by volume, particularly preferably in the range from 1.0 to 5.0% by volume.
• the indicated reduced oxygen contents are obtained during the entire first stage of the dyeing process, ie during the extraction of the at least partially reduced and soluble dye (S A ').
• Two categories of dyeing machines, in which the method described here is used with advantage are nozzle dyeing machines and reel skid dyeing machines.
• the reason why these devices used with advantage lies in the way in which the substrate to be colored is handled in both machines, the substrate is transported mechanically through the dyeing liquor and then through the trapped atmosphere within the apparatus and then in and through the dye bath; and this process continues until a sufficient color is obtained.
• This repeated mechanical transport through the captured atmosphere and then through the Dyeing liquor etc. is a cause, why the gas content of the captured atmosphere by the Carrying gas trapped in the substrate is introduced into the fleet.
• This appearance is understandable to the person skilled in the art and is a main means by which entrained atmospheric oxygen is introduced into the aqueous sulfur dye dye liquor composition can be.
• water vapor can also be used as a rinsing agent.
• the vapor can be unsaturated, saturated or supersaturated, but is preferably unsaturated or saturated steam, and the steam pressure should be sufficient to remove the captured atmosphere the dyeing machine and rinsing them out. After the steam the atmosphere inside of the dyeing machine at a temperature below the boiling point, it cools in generally condenses and condenses so that vacuum conditions or conditions of a reduced Pressure (i.e. less than one atmosphere, i.e. ⁇ 0.98 bar) within the dyeing device, what conditions may be desirable or undesirable.
• a reduced Pressure i.e. less than one atmosphere, i.e. ⁇ 0.98 bar
• the dyeing machine can be equipped with a Vacuum suction device, e.g. a vacuum pump, which connects the captured Atmosphere of the dyeing vessel is carried out under reduced pressure or vacuum.
• a vacuum apparatus can offer the advantage that a regular flow of inert gas from the Gas supply through the internal volume of the vessel not occupied by liquid and beyond the vacuum suction device can be maintained. Because this method is a regular sweep of inert gas required by the dyeing machine, it offers the further advantage that any atmospheric oxygen that can enter the interior of the equipment if the equipment is not is properly airtight, is also sucked out and is not retained.
• the Operating pressure of such a vacuum apparatus can be at any pressure which is used Achieving the above effects is suitable, preferably at a pressure slightly below the Inlet pressure of the inert gas, which is fed into the dyeing apparatus.
• the vacuum apparatus can be used alone without simultaneous feeding of inert gas, etc. so that the previously placed in the dyeing machine Inert gas is slowly sucked out, and a reduced pressure in the not occupied by liquid The interior of the dyeing machine is created.
• further dyeing aids can be used in the process according to the invention, especially wetting agents, defoamers, deaerating agents, water-soluble mineral salts (preferably Sodium sulfate or chloride) and - to adjust the pH to the desired value - bases (e.g. alkali metal hydroxides or carbonates) or acids (especially low molecular weight aliphatic ones Carboxylic acids, e.g. with 2 to 4 carbon atoms, preferably acetic acid), as such in dyeings common.
• the concentration of added soluble mineral salts can be kept at a very low level, e.g. ⁇ 30 g / l (0 to 30 g / l) based on the dyeing liquor.
• the first stage (exhaust phase) of the dyeing process is preferably carried out by rinsing out the liquor completed, which is advantageously carried out as long as the atmosphere lowered oxygen content is still preserved. It is particularly preferred to rinse with water until the rinsing liquor it's clear.
• the treated substrates become one in a second phase subjected to oxidative treatment, in particular with an oxidizing agent (B).
• B oxidizing agent
• the stage which is advantageously carried out under acidic conditions, is the dye on the Substrate oxidized, especially to achieve color development and a level of authenticity.
• Sulfur dyes are useful, e.g. a gaseous form of oxygen (oxygen, ozone, air or air enriched with oxygen and / or ozone or a mixture of inert gas and Oxygen and / or ozone), hydrogen peroxide or preferably an oxidizing salt, e.g. Sodium or potassium perborate, percarbonate, bichromate, chlorate, iodate or bromate, the latter preferably in the presence of a suitable activator, e.g. alkali metal metavanadate; among them the bromate is particularly preferred, especially in the presence of sodium or potassium metavanadate.
• a gaseous form of oxygen oxygen, ozone, air or air enriched with oxygen and / or ozone or a mixture of inert gas and Oxygen and / or ozone
• hydrogen peroxide or preferably an oxidizing salt e.g. Sodium or potassium perborate, percarbonate, bichromate, chlorate, iodate or bromate
• the atmosphere can be of reduced oxygen level the first stage, relieved or set to a higher oxygen level, advantageous > 12% by volume, preferably> 15% by volume, particularly preferably> 18% by volume, e.g. up to 21 vol .-% or higher.
• a gaseous form of oxygen such as described above, e.g. by relieving a previous vacuum or reduced Pressure or by ventilating the highly inert atmosphere of the first stage or by introducing one gaseous form of oxygen at positive pressure, e.g. between 0.1 and 2 bar, e.g.
• the oxygen level is increased before the second stage by introducing air, advantageous in the event of overpressure in the area from 0.2 to 1.5 bar, preferably 0.4 to 1 bar. Oxidation with the dissolved oxidizing agent in the presence of this "air cushion" is particularly advantageous and leads to colorations more optimally Yield and fastness.
• the oxidation bath suitably contains an effective amount of oxidizing agent (B), which is preferably an oxidizing salt (B,), advantageously in the range from 0.2 to 12 g / l, preferably 0.5 to 5 g / l, particularly preferably 1 to 2 g / l, based on the liquor volume.
• B oxidizing agent
• the fleet ratio is advantageously in the same range as in the first stage.
• the oxidation is advantageous under carried out mild heating, preferably in the temperature range from 40 to 75 ° C, especially preferably 49 to 71 ° C, and at a pH in the range of 4 to 6, preferably 4.5 to 5.5.
• the oxidized material can be rinsed and neutralized, e.g. with sodium carbonate, as is customary after a sulfur dye dyeing, and as usual Way, e.g. by rinsing, drying and / or finishing if desired suitably with usual equipment.
• Very level, clear dyeings of high yield and depth can be obtained by the process according to the invention and excellent fastness properties, e.g. Light fastness, wet fastness (especially fastness to washing and Crocking).
• the method according to the invention allows the application of all Sulfur dye nuances on cellulose fiber material and / or cellulose mixed fiber material in one closed vessel, such as a jet dyeing machine or a reel runner, especially from others Sulfur dyes as black sulfur dyes.
• one closed vessel such as a jet dyeing machine or a reel runner
• a textile substrate is colored in a nozzle dyeing machine as follows: 500 g of 100% cotton jersey are placed in a MATHIS Laboratory Jet type JFO dyeing machine loaded. The dyeing machine is then filled with 4500 g of an aqueous solution containing 1 g of ethylenediaminetetraacetic acid sodium salt, 60 g sodium carbonate, 35 g glucose and 175 g sodium sulfate contains. This liquor is then heated to 49 ° C as the substrate is conveyed through the machine becomes. During this time, to make the atmosphere inert, nitrogen is added to the dyeing vessel charged until an overpressure of 0.6 bar is reached and at this point the vessel is degassed and reloaded with nitrogen.
• the dyeing process is carried out under identical conditions, as described in Example 1, with the exception that the inerting process via nitrogen purge is omitted; it only became one medium-deep black coloring of insufficient levelness preserved.
• a textile substrate is colored in a nozzle dyeing apparatus as follows: 500 g 100% cotton jersey is loaded into a MATHIS Laboratory Jet type JFO dyeing machine. The dyeing machine is then washed with 4500 g of an aqueous liquor containing 1 g of ethylenediaminetetraacetic acid sodium salt, Contains 60 g sodium carbonate, 35 g glucose and 175 g sodium sulfate. This Treatment bath is then heated to 49 ° C as the substrate is fed through the machine. In order to make the atmosphere inert, nitrogen is loaded into the dyeing vessel until an overpressure of 0.6 bar is reached and at this point the vessel is degassed and again charged with nitrogen.
• the dyeing process is repeated under identical conditions, as described in Example 2, with the difference that the atmosphere inerting process via the nitrogen purges is omitted becomes; a pale blue color of the fabric was obtained, of poor levelness.
• a textile substrate is dyed in a nozzle dyeing apparatus as follows: 500 g of 100% cotton jersey are placed in a MATHIS Laboratory Jet type JFO dyeing machine loaded. The dyeing machine is then treated with 4500 g of an aqueous solution containing 1 g of ethylenediaminetetraacetic acid sodium salt, 60 g sodium carbonate, 35 g glucose and 175 g sodium sulfate, filled. This liquor is then heated to 49 ° C as the fabric moves through the machine becomes. During this time, to make the atmosphere inert, nitrogen is added to the dyeing vessel charged until an overpressure of 0.6 bar is reached, at which point the vessel is degassed and is reloaded with nitrogen.
• a textile substrate is colored in a nozzle dyeing machine as follows: 500 g of 100% cotton interlock jersey are placed in a MATHIS Laboratory Jet type JFO dyeing machine loaded. The dyeing machine is then treated with 4500 g of an aqueous solution containing 1 g Ethylenediaminetetraacetic acid sodium salt, 15 g sodium carbonate, 25 g sodium hydroxide 50%, 17.7 g of glucose and 100 g of sodium sulfate filled. This liquor is then heated to 49 ° C while the fabric is transported through the machine. During this time nitrogen is added to the staining jar charged until an overpressure of 0.6 bar is reached and then the vessel is degassed and with nitrogen reloaded.
• the dyeing process is repeated under identical conditions, as described in Example 4, with the difference that the atmosphere inerting process is via the nitrogen purge process is omitted. There was a pale blue coloring of the substrate with poor levelness receive.
• Example 4 The dyeing procedure described in Example 4 is repeated, with the difference that instead of 2.7 g C.I. Leuco Sulfur Blue 13, 16 g C.I. Index Leuco Sulfur Blue 20 can be used and the Staining is done for 45 minutes at 71 ° C instead of 93 ° C. You get a deep one navy blue coloring of the fabric with good levelness.
• the fabric is rinsed for 5 minutes and the washing liquor is drained and then the machine is refilled with water.
• To this fleet 50 g of sodium carbonate are added and the machine is then heated to 71 ° C. and Maintained at this temperature for 10 minutes. A full black color of good levelness is obtained.
• Example 6 The dyeing process described in Example 6 is repeated under identical conditions with the Difference in that the atmosphere inerting process via the nitrogen purge is omitted becomes; a full black color of the fabric is obtained, which has poor levelness having.
• a nozzle dyeing machine is coated with a cotton fabric to be dyed and with enough water to give a liquor ratio of 1:10, and the contents are heated to 49 ° C.
• 0.5 g / l of a 40% aqueous ethylenediaminetetraacetic acid sodium salt solution, 0.5 g / l SODYECO Defoamer DSV (mixture of petroleum derivatives - trademark), 25 g / l Sodium sulfate, 5 g / l soda ash, 5 g / l aqueous 50% sodium hydroxide solution and 5 g / l one Mixture of 94.5% by weight glucose, 5% by weight sodium lignin sulfonate and 0.5% by weight Dusting oil added to the bath.
• the mixture obtained is gradually, in the course of 5 minutes, such an amount of 33% by weight C.I. Sulfur Black 1 containing Suspended, which is sufficient to a concentration of 16% dye, based on the To reach weight of the textile material, and the mixture obtained is at a Heating rate of 2.75 ° C / min. heated to 71 ° C while the atmosphere above Liquor in the apparatus is flushed with nitrogen.
• the dye bath obtained is then at a Speed of 2.75 ° C / min. heated to 93 ° C and at this temperature for 45 minutes held.
• the dyebath is then cooled to 71 ° C and the contents are overflowed with unheated Rinse water until the liquor water is clear.
• the fleet ratio is again 1:10 adjusted and the liquor is heated to 49 ° C while the interior of the apparatus is ventilated. Now 2 g / l of 56% acetic acid and 2 g / l of an aqueous solution containing 12% Sodium bromate and 1% sodium metavanadate added and the oxidation liquor obtained is on Heated 65 ° C and held at this temperature for 10 minutes. The fleet is then in the Overflow rinsed and drained and the apparatus is refilled with water, which is 1 g / l calcined soda can be added. The dyed textile material is then in the resulting fleet rinsed at 88 ° C for 10 minutes. Then the liquor is cooled to 71 ° C and the colored Material unloaded.
• ethylenediaminetetraacetic acid sodium salt can be in the form of the commercially available Chelating agent SULFALOX 100 (an aqueous alkaline solution of ethylenediaminetetraacetic acid) are used, C.I. Leuco Sulfur Black 1 can be in the form of a commercial dye SANDOZOL Black 4G-RDT can be used in liquid form, C.I. Leuco Sulfur Blue 13 can be in shape of the commercial preparation SANDOZOL Blue 2GB-RDT can be used in liquid form, C.I. Leuco Sulfur Blue 20 can be used in liquid form in the form of the commercial dye SANDOZOL Navy Blue GF-RDT be, C.I.
• Solubilized Sulfur Black 2 can be in the form of the commercial preparation SANDOZOL Black R powder can be used and the mixture of sodium bromate and sodium metavanadate can be in Form of commercially available aqueous solutions of sodium bromate / sodium metavanadate, e.g. DYETONE or CHEM-OXY SG.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Coloring (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)

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• 1995
  • 1995-08-23 US US08/518,626 patent/US5632782A/en not_active Expired - Fee Related
  • 1995-08-30 PT PT95810536T patent/PT699797E/pt unknown
  • 1995-08-30 EP EP95810536A patent/EP0699797B1/de not_active Expired - Lifetime
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• 1997
  • 1997-01-28 US US08/788,470 patent/US5873912A/en not_active Expired - Fee Related

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