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 which are suitable for dyeing cellulose-containing fiber material.
• sulfur dyes are advantageously used for dyeing and / or printing cellulosic fiber material and / or cellulosic textile fiber mixtures.
• the sulfur dyes are in a water-soluble (pre) reduced form, i.e. applied in leuco form and are applied to the cellulose fiber in a variety of methods and then oxidized in order to achieve a color development and / or a level of authenticity of the colored cellulose substrate.
• Reducing agents which are usually used for the application of sulfur dyes are in particular: sodium hydrogen sulfide, sodium sulfide and sodium polysulfides.
• sodium hydrogen sulfide sodium hydrogen sulfide
• sodium sulfide sodium polysulfides.
• Japanese Kokai 60-17185 and 60-119285 and US Pat. No. 4,082,502 describe dyeing processes in which sulfur dyes are reduced with sulfide, the dyeing being carried out in closed apparatus, specifically in Japanese Kokai 60 -17185 and 60-119285 with the addition of nitrogen or an inert gas and in US Pat. No. 4,802,502 under HT conditions with the addition of steam.
• sulfide-free reducing agents that do not contain sulfide ions
• sulfur dyes include: sodium borohydride, formamidine sulfinic acid, glyceraldehyde, hydroxyacetone, hydroxylamine sulfate, lignin sulfonates, sodium formaldehyde sulfoxylate, sodium hydrosulfite, thioglycolic acid, and various reducing agents.
• sodium borohydride formamidine sulfinic acid
• glyceraldehyde hydroxyacetone
• hydroxylamine sulfate lignin sulfonates
• sodium formaldehyde sulfoxylate sodium formaldehyde sulfoxylate
• sodium hydrosulfite sodium hydrosulfite
• thioglycolic acid and various reducing agents.
• sulfide-free reducing agents offer the advantage that they do not cause the same environmental concerns and appropriate waste disposal as sulfide-containing reducing agents, but their applicability is largely limited because of the instability of their corresponding reducing liquors against oxidation in the presence of atmospheric oxygen. This is particularly the case for sulfur dyes other than black sulfur dyes.
• sulfur dyes other than black sulfur dyes.
• special dyeing machines especially reel runners and jet dyeing machines, in which, due to the manner in which the textile material to be dyed is carried, which entrains the adhering air (and consequently oxygen)
• the use of such sulfide-free reducing agents is mostly unsuccessful except to a certain extent if the dye used is a black sulfur dye .
• the object of the invention to provide an improved process for dyeing cellulose fiber materials and cellulose mixed 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 cellulose-containing fiber material with a sulfur dye by the exhaust process, which is characterized in that the fiber material in an enclosed vessel and under an atmosphere with reduced oxygen content with an aqueous dye liquor containing at least one sulfur dye (p ) in at least partially soluble form (S A ) and contains at least one sulfide-free reducing agent (R), brings them into contact and then oxidizes them.
• An atmosphere with a reduced oxygen content is here an atmosphere in which the oxygen content is lower than that of normal air, which contains about 21% by volume of oxygen.
• the atmosphere with reduced oxygen content advantageously contains no more than 12 volume% oxygen, preferably no more than 10 volume%.
• the cellulose-containing fiber material means a substrate which contains cellulose fibers and may optionally contain fibers other than cellulose fibers which can be mixed with the cellulose fibers, and is preferably textile material.
• Other fibers than cellulose fibers are semisynthetic and fully synthetic polymeric fiber materials, in particular cellulose acetates, polyamides (also aramids), polyesters, polyolefins, polyacrylonitriles and also others which are known in the art as being suitable for forming fiber mixtures with cellulose fibers.
• the fibers can be in any customary processing form, in particular as loose fibers, threads, yarns or semi-finished products, primarily in the form of twisted yarn or fiber strands or docks, yarn spools, knitted fabrics or fabrics, or also finished products such as clothing.
• the fiber material, in particular the textile material advantageously contains at least 15% by weight of cellulose fibers, primarily at least 40% by weight, ie 40-100% by weight of cellulose fibers.
• Suitable sulfur dyes (S) which can be used according to the invention are those which are used either in non-reduced form (S1) for subsequent reduction by sulfide-free reducing agents for sulfur dyes in the dyebath, or (pre) reduced sulfur dyes (S2) in particular as liquid concentrated preparations, which are mostly aqueous alkaline solutions containing alkali-soluble leucosulfur dye thiolates, or as dry dye preparations.
• reduced sulfur dyes are in particular (pre) reduced sulfur dyes (S2 '), 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, as well as further or fully reduced sulfur dyes (S2 ''), which are easily soluble in alkaline solutions and can be used directly for application. Both (S2 ') and (S2'') are included in the term "leuco sulfur dyes”. Thiosulfonate sulfur dyes (colored salts) (S3) 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 (S3), pre-reduced sulfur dyes (S2 '), further reduced sulfur dyes (S2'') or alkali-soluble thionation products (S1''). If the dye is in insoluble form (S1 '), 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 (S2) and at least partially reduced forms of (S3), ie (S3') , includes.
• S3 colored salts
• S2 ' pre-reduced sulfur dyes
• S2'' further reduced sulfur dyes
• S1'' alkali-soluble thionation products
• Suitable sulfur dyes (S) which can be used in the process according to the invention are, for example, those of the following “Color Index” names ("CI” stands for "Color Index”): CI Sulfur Yellow 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, 16, 20 and 23, CI Leuco Sulfur Yellow 2, 4, 7, 9, 12, 15 , 17, 18, 21, 22 and 23 and CI Solubilized Sulfur Yellow 2, 4, 5, 19, 20 and 23; CI Sulfur Orange 1, 2, 3, 4, 5, 6, 7 and 8, CI Leuco Sulfur Orange 1, 3, 5 and 9 and CI Solubilized Sulfur Orange 1, 3, 5, 6, 7 and 8; CI Sulfur Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 and 13, CI Leuco Sulfur Red 1, 4, 5, 6, 11 and 14 and CI Solubilized Sulfur Red 3, 6 , 7, 11 and 13; CI Sulfur Violet 1, 2, 3, 4 and 5, CI Leuco Sulfur Violet 1 and 3 and CI Solubilized Sulfur Violet 1; CI Sul
• Particular nuances of sulfur dyes for which the process according to the invention is particularly suitable include shades of yellow, orange, red, violet, blue, green and brown and combinations thereof, blue (also navy blue) dyes being particularly preferred.
• a sulfur-free reducing agent (R) is used in the dye liquor; it can be used to reduce a sulfur dye (S1) and (S3) or a pre-reduced dye (S2 ') present in the dyeing liquor or to obtain the reduced state (leuco form) of a (pre) reduced dye (S2).
• the dyes (S) can be used in a commercially available form: the soluble, reduced or pre-reduced dyes, ie leucosulfur dyes (S2), can be used in particular in commercially available forms, which may contain other reducing agents from their production and, if necessary, especially in liquid form or if desired may contain additional reducing agent to stabilize the reduced form against the oxidizing influence of the ambient air.
• S2 ie leucosulfur dyes
• the sulfide content of (S) be as low as possible, preferably ⁇ 3%, particularly preferably ⁇ 0.1%, based on the dry weight of the dye.
• Suitable sulfide-free reducing agents are those mentioned above, among which the organic ones are preferred, in particular reducing sugars, hydroxyacetone, glyceraldehyde, sodium formaldehyde sulfoxylate, formamidine sulfinic acid and thioglycolic acid.
• R is particularly preferred a reducing agent which contains neither nitrogen atoms nor sulfur atoms, in particular a reducing sugar, hydroxyacetone or glyceraldehyde, among which reducing sugars are most preferred.
• 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 (S1) and also (S3) or (S2 ') to their reduced forms, and consequently particularly suitable for dyeing cellulose fiber material or cellulose fiber mixtures are.
• Effective reducing sugars are meant those that are capable of reducing Fehling's solution and include a variety of carbohydrates, especially mono- and oligosaccharides, some of which are already known in the art.
• Usable 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 which 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 dye reductant
• Vat Dyes as defined in the Color Index
• An over-reduction of some sulfur dyes leads to the destruction of the dye chromophore, while an under-reduction makes the reduced dye bath unstable against air oxidation, which can lead to "bronzed” dyeings; both of these disadvantages lead to nuance variations and deviations that are observed in the ultimately colored product compared to the expected pattern.
• Thiourea dioxide also called formamidine sulfinic acid
• the dyeing is expediently carried out under alkaline conditions, advantageously at pH values ⁇ 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 reducing a sulfur dye, in particular (S1) and also (S3) or (S2 '), in a suitable manner to its reduced form under the dyeing conditions used and / or to obtain the reduced state of a (pre) reduced sulfur dye, in particular (S2).
• 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 can also vary depending on the dyeing method and the dyeing apparatus and is advantageously in the range from 35 to 130 ° C., primarily 45 to 105 ° C., preferably 60 to 100 ° C.
• Concentrations of 1 to 10 g / l reducing sugar, e.g. Glucose is preferred in order to achieve a reduction at dyeing temperatures in the range from 70 to 130 ° C., the sulfur dye being present in such a concentration as is required by the dyeing conditions and the desired depth and shade of dyeing.
• the sodium hydrosulfite is advantageously used in concentrations of 1 to 4 g / l in order to effectively reduce a sulfur dye (S1) and (S3) or (S2 '). Concentrations higher or lower than these can be considered, depending on the aqueous sulfur dye liquor in which the sodium hydrosulfite is used.
• the dyeing temperatures can generally correspond to those used for sulfide-reduced sulfur dye liquors and are primarily above 38 ° C., with good results in the temperature range from 49 to 105 ° C., preferably 60 to 100 ° C., in particular 70 to 93 ° C. , can be achieved.
• the concentration of thiourea dioxide is preferably in the range from 1 to 4 g / l in order to effectively reduce a sulfur dye (S1) and (S3) or (S2 '). Higher or lower concentrations can also be considered, depending on the aqueous sulfur dye liquor used in which the thiourea dioxide is used.
• the dyebath temperatures can generally correspond to those used for sulfide-reduced sulfur dye liquors and are primarily in the range above 38 ° C, with good results in the temperature range from 49 to 105 ° C, preferably 60 to 100 ° C, in particular 70 to 93 ° C, can be achieved.
• the thioglycolic acid is advantageously used in concentrations of 1 to 5 g / l in order to effectively reduce the sulfur dye (S1) or (S3) or (S2 ') to achieve. Concentrations lower or higher than this can be considered depending on the aqueous sulfur dye liquor in which the thioglycolic acid is used.
• the dye liquor temperatures can generally correspond to those used for sulfide-reduced sulfur dye fleets and are predominantly above 38 ° C., good results in the temperature range from 49 to 105 ° C., preferably 60 to 100 ° C., in particular 70 to 93 ° C. can be achieved.
• sulfide-free reducing agents which are known to be useful for the reduction of sulfur dyes can also be used according to the invention.
• An additional advantage of the process according to the invention is that less reducing agent can be used than is otherwise 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 (S2), 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 Amount of trapped air that is carried through and in the substrate and to maintain unoxidized conditions during dyeing.
• the amount of reducing agent (R) which may optionally be in a commercial form of (S2), 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 reducing agent for example, in the case of a non-reduced form of a sulfur dye (S1) or (S3) a sulfide-free reducing agent (R) is used, while in the case of a (pre) reduced form of a sulfur dye (S2), as indicated 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 (S2) is used in the form of a concentrated (R) -containing preparation
• a chelating agent (C) can also 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 (S2).
• the (S2) content is preferably ⁇ 8.5% by weight, mainly ⁇ 12% by weight; they can be aqueous or dry and are preferably alkaline.
• the first stage of the process according to the invention is characterized in that the cellulose fiber is brought into contact with a sulfur dye dyeing liquor in the presence of a sulfide-free reducing agent (R) and in the presence of an inert gas, the inert gas to form an inert gas atmosphere or / and for flushing out the atmosphere that is in contact with the dye liquor.
• R sulfide-free reducing agent
• the inert gas is used to maintain the inert gas atmosphere above or in contact with the dye liquor, so that an inert atmosphere is obtained within the dyeing apparatus.
• the first stage is carried out under vacuum or reduced pressure.
• the first stage of the dyeing process is carried out after or after purging the atmosphere with steam and introducing another inert gas, which is then used to maintain the inert gas atmosphere within the dyeing apparatus.
• the process described here is particularly advantageous in reel runners and nozzle dyeing machines.
• Inert gases which are suitable for the process according to the invention are in particular one or more of the following: noble gases (preferably argon), nitrogen or water vapor and, if appropriate, carbon dioxide.
• Inert gases are understood in particular to mean those which do not tend to react, in particular to oxidize, with the reduced sulfur dye in the dyeing liquor which is contained in the dyeing apparatus, and which are capable of reducing the amount of oxygen which is present in the Vessel captured atmosphere is included to effectively degrade to the values given above.
• the inert gas is advantageously nitrogen, a noble gas or carbon dioxide, preferably nitrogen or a noble 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 the amount of oxygen contained in the trapped atmosphere to not more than 12% by volume, preferably not more than 10% by volume, especially not more than 7% by volume belittling.
• 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 advantageously 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 set out here is advantageously used are nozzle dyeing machines and reel skid dyeing machines.
• the reason why these devices are used with advantage is because of the way in which the substrate to be colored is handled: in both devices the substrate is transported mechanically through the dyeing liquor and then through the captured atmosphere inside the device and then back into and by the dye liquor; and this process continues until a sufficient color is obtained.
• This repeated mechanical conveyance through the captured atmosphere and then through the dye liquor, etc. is a cause why the gas content of the captured atmosphere is introduced into the liquor by carrying gas trapped in the substrate.
• This phenomenon will be understood by those skilled in the art and is a major means by which entrained atmospheric oxygen can be introduced into the aqueous sulfur dye liquor composition.
• water vapor can also be used as a rinsing agent.
• the vapor may be unsaturated, saturated or supersaturated, but is preferably unsaturated or saturated vapor, and the vapor pressure should be sufficient to remove and purge the trapped atmosphere from the dyeing machine.
• the vapor After rinsing the atmosphere within the dyeing apparatus at a temperature below the boiling point, the vapor generally cools and condenses so that vacuum or reduced pressure (ie less than one atmosphere, ie ⁇ 0.98 bar) conditions within the dyeing apparatus arise which conditions may be desired or undesirable. If such a reduced pressure is compatible with the equipment used and if a reduced pressure can be obtained, no further measures are required to achieve the desired reduced To reach oxygen level. However, if such reduced pressures are undesirable, after steam condensation within the dyeing apparatus, an amount of inert gas may be introduced into the dyeing apparatus to form an inert gas atmosphere therein.
• the dyeing machine can be equipped with a vacuum suction device, e.g. a vacuum pump, are connected, whereby the captured atmosphere of the dyeing vessel is conducted under reduced pressure or vacuum.
• a vacuum suction device e.g. a vacuum pump
• the use of such a vacuum apparatus can offer the advantages that a regular flow of inert gas can be maintained from the gas feed through the internal volume of the vessel not occupied by liquid and also through the vacuum suction apparatus. Since this method requires a regular sweeping of inert gas through the dyeing machine, it offers the further advantage that any atmospheric oxygen that can penetrate into the interior of the apparatus, if the apparatus is not properly sealed, is also extracted and is not retained.
• the operating pressure of such a vacuum apparatus can be at any pressure which is suitable for achieving the above effects, preferably at a pressure which is 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 in of inert gas, etc. so that the inert gas previously introduced into the dyeing apparatus is slowly extracted and a reduced pressure is created in the interior of the dyeing apparatus which is not occupied by liquid.
• further dyeing aids can be used in the process according to the invention, in particular 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 carboxylic acids, for example with 2 to 4 carbon atoms, preferably acetic acid), as is customary per se in dyeings.
• bases e.g. alkali metal hydroxides or carbonates
• acids especially low molecular weight aliphatic carboxylic acids, for example with 2 to 4 carbon atoms, preferably acetic acid
• concentration of soluble mineral salts added can be kept at a very low level, e.g. ⁇ 30 g / l (0 to 30 g / l) based on the dye liquor.
• the first stage (exhaust phase) of the dyeing process is completed with a rinsing out of the liquor, which is advantageously carried out as long as the atmosphere's oxygen content has decreased is still preserved. It is particularly preferred to rinse with water until the rinsing liquor is clear.
• the treated substrates are subjected to an oxidative treatment in a second phase, in particular using an oxidizing agent (B).
• a second phase which is advantageously carried out under acidic conditions, the dye on the substrate is oxidized, in particular in order to achieve color development and a fastness level.
• Any (oxidizing agents) which can usually be used per se for sulfur dyes 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,
• the atmosphere can be relieved of the reduced oxygen level of the first stage or set to a higher oxygen level, advantageously> 12% by volume, preferably> 15% by volume, particularly preferably> 18% by volume, e.g. up to 21 vol.% or higher.
• This is advantageously accomplished by introducing a gaseous form of oxygen 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 a gaseous form of oxygen at excess pressure, e.g. between 0.1 and 2 bar, e.g.
• the oxygen level is increased before the second stage by introducing air, advantageously at an excess pressure in the range from 0.2 to 1.5 bar, preferably 0.4 to 1 bar.
• air advantageously at an excess pressure in the range from 0.2 to 1.5 bar, preferably 0.4 to 1 bar.
• the oxidation bath suitably contains an effective amount of oxidizing agent (B), which is preferably an oxidizing salt (B1), 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.
• the liquor ratio is advantageously in the same range as in the first stage.
• the oxidation is advantageously carried out with mild heating, preferably in the temperature range from 40 to 75 ° C., particularly preferably 49 to 71 ° C., and at a pH in the range from 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 can be finished in a conventional manner, e.g. by rinsing, drying and / or, if desired, finishing in a suitable manner with conventional finishing agents.
• Very level, clear dyeings of high yield and depth and excellent fastness properties e.g. Light fastness, wet fastness, especially wash fastness and fastness to staining.
• the method according to the invention allows the application of all nuances of sulfur dye to cellulose fiber material and / or cellulose blend fiber material in a closed vessel, such as a nozzle dyeing apparatus or a reel runner, especially of sulfur dyes other than black sulfur dyes. Further advantages, even if not expressly described, will be obvious to the person skilled in the art.
• a textile substrate is dyed in a nozzle dyeing machine as follows: 500 g of 100% cotton jersey are loaded into a MATHIS Laboratory Jet type JFO dyeing machine. The dyeing machine is then filled with 4500 g of an aqueous solution containing 1 g of ethylenediaminetetraacetic acid sodium salt, 60 g of sodium carbonate, 35 g of glucose and 175 g of sodium sulfate. This liquor is then heated to 49 ° C as the substrate is transported through the machine. During this time to make the atmosphere inert, nitrogen is loaded into the dyeing vessel until an overpressure of 0.6 bar is reached, at which point the vessel is degassed and reloaded with nitrogen.
• the dyeing process is carried out under identical conditions as described in Example 1, except that the inerting process via nitrogen flushing is omitted; only a medium-deep black color of insufficient levelness was obtained.
• a textile substrate is dyed in a nozzle dyeing machine as follows: 500 g of 100% cotton jersey are loaded into a MATHIS Laboratory Jet type JFO dyeing machine. The dyeing machine is then filled with 4500 g of an aqueous liquor which contains 1 g of ethylenediaminetetraacetic acid sodium salt, 60 g of sodium carbonate, 35 g of glucose and 175 g of sodium sulfate. This treatment bath is then heated to 49 ° C as the substrate is passed through the machine. In order to make the atmosphere inert, nitrogen is loaded into the staining vessel during this time until an overpressure of 0.6 bar is reached, at which point the vessel is degassed and reloaded with nitrogen.
• the dyeing process is repeated under identical conditions as described in Example 2, with the difference that the atmospheric inerting process via the nitrogen purges is omitted; a pale blue color of the fabric, of poor levelness, was obtained.
• a textile substrate is dyed in a nozzle dyeing machine as follows: 500 g of 100% cotton jersey are loaded into a MATHIS Laboratory Jet type JFO dyeing machine. The dyeing machine is then filled with 4500 g of an aqueous solution containing 1 g of ethylenediaminetetraacetic acid sodium salt, 60 g of sodium carbonate, 35 g of glucose and 175 g of sodium sulfate. This liquor is then heated to 49 ° C as the fabric is carried through the machine. During this time, in order to render the atmosphere inert, nitrogen is loaded into the dyeing vessel until an overpressure of 0.6 bar is reached, at which point the vessel is degassed and reloaded with nitrogen.
• a textile substrate is dyed in a nozzle dyeing machine as follows: 500 g of 100% cotton interlock jersey are loaded into a MATHIS Laboratory Jet type JFO dyeing machine. The dyeing machine is then filled with 4500 g of an aqueous solution containing 1 g of ethylenediaminetetraacetic acid sodium salt, 15 g of sodium carbonate, 25 g of 50% sodium hydroxide, 17.7 g of glucose and 100 g of sodium sulfate. This liquor is then heated to 49 ° C as the fabric is carried through the machine. During this time, nitrogen is loaded into the coloring vessel until an overpressure of 0.6 bar is reached and then the vessel is degassed and reloaded with nitrogen.
• the dyeing process is repeated under identical conditions as described in Example 4, with the difference that the atmospheric inerting process is carried out via the nitrogen purge process is omitted. A pale blue coloration of the substrate with poor levelness was obtained.
• Example 4 The dyeing procedure described in Example 4 is repeated, with the difference that instead of 2.7 g of C.I. Leuco Sulfur Blue 13, 16 g C.I. Index Leuco Sulfur Blue 20 are used and the staining is carried out for 45 minutes at 71 ° C instead of 93 ° C. A deep navy blue dyeing of the fabric with good levelness is obtained.
• 2500 g of a 100% cotton knitwear are loaded into a reel runner BENZ Laboratory Winch-Beck type LH dyeing machine.
• the dyeing machine is then filled with 50 l of an aqueous solution containing 2.6 g of ethylenediaminetetraacetic acid sodium salt, 200 g of an aqueous 25% sodium hydroxide solution, 200 g of glucose and 2250 g of sodium sulfate.
• This liquor is then heated to 49 ° C as the fabric is fed through the machine.
• nitrogen is loaded into the dyeing vessel, blowing it through the liquor and flushing the atmosphere in the vessel and forming an inert gas atmosphere over the liquor.
• Example 6 The dyeing process described in Example 6 is repeated under identical conditions with the Difference that the atmosphere inerting process via the nitrogen purge is omitted; a full black color of the fabric is obtained, which has poor levelness.
• a jet dyeing machine is loaded 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.
• the dye bath obtained is then at a rate of 2.75 ° C / min. heated to 93 ° C and held at this temperature for 45 minutes.
• the dyebath is then cooled to 71 ° C and the contents are rinsed in the overflow with unheated water until the liquor water is clear.
• the liquor ratio is reset to 1:10 and the liquor is heated to 49 ° C.
• ethylenediaminetetraacetic acid sodium salt can be in the form of the commercially available chelating agent SULFALOX 100 (an aqueous alkaline solution of ethylenediaminetetraacetic acid).
• SULFALOX 100 an aqueous alkaline solution of ethylenediaminetetraacetic acid.
• CI Leuco Sulfur Black 1 can be used in the form of the commercial dye SANDOZOL Black 4G-RDT
• CI Leuco Sulfur Blue 13 can be used in the form of the commercial preparation SANDOZOL Blue 2GB-RDT in liquid form
• CI Leuco Sulfur Blue 20 can be used in the form of Commercial dye SANDOZOL navy blue GF-RDT can be used in liquid form
• CI Solubilized Sulfur Black 2 can be used in the form of the commercial preparation SANDOZOL Black R powder and the mixture of sodium bromate and sodium metavanadate can be used in the form of commercially available aqueous solutions of

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