EP0023341B1 - Padding aid, process for its preparation and process for dyeing cellulosic fibres or mixtures of cellulosic fibres together with synthetic fibres with sulphur, sulphur vat, vat and reactive dyestuffs - Google Patents

Padding aid, process for its preparation and process for dyeing cellulosic fibres or mixtures of cellulosic fibres together with synthetic fibres with sulphur, sulphur vat, vat and reactive dyestuffs Download PDF

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Publication number
EP0023341B1
EP0023341B1 EP80104312A EP80104312A EP0023341B1 EP 0023341 B1 EP0023341 B1 EP 0023341B1 EP 80104312 A EP80104312 A EP 80104312A EP 80104312 A EP80104312 A EP 80104312A EP 0023341 B1 EP0023341 B1 EP 0023341B1
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Prior art keywords
weight
denotes
compound
general formula
atoms
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP80104312A
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German (de)
French (fr)
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EP0023341A3 (en
EP0023341A2 (en
Inventor
Friedrich Dr. Engelhardt
Karl Heinz Dr. Keil
Gerhard Dr. Weckler
Klaus Sternberger
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Sanofi Aventis Deutschland GmbH
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Cassella AG
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Priority to AT80104312T priority Critical patent/ATE5981T1/en
Publication of EP0023341A2 publication Critical patent/EP0023341A2/en
Publication of EP0023341A3 publication Critical patent/EP0023341A3/en
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Publication of EP0023341B1 publication Critical patent/EP0023341B1/en
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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
    • D06P1/667—Organo-phosphorus 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
    • D06P1/22—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 vat dyestuffs including indigo
    • 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
    • D06P1/60—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
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
    • 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
    • D06P1/62—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 with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • 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
    • D06P3/66—Natural or regenerated cellulose using reactive 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
    • Y10S8/918—Cellulose textile

Definitions

  • the continuous dyeing process consists of three process steps: padding, fixing and washing.
  • padding the pretreated goods are immersed in a concentrated padding liquor that contains dye and auxiliaries.
  • This process is preferably carried out in the temperature range from 10 to 20 ° C., that is to say at room temperature. Since the dwell time of the goods in the padding fleet is only a few seconds at the high goods speeds, the goods must have a quick and even absorption capacity for the dye.
  • Padding is followed by dye fixation, whereby the dye is fixed to the goods to be dyed by heat treatment with hot air, steam or contact heat.
  • the unfixed dye is removed from the textile material by one or more washing processes.
  • esters of monohydric alkanols with a branched or unbranched chain with 5 to 8 carbon atoms are used in the form of the technical mixtures of the mono- and diesters of orthophosphoric acid.
  • these products also have decisive disadvantages, since they too develop too much foam in the water glass-containing liquors in the pH range above 9 when dyeing with reactive dyes.
  • the foam development or the foam stability has an unfavorable effect on the regularity of the dyeings and can give rise to stains.
  • the wetting times in the hydrosulfite and electrolyte-containing liquors for sulfur and vat dyes are not yet sufficient.
  • FR-A-1 396 294 discloses leveling, low-foaming wetting agents which, in addition to an optionally partially saponified phosphoric acid ester, a fatty acid or soap and e.g. still contain tetrapropylene benzene sulfonate, dodecyl benzene sulfonate, a certain urethane, eicosane glycol ether of 2,4,6-triisobutylphenol.
  • leveling, low-foaming wetting agents which, in addition to an aliphatic carboxylic acid ester, an optionally partially saponified phosphoric acid ester, a fatty acid or soap and a high molecular weight alkoxylation product of an aliphatic or aliphatic-aromatic hydroxyl compound or a salt of an alkylsulfuric acid ester or a Contain salt of an aliphatic or aliphatic-aromatic sulfonic acid.
  • the liquor absorption which can be achieved by means of these known auxiliaries and the foam behavior leave something to be desired.
  • the compounds of general formula I represent salts of orthophosphoric acid diesters and the compounds of general formula Ib represent salts of orthophosphoric acid monoesters.
  • R I , R 2 and R 3 are in particular alkyl radicals, preferably branched alkyl radicals having 7 to 10 carbon atoms, such as isooctyl, isononyl and isodecyl. If R 1 , R 2 , R 3 represent an araliphatic radical, the benzyl radical is preferred.
  • the aliphatic radical representing R 4 is in particular an alkyl radical with 1 to 5 carbon atoms.
  • alkylphenyl group representing R 4 are: 1-, 2- or 3-methyl-, ethyl- or n-butylphenyl. If R 4 represents a phenalkyl group, the benzyl group is preferred.
  • Xet, Y ⁇ and Z ⁇ can also be a monoalkyl, dialkyl or trialkylammonium cation with 1 to 4 carbon atoms in the individual alkyl radicals or a mono-hydroxyalkyl-dialkyl, di-hydroxyalkyl-monoalkyl- or tri-hydroxyalkyl-ammonium cation with 1 to 4 carbon atoms in the individual alkyl radicals.
  • the compounds III are block copolymers of ethylene and propylene oxide, where m and p are identical in the statistical sense. Such compounds III are preferably used. at them ie where the proportion by weight of ethylene oxide is 10 to 40 percent by weight.
  • the padding aids according to the invention can be produced in a simple manner by stirring the compound mixture (Ia + Ib), the compound II and / or III in water in the stated weight ratios.
  • the free diester acids or monoester acids of the general formula Ic or Id can also be used be used to manufacture the block aid.
  • the pH of the solution or dispersion obtained is then adjusted to values above 7, preferably from 7 to 8, with alkali metal hydroxides, ammonia or organic amines.
  • Sodium hydroxide or potassium hydroxide solution, aqueous ammonia solution or triethanolamine are preferably used to adjust the pH.
  • the padding aid according to the invention is used for dyeing cellulose fibers or cellulose-synthetic fiber mixtures with sulfur, sulfur vats, vat or reactive dyes by continuous, semi-continuous or discontinuous dyeing processes in amounts of 1 to 40 g / l of dye liquor, preferably in amounts of 1 to 15 g / I dye liquor used.
  • dyeing is carried out with liquor ratios between 1: 2 to 1:30, preferably between 1: 2 to 1:12.
  • the dyeing process according to the invention can of course also be carried out in such a way that not the ready-to-use padding aid, but rather the active substances listed under a), b) and c) in amounts of in total from 0.2 to 24 g / l, preferably 0.2 to 9 g / l, added to the dye liquor.
  • the padding aids according to the invention for dyeing with sulfur, sulfur vat and vat dyes preferably do not contain any of the compounds III listed under c).
  • the padding aids according to the invention for dyeing with reactive dyes preferably do not contain any of the compounds II listed under b).
  • the actual dyeing process is also carried out as usual in dyeing processes with long liquor ratios after adding the padding aid according to the invention or the above-mentioned combination of active ingredients to the dye liquor.
  • the coloring can e.g. according to the Riepen-Klotz-Dämpf-, (Pad-Steam-), Williams-Unit, Cold Dwell, Pad-Jig or Pad-Roll process.
  • a continuous process it is possible to work with or without intermediate drying after padding.
  • Suitable sulfur dyes are e.g. following: C.I. Sulfur Blue 1, C.I. Leuco Sulfur Blue 1, C.I. Sulfur Blue 3, C.I., Leuco Sulfur Blue 3, C.I. Sulfur Blue 4, C.I. Solubilized Sulfur Blue 4, C.I. Sulfur Blue 5, C.I. Leuco Sulfur Blue 5, C.I. Solubilized Sulfur Blue 5, C.I. Sulfur Blue 7, C.I. Leuco Sulfur Blue 7, C.I. Solubilized Sulfur Blue 10, C.I. Solubilized Sulfur Blue 10, C.I. Solubilized Sulfur Blue 10, C.I.
  • Solubilized Sulfur Green 3 C.I. Sulfur Green 5, C.I. Sulfur Brown 5, C.I. Leuco Sulfur Brown 5, C.I. Solubilized Sulfur Brown 5, C.I. Sulfur Brown 10, C.I. Leuco Sulfur Brown 10, C.I. Sulfur Brown 16, C.I. Solubilized Sulfur Brown 16, C.I. Sulfur Brown 51, C.I. Solubilized Sulfur Brown 51, C.I. Sulfur Black 8, C.I. Sulfur Red 3, C.I. Solubilized Sulfur Red 3, C.I. Sulfur Red 7, C.I. Solubilized Sulfur Red 7.
  • Suitable sulfur vat dyes are e.g. C.I. Vat Blue 42, C.I. Reduced Vat Blue 42, C.I. Vat Blue 43, C.I. Reduced Vat Blue 43, C.I. Vat Blue 44, C.I. Vat Blue 45, C.I. Vat Blue 47, C.I. Vat Blue 49, C.I. Vat Blue 50, C.I. Sulfur Black 10, C.I. Leuco Sulfur Black 10.
  • Suitable vat dyes are e.g. C.I. VatOrange 7, C.I. Vat Red 13, C.I. Vat Red 14, C.I. Vat Red 15, C.I. Vat Brown 1, C.I. Vat Brown 3, C.I. Vat Blue 13, C.I. Vat Blue 16, C.I. Vat Violet 1, C.I. Vat Blue 4: 1.
  • Suitable reactive dyes are e.g. C.I. Reactive Yellow 17, C.I. Reactive Orange 7, C.I. Reactive Orange 16, C.I. Reactive Red 22, C.I. Reactive Red 23, C.I. Reactive Blue 5, C.I. Reactive Blue 19, C.I. Reactive Violet 4, C.I. Reactive Violet 5.
  • Pretreated as well as non-pretreated cellulose fiber-containing materials or materials made from cellulose fiber-synthetic fiber mixtures can be used as textile materials.
  • Mixtures such as cotton / polyester, rayon / polyester, cotton / polyamide, polyamide / rayon are particularly suitable.
  • the dyeing process according to the invention and the use of the padding aid according to the invention achieve perfect dyeings with the same depth of color from edge to edge and start to end.
  • the synergistic reduction in wetting times and the reduction in foam volume achieved by the active ingredient combination according to the invention can be seen from the tables below.
  • fleet 1 means a dyeing liquor for dyeing using sulfur, sulfur vat and vat dyes according to the pad-steam process, which contains 50 g of NaOH 32 ° Be and 40 g of Na 2 S 2 0 4 in liters.
  • a dyeing liquor for dyeing with sulfur, sulfur vat and vat dyes according to the pad-steam process which contains 50 g of NaOH 32 ° Be, 40 g of Na 2 S 2 O 4 and 20 g of NaCI per liter.
  • a liquor for dyeing with reactive dyes which contains 125 g water glass, 30 g NaOH 38 ° Be and 20 g Na 2 S0 4 per liter.
  • a liquor for dyeing with reactive dyes which contains 125 g water glass, 30 g NaOH 38 ° Be, 20 g Na 2 SO 4 and 100 g urea per liter.
  • a liquor for dyeing with reactive dyes which contains 20 g NaOH 38 ° Be, 30 g NaCl and 20 g Na 2 S0 4 per liter.
  • Blocking aids according to the invention are given in Tables I to IV under No. 1 and in Table V under No. V / 1, V / 4 to 6.
  • the padding aids according to the invention provide surprisingly stable padding liquors for sulfur, sulfur vat and vat dyes.
  • a raw cotton moleskin that is difficult to dye through and a raw tarpaulin material are padded with a liquor that contains 30 g / l of hydron blue R f. Sol (Vat Blue, CI 53630), 50 ml / l sodium hydroxide solution 32 ° Be, 40 g / l, hydrosulfite and 4 g / l of an auxiliary preparation consisting of 16 parts of mono- (2-ethylhexyl) phosphate and 24 parts of di- ( Contains 2-ethylhexyl) phosphate, each as potassium salts and 2.5 parts of 10-hydroxy-octadecanecarboxylic acid di-n-butylamide as Naids salt of the sulfuric acid half-ester.
  • the block temperature is approx. 20 ° C.
  • the liquor absorption of the two-roll foulard used is 55% for the cotton moleskin and 47% for the cotton tent fabric.
  • the raw cotton moleskin of Example 1 is mixed with a liquor containing 25 g / l indanthrene yellow F 2 GC Colloisol (Vat Yellow 33) and 4 g / l of a padding aid consisting of 5 parts mono- (2-ethylhexyl) phosphate, 35 parts Di- (2-ethylhexyl) phosphate, in each case as potassium salts, and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight contains less than 2000 and with an ethylene oxide content of 10%, padded, then dried at 120 to 140 ° C on the hot flue, soaked in a chemical trough with a liquor with 60 ml / I sodium hydroxide solution 38 ° Be and 30 g / I hydrosulfite, steamed and Completed on a wide washing machine by rinsing, oxidizing, boiling soap and rinsing again. A perfect color is obtained.
  • a raw tarpaulin is made with a liquor that is 80 g / l Cassulfon light brown GGL liquid (Solubilized Sulfur Brown 51, CI 53328) and 4 g / l of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts Di- (2-ethylhexyl) phosphate each as triethanolamine salt and 5 parts of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanoic acid-N-methylanilide contains, padded, then dried at 120 to 140 ° C on the hot flue, soaked in a chemical trough with a liquor , which contains 12 g / l soda, 40 ml / 1 sulfhydrate F 150 (commercial product from Cassella AG, Frankfurt / Main - 61) and 3 ml / l Stabilisal S liquid (commercial product from Cassella AG, Frankfurt / Main
  • a raw tent fabric is mixed with a liquor containing 30 g / l Indocarbon CL for Sol (Sulfur Black 11, CI 53290) and 4 g / I of a padding aid made up of 5 parts mono- (2-ethylhexyl) phosphate, 35 parts di- ( 2 - ethylhexyl) phosphate each as potassium salt, 0.5 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and 2 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 3500 and with an ethylene oxide weight fraction of 40% contains, padded, developed without or after drying on the hot flue in a jigger with sodium hydroxide solution and hydrosulfite and finished by rinsing and oxidizing. A perfect color is obtained.
  • a raw cotton moleskin is mixed with a liquor containing 25 g / l indanthrene brilliant orange RK Colloisol (Vat Orange 3, CI 59300) and 4 g / 1 of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts of di- (2-ethylhexyl) phosphate each as the sodium salt, 1 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadedancarboxylic acid di-n-butylamide and 4 parts of an ethylene oxide / Propylene oxide copolymer with a molecular weight below 2000 and with a weight fraction of 10% contains ethylene oxide, padded and processed as indicated in Example 4. A perfect color is obtained.
  • a raw cotton moleskin is mixed with a liquor containing 40 g / l of hydrosol light brown GGL and 4 g / l of a padding aid consisting of 20 parts of monobenzyl phosphate, 20 parts of di-benzyl phosphate, each as a triethanolamine salt, 2.5 parts contains the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide, padded, developed without liquid or after drying on the hot flue in a jigger with soda, sulfhydrate F 150 and Stabilisal S and finished by rinsing and oxidizing. A perfect color is obtained.
  • a cotton yarn is mixed with a liquor containing 1.5% indanthrene reddish brown RR Colloisol (Vat Brown 45, CI 59500), 10 ml / l sodium hydroxide solution 38 ° Be, 4 g / I hydrosulfite and 10 g / I NaCl and 1 g / l of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts of di- (2-ethylhexyl) phosphate, each as the potassium salt, and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 2000 and with an ethylene oxide content of 10% dyed at 50 ° C and finished by oxidation and boiling soap. Level and well-dyed cotton yarns are obtained.
  • Cotton yarn is dyed at 70 ° C. with a liquor which contains 1% Hydron-Blue RB powder, highly concentrated (Vat Blue 43, CI 53630) and 1 g / l of a padding aid, consisting of 16 parts of mono- (2-ethylhexyl ) phosphate, 24 parts of di- (2-ethylhexyl) phosphate, each as the potassium salt, and 2.5 parts of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and the chemicals specified in Example 7. Completion is as in example 7.
  • Cotton yarn is concentrated in a fleet that contains 6% Immedial Carbon CMR. Grains (Sulfur Black 1, CI 53185), 7 g / I soda, 10 ml / I sulfhydrate F 150 (commercial product from Cassella AG, Frankfurt / Main - 61), 2 ml / l Stabilisal S liquid (commercial product from Cassella AG, Frankfurt / Main - 61), 10 g / I sodium chloride and 1 g / l of a padding aid, made from 20 parts of the mono- (isononyl) phosphate, 20 parts of the di- (isononyl) phosphate, each as the potassium salt, and 4.0 parts of the sodium salt of the sulfuric acid half ester of 10-hydroxyoctadecanecarboxylic acid - di-n-butylamide, contains, colored at 90 ° C and finished by oxidation and rinsing. A perfectly dyed cotton yarn is obtained.
  • Easy-care cotton twill is made with a liquor containing 60 g / I Remazol Red B (Reactiv Red 22, CI 14824), 35 ml / 1 sodium hydroxide solution 38 ° Be, 95 ml / I sodium water glass 38 ° Bé and 4 g / I a padding aid from 5 Parts of mono- (2-ethylhexyl) phosphate potassium salt, 3.5 parts of di- (2-ethylhexyl) phosphate potassium salt, 0.5 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and 2 parts of an ethylene oxide / propylene oxide -Copolymerisats with a molecular weight below 3500 and with a weight fraction of ethylene oxide of 40%, at 20 to 25 ° C. padded on a foulard, docked and left for 4 hours. Then the usual completion is carried out by rinsing at 70
  • Easy-care cotton tricot is made from 16 parts with a liquor containing 30 g / l Remazol Goldgelb G (Reactiv Yellow 17, CI 18852), 14 ml / l sodium hydroxide solution 38 ° Be, 30 g / l table salt and 6 g / l padding aid Mono- (2-ethylhexyl) phosphate potassium salt, 24 parts di- (2-ethylhexyl) phosphate potassium salt and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 2000 and with an ethylene oxide content of 10%, contains, padded on a foulard, docked and left for 12 hours. It is then rinsed cold, neutralized with acetic acid at 40 ° C, rinsed hot, soaped at the boil and completed by cold and hot rinsing. A dyeing with a perfect product appearance is obtained.

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  • Textile Engineering (AREA)
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Description

Die Entwicklung halbkontinuierlicher und vollkontinuierlicher Färbeverfahren, bei denen Stückware aus Geweben und/oder Gewirken, Garne oder Kammzug gefärbt wird, hat in den letzten Jahren zunehmend an Bedeutung gewonnen. Mit diesen Verfahren gelingt es, grosse Metragen unter beträchtlicher Kosteneinsparung im gleichen Farbton einzufärben. Die Schwierigkeit bei der Durchführung solcher Färbeverfahren besteht darin, das zu färbende Material am Anfang und am Ende sowie von Kante zu Kante mit gleicher Farbtiefe und gleicher Egalität anzufärben. Um eine derartige einwandfreie Färbung bei halbkontinuierlichen und vollkontinuierlichen Färbeverfahren zu erhalten, muss man mit sorgfältig durch Abkochen und Bleichen vorbehandeltem Material arbeiten, was jedoch mit einem erheblichen Zeit- und Kostenaufwand verbunden ist.The development of semi-continuous and fully continuous dyeing processes in which piece goods are dyed from woven and / or knitted fabrics, yarns or combed fabrics has become increasingly important in recent years. With these processes it is possible to color large batches in the same color at considerable cost savings. The difficulty in carrying out such dyeing processes is to dye the material to be dyed at the beginning and end and from edge to edge with the same depth of color and the same levelness. In order to obtain such a perfect dyeing in semi-continuous and fully continuous dyeing processes, it is necessary to work with material which has been carefully pretreated by boiling and bleaching, but this is associated with a considerable expenditure of time and money.

Die kontinuierlichen Färbeverfahren bestehen aus drei Verfahrensschritten: Klotzen, Fixieren und Waschen. Bei dem ersten Verfahrensschritt, dem Klotzen, wird die vorbehandelte Ware in eine konzentrierte Klotzflotte, die Farbstoff und Hilfsmittel enthält, eingetaucht. Dieser Vorgang wird bevorzugt im Temperaturbereich von 10 bis 20°C, also bei Raumtemperatur, ausgeführt. Da bei den hohen Warengeschwindigkeiten die Verweilzeit der Ware in der Klotzflotte nur bei wenigen Sekunden liegt, muss die Ware ein schnelles und gleichmässiges Aufnahmevermögen für den Farbstoff besitzen. Auf das Klotzen folgt die Farbstoff-Fixierung, wobei der Farbstoff durch eine Hitzebehandlung mit Heissluft, Dampf oder Kontakthitze auf der zu färbenden Ware fixiert wird. Als letzter Schritt wird der nicht fixierte Farbstoff durch einen oder mehrere Waschprozesse aus dem Textilmaterial entfernt.The continuous dyeing process consists of three process steps: padding, fixing and washing. In the first process step, padding, the pretreated goods are immersed in a concentrated padding liquor that contains dye and auxiliaries. This process is preferably carried out in the temperature range from 10 to 20 ° C., that is to say at room temperature. Since the dwell time of the goods in the padding fleet is only a few seconds at the high goods speeds, the goods must have a quick and even absorption capacity for the dye. Padding is followed by dye fixation, whereby the dye is fixed to the goods to be dyed by heat treatment with hot air, steam or contact heat. As a last step, the unfixed dye is removed from the textile material by one or more washing processes.

Es hat nicht an Versuchen gefehlt, durch den Einsatz von speziellen Hilfsmitteln bei den kontinuierlichen Färbeverfahren das gefärbte Textilmaterial in gleicher Farbtiefe und gleicher Egalität bezüglich der Kanten und Enden zu erhalten. Vor allem für das Färben von unbehandelter Rohware im kontinuierlichen Färbeverfahren besteht ein technisches Bedürfnis, wobei durch den Zusatz von Hilfsmitteln eine egale und kanten- und endengleiche Metrage ohne weitere zeitraubende Vorbehandlung erhalten werden soll.There has been no shortage of attempts to obtain the dyed textile material with the same depth of color and the same levelness with regard to the edges and ends by using special aids in the continuous dyeing process. There is a technical need especially for the dyeing of untreated raw goods in the continuous dyeing process, whereby the addition of auxiliaries should result in a level and flush-to-edge metering without any time-consuming pretreatment.

So werden heute vielfach Hilfsmittel auf der Basis derAlkalisalze von Alkansulfonaten mit einer Kettenlänge von 10 bis 20 C-Atomen und mehr als einer Sulfonsäuregruppe im Molekül eingesetzt. Beim Einsatz dieser Verbindungen in kontinuierlichen Färbeverfahren zeigen sich bei den heute üblichen hohen Warengeschwindigkeiten jedoch schwerwiegende Nachteile dieser Verbindungsklasse, weil sich in den stark elektrolythaltigen Färbeflotten und im pH-Bereich über 8 zu viel Schaum entwickelt. Um mit diesen Verbindungen zu einwandfreien Färbungen zu kommen, ist es daher unbedingt erforderlich, zusätzliche Entschäumer in die Färbeflotte einzubringen. Die Anwendung von Entschäumern bringt jedoch anwendungstechnisch die Gefahr ihrer ungleichmässigen Verteilung in der Flotte mit sich, und daher ist in der Regel eine Fleckenbildung auf der Ware nicht auszuschliessen. Gleichzeitig ist die Anwendung von Entschäumern mit zusätzlichen Kosten und der Gefahr der Abwasserbelastung verbunden, die bei der Anwendung von Entschäumern auf der Basis von Silikonen erheblich ist.Thus, aids based on the alkali salts of alkanesulfonates with a chain length of 10 to 20 carbon atoms and more than one sulfonic acid group in the molecule are often used today. When these compounds are used in continuous dyeing processes, however, serious disadvantages of this class of compound are evident at the high product speeds that are customary today, because too much foam develops in the strongly electrolyte-containing dyeing liquors and in the pH range above 8. In order to achieve perfect dyeings with these compounds, it is therefore absolutely necessary to add additional defoamers to the dyeing liquor. However, the use of defoamers entails the risk of their uneven distribution in the liquor, and therefore stains on the goods cannot usually be ruled out. At the same time, the use of defoamers is associated with additional costs and the risk of wastewater pollution, which is considerable when using defoamers based on silicones.

Neben den oben beschriebenen Verbindungen kommen auch die Ester einwertiger Alkanole mit einer verzweigten oder unverzweigten Kette mit 5 bis 8 C-Atomen in Form der technischen Gemische aus den Mono- und Diestern der Orthophosphorsäure zum Einsatz. Diese Produkte haben jedoch ebenfalls entscheidende Nachteile, da auch sie in den wasserglashaltigen Flotten im pH-Bereich über 9 beim Färben mit Reaktivfarbstoffen noch zu viel Schaum entwickeln. Die Schaumentwicklung bzw. die Schaumstabilität wirkt sich ungünstig auf die Eg=alität der Färbungen aus und kann zu Fleckenbildung Anlass geben. Ausserdem sind die Netzzeiten in den hydrosulfithaltigen und elektrolythaltigen Flotten bei Schwefel- und Küpenfarbstoffen noch nicht ausreichend.In addition to the compounds described above, the esters of monohydric alkanols with a branched or unbranched chain with 5 to 8 carbon atoms are used in the form of the technical mixtures of the mono- and diesters of orthophosphoric acid. However, these products also have decisive disadvantages, since they too develop too much foam in the water glass-containing liquors in the pH range above 9 when dyeing with reactive dyes. The foam development or the foam stability has an unfavorable effect on the regularity of the dyeings and can give rise to stains. In addition, the wetting times in the hydrosulfite and electrolyte-containing liquors for sulfur and vat dyes are not yet sufficient.

Aus der FR-A-1 396 294 sind egalisierende, wenig schäumende Netzmittel bekannt, die neben einem gegebenenfalls teilweise verseiften Phosphorsäureester eine Fettsäure oder Seife und z.B. noch Tetrapropylen-benzol-sulfonat, Dodecyl-benzol-sulfonat, ein bestimmtes Urethan, Eicosan-glykol-ether des 2,4,6-Triisobutylphenols enthalten. Aus der GB-A-1 120 254 sind egalisierende, wenig schäumende Netzmittel bekannt, die neben einem aliphatischen Carbonsäureester einen gegebenenfalls teilweise verseiften Phosphorsäureester, eine Fettsäure oder Seife und ein hochmolekulares Alkoxylierungsprodukt einer aliphatischen oder aliphatisch-aromatischen Hydroxylverbindung oder ein Salz eines AIkylschwefelsäureesters oder ein Salz einer aliphatischen oder aliphatisch-aromatischen Sulfonsäure enthalten. Bei schwierig zu färbenden Materialien lässt die durch diese bekannten Hilfsmittel erzielbare Flottenaufnahme sowie das Schaumverhalten zu wünschen übrig.FR-A-1 396 294 discloses leveling, low-foaming wetting agents which, in addition to an optionally partially saponified phosphoric acid ester, a fatty acid or soap and e.g. still contain tetrapropylene benzene sulfonate, dodecyl benzene sulfonate, a certain urethane, eicosane glycol ether of 2,4,6-triisobutylphenol. From GB-A-1 120 254, leveling, low-foaming wetting agents are known which, in addition to an aliphatic carboxylic acid ester, an optionally partially saponified phosphoric acid ester, a fatty acid or soap and a high molecular weight alkoxylation product of an aliphatic or aliphatic-aromatic hydroxyl compound or a salt of an alkylsulfuric acid ester or a Contain salt of an aliphatic or aliphatic-aromatic sulfonic acid. In the case of materials which are difficult to dye, the liquor absorption which can be achieved by means of these known auxiliaries and the foam behavior leave something to be desired.

Überraschenderweise wurde nun gefunden, dass durch die Verwendung des erfindungsgemässen Klotzhilfsmittels die bisher auftretenden Nachteile beseitigt werden.Surprisingly, it has now been found that the disadvantages which have arisen up to now are eliminated by the use of the block aid according to the invention.

Das erfindungsgemässe Klotzhilfsmittel zum Färben von Cellulosefasern oder von Cellulosefaser-Synthesefaser-Gemischen mit Schwefel-, Schwefelküpen-, Küpen- oder Reaktivfarbstoffen besteht aus einer wässrigen Lösung oder Dispersion mit einem Gehalt von

  • a) 20 bis 50 Gewichtsprozent eines Gemisches aus 50 bis 100 Gewichtsprozent einer Verbindung der allgemeinen Formel la
    Figure imgb0001
    und 50 bis 0 Gewichtsprozent einer Verbindung der allgemeinen Formel lb
    Figure imgb0002
  • b) b Gewichtsprozent einer Verbindung der allgemeinen Formel II
    Figure imgb0003
  • c) c Gewichtsprozent einer Verbindung der allgemeinen Formel III
    Figure imgb0004
    wobei b eine Zahl von 0 bis 5, c eine Zahl von 0 bis 5 bedeutet und b und c so gewählt werden, dass (b+c) eine Zahl von 1 bis 10 bedeutet, und wobei Rl, R2, R3 einen aliphatischen Rest mit 5 bis 12 C-Atomen oder einen araliphatischen Rest mit 7 bis 13 C-Atomen, X⊕, Y⊕, Z⊕ ein Alkalimetall- oder Ammoniumkation oder ein Kation eines Alkyl- oder Hydroxyalkylamins, R4 einen aliphatischen Rest mit 1 bis 8 C-Atomen, eine Phenylgruppe, Alkylphenylgruppe oder Phenylalkylgruppe mit jeweils 1 bis 4 C-Atomen im Alkylrest, R5 Wasserstoff oder R4, y, z ganze Zahlen von 6 bis 8, wobei vorzugsweise (y + z) = 15, n eine Zahl von 15 bis 35, (m + p) eine Zahl von 2 bis 120 bedeuten, und n und (m + p) so gewählt werden, dass
    Figure imgb0005
The padding aid according to the invention for dyeing cellulose fibers or cellulose fiber-synthetic fiber mixtures with sulfur, sulfur vat, vat or reactive dyes consists of an aqueous solution or dispersion with a content of
  • a) 20 to 50 percent by weight of a mixture of 50 to 100 percent by weight of a compound of general formula la
    Figure imgb0001
     and 50 to 0 percent by weight of a compound of general formula Ib
    Figure imgb0002
  • b) b percent by weight of a compound of general formula II
    Figure imgb0003
  • c) c percent by weight of a compound of general formula III
    Figure imgb0004
     where b is a number from 0 to 5, c is a number from 0 to 5 and b and c are chosen such that (b + c) is a number from 1 to 10, and where R 1 , R 2 , R 3 are one aliphatic radical with 5 to 12 carbon atoms or an araliphatic radical with 7 to 13 carbon atoms, X⊕, Y⊕, Z⊕ an alkali metal or ammonium cation or a cation of an alkyl or hydroxyalkylamine, R 4 an aliphatic radical with 1 to 8 C atoms, a phenyl group, alkylphenyl group or phenylalkyl group each having 1 to 4 C atoms in the alkyl radical, R 5 is hydrogen or R 4 , y, z are integers from 6 to 8, preferably (y + z) = 15, n is a number from 15 to 35, (m + p) is a number from 2 to 120, and n and (m + p) are chosen such that
    Figure imgb0005

Die Verbindungen der allgemeinen Formel I stellen Salze von Orthophosphorsäure-diestern und die Verbindungen der allgemeinen Formel Ib stellen Salze von Orthophosphorsäure-monoestern dar. Der Anteil des Diesters la in dem Gemisch der Verbindungen la und Ib muss mindestens 50 Gewichtsprozent betragen, vorzugsweise sollte der Diestergehalt im Gemisch mehr als 70 Gewichtsprozent betragen. Es ist selbstverständlich auch möglich, nur einen Diester der allgemeinen Formel la (Gehalt des Diesters im Gemisch = 100 Gewichtsprozent, Gehalt des Monoesters im Gemisch = 0 Gewichtsprozent) zu verwenden. Gemische von Verbindungen la mit Verbindungen Ib, die mindestens 50 Gewichtsprozent des Diesters la enthalten, sind als technische Produkte erhältlich, bei denen R1 = R2 = R3 und X⊕=Y⊕ ist. Diese technischen Produkte können noch 0 bis 15 Gewichtsprozent des für die Veresterung benutzten Alkanols (R1OH) enthalten, was jedoch für die Herstellung des erfindungsgemässen Klotzhilfsmittels nicht stört.The compounds of general formula I represent salts of orthophosphoric acid diesters and the compounds of general formula Ib represent salts of orthophosphoric acid monoesters. The proportion of diester la in the mixture of compounds la and Ib must be at least 50 percent by weight, preferably the diester content be more than 70 percent by weight in the mixture. It is of course also possible to use only one diester of the general formula Ia (content of the diester in the mixture = 100 percent by weight, content of the monoester in the mixture = 0 percent by weight). Mixtures of compounds la with compounds Ib, which contain at least 50 percent by weight of the diester la, are available as technical products in which R 1 = R 2 = R 3 and X⊕ = Y⊕. These technical products can still contain 0 to 15 percent by weight of the alkanol (R 1 OH) used for the esterification, but this does not interfere with the production of the padding aid according to the invention.

RI, R2 und R3 bedeuten insbesondere Alkylreste, vorzugsweise verzweigte Alkylreste mit 7 bis 10 C-Atomen, wie z.B. Isooctyl, Isononyl und Isodecyl. Sofern Rl, R2, R3 für einen araliphatischen Rest stehen, ist der Benzylrest bevorzugt.R I , R 2 and R 3 are in particular alkyl radicals, preferably branched alkyl radicals having 7 to 10 carbon atoms, such as isooctyl, isononyl and isodecyl. If R 1 , R 2 , R 3 represent an araliphatic radical, the benzyl radical is preferred.

Der für R4 stehende aliphatische Rest ist insbesondere ein Alkylrest mit 1 bis 5 C-Atomen. Beispiele für eine für R4 stehende Alkylphenylgruppe sind: 1 -, 2- oder 3-Methyl-, Äthyl- oder n-Butyl-phenyl. Steht R4 für eine Phenalkylgruppe, dann ist die Benzylgruppe bevorzugt.The aliphatic radical representing R 4 is in particular an alkyl radical with 1 to 5 carbon atoms. Examples of an alkylphenyl group representing R 4 are: 1-, 2- or 3-methyl-, ethyl- or n-butylphenyl. If R 4 represents a phenalkyl group, the benzyl group is preferred.

X⊕, Y⊕ und Z⊕ können neben einem Alkalimetallkation oder dem Ammoniumkation auch ein Monoalkyl-, Dialkyl- oder Trialkylammoniumkation mit 1 bis 4 C-Atomen in den einzelnen Alkylresten oder ein Mono-hydroxyalkyl-dialkyl-, Di-hydroxyalkyl-monoalkyl- oder Tri-hydroxyalkyl-ammoniumkation mit 1 bis 4 C-Atomen in den einzelnen Alkylresten bedeuten. Vorzugsweise stehen X⊕, Y⊕ und Z⊕ für Na⊕, K⊕, NH4o, Trimethylammonium und Triäthanolammonium. In vielen Fällen ist X⊕=Y⊕=Z⊕.In addition to an alkali metal cation or the ammonium cation, Xet, Y⊕ and Z⊕ can also be a monoalkyl, dialkyl or trialkylammonium cation with 1 to 4 carbon atoms in the individual alkyl radicals or a mono-hydroxyalkyl-dialkyl, di-hydroxyalkyl-monoalkyl- or tri-hydroxyalkyl-ammonium cation with 1 to 4 carbon atoms in the individual alkyl radicals. X⊕, Y⊕ and Z⊕ are preferably Na⊕, K⊕, NH 4 o, trimethylammonium and triethanolammonium. In many cases, X⊕ = Y⊕ = Z⊕.

Vertreter der Verbindungen la, Ib, II und III sind Handelsprodukte. Die Verbindungen III sind Blockmischpolymerisate von Äthylen- und Propylenoxyd, wobei m und p im statistischen Sinne gleich sind. Vorzugsweise werden solche Verbindungen III einaesetzt. bei denen

Figure imgb0006
d.h. bei denen der Gewichtsanteil des Äthylenoxyds 10 bis 40 Gewichtsprozent beträgt.Representatives of the compounds la, Ib, II and III are commercial products. The compounds III are block copolymers of ethylene and propylene oxide, where m and p are identical in the statistical sense. Such compounds III are preferably used. at them
Figure imgb0006
 ie where the proportion by weight of ethylene oxide is 10 to 40 percent by weight.

Die erfindungsgemässen Klotzhilfsmittel können in einfacher Weise dadurch hergestellt werden, dass das Verbindungsgemisch (la + Ib), die Verbindung II und/oder III in den angegebenen Gewichtsverhältnissen in Wasser eingerührt wird. Anstelle der Diestersalze der allgemeinen Formel la bzw. der Monoestersalze der allgemeinen Formel lb können auch die freien Diestersäuren bzw. Monoestersäuren der allgemeinen Formel Ic bzw. Id

Figure imgb0007
zur Herstellung des Klotzhilfsmittels benutzt werden. Der pH-Wert der erhaltenen Lösung oder Dispersion wird dann mit Alkalimetallhydroxiden, Ammoniak oder organischen Aminen auf Werte über 7, vorzugsweise auf Werte von 7 bis 8, eingestellt. Zur Einstellung des pH-Wertes werden vorzugsweise Natron- oder Kalilauge, wässrige Ammoniaklösung oder Triäthanolamin benutzt.The padding aids according to the invention can be produced in a simple manner by stirring the compound mixture (Ia + Ib), the compound II and / or III in water in the stated weight ratios. Instead of the diester salts of the general formula Ia or the monoester salts of the general formula Ib, the free diester acids or monoester acids of the general formula Ic or Id can also be used
Figure imgb0007
 be used to manufacture the block aid. The pH of the solution or dispersion obtained is then adjusted to values above 7, preferably from 7 to 8, with alkali metal hydroxides, ammonia or organic amines. Sodium hydroxide or potassium hydroxide solution, aqueous ammonia solution or triethanolamine are preferably used to adjust the pH.

Das erfindungsgemässe Klotzhilfsmittel wird zum Färben von Cellulosefasern oder von Cellulose-Synthesefaser-Gemischen mit Schwefel-, Schwefelküpen, Küpen- oder Reaktivfarbstoffen nach kontinuierlichen, halbkontinuierlichen oder diskontinuierlichen Färbeverfahren in Mengen von 1 bis 40 g/I Färbeflotte, vorzugsweise in Mengen von 1 bis 15 g/I Färbeflotte, eingesetzt. In der Regel wird dabei mit Flottenverhältnissen zwischen 1 : 2 bis 1 : 30, vorzugsweise zwischen 1 : 2 bis 1 : 12, gefärbt. Das erfindungsgemässe Färbeverfahren kann selbstverständlich auch so durchgeführt werden, dass nicht das anwendungsfertige Klotzhilfsmittel, sondern die unter a), b) und c) aufgeführten Wirkstoffe in Mengen von insgesamt 0,2 bis 24 g/I, vorzugsweise 0,2 bis 9 g/l, der Färbeflotte zugefügt werden. Dabei werden von den unter a) aufgeführten Wirkstoffen 83,5 bis 95 Gewichtsprozent, von den unter b) aufgeführten Wirkstoffen 0 bis 8,25 Gewichtsprozent, von den unter c) aufgeführten Wirkstoffen 0 bis 8,25 Gewichtsprozent benötigt, wobei die Werte für b) und c) so gewählt werden, dass die Summe der unter b) + c) aufgeführten Wirkstoffe 5 bis 16,5 Gewichtsprozent beträgt.The padding aid according to the invention is used for dyeing cellulose fibers or cellulose-synthetic fiber mixtures with sulfur, sulfur vats, vat or reactive dyes by continuous, semi-continuous or discontinuous dyeing processes in amounts of 1 to 40 g / l of dye liquor, preferably in amounts of 1 to 15 g / I dye liquor used. As a rule, dyeing is carried out with liquor ratios between 1: 2 to 1:30, preferably between 1: 2 to 1:12. The dyeing process according to the invention can of course also be carried out in such a way that not the ready-to-use padding aid, but rather the active substances listed under a), b) and c) in amounts of in total from 0.2 to 24 g / l, preferably 0.2 to 9 g / l, added to the dye liquor. 83.5 to 95 percent by weight of the active ingredients listed under a), 0 to 8.25 percent by weight of the active ingredients listed under b), 0 to 8.25 of the active ingredients listed under c) Percent by weight is required, the values for b) and c) being chosen such that the sum of the active ingredients listed under b) + c) is 5 to 16.5 percent by weight.

Die erfindungsgemässen Klotzhilfsmittel für das Färben mit Schwefel-, Schwefelküpen- und Küpenfarbstoffen enthalten vorzugsweise keine der unter c) aufgeführten Verbindungen III.The padding aids according to the invention for dyeing with sulfur, sulfur vat and vat dyes preferably do not contain any of the compounds III listed under c).

Die erfindungsgemässen Klotzhilfsmittel für das Färben mit Reaktivfarbstoffen enthalten vorzugsweise keine der unter b) aufgeführten Verbindungen II.The padding aids according to the invention for dyeing with reactive dyes preferably do not contain any of the compounds II listed under b).

Der eigentliche Färbevorgang wird auch bei Färbeverfahren mit langen Flottenverhältnissen nach Zusatz des erfindungsgemässen Klotzhilfsmittels oder der oben erwähntenwirkstoffkombination zu derFärbeflotte wie üblich durchgeführt. Das Färben kann z.B. nach dem Küpen-Klotz-Dämpf-, (Pad-Steam-), Williams-Unit-, Kaltverweil-, Pad-Jig- oder Pad-Roll-Verfahren erfolgen. Beim Färben nach kontinuierlichen Verfahren kann dabei mit oder ohne Zwischentrocknung nach dem Klotzen gearbeitet werden.The actual dyeing process is also carried out as usual in dyeing processes with long liquor ratios after adding the padding aid according to the invention or the above-mentioned combination of active ingredients to the dye liquor. The coloring can e.g. according to the Küpen-Klotz-Dämpf-, (Pad-Steam-), Williams-Unit, Cold Dwell, Pad-Jig or Pad-Roll process. When dyeing using a continuous process, it is possible to work with or without intermediate drying after padding.

Alle bekannten Modifikationen der Schwefelfarbstoffe können verwendet werden. Geeignete Schwefelfarbstoffe sind z.B. folgende: C.I. Sulphur Blue 1, C.I. Leuco Sulphur Blue 1, C.I. Sulphur Blue 3, C.I, Leuco Sulphur Blue 3, C.I. Sulphur Blue 4, C.I. Solubilised Sulphur Blue 4, C.I. Sulphur Blue 5, C.I. Leuco Sulphur Blue 5, C.I. Solubilised Sulphur Blue 5, C.I. Sulphur Blue 7, C.I. Leuco Sulphur Blue 7, C.I. Solubilised Sulphur Blue 7, C.I. Sulphur Blue 10, C.I. Solubilised Sulphur Blue 10, C.I. Sulphur Blue 15, C.I. Leuco Sulphur Blue 15, C.I. Solubilised Sulphur Blue 15, C.I. Sulphur Yellow 2, C.I. Leuco Sulphur Yellow 2, C.I. Solubilised Sulphur Yellow 2, C.I. Sulphur Yellow 4, C.I. Leuco Sulphur Yellow 4, C.I. Solubilised Suiphur Yellow 4, C.I. Leuco Sulphur Yellow 7, C.I. Sulphur Yellow 9, C.I. Leuco Sulphur Yellow 9, C.I. Sulphur Green 2, C.I. Leuco Sulphur Green 2, C.I. Solubilised Sulphur Green 2, C.I. Sulphur Green 3, C.I. Leuco Sulphur Green 3, C.I. Solubilised Sulphur Green 3, C.I. Sulphur Green 5, C.I. Sulphur Brown 5, C.I. Leuco Sulphur Brown 5, C.I. Solubilised Sulphur Brown 5, C.I. Sulphur Brown 10, C.I. Leuco Sulphur Brown 10, C.I. Sulphur Brown 16, C.I. Solubilised Sulphur Brown 16, C.I. Sulphur Brown 51, C.I. Solubilised Sulphur Brown 51, C.I. Sulphur Black 8, C.I. Sulphur Red 3, C.I. Solubilised Sulphur Red 3, C.I. Sulphur Red 7, C.I. Solubilised Sulphur Red 7.All known modifications of the sulfur dyes can be used. Suitable sulfur dyes are e.g. following: C.I. Sulfur Blue 1, C.I. Leuco Sulfur Blue 1, C.I. Sulfur Blue 3, C.I., Leuco Sulfur Blue 3, C.I. Sulfur Blue 4, C.I. Solubilized Sulfur Blue 4, C.I. Sulfur Blue 5, C.I. Leuco Sulfur Blue 5, C.I. Solubilized Sulfur Blue 5, C.I. Sulfur Blue 7, C.I. Leuco Sulfur Blue 7, C.I. Solubilized Sulfur Blue 7, C.I. Sulfur Blue 10, C.I. Solubilized Sulfur Blue 10, C.I. Sulfur Blue 15, C.I. Leuco Sulfur Blue 15, C.I. Solubilized Sulfur Blue 15, C.I. Sulfur Yellow 2, C.I. Leuco Sulfur Yellow 2, C.I. Solubilized Sulfur Yellow 2, C.I. Sulfur Yellow 4, C.I. Leuco Sulfur Yellow 4, C.I. Solubilized Suiphur Yellow 4, C.I. Leuco Sulfur Yellow 7, C.I. Sulfur Yellow 9, C.I. Leuco Sulfur Yellow 9, C.I. Sulfur Green 2, C.I. Leuco Sulfur Green 2, C.I. Solubilized Sulfur Green 2, C.I. Sulfur Green 3, C.I. Leuco Sulfur Green 3, C.I. Solubilized Sulfur Green 3, C.I. Sulfur Green 5, C.I. Sulfur Brown 5, C.I. Leuco Sulfur Brown 5, C.I. Solubilized Sulfur Brown 5, C.I. Sulfur Brown 10, C.I. Leuco Sulfur Brown 10, C.I. Sulfur Brown 16, C.I. Solubilized Sulfur Brown 16, C.I. Sulfur Brown 51, C.I. Solubilized Sulfur Brown 51, C.I. Sulfur Black 8, C.I. Sulfur Red 3, C.I. Solubilized Sulfur Red 3, C.I. Sulfur Red 7, C.I. Solubilized Sulfur Red 7.

Geeignete Schwefelküpenfarbstoffe sind z.B. C.I. Vat Blue 42, C.I. Reduced Vat Blue 42, C.I. Vat Blue 43, C.I. Reduced Vat Blue 43, C.I. Vat Blue 44, C.I. Vat Blue 45, C.I. Vat Blue 47, C.I. Vat Blue 49, C.I. Vat Blue 50, C.I. Sulphur Black 10, C.I. Leuco Sulphur Black 10.Suitable sulfur vat dyes are e.g. C.I. Vat Blue 42, C.I. Reduced Vat Blue 42, C.I. Vat Blue 43, C.I. Reduced Vat Blue 43, C.I. Vat Blue 44, C.I. Vat Blue 45, C.I. Vat Blue 47, C.I. Vat Blue 49, C.I. Vat Blue 50, C.I. Sulfur Black 10, C.I. Leuco Sulfur Black 10.

Geeignete Küpenfarbstoffe sind z.B. C.I. VatOrange 7, C.I. Vat Red 13, C.I. Vat Red 14, C.I. Vat Red 15, C.I. Vat Brown 1, C.I. Vat Brown 3, C.I. Vat Blue 13, C.I. Vat Blue 16, C.I. Vat Violet 1, C.I. Vat Blue 4 : 1.Suitable vat dyes are e.g. C.I. VatOrange 7, C.I. Vat Red 13, C.I. Vat Red 14, C.I. Vat Red 15, C.I. Vat Brown 1, C.I. Vat Brown 3, C.I. Vat Blue 13, C.I. Vat Blue 16, C.I. Vat Violet 1, C.I. Vat Blue 4: 1.

Geeignete Reaktivfarbstoffe sind z.B. C.I. Reactive Yellow 17, C.I. Reactive Orange 7, C.I. Reactive Orange 16, C.I. Reactive Red 22, C.I. Reactive Red 23, C.I. Reactive Blue 5, C.I. Reactive Blue 19, C.I. Reactive Violet 4, C.I. Reactive Violet 5.Suitable reactive dyes are e.g. C.I. Reactive Yellow 17, C.I. Reactive Orange 7, C.I. Reactive Orange 16, C.I. Reactive Red 22, C.I. Reactive Red 23, C.I. Reactive Blue 5, C.I. Reactive Blue 19, C.I. Reactive Violet 4, C.I. Reactive Violet 5.

Als textile Materialien können vorbehandelte, wie auch nicht vorbehandelte cellulosefaserhaltige Materialien oder Materialien aus Cellulosefaser-Synthesefaser-Mischungen verwendet werden. Dabei kommen vor allem Mischungen wie Baumwolle/Polyester, Zellwolle/Polyester, Baumwolle/Polyamid, Polyamid/Zellwolle in Frage.Pretreated as well as non-pretreated cellulose fiber-containing materials or materials made from cellulose fiber-synthetic fiber mixtures can be used as textile materials. Mixtures such as cotton / polyester, rayon / polyester, cotton / polyamide, polyamide / rayon are particularly suitable.

Durch das erfindungsgemässe Färbeverfahren bzw. durch Verwendung des erfindungsgemässen Klotzhilfsmittels werden einwandfreie Färbungen mit gleicher Farbtiefe von Kante zu Kante und Anfang zu Ende erreicht. Die durch die erfindungsgemässe Wirkstoffkombination erzielte synergistische Verkürzung der Netzzeiten und die Verminderung des Schaumvolumens ist aus den nachfolgenden Tabellen ersichtlich.The dyeing process according to the invention and the use of the padding aid according to the invention achieve perfect dyeings with the same depth of color from edge to edge and start to end. The synergistic reduction in wetting times and the reduction in foam volume achieved by the active ingredient combination according to the invention can be seen from the tables below.

In den Tabellen und Beispielen angegebene Prozente sind Gewichtsprozente, Teile sind Gewichtsteile, sofern nichts anderes angegeben. Ferner bedeuten: Flotte 1: Eine Färbeflotte zum Färben mit Schwefel-, Schwefelküpen- und Küpenfarbstoffen nach dem Pad-Steam-Verfahren, die im Liter 50 g NaOH 32° Be und 40 g Na2S204 enthält.Percentages given in the tables and examples are percentages by weight, parts are parts by weight unless otherwise stated. Furthermore, fleet 1 means a dyeing liquor for dyeing using sulfur, sulfur vat and vat dyes according to the pad-steam process, which contains 50 g of NaOH 32 ° Be and 40 g of Na 2 S 2 0 4 in liters.

Flotte 2: Eine Färbeflotte zum Färben mit Schwefel-, Schwefelküpen- und Küpenfarbstoffen nach dem Pad-Steam-Verfahren, die im Liter 50 g NaOH 32° Be, 40 g Na2S2O4 und 20 g NaCI enthält.Fleet 2: A dyeing liquor for dyeing with sulfur, sulfur vat and vat dyes according to the pad-steam process, which contains 50 g of NaOH 32 ° Be, 40 g of Na 2 S 2 O 4 and 20 g of NaCI per liter.

Flotte 3: Eine Flotte zum Färben mit Reaktivfarbstoffen, die im Liter 125 g Wasserglas, 30 g NaOH 38° Be und 20 g Na2S04 enthält.Fleet 3: A liquor for dyeing with reactive dyes, which contains 125 g water glass, 30 g NaOH 38 ° Be and 20 g Na 2 S0 4 per liter.

Flotte 4: Eine Flotte zum Färben mit Reaktivfarbstoffen, die im Liter 125 g Wasserglas, 30 g NaOH 38° Be, 20 g Na2SO4 und 100 g Harnstoff enthält.Fleet 4: A liquor for dyeing with reactive dyes, which contains 125 g water glass, 30 g NaOH 38 ° Be, 20 g Na 2 SO 4 and 100 g urea per liter.

Flotte 5: Eine Flotte zum Färben mit Reaktivfarbstoffen, die im Liter 20 g NaOH 38° Be, 30 g NaCl und 20 g Na2S04 enthält.Fleet 5: A liquor for dyeing with reactive dyes, which contains 20 g NaOH 38 ° Be, 30 g NaCl and 20 g Na 2 S0 4 per liter.

Flotte 6: Eine Flotte zum Färben mit Reaktivfarbstoffen, die im Liter 20 g NaOH 38° Be, 30 g NaCl, 20 g NazS04 und 100 g Harnstoff enthält.

  • A 1: Mono-benzyl-phosphat-triäthanolaminsalz.
  • A 2: Di-benzyl-phosphat-triäthanolaminsalz.
  • A 3: Di-(2-äthyl-hexyl)-phosphat-kaliumsalz.
  • A 4: Mono-(2-äthyl-hexyl)-phosphat-kaliumsalz.
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
  • C 1: Ein Äthylenoxyd-Propylenoxyd-Block-Copolymerisat mit einem Molgewicht unter 2000 und mit einem Äthylenoxydanteil von 10 Gewichtsprozent (Verbindung III mit
    Figure imgb0011
  • C 2: Ein Äthylenoxyd-Propylenoxyd-Block-Copolymerisat mit einem Molgewicht unter 3500 und mit einem Äthylenoxydanteil von 40 Gewichtsprozent (Verbindung III mit
    Figure imgb0012
Fleet 6: A liquor for dyeing with reactive dyes, which contains 20 g NaOH 38 ° Be, 30 g NaCl, 20 g Na z S0 4 and 100 g urea per liter.
  • A 1: Mono-benzyl-phosphate-triethanolamine salt.
  • A 2: Di-benzyl-phosphate-triethanolamine salt.
  • A 3: di (2-ethylhexyl) phosphate potassium salt.
  • A 4: mono- (2-ethylhexyl) phosphate potassium salt.
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
  • C 1: An ethylene oxide-propylene oxide block copolymer with a molecular weight below 2000 and with an ethylene oxide content of 10 percent by weight (compound III with
    Figure imgb0011
  • C 2: An ethylene oxide-propylene oxide block copolymer with a molecular weight below 3500 and with an ethylene oxide content of 40 percent by weight (compound III with
    Figure imgb0012

Die Netzzeiten wurden unter Verwendung der in der DIN-Vorschrift 53901 beschriebenen Methode bestimmt; die Schaumwerte wurden nach der Methode der DIN-Vorschrift 53902 bestimmt.The network times were calculated using the in the method described in DIN specification 53901; the foam values were determined according to the method of DIN specification 53902.

In den Tabellen I bis IV sind erfindungsgemässe Klotzhilfsmittel unter der Nr. 1 und in Tabelle V unter den Nr. V/1, V/4 bis 6 angegeben. Wie aus den Tabellen IV und V ferner zu ersehen ist, liefern die erfindungsgemässen Klotzhilfsmittel erstaunlich stabile Klotzflotten für Schwefel-, Schwefelküpen- und Küpenfarbstoffe. Die Tatsache, dass die ionogenen Hilfsmittel in der erfindungsgemässen Kombination nicht ausflockend wirken, obwohl die Flotte stark alkalisch ist und einen hohen Elektrolytgehalt aufweist, war überraschend.Blocking aids according to the invention are given in Tables I to IV under No. 1 and in Table V under No. V / 1, V / 4 to 6. As can also be seen from Tables IV and V, the padding aids according to the invention provide surprisingly stable padding liquors for sulfur, sulfur vat and vat dyes. The fact that the ionogenic auxiliaries in the combination according to the invention do not have a flocculating effect, although the liquor is strongly alkaline and has a high electrolyte content, was surprising.

In den nachfolgenden Beispielen wird die Anwendung erfindungsgemässer Klotzhilfsmittel näher erläutert.

Figure imgb0013
Figure imgb0014
Figure imgb0015
 The use of block auxiliaries according to the invention is explained in more detail in the examples below.
Figure imgb0013
Figure imgb0014
Figure imgb0015

Beispiel 1example 1

Ein schwierig durchzufärbender Roh-Baumwollmoleskin und ein Roh-Zeltplanstoff werden mit einer Flotte geklotzt, die 30 g/I Hydron-Blau R f. Sol (Vat Blue, C.I. 53630), 50 ml/I Natronlauge 32°Be, 40 g/l, Hydrosulfit sowie 4 g/I einer Hilfsmittelzubereitung, die aus 16 Teilen Mono-(2-äthylhexyl)phosphat und 24 Teilen Di-(2-äthylhexyl)phosphat, jeweils als Kaliumsalze und 2,5 Teilen des 10-Hydroxy-octadecancarbonsäure-di-n-butylamids als Na⊕-Salz des Schwefelsäurehalbesters enthält.A raw cotton moleskin that is difficult to dye through and a raw tarpaulin material are padded with a liquor that contains 30 g / l of hydron blue R f. Sol (Vat Blue, CI 53630), 50 ml / l sodium hydroxide solution 32 ° Be, 40 g / l, hydrosulfite and 4 g / l of an auxiliary preparation consisting of 16 parts of mono- (2-ethylhexyl) phosphate and 24 parts of di- ( Contains 2-ethylhexyl) phosphate, each as potassium salts and 2.5 parts of 10-hydroxy-octadecanecarboxylic acid di-n-butylamide as Naids salt of the sulfuric acid half-ester.

Die Klotztemperatur beträgt ca. 20°C. die Flottenaufnahme des verwendeten Zweiwalzenfoulards beträgt bei dem Baumwollmoleskin 55% und bei dem Baumwollzeltstoff 47,%. Nach dem Klotzen, Dämpfen und Fertigstellen der Färbungen auf einer Breitwaschmaschine durch Spülen, Oxydieren und nochmaliges Spülen erhält man gut durchgefärbte Färbungen mit ruhigem Warenbild.The block temperature is approx. 20 ° C. the liquor absorption of the two-roll foulard used is 55% for the cotton moleskin and 47% for the cotton tent fabric. After padding, steaming and finishing the dyeings on a wide washing machine by rinsing, oxidizing and rinsing again, well-colored dyeings with a smooth fabric appearance are obtained.

Beispiel 2Example 2

Der Roh-Baumwollmoleskin des Beispiels 1 wird mit einer Flotte, die 25 g/I Indanthren-Gelb F 2 GC Colloisol (Vat Yellow 33) und 4 g/I eines Klotzhilfsmittels aus 5 Teilen Mono-(2-äthylhexyl)phosphat, 35 Teilen Di-(2-äthylhexyl)-phosphat, jeweils als Kalium-Salze, und 5 Teilen eines Äthylenoxyd/Propylenoxyd-Copolymerisats mit einem Molgewicht unter 2000 und mit einem Äthylenoxydgehalt von 10% enthält, geklotzt, dann bei 120 bis 140°C auf der Hotflue getrocknet, in einem Chemikalientrog mit einer Flotte mit 60 ml/I Natronlauge 38° Be und 30 g/I Hydrosulfit getränkt, gedämpft und auf einer Breitwaschmaschine durch Spülen, Oxydieren, kochendes Seifen und nochmaliges Spülen fertiggestellt. Es wird eine einwandfreie Färbung erhalten.The raw cotton moleskin of Example 1 is mixed with a liquor containing 25 g / l indanthrene yellow F 2 GC Colloisol (Vat Yellow 33) and 4 g / l of a padding aid consisting of 5 parts mono- (2-ethylhexyl) phosphate, 35 parts Di- (2-ethylhexyl) phosphate, in each case as potassium salts, and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight contains less than 2000 and with an ethylene oxide content of 10%, padded, then dried at 120 to 140 ° C on the hot flue, soaked in a chemical trough with a liquor with 60 ml / I sodium hydroxide solution 38 ° Be and 30 g / I hydrosulfite, steamed and Completed on a wide washing machine by rinsing, oxidizing, boiling soap and rinsing again. A perfect color is obtained.

Beispiel 3Example 3

Ein Roh-Zeltplanstoff wird mit einer Flotte, die 80 g/l Cassulfon-Lichtbraun GGL flüssig (Solubilised Sulphur Brown 51, C.I. 53328) und 4 g/l eines Klotzhilfsmittels aus 16 Teilen Mono-(2-äthylhexyl)-phosphat, 24 Teilen Di-(2-äthylhexyl)phosphat jeweils als Triäthanolaminsalz und 5 Teilen des Natriumsalzes des Schwefelsäurehalbesters des 10--Hydroxyoctadecansäure-N-methylanilids enthält, foulardiert, dann bei 120 bis 140°C auf der Hotflue getrocknet, in einem Chemikalientrog mit einer Flotte getränkt, die 12 g/l Soda, 40 ml/1 Sulfhydrat F 150 (Handelsprodukt der Cassella AG, Frankfurt/Main - 61) und 3 ml/l Stabilisal S flüssig (Handelsprodukt der Cassella AG, Frankfurt/Main - 61) enthält, gedämpft und auf einer Breitwaschmaschine durch Spülen, Oxydieren und nochmaliges Spülen fertiggestellt. Es wird eine einwandfreie Färbung erhalten.A raw tarpaulin is made with a liquor that is 80 g / l Cassulfon light brown GGL liquid (Solubilized Sulfur Brown 51, CI 53328) and 4 g / l of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts Di- (2-ethylhexyl) phosphate each as triethanolamine salt and 5 parts of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanoic acid-N-methylanilide contains, padded, then dried at 120 to 140 ° C on the hot flue, soaked in a chemical trough with a liquor , which contains 12 g / l soda, 40 ml / 1 sulfhydrate F 150 (commercial product from Cassella AG, Frankfurt / Main - 61) and 3 ml / l Stabilisal S liquid (commercial product from Cassella AG, Frankfurt / Main - 61), steamed and finished on a wide washing machine by rinsing, oxidizing and rinsing again. A perfect color is obtained.

Beispiel 4Example 4

Ein Roh-Zeltplanstoff wird mit einer Flotte, die 30 g/l Indocarbon CL für Sol (Sulphur Black 11, C.I. 53290) und 4 g/I eines Klotzhilfsmittels aus 5 Teilen Mono-(2-äthylhexyl)phosphat, 35 Teilen Di-(2--äthylhexyl)phosphatjeweils als Kaliumsalz, 0,5 Teilen des Natriumsalzes des Schwefelsäurehalbesters des 10-Hydroxyoctadecancarbonsäure-di-n-butylamids und 2 Teilen eines Äthylenoxyd/Propylenoxyd-Copolymerisats mit einem Molgewicht unter 3500 und mit einem Äthylenoxyd-Gewichtsanteil von 40% enthält, geklotzt, ohne oder nach Trocknung auf der Hotflue im Jigger mit Natronlauge und Hydrosulfit entwickelt und durch Spülen und Oxydieren fertiggestellt. Es wird eine einwandfreie Färbung erhalten.A raw tent fabric is mixed with a liquor containing 30 g / l Indocarbon CL for Sol (Sulfur Black 11, CI 53290) and 4 g / I of a padding aid made up of 5 parts mono- (2-ethylhexyl) phosphate, 35 parts di- ( 2 - ethylhexyl) phosphate each as potassium salt, 0.5 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and 2 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 3500 and with an ethylene oxide weight fraction of 40% contains, padded, developed without or after drying on the hot flue in a jigger with sodium hydroxide solution and hydrosulfite and finished by rinsing and oxidizing. A perfect color is obtained.

Beispiel 5Example 5

Ein Roh-Baumwollmoleskin wird mit einer Flotte, die 25 g/l Indanthren-Brillantorange RK Colloisol (Vat Orange 3, C.I. 59300) und 4 g/1 eines Klotzhilfsmittels aus 16 Teilen Mono-(2-äthylhexyl)phosphat, 24 Teilen Di-(2-äthylhexyl)phosphat jeweils als Natriumsalz, 1 Teil des Natriumsalzes des Schwefelsäurehalbesters des 10-Hydroxyoctadedancarbonsäure-di-n-butylamids und 4 Teilen eines Äthylenoxyd/
Propylenoxyd Copolymerisats mit einem Molgewicht unter 2000 und mit einem Gewichtsanteil von 10% Äthylenoxyd enthält, geklotzt und wie im Beispiel 4 angegeben weiterverarbeitet. Es wird eine einwandfreie Färbung erhalten.A raw cotton moleskin is mixed with a liquor containing 25 g / l indanthrene brilliant orange RK Colloisol (Vat Orange 3, CI 59300) and 4 g / 1 of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts of di- (2-ethylhexyl) phosphate each as the sodium salt, 1 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadedancarboxylic acid di-n-butylamide and 4 parts of an ethylene oxide /
Propylene oxide copolymer with a molecular weight below 2000 and with a weight fraction of 10% contains ethylene oxide, padded and processed as indicated in Example 4. A perfect color is obtained.

Beispiel 6Example 6

Ein Roh-Baumwollmoleskin wird mit einer Flotte, die 40 g/I Hydrosol-Lichtbraun GGL und 4 g/I eines Klotzhilfsmittels aus 20 Teilen Mono-benzyl-phosphat, 20 Teilen Di-benzyl-phosphat, jeweils als Triäthanolaminsalz, 2,5 Teilen des Natriumsalzes des Schwefelsäurehalbesters des 10-Hydroxyoctadecancarbonsäure-di-n-butylamids enthält, geklotzt, ohne oder nach der Trocknung auf der Hotflue im Jigger mit Soda, Sulfhydrat F 150 und Stabilisal S flüssig entwickelt und durch Spülen und Oxydieren fertiggestellt. Es wird eine einwandfreie Färbung erhalten.A raw cotton moleskin is mixed with a liquor containing 40 g / l of hydrosol light brown GGL and 4 g / l of a padding aid consisting of 20 parts of monobenzyl phosphate, 20 parts of di-benzyl phosphate, each as a triethanolamine salt, 2.5 parts contains the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide, padded, developed without liquid or after drying on the hot flue in a jigger with soda, sulfhydrate F 150 and Stabilisal S and finished by rinsing and oxidizing. A perfect color is obtained.

Beispiel 7Example 7

Ein Baumwollgarn wird mit einer Flotte, die 1,5% Indanthren-Rotbraun RR Colloisol (Vat Brown 45, C.I. 59500), 10 ml/l Natronlauge 38° Be, 4 g/I Hydrosulfit und 10 g/I NaCl und 1 g/l eines Klotzhilfsmittels aus 16 Teilen Mono-(2-äthylhexyl)phosphat, 24 Teilen Di-(2-äthylhexyl)phosphat, jeweils als Kaliumsalz, und 5 Teilen eines Äthylenoxyd/Propylenoxyd Copolymerisats mit einem Molgewicht unter 2000 und mit einem Äthylenoxydgehalt von 10% bei 50°C gefärbt und durch Oxydation und kochendes Seifen fertiggestellt. Man erhält egale und gut durchgefärbte Baumwollgarne.A cotton yarn is mixed with a liquor containing 1.5% indanthrene reddish brown RR Colloisol (Vat Brown 45, CI 59500), 10 ml / l sodium hydroxide solution 38 ° Be, 4 g / I hydrosulfite and 10 g / I NaCl and 1 g / l of a padding aid consisting of 16 parts of mono- (2-ethylhexyl) phosphate, 24 parts of di- (2-ethylhexyl) phosphate, each as the potassium salt, and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 2000 and with an ethylene oxide content of 10% dyed at 50 ° C and finished by oxidation and boiling soap. Level and well-dyed cotton yarns are obtained.

Beispiel 8Example 8

Baumwollgarn wird bei 70°C mit einer Flotte gefärbt, die 1 % Hydron-Blau RB Pulver, hochkonzentriert, (Vat Blue 43, C.I. 53630) und 1 g/I eines Klotzhilfsmittels, bestehend aus 16 Teilen Mono-(2-äthyl- hexyl)phosphat, 24 Teilen Di-(2-äthylhexyl)phosphat, jeweils als Kaliumsalz, und 2,5 Teilen des Natriumsalzes des Schwefelsäurehalbesters des 10-Hydroxyoctadecancarbonsäure-di-n-butylamids sowie die im Beispiel 7 angegebenen Chemikalien enthält. Fertiggestellt wird wie im Beispiel 7.Cotton yarn is dyed at 70 ° C. with a liquor which contains 1% Hydron-Blue RB powder, highly concentrated (Vat Blue 43, CI 53630) and 1 g / l of a padding aid, consisting of 16 parts of mono- (2-ethylhexyl ) phosphate, 24 parts of di- (2-ethylhexyl) phosphate, each as the potassium salt, and 2.5 parts of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and the chemicals specified in Example 7. Completion is as in example 7.

Beispiel 9Example 9

Baumwollgarn wird in einer Flotte, die 6% Immedial Carbon CMR hochkonz. Körner (Sulphur Black 1, C.I. 53185), 7 g/I Soda, 10 ml/I Sulfhydrat F 150 (Handelsprodukt der Cassella AG, Frankfurt/Main - 61), 2 ml/l Stabilisal S flüssig (Handelsprodukt der Cassella AG, Frankfurt/Main - 61), 10 g/I Kochsalz und 1 g/l eines Klotzhilfsmittels, hergestellt aus 20 Teilen des Mono-(isononyl)phosphats, 20 Teilen des Di-(isononyl)phosphats, jeweils als Kaliumsalz, und 4,0 Teilen des Natriumsalzes des Schwefelsäure halbesters des 10-Hydroxyoctadecancarbonsäure--di-n-butylamids, enthält, bei 90°C gefärbt und durch Oxydation und Spülen fertiggestellt. Man erhält ein einwandfrei durchgefärbtes Baumwollgarn.Cotton yarn is concentrated in a fleet that contains 6% Immedial Carbon CMR. Grains (Sulfur Black 1, CI 53185), 7 g / I soda, 10 ml / I sulfhydrate F 150 (commercial product from Cassella AG, Frankfurt / Main - 61), 2 ml / l Stabilisal S liquid (commercial product from Cassella AG, Frankfurt / Main - 61), 10 g / I sodium chloride and 1 g / l of a padding aid, made from 20 parts of the mono- (isononyl) phosphate, 20 parts of the di- (isononyl) phosphate, each as the potassium salt, and 4.0 parts of the sodium salt of the sulfuric acid half ester of 10-hydroxyoctadecanecarboxylic acid - di-n-butylamide, contains, colored at 90 ° C and finished by oxidation and rinsing. A perfectly dyed cotton yarn is obtained.

Beispiel 10Example 10

Pflegeleichter Baumwollköper wird mit einer Flotte, die 60 g/I Remazol Rot B (Reactiv Red 22, C.I. 14824), 35 ml/1 Natronlauge 38° Be, 95 ml/I Natriumwasserglas 38° Bé und 4 g/I eines Klotzhilfsmittels aus 5 Teilen Mono-(2-äthylhexyl)phosphat Kaliumsalz, 3,5 Teilen Di-(2-äthylhexyl)phosphat Kaliumsalz, 0,5 Teilen des Natriumsalzes des Schwefelsäurehalbesters des 10-Hydroxyoctadecancarbonsäure-di-n-butylamids und 2 Teilen eines Äthylenoxyd/Propylenoxyd-Copolymerisats mit einem Molgewicht unter 3500 und mit einem Gewichtsanteil an Äthylenoxyd von 40% enthält, bei 20 bis 25°C auf einem Foulard geklotzt, aufgedockt und 4 Stunden verweilen gelassen. Anschliessend erfolgt die übliche Fertigstellung durch Spülen bei 70°C, kochendes Seifen sowie nochmaliges heisses und kaltes Spülen. Es wird eine gut durchgefärbte einwandfreie Färbung erhalten.Easy-care cotton twill is made with a liquor containing 60 g / I Remazol Red B (Reactiv Red 22, CI 14824), 35 ml / 1 sodium hydroxide solution 38 ° Be, 95 ml / I sodium water glass 38 ° Bé and 4 g / I a padding aid from 5 Parts of mono- (2-ethylhexyl) phosphate potassium salt, 3.5 parts of di- (2-ethylhexyl) phosphate potassium salt, 0.5 part of the sodium salt of the sulfuric acid half-ester of 10-hydroxyoctadecanecarboxylic acid di-n-butylamide and 2 parts of an ethylene oxide / propylene oxide -Copolymerisats with a molecular weight below 3500 and with a weight fraction of ethylene oxide of 40%, at 20 to 25 ° C. padded on a foulard, docked and left for 4 hours. Then the usual completion is carried out by rinsing at 70 ° C, boiling soap and repeated hot and cold rinsing. A well-colored, perfect coloring is obtained.

Beispiel 11Example 11

Pflegeleichter Baumwolltrikotstoff wird mit einer Flotte, die 30 g/I Remazol Goldgelb G (Reactiv Yellow 17, C.I. 18852), 14 ml/l Natronlauge 38° Be, 30 g/I Kochsalz und 6 g/l eines Klotzhilfsmittels, hergestellt aus 16 Teilen Mono-(2-äthylhexyl)phosphat Kaliumsalz, 24 Teilen Di-(2-äthylhexyl)phosphat Kaliumsalz und 5 Teilen eines Äthylenoxyd/Propylenoxyd-Copolymerisats mit einem Molgewicht unter 2000 und mit einem Äthylenoxydanteil von 10%, enthält, auf einem Foulard geklotzt, aufgedockt und 12 Stunden verweilen gelassen. Anschliessend wird kalt gespült, mit Essigsäure bei 40° C neutralisiert, heiss gespült, kochend geseift und durch kaltes und heisses Spülen fertiggestellt. Man erhält eine Färbung mit einwandfreiem Warenbild.Easy-care cotton tricot is made from 16 parts with a liquor containing 30 g / l Remazol Goldgelb G (Reactiv Yellow 17, CI 18852), 14 ml / l sodium hydroxide solution 38 ° Be, 30 g / l table salt and 6 g / l padding aid Mono- (2-ethylhexyl) phosphate potassium salt, 24 parts di- (2-ethylhexyl) phosphate potassium salt and 5 parts of an ethylene oxide / propylene oxide copolymer with a molecular weight below 2000 and with an ethylene oxide content of 10%, contains, padded on a foulard, docked and left for 12 hours. It is then rinsed cold, neutralized with acetic acid at 40 ° C, rinsed hot, soaped at the boil and completed by cold and hot rinsing. A dyeing with a perfect product appearance is obtained.

Claims (10)

1. Padding auxiliary for dyeing cellulose fibres or cellulose fibre/synthetic fibre mixture with sulphur dyestuffs, sulphur vat dyestuffs, vat dyestuffs or reactive dyestuffs, consisting of an aqueous solution or dispersing containing
a) 20 to 50 per cent by weight of a mixture of 50 to 100 per cent by weight of a compound of the general formula la
Figure imgb0051
and 50 to 0 per cent by weight of a compound of the general formula Ib
Figure imgb0052
b) b per cent by weight of a compound of the general formula II
Figure imgb0053
and
c) c per cent by weight of a compound of the general formula III
Figure imgb0054
wherein b denotes a number from 0 to 5, c denotes a number from 0 to 5 and b and c are chosen such that (b+c) denotes a number from 1 to 10, and wherein R', R2 and R3 denote an aliphatic radical with 5 to 12 C atoms or an araliphatic radical with 7 to 13 C atoms, X⊕, Y⊕ and Z⊕ denote an alkali metal cation or ammonium cation or a cation of an alkylamine or hydroxyalkylamine, R4 denotes an aliphatic radical with 1 to 8 C atoms, a phenyl group or an alkylphenyl group or phenylalkyl group with in each case 1 to 4 C atoms in the alkyl radical, R5 denotes hydrogen or R4, y and z denote integers from 6 to 8, n denotes a number from 15 to 35 and (m+p) denotes a number from 2 to 120, n and (m + p) being chosen such that
Figure imgb0055
2. Padding auxiliary according to claim 1, characterised in that the mixture of compounds la und Ib contains at least 70 per cent by weight of compound la.
3. Padding auxiliary according to claims 1 and 2, characterised in that it contains a compound of the general formula III for which
Figure imgb0056
4. Padding auxiliary according to claims 1 to 3, characterised in that R1, R2 or R3 denote a branched alkyl radical with 7 to 10 C atoms.
5. Padding auxiliary according to claims 1 to 4, characterised in that (y + z) = 15.
6. Process for preparing a padding auxiliary for dyeing cellulose fibres or cellulose fibre/sinthetic fibre mixtures with sulphur dyestuffs, sulphur vat dyestuffs, vat dyestuffs or reactive dyestuffs, consisting of an aqueous solution or dispersion characterised in that for preparing 100 parts by weight each of solution or dispersion
a) a parts by weight of a mixture of 50 to 100, per cent by weight of a compound of the general formula la
Figure imgb0057
and 50 to 0, preferably 30 to 0, per cent by weight of a compound of the general formula Ib
Figure imgb0058
b) b parts by weight of a compound of the general formula II
Figure imgb0059
and
c) c parts by weight of a compound of the general formula III
Figure imgb0060
wherein a denotes a number from 20 to 50, b denotes a number from 0 to 5, c denotes a number from 0 to 5 and b and c are chosen such that (b + c) denotes a number from 1 to 10, and wherein R1, R2 and R3 denote an aliphatic radical with 5 to 12 C atoms or an araliphatic radical with 7 to 13 C atoms, X⊕, Y⊕ and Z⊕ denote an alkali metal cation or ammonium cation or a cation of an alkylamine or hydroxyalkylamine, R4 denotes an aliphatic radical with 1 to 8 C atoms, a phenyl group or an alkylphenyl group or phenylalkyl group with in each case 1 to 4 C atoms in the alkyl radical, R5 denotes hydrogen or R4, y and z denote integers from 6 to 8, n denotes a number from 15 to 35 and (m + p) denotes a number from 2 to 120, n and (m+p) being chosen such that
Figure imgb0061
are stirred into 100-(a+b+c) parts by weight of water.
7. Process according to claim 6, characterised in that instead of compound la and/or Ib compounds of the formulae
Figure imgb0062
are employed and the pH of the solution or dispersion obtained is adjusted to values greater than 7, preferably to values of 7 to 8.
8. Process for dyeing cellulose fibres or cellulose fibre/synthetic fibre mixture with sulphur dyestuffs, sulphur vat dyestuffs, vat dyestuffs or reactive dyestuffs, characterised in that a padding auxiliary according to claims 1 to 5 or a padding auxiliary prepared according to claim 6 or 7 is added to the padding liquor in amounts of 1 to 40 g/l, and dyeing and finishing are carried out in the customary manner.
9. Process according to claim 8, characterised in that the padding auxiliary is added to the padding liquor in amounts of 1 to 15 g/l.
10. Process for dyeing cellulose fibres or cellulose fibre/synthetic fibre mixtures with sulphur dyestuffs, sulphur vat dyestuffs, vat dyestuffs or reactive dyestuffs, characterised in that a mixture of active substances is added to the padding auxiliary in amounts of 0.2 to 24 g/I, preferably 0.2 to 9 g/I, which mixture contains
a) 83.5 to 95 per cent by weight of a mixture of 50 to 100 per cent by weight of a compound of the general formula la
Figure imgb0063
and 50 to 0 per cent by weight of a compound of the general formula Ib
Figure imgb0064
b) b = 0 to 8.25 per cent by weight of a compound of the general formula II
Figure imgb0065
and
c) c = 0 to 8.25 per cent by weight of a compound of the general formula III
Figure imgb0066
wherein b and c are chosen such that (b + c) denotes a number from 5 to 16.5, and wherein R1, R2 and R3 denote an aliphatic radical with 5 to 12 C atoms or an araliphatic radical with 7 to 13 C atoms, X⊕, Y⊕ and Z⊕ denote an alkali metal cation or ammonium cation or a cation of an alkylamine or hydroxyalkylamine, R4 denotes an aliphatic radical with 1 to 8 C atoms, a phenyl group or an alkylphenyl group or phenylalkyl group with in each case 1 to 4 C atoms in the alkyl radical, R5 denotes hydrogen or R4, y and z denote integers from 6 to 8, n denotes a number from 15 to 35 and (m+p) denotes a number from 2 to 120, n and (m+p) being chosen such that
Figure imgb0067
and dyeing and finishing are carried out in the customary manner.
EP80104312A 1979-07-28 1980-07-23 Padding aid, process for its preparation and process for dyeing cellulosic fibres or mixtures of cellulosic fibres together with synthetic fibres with sulphur, sulphur vat, vat and reactive dyestuffs Expired EP0023341B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80104312T ATE5981T1 (en) 1979-07-28 1980-07-23 BLOCK AID, METHOD OF PRODUCTION AND METHOD OF DYING CELLULOSE FIBERS RESPECTIVELY. MIXTURES OF CELLULOSE FIBERS TOGETHER WITH SYNTHETIC FIBERS WITH SULFUR, SULFUR KUEPEN, KUEPEN AND REACTIVE DYES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792930756 DE2930756A1 (en) 1979-07-28 1979-07-28 BLOCKING AIDS AND METHOD FOR COLORING CELLULOSE FIBERS OR MIXTURES OF CELLULOSE FIBERS TOGETHER WITH SYNTHESIS FIBERS WITH SULFUR, SULFUR COAT, COW AND REACTIVE DYES
DE2930756 1979-07-28

Publications (3)

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EP0023341A2 EP0023341A2 (en) 1981-02-04
EP0023341A3 EP0023341A3 (en) 1981-07-08
EP0023341B1 true EP0023341B1 (en) 1984-01-25

Family

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EP80104312A Expired EP0023341B1 (en) 1979-07-28 1980-07-23 Padding aid, process for its preparation and process for dyeing cellulosic fibres or mixtures of cellulosic fibres together with synthetic fibres with sulphur, sulphur vat, vat and reactive dyestuffs

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US (1) US4300903A (en)
EP (1) EP0023341B1 (en)
JP (1) JPS5620685A (en)
AR (1) AR222237A1 (en)
AT (1) ATE5981T1 (en)
BR (1) BR8004717A (en)
DE (2) DE2930756A1 (en)
ZA (1) ZA804515B (en)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN110105228A (en) * 2019-06-05 2019-08-09 中国科学院兰州化学物理研究所 A kind of proton type ionic liquid and preparation method thereof and application as Water-based Lubricating Additives

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FR2551474B1 (en) * 1983-09-01 1986-12-05 Sandoz Sa PROCESS FOR TREATING CELLULOSIC TEXTILE MATERIALS
DE3760745D1 (en) * 1986-04-07 1989-11-16 Ciba Geigy Ag Process for dyeing cellulosic fibres without tailing
US4801303A (en) * 1987-06-01 1989-01-31 Sandoz Ltd. One-bath dyeing of polyester-cellulosic blends using disperse and sulfur dyes
JPS63315680A (en) * 1987-06-17 1988-12-23 日本サ−ファクタント工業株式会社 Leveling agent for reactive dye and dyeing method
US4886518A (en) * 1987-10-01 1989-12-12 Ciba-Geigy Corporation Dyeing cellulose fibres without incurring ending with colorless pyrimidine, triazine, aromatic, furfuryl or quinolinyl compound
JPH0241479A (en) * 1988-07-27 1990-02-09 Dai Ichi Kogyo Seiyaku Co Ltd One-dip scouring dyeing aid for cellulose fiber and semisynthetic fiber
IL137672A0 (en) * 2000-08-03 2001-10-31 Dpharm Ltd Derivatives of branched-chain lipophilic molecules and uses thereof
EP4011987A1 (en) 2020-12-10 2022-06-15 Clariant International Ltd Salts of n,n-dialkyl (sulfooxy) fatty acid amidate as dispersants for pigment preparations

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US2067927A (en) * 1934-09-03 1937-01-19 Nat Aniline & Chem Co Inc Art of dyeing with vat dyes
FR847911A (en) * 1937-12-22 1939-10-19 Ig Farbenindustrie Ag Printing preparations and pastes based on vat dyes and printing process using these products
FR1396294A (en) * 1963-05-28 1965-04-16 Hoechst Ag Wetting even foaming little
DE1245898C2 (en) * 1964-10-23 1973-01-25 Hoechst Ag Low-foaming, leveling wetting agent
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Publication number Priority date Publication date Assignee Title
CN110105228A (en) * 2019-06-05 2019-08-09 中国科学院兰州化学物理研究所 A kind of proton type ionic liquid and preparation method thereof and application as Water-based Lubricating Additives

Also Published As

Publication number Publication date
DE3066276D1 (en) 1984-03-01
JPS5620685A (en) 1981-02-26
ZA804515B (en) 1981-07-29
DE2930756A1 (en) 1981-02-26
JPS6343508B2 (en) 1988-08-31
EP0023341A3 (en) 1981-07-08
ATE5981T1 (en) 1984-02-15
US4300903A (en) 1981-11-17
BR8004717A (en) 1981-02-10
AR222237A1 (en) 1981-04-30
EP0023341A2 (en) 1981-02-04

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