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
  • D06P1/673—Inorganic 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
  • 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
  • D06P3/06—Material containing basic nitrogen containing amide groups using acid 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
  • D06P1/60—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 polyethers
  • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
  • D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
• • 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
  • D06P3/02—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
  • 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
  • D06P3/24—Polyamides; Polyurethanes
  • D06P3/241—Polyamides; Polyurethanes using acid dyes
• • 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

Definitions

• the present invention relates to new mixtures of leveling agents and ammonium fluorosilicate, containing a compound of the formula wherein R is an alkyl or alkenyl radical having 12 to 22 carbon atoms, M is hydrogen, alkali metal or ammonium and m and n are integers, the sum of m and n being 2 to 14, or of the formula wherein R 'independently of R has the meaning given for R, A is an anion, Q is an optionally substituted alkyl radical and p and q are integers, the sum of p and q being 2 to 50, or of the formula wherein R ′′ independently of R has the meaning given for R and x and y are integers, the sum of x and y being 80 to 140, containing a mixture of compounds of the formula (1) and (2) or a mixture Compounds of the formulas (1), (2) and (3) or (1a), (2) and (3) and 5 to 25 percent by weight (NH4) 2SiF6 based on that Weight of the compounds of the formulas (1)
• the mixtures according to the invention are suitable for a process for fiber and flat dyeing of natural and synthetic polyamide fiber materials with 1: 1 metal complex dyes containing sulfo groups or with dye mixtures containing 1: 1 metal complex dyes containing sulfo groups and metal-free dyes containing sulfonic acid groups in the presence of 10 to 45 liquors Weight percent of an ammonium hexafluorosilicate, or alkali fluorosilicate and ammonium hexafluorosilicate, based on the amount by weight of the 1: 1 metal complex dye used in the presence of an auxiliary, dyeing at a fiber-preserving pH of 3 to 5, the dye bath being practically completely extracted, the dyeing is well-colored and has good overall fastness properties, in particular good wet fastness properties and good light fastness properties.
• a disadvantage of the dyeing processes used hitherto for natural or synthetic polyamide materials with 1: 1 metal complex dyes or mixtures of 1: 1 metal complex dyes with metal-free acid dyes is that these dyes or mixtures are dyed at a pH of approximately 1.9 to 2.8 must be in order to obtain level coloring.
• the pH value of the dyebath is of crucial importance in addition to the dyeing time, since natural and synthetic polyamide materials, especially wool, are strong both in the strongly acidic and in the alkaline pH range to be attacked.
• the mixtures according to the invention can be used to carry out a process which does not have the disadvantages mentioned and which allows natural or synthetic textile polyamide fiber materials in the fiber-protecting pH range from 3 to 5, in particular 3.5 to 4.5, to be carried out in a simple manner. preferably 3.7 to 4.2 to color.
• the leveling aids of the mixtures according to the invention are known per se and are produced by known methods.
• the mixtures according to the invention preferably contain, as leveling aid mixtures, 5 to 70 parts by weight of the compounds of the formula (1) or (1a), 15 to 60 parts by weight of the compound of the formula (2) and 5 to 60 parts by weight of the compound of the formula (3) to 100 parts by weight of the leveling agent mixture, where in the formulas (1), (1a), (2) and (3) R, R 'and R' 'independently of one another denote an alkyl or alkenyl radical having 16 to 22 carbon atoms.
• the mixtures according to the invention advantageously contain a compound of the formula (2) in which A and Q are derived from the quaternizing agents chloroacetamide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromohydrin or preferably dimethyl sulfate.
• the mixtures according to the invention contain in particular a leveling aid mixture which, in addition to compounds of the formulas (1) or (1a), (2) and (3), the sum of p and q in formula (2) preferably being 20 to 50, also an adduct from 60 to 100 moles of ethylene oxide to one mole of C15-C20 alkenyl alcohol.
• the mixtures according to the invention likewise preferably contain a leveling aid mixture which contains the compounds of the formulas (1) and (2) or (1a) and (2), in which the sum of the symbols p and q in formula (2) is 4 to 10.
• the mixtures according to the invention preferably also contain a leveling aid mixture of compounds of the formula (2), in which the sum of the symbols p and q in formula (2) is 30 to 40 and R 'is an alkyl radical having 15 to 22 carbon atoms.
• the leveling agent mixture which is very particularly preferred for the mixtures according to the invention can, in addition to water, contain, for example, an adduct of 60 to 100 moles of ethylene oxide with one mole of C15-C20 alkenyl alcohol, preferably 80 moles of ethylene oxide with one mole of oleyl alcohol.
• the mixture according to the invention is produced by mixing at least one compound of the formulas (1), (1a), (2) or (3) with 5 to 25 percent by weight ammonium hexafluorosilicate.
• the mixing process takes place, for example, in suitable mixers.
• the mixture according to the invention can be used together with a dye mixture containing alkali and / or ammonium hexafluorosilicate for dyeing natural or synthetic polyamide fiber materials.
• mixtures which can be used together with the mixtures according to the invention are solid mixtures comprising at least one 1: 1 metal complex dye containing sulfo groups, in particular 1: 1 chromium complex dye, and optionally at least one metal-free dye containing sulfo groups and 10 to 45% by weight of an alkali metal or ammonium hexafluorosilicate based on the 1: 1 metal complex weight amount.
• sulfo-containing 1: 1 chromium complex dye and optionally at least one sulfo-containing metal-free dye with 10 to 45 percent by weight (based on the weight of the 1: 1 metal complex dye) alkali and / or Mixes ammonium hexafluorosilicate.
• the mixing process takes place, for example, in suitable mills, for example ball or pin mills, as well as in kneaders or mixers.
• the solid mixtures can be used for dyeing natural or synthetic textile polyamide fiber materials.
• the usable 1: 1 metal complex dyes containing sulfo groups are preferably monoazo or disazo dyes which contain a chromium ion as the metal ion.
• 1: 1 metal complex azomethine dyes, which preferably contain a chromium ion, can also be used.
• the usable sulfo-containing metal-free dyes are preferably acidic to strongly acidic acid dyes from the series of monoazo or polyazo, anthraquinone, triphenylmethane or xanthene dyes, which can contain the substituents customary for acid dyes.
• the sulfo-containing metal-free dyes can be substituted by fiber-reactive radicals.
• the amounts in which the defined dyes or dye mixtures are used in the dyebaths can vary within wide limits depending on the desired depth of color, in general amounts of from 0.01 to 10 percent by weight, based on the material to be dyed, of one or more dyes proven advantageous.
• Alkali metal salts of hexafluorosilicic acid are used as alkali metal fluorosilicates.
• NH4 2SiF6 or a mixture of Na2SiF6 and (NH4) 2SiF6 is used.
• the amount in which the ammonium hexafluorosilicate, or alkali fluorosilicate and ammonium hexafluorosilicate, is used in the dyebaths is 10 to 45 percent by weight, preferably 15 to 45 percent by weight, in particular 20 to 35 percent by weight, based on the amount by weight of the 1: 1 metal complex dye.
• amount by weight of the 1: 1 metal complex dye refers to the raw dye, i.e. to the amount by weight of a dye isolated by customary methods (e.g. salting out), which contains about 20 to 40 percent by weight of salt.
• the amount in which the leveling aid or the leveling aid mixture is used in the dyebaths can vary within wide limits, in general an amount of 0.3 to 3 percent by weight, preferably 1 to 2 percent by weight, based on the fiber material, of leveling aid or Leveling agent mixture proved to be advantageous.
• the dyebaths can contain mineral acids, such as sulfuric acid, sulfamic acid or phosphoric acid, organic acids, expediently lower, aliphatic carboxylic acids, such as formic, acetic or maleic acid.
• the acids primarily serve to adjust the pH of the liquors used.
• the pH is preferably adjusted from 3 to 5 using an organic acid, in particular formic acid or acetic acid.
• the dye liquor of alkali fluorosilicate or ammonium hexafluorosilicate can be various salts, in particular ammonium or alkali salts such as e.g. Contain ammonium sulfate or preferably sodium sulfate as an auxiliary. Preferably 1 to 10 percent by weight of ammonium or alkali salts, based on the fiber material, are used.
• the 1: 1 metal complex dyes which can be used are preferably those which have at least one 1: 1 chromium complex azo or azomethine dye with 1 to 3 sulfonic acid groups, in particular 1 to 2 sulfonic acid groups, and in the case of dye mixtures, at least one metal-free dye with 1 to 2 sulfonic acid groups included.
• metal-free dyes containing sulfo groups those with good migration properties are used.
• the migrating ability of these dyes should correspond to the migrating ability of the 1: 1 chromium complex azo or azomethine dyes.
• the migratory capacity on wool is determined by treating a sample dyed to 1/1 standard depth together with an uncolored sample of the same weight in a blind bath.
• the treatment conditions for determining the migratory capacity correspond to the conditions given in Example 1 with regard to liquor ratio, pH and treatment duration.
• the evaluation is done by spectrophotometric Determination of the amount of dye on the originally undyed wool in percent of the originally colored wool.
• a range of 25 to 50% has proven to be advantageous as good migratory power, colored at pH 4 to 5 and measured as a difference in strength.
• Suitable metal-free dyes containing sulfo groups are, for example, C-I. Acid Blue 1, 7, 13, 23, 40, 40: 1, 43, 45, 47, 72, 147, 258 and 277; C.I. Acid Red 1, 5, 37, 42, 52, 57 and 361; C.I. Acid Yellow 10, 17, 25, 27, 99 and 219; C.I. Acid Orange 1, 3 and 156; C.I. Acid Green 3, 9 and 16; C.I. Acid Violet 9 and 36; C.I. Acid Brown 10, 11 and 248.
• the color mixture of suitably selected yellow or understand orange, red and blue coloring dyes with which any desired shade of the visible color spectrum can be adjusted by a suitable choice of the proportions of the dyes.
• 1: 1 chromium complex azo or azomethine dyes are those of the formula used, in which - (CO) 0-1 -O- and (0 or NR1) in the vicinity of the azo bridge are bonded to D and K, D the rest of a diazo component of the benzene or naphthalene series, K the rest of a coupling component of the benzene, Naphthalene or heterocyclic series or the acetoacetic acid arylide series, R1 hydrogen, or an optionally substituted alkyl or phenyl radical, M is a cation and An is an anion, and Y represents the nitrogen atom or the CH group.
• sulfo group-containing 1: 1 chromium complex azo or azomethine dyes of the formula (4) are used, in which D is a benzene or naphthalene radical optionally substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, nitro or sulfamoyl, K an optionally by halogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino, sulfamoyl or hydroxy-substituted phenyl, naphthyl, 1-phenyl-3-methylpyrazolone- (5) -, acetoacetamide, especially acetoacetoanilide or quinoline residue, R1 is hydrogen and M is an alkali application.
• Y in formula (4) preferably denotes the nitrogen atom.
• the metal-free dyes containing sulfonic acid groups used are those of the dye series mentioned above, which can be substituted, for example, by alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, Propoxy, isopropoxy and butoxy, acylamino groups with 1 to 6 carbon atoms, such as acetylamino and propionylamino, benzoylamino, amino, alkylamino with 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, nitro, acetyl, cyano, trifluoromethyl, halogen, such as fluorine, chlorine and bromine, sulfamoyl, carbamoyl, ureido, hydroxy, carboxy and
• the metal-free dyes containing sulfonic acid groups can be substituted by one or more fiber-reactive radicals.
• Suitable fiber-reactive radicals are, for example, the radicals mentioned in DE-OS 29 13 102.
• Mixtures of sulfo-containing 1: 1 metal complex dyes and sulfo-containing metal-free dyes are preferably used in a weight ratio of 40:60 to 95: 5.
• the sulfo-containing dyes used are either in the form of their free sulfonic acid or, preferably, as their salts.
• suitable salts are the alkali, alkaline earth or ammonium salts or the salts of an organic amine.
• suitable salts include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
• the 1: 1 metal complex dyes containing sulfo groups and the metal-free dyes containing sulfo groups are known per se and are obtained by known methods.
• the dye mixtures used can be prepared by mixing the individual dyes. This mixing process takes place, for example, in suitable mills, e.g. Ball or pin mills, as well as in kneaders or mixers.
• the dye mixtures can be prepared by spray drying the aqueous dye mixtures.
• the dyebaths can also contain other customary additives, such as wool protection agents, wetting agents and defoamers.
• the liquor ratio can be selected within a wide range, from 1: 6 to 1:80, preferably 1:10 to 1:30.
• Dyeing is carried out from an aqueous liquor using the exhaust process, e.g. at temperatures between 80 and 105 ° C or 110 ° C when using a formaldehyde-releasing wool protection agent, preferably between 98 and 103 ° C.
• the dyeing time is usually 30 to 120 minutes.
• the usual dyeing apparatus and machines for example for flake, sliver, strand yarn, bobbins, piece goods and carpets, can be used.
• the leveling aid and the alkali fluorosilicate or ammonium hexafluorosilicate are expediently admixed with the aqueous dye liquor and applied simultaneously with the dye mixture.
• An interesting procedure is characterized in that one enters into a liquor with the fiber material, which contains acid and a leveling agent containing ammonium hexafluorosilicate as well as Na2SO4 and has a temperature of 30 to 70 ° C. Subsequently, the dyes or dye mixtures which contain alkali and / or ammonium hexafluorosilicate are added, and the temperature of the dyebath is increased by a heating rate of 0.75 to 3 ° C. per minute, if appropriate with a temperature stop during the heating, in order to Color range from 80 ° C to 105 ° C. The bath is then cooled and the colored material rinsed and dried as usual.
• the fiber material can be in a wide variety of forms, such as loose material, sliver, yarn and piece goods or as a carpet.
• fiber material made of synthetic polyamides which can be dyed, it comes into consideration from all known, suitable synthetic polyamides.
• the fiber material can be in a wide variety of forms, e.g. as loose material, sliver, yarn and piece goods or as carpet.
• the metal-free dyes containing sulfo groups can contain one or more fiber-reactive groups.
• Such dye mixtures of the defined 1: 1 metal complex dyes and the sulfo-containing metal-free dyes are preferably used, in which the metal-free dyes used are either all reactive dyes or are all free of fiber-reactive groups; in particular, metal-free dyes containing sulfo groups are used, free of fiber-reactive groups.
• a particularly interesting embodiment is characterized in that the dye mixtures used consist of such defined metal-containing and metal-free dyes which give colorations of the same nuances, i.e., the use of a mixture of at least one blue-coloring, 1: 1 metal complex dye containing sulfo groups and at least one blue-coloring, metal-free dye containing sulfo groups.
• the process which can be carried out with the mixtures according to the invention has the following advantages over the known processes for fiber material made from natural or synthetic polyamides, in addition to those already mentioned.
• the material dyed under the dyeing conditions mentioned has better overall fastness properties, in particular better wet fastness properties. Another important advantage is that the dyes are almost completely absorbed.
• the method for dyeing wool is used.
• the process which can be carried out with the mixtures according to the invention surprisingly manages with a significantly smaller amount of ammonium hexafluorosilicate, or alkali fluorosilicate and ammonium hexafluorosilicate.
• the following examples serve to illustrate the invention.
• the parts are parts by weight and the percentages are percentages by weight.
• the temperatures are given in degrees Celsius.
• the relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.
• the indicated amounts of dye refer to raw dye.
• the dye liquor After adding a solution of 1.1 parts of the 1: 1 chromium complex of the dye of the formula 0.5 parts of the 1: 1 chromium complex of the dye of the formula 0.23 parts of the 1: 1 chromium complex of the dye of the formula 0.23 parts of the 1: 1 chromium complex of the dye of the formula 0.64 parts of the dye of the formula 0.97 parts of the dye of the formula and 0.4 parts of the dye of the formula the dye liquor is kept at 50 ° for a further 10 minutes and then heated to 98 ° at a heating rate of 0.8 ° / minute. The pH at the beginning of dyeing is 3.8. After 90 minutes at 98 °, the mixture is cooled to 50 ° and the dye liquor is drained off. The brown-colored wool yarn is rinsed at 50 ° for 10 minutes, then at room temperature and dried as usual. The medium brown color obtained is excellent in fiber and has good fastness properties.
• the dye liquor After adding a 50 ° warm solution containing 1.72 parts of the mixture 0.96 parts of the dye of the formula 0.45 parts of the dye of the formula and 0.31 parts (NH4) 2SiF6; 1.88 parts of the mixture 1.2 parts of the dye of the formula 0.3 parts of the dye of the formula and 0.38 parts (NH4) 2SiF6; and 1.91 parts of a mixture of 1.5 parts of the dye of the formula and 0.41 parts (NH4) 2SiF6 in 1000 parts of water, the dye liquor is kept at 50 ° for 10 minutes and then heated to 98 ° at a rate of 1 ° / minute. The pH is 3.5 at the start of dyeing.
• the mixture After 90 minutes of dyeing at 98 °, the mixture is allowed to cool to 50 °, the light brown colored wool yarn is rinsed at 50 ° and then at room temperature for 10 minutes and dried as usual.
• the pH towards the end of dyeing is 3.8.
• the beige color obtained is excellently fibrous; the dyed worsted shows a full, soft feel.
• the final fleet is undyed.

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• 1987
  • 1987-09-30 US US07/102,942 patent/US4818248A/en not_active Expired - Lifetime
  • 1987-10-05 ES ES198787810571T patent/ES2030094T3/es not_active Expired - Lifetime
  • 1987-10-05 EP EP91104413A patent/EP0443631A1/de not_active Withdrawn
  • 1987-10-05 DE DE8787810571T patent/DE3777746D1/de not_active Expired - Lifetime
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  • 1987-10-09 AU AU79523/87A patent/AU608778B2/en not_active Ceased
  • 1987-10-09 JP JP62253952A patent/JPS63105193A/ja active Granted
  • 1987-10-09 ZA ZA877607A patent/ZA877607B/xx unknown
  • 1987-10-10 KR KR1019870011227A patent/KR960003085B1/ko not_active IP Right Cessation
• 1994
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