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
  • 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
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/14—Wool
  • D06P3/16—Wool using acid dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/30—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using reducing agents
• • 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
  • D06P1/0024—Dyeing and bleaching in one process
• • 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
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6424—Compounds containing isocyanate or isothiocyanate 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
  • D06P1/67375—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341 with sulfur-containing anions
• • 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
  • Y10S8/917—Wool or silk
• • 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
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/924—Polyamide fiber
• • 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
  • Y10S8/93—Pretreatment before dyeing
  • Y10S8/931—Washing or bleaching

Definitions

• ABSTRACT OF THE DISCLOSURE Applicants dye and bleach wool and synthetic polyamide fibers with an acid dye solution containing alkali metal salts of the oxygen acids of tetravalent sulfur, e.g. alkali metal bisulfites and hydrogen pyrosulfites, and a metal complexing agent such as polymetaphosphates and aminocarboxylic acids such as ethylene diamine tetracetic acid.
• alkali metal salts of the oxygen acids of tetravalent sulfur e.g. alkali metal bisulfites and hydrogen pyrosulfites
• a metal complexing agent such as polymetaphosphates and aminocarboxylic acids such as ethylene diamine tetracetic acid.
• the present invention concerns a process for the simultaneous dyeing and bleaching of polyamide fibers, the dye liquor used for this purpose as well as, as industrial products, the polyamide fiber materials such as wool, dyed and bleached according to this process or with this dye liquor.
• the process according to the invention comprises treating the polyamide fiber material with a dye liquor which contains Water-soluble dyestutf, a water-soluble, preferably colorless, salt of an oxygen acid of tetravalent sulfur, a compound which is capable of forming stable, water-soluble, colorless complexes with certain metal ions, present in said dyebath, which are detrimental to the dyeing effect, as well as, optionally, salts known as coupage.
• a dye liquor which contains Water-soluble dyestutf, a water-soluble, preferably colorless, salt of an oxygen acid of tetravalent sulfur, a compound which is capable of forming stable, water-soluble, colorless complexes with certain metal ions, present in said dyebath, which are detrimental to the dyeing effect, as well as, optionally, salts known as coupage.
• Hithereto water-soluble hydrogen sulfites as representatives of the salts of an oxygen acid of tetravalent sulfur as defined have already been used as bleaching agents, but their action is relatively slight. In addition, because of their reducing properties, many of them tend to decompose the dyestuif. This decomposition of the dyestuff, which is a great disadvantage, is often considerably increased by certain metal ions, especially heavy metal ions such as iron ions and the like, which are very often present in technical dye liquors.
• the source of these metal ions may be the water used for the preparation of the dyebath or one or several of the ingredients thereof. Such metal ions are referred to hereinafter in the specification as well as the appended claims as detrimental metal ions.
• Alkali metal hydrogen sulfites are employed as water-soluble salts of an oxygen acid of tetravalent sulfur; but also salts of pyrosulfurous acid, above all alkali metal hydrogen pyrosulfites such as sodium hydrogen pyrosulfite, can be used according to the invention.
• inorganic complex-forming compounds such as water-soluble polyphosphates or polymetaphosphates, preferably in the form of their alkali metal salts, and, still more preferably organic compex-forming compounds, especially basic nitrogen compounds are employed, which latter nitrogen compounds contain two unsubstituted or, optionally, substituted carboxymethyl groups bound to the nitrogen atom.
• Such preferred organic basic nitrogen compounds are, for example, nitrilotriacetic acid, ethylenediamine tetraacetic acid, B-hydroxyethylethylenediamine triacetic acid, cyclohexylenediamine tetraacetic acid or diethylenetriamine pentaacetic acid, especially in the form of their Water-soluble salts, in particular their alkali metal salts.
• Other organic complex-forming substances as defined as, for instance, poycarboxylic acids containing hydroxyl groups such as citric acid or gluconic acid, also preferably in the form of their water-soluble salts.
• a preferred compound which is capable of forming stable, water-soluble, colorless complexes with metal ions is ethylenediamine tetraacetic acid preferably in the form of its water-soluble salts, such as its alkali metal salts, especially its triand/or tetranatrium salts, since the dye assistants containing the same impart to the deyings produced with their aid superior brilliancy and better color yields than are attained especially with the aforementioned inorganic complex formers.
• Dyestuffs usable according to the invention are those which draw onto polyamide fibers, especially onto wool, and which are stable under the dyeing and bleaching conditions.
• dyestuffs are referred to as being substantive to polyamides.
• These are technically readily accessible dyestuffs, for example, metal-free or heavy metel-containing monoazo or polyazo dyestuffs, anthraquinone, phthalocyanine, nitro, diphenylmethane, triphenylmethane or rhodamine dyestuffs.
• auxiliaries which may be contained in the dyeing liquor are those conventional in the dyeing industry, especially acids when acid wool dyestuffs are used, also for example, wetting, leveling and dispersing agents, softeners which improve the handle, neutral and buffer salts, bactericides, fungicides and insecticides.
• Natural and synthetic polyamide fibers for example wool, silk and nylon, can be dyed by the process according to the invention.
• the polyamide fiber material can be used in this process in any form desired, for example, in the form of flocks, slub'bing, yarn or fabrics.
• the polyamide fiber material can also be dyed in the form of mixed fibers such as cellulose fibers mixed or encrusted with polyamides, particularly in the form of mixed fabtics of wool and polyester fibers such as cellulose acetate, cellulose triacetate and, particularly, polyterephthalic acid diol ester fibers, or polyacrylonitrile fibers.
• the dye liquor to be used according to the invention should have a content of 0.1 to 1 g. per liter, more preferably of 0.4 to 0.8 g. per liter, of water-soluble salt of an oxygen acid of tetravalent sulfur and of 0.1 to l g.
• the liquor should contain, as further auxiliary, a conventional acid agent such as acetic, formic or sulfuric acid.
• a conventional acid agent such as acetic, formic or sulfuric acid.
• the exhaustion method is used for the simultaneous dyeing and bleaching process according to the invention, at temperatures of 55-95 C., but with sufficiently heat-stable dyes also at the boiling temperature.
• such dye liquors are prepared by adding to the aqueous dyebath containing the dyestufl a dyeing assistant which contains (a) a water-soluble salt of an oxygen acid of tetravalent sulfur as defined above, and
• the dye assistants according to the invention do not substantially alter the pH of the dyebath to which they have been added, and thus do not require special readjustment of the dyebath pH. Neither should they have any substantial buffering effect on the dyebath. Moreover, these dye assistants do not create any specific occupational hazards to the dyer and thus do not make any special precautions necessary beyond those in conventional dyeing processes.
• the preferred dye assistant according to the invention contains an alkali metal bisulfite, such as sodium bisulfite, or an alkali metal hydrogen pyrosulfite, such as sodium hydrogen pyrosulfite, as water-soluble salt of an oxygen acid of tetravalent sulfur, and ethylenediamine tetraacetic acid, preferably in the form of its water-soluble salts, especially triand/ or tetrasodium salt of ethylenediamine tetraacetic acid as compound capable of forming water-soluble metal complex.
• an alkali metal bisulfite such as sodium bisulfite
• an alkali metal hydrogen pyrosulfite such as sodium hydrogen pyrosulfite
• the dyeings obtained by the process according to the invention are distinguished by excellent purity and brilliancy. This is particularly the case with dyeings in delicate pastel shades (so-called baby colors).
• Example I g. of previously wetted woolen yarn are introduced into a warm dye liquor (goods-to-liquor ratio 1:40) which contains,
• the bath is kept at this temperature for 10 minutes, then heated to 85 within 30 minutes and kept at this temperature for about minutes.
• the dyed goods are then rinsed with cold water and afterwards dried at about 60.
• the ethylenediamine tetraacetic acid disodium salt is not added then, with the same pro- (cedure, noticeably duller and generally more weakly colored dyeings are obtained.
• Good dyeings are also obtained by using 0.4 g./liter of tetrasodium ethylenediamine tetraacetate, mono 'sodiumnitrilotriacetate, sodium citrate, sodium tripolyphosphate, trisodium phosphate or sodium hexametaphosphate instead of the 0,4 g./liter of ethylenediamine tetraacetic' acid disodium salt and otherwise following the procedure given in the example.
• nylon yarn can be dyed as described in this example with the same result.
• Example 14 If instead of the 0.5 g./liter of 40% acetic acid given in Example 1, 0.5 g./liter of concentrated formic acid and 1.25 g./liter of calcined sodium sulfate are used and if instead of the dyestutf given, the acid anthraquinone dyestuff described in Example 8 of German Patent 631,518 is used and otherwise the procedure given in Example 1 is followed, then brilliant, pure blue wool dyeings are obtained.
• Example 17 If instead of the 0.5 g./liter of 40% acetic acid, 0.75 g./liter of sulfuric acid and 1.25 g./liter of calcined sodium sulfate are used and instead of the dyestufi given in Example 1, the dyestuffs mentioned in the following Table 3 are used and otherwise the procedure given in Example 1 is followed, then brilliant, pure wool dyeings are obtained having the shades given in Column III of this table.
• Example 24 25 g. of previously wetted woolen yarn are introduced into a 40 warm dye liquor (goods-to-liquor ratio 1:40) which contains 0.6 g./liter of solid sodium bisulfite (with 62% active S content),
• the bath is kept at this temperature for minutes, then heated to the boil within minutes and kept at boiling temperature for about 60 minutes.
• the dyed goods are then rinsed with cold water and afterwards dried at about 50-60.
• the ethylenediamine tetraacetic acid tetrasodium salt is not added then, with the same procedure, noticeably duller and generally more weakly colored dyeings are obtained.
• nylon yarn can be dyed as described in this eX- ample with the same result, instead of woolen yarn.
• Acid disazo dyestuii Di-(p-oxy-phcnyl)dimethyl- Yellow metl1ane-bis- (2-amino phenyl l -sulfonic acid)- ester31-(3-sullophenyl)-3-methyl-5-aminopyrazole.
• the resulting product is ready to be added to conventional exhaustion dyebaths destined for dyeing with baby colors. It can also be stored in a closed container for years.
• Example 38 40 kg. of sodium pyrosulfite (S0 content of 67%), 20 kg. of a technical mixture of trisodium and tetrasodium ethylene diamine-tetraacetate [obtained from one mol of the free acid and 1.1 mol of aqueous sodium hydr-oxide solution (36 B.) and referred hereinafter for the sake of brevity as EDTA], and 35 kg. of calcined sodium sulfate.
• Example 39 Kilograms Sodium bisulfite (S0 content of 60%) 50 Pentasodium diethylenetriamine-pentaacetate 25
• Example 40 Sodium metabisulfite 4'0 EDTA 19 Oaloined sodium sulfate 41
• Example 41 Disodium nitrilotriacetate 12 Sodium bisulfate 45 Calcined sodium sulfate 48
• Example 42 Trisodium diethylenetriaminepentaacetate 23.5
• Sodium pyrosulfite 40 Calcined sodium sulfate 36.5
• Example 43 Disodium cyclohexanediaminetetraacetate 20
• Sodium pyrosulfite 40 Calcined sodium sulfate 40
• Example 44 Disodium 3 hydroxyethyl ethylenediaminetriacetate 16.5
• Sodium bisulfite 45 Calcined sodium sulfate 43.0
• Example 45 Trisodium citrate 13.5
• Example 46 Sodium gluconate 12-0 Sodium metabisulfite 40 Calcined sodium sulfate 48
• Example 47 EDTA 20 Sodium pyrosulfite 40 Sodium chloride 5 Oalcined sodium sulfate 35
• a process for dyeing and simultaneous bleaching of polyamide fibers comprising treating the material with a dye liquor which contains as essential ingredients Watersoluble dyestuil substantive to polyamides, a water-soluble alkali metal salt of an oxygen acid of tetravalent sulfur, an acidifying agent, and a compound selected from the group consisting of water-soluble alkali metal polyphosphates, water-soluble alkali metal polymetaphosphates, a basic nitrogen compound selected from the group of nitrilotriacetic acid, ethylenediamine tetraacetic acid, ,8- hydroxyethyl-ethylenediamine triacetic acid, cyclohexylened-iamine tetraacetic acid, diethylenetri-amine pentaacetic acid, and water-soluble salts of such basic nitrogen compounds and a polycarboxylic acid from the group of citric acid and gluconic acid and watersoluble salts of such acids.
• said dye liquor contains sodium bisulfite as the water-soluble salt of an oxygen acid of tetravalent sulfur.
• said dye liquor contains a member selected from the group consisting of ethylenediamine tetraacetic acid and its watersoluble salts.
• a dye liquor suitable as bath for the simultaneous dyeing and bleaching of polyamide fibers which dye liquor contains:

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