EP0150405B1 - Procédé d'impression de fibres synthétiques - Google Patents

Procédé d'impression de fibres synthétiques Download PDF

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Publication number
EP0150405B1
EP0150405B1 EP84115523A EP84115523A EP0150405B1 EP 0150405 B1 EP0150405 B1 EP 0150405B1 EP 84115523 A EP84115523 A EP 84115523A EP 84115523 A EP84115523 A EP 84115523A EP 0150405 B1 EP0150405 B1 EP 0150405B1
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EP
European Patent Office
Prior art keywords
acid
alkali metal
ammonium
formula
mixture
Prior art date
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.)
Expired
Application number
EP84115523A
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German (de)
English (en)
Other versions
EP0150405A3 (en
EP0150405A2 (fr
Inventor
Adolf Blum
Norbert Dr.-Chem. Grund
Siegfried Dr.-Chem. Schreiner
Gert Dr.-Chem. Treiber
Norbert Zimmermann
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BASF SE
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BASF SE
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Publication of EP0150405A3 publication Critical patent/EP0150405A3/de
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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
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants

Definitions

  • etching agents are mostly used which contain reducing agents, e.g. B. according to DE-PS 2 753 696, a mixture of an ammonia derivative which has at least one residue of an alkali metal or ammonium salt of methanesulfinic acid and glucose and according to the method of DE-OS 3 106 036 a mixture of alkali or ammonium salts Hydroximethanesulfinic acid and hexamethylenetetramine.
  • Reducible dyes are used for the base coloring, which are to be destroyed as completely as possible by the etching agents. To achieve colorful effects, non-reducible dyes are used, which must not be attacked by the etchant.
  • the reducing etchants most often used in the known methods still have disadvantages.
  • destruction of the so-called “etch-resistant illumination dyes by strong reducing agents is observed, while on the other hand, when using weaker reducing agents, especially in deeply colored funds, the fund dyes are not completely destroyed. This leads to cloudy printing.
  • the printing pastes containing caustic also show insufficient stability due to premature decomposition of the reducing agent and / or partial destruction of the so-called “caustic-resistant” illumination dye.
  • the invention has for its object a method for printing synthetic fibers made of polyester, triacetate, acetate, polyamide or their mixtures with one another with disperse dyes by the etching or etching reserve method with mixtures containing hydroxymethanesulfinate as an etchant or a method for white etching using only the etchant To make available in which one can fall back on more stable printing pastes containing caustic agents and in which one achieves clearer nuances of the illuminating dyes even on deep-colored bases than is possible with the known methods.
  • textile goods for. B. woven or knitted fabrics made of polyester, cellulose triacetate, cellulose acetate and polyamide or mixtures thereof. Textiles made from the materials mentioned are commercially available.
  • the etching reserve process can, for example, do this be carried out by first padding the fabric with a liquor containing an etchable disperse dye.
  • the textile material can also be printed with a printing paste which contains an etchable disperse dye and a synthetic or natural thickener. The textile material is then dried under conditions such that the dyes are not yet fixed. Then it is printed with a mixture of an etch-resistant disperse dye and the etchant mixture and dried. The dyes are then fixed, for. B.
  • the etchable dye is destroyed at the locations on which the mixture of the etch-resistant dye and the etchant has been printed. This procedure is called the etching reserve because the base of the goods is colored, but the dye is not yet fixed.
  • a variant of the etching reserve process consists in printing the mixture of etching-resistant dye and etching agent on the textile material, and then immediately overprinting the etching dye over the entire surface and then drying the material and fixing the dyes.
  • an etchable dye that has already been fixed on the tissue is etched with the etchant mixture according to the pattern.
  • White etching is also possible with all process variants, i. H. In this case, a printing paste is used which contains the etchant mixture but does not contain any dye.
  • the etchant mixture contains as component a) at least one compound of the formula or mixtures of compounds of the formula I with an alkali metal or ammonium thiocyanate.
  • the compounds of formula I are known, sometimes even large-scale products.
  • Preferred compounds of the formula are the sodium, potassium or ammonium salts of anthranilic acid and phenylglycine.
  • Compounds of formula II are e.g. B. from DE-PS-1 104484 known. They can be produced by known methods, such as e.g. B. by reacting the compounds of the formulas with sodium hydroximethanesulfinate.
  • the etchant mixture contains, for example, an alkali or ammonium salt of anthranilo-N-methanesulfinic acid or N-phenylglycino-N-methanesulfinic acid (compounds of the formula 11).
  • an alkali or ammonium salt of anthranilo-N-methanesulfinic acid or N-phenylglycino-N-methanesulfinic acid compounds of the formula 11
  • the sodium and potassium salts are used as alkali salts. It is of course also possible to use mixtures of sodium and potassium salts or of sodium and ammonium salts of the compounds of the formulas I, II and thiocyanic acid.
  • the etchant mixture can also contain a water-soluble hydroxymethane or hydroxyethanesulfinate.
  • Suitable reducing agents are also ammonia derivatives which contain at least one residue of an alkali metal or ammonium salt of methanesulfinic acid or ethanesulfinic acid.
  • Compounds of this type are obtained by one or more of the hydrogen atoms of ammonia bonded to a nitrogen atom or of derivatives of ammonia, for example primary or secondary aliphatic amines, e.g. B.
  • ammonia derivatives are prepared in a known manner by reacting ammonia or its derivatives which carry at least one hydrogen atom bound to nitrogen with alkali metal or ammonium salts of hydroxymethanesulfinic acid or hydroxyethanesulfinic acid (compounds of the formula III). This reaction proceeds with the elimination of water.
  • alkali metal or ammonium salts of the ammonia derivatives of methanesulfinic acid e.g. B.
  • iminodimethanesulfinic sodium which has the formula has and is prepared by reacting ammonia with hydroxymethanesulfinic sodium in a molar ratio of 1: 2 and the compound of the formula which is obtained by reacting ammonia with the sodium salt of hydroxymethanesulfinic acid in a molar ratio of 1: 1.
  • Mixtures of different water-soluble sulfinic acids can also be used as component b) use group-containing connections. At least 100 g of water-soluble compounds dissolve per liter of water at a temperature of 20 ° C.
  • Water-insoluble alkaline earth metal salts of compounds of the formula are used as component c) of the etchant to be used according to the invention in which R represents H or a C 1 - to C 3 -alkyl group.
  • water-insoluble means that less than 2.5 g of the alkaline earth metal salt can be dissolved in 1 liter of water at a temperature of 20 ° C.
  • the calcium salts of sulfinic acid ie the calcium salts of hydroxymethanesulfinic acid, hydroxyethanesulfinic acid, hydroxypropanesulfinic acid or hydroxylbutanesulfinic acid, are preferably used. It is of course also possible to use mixtures of the alkaline earth metal salts, for.
  • the water-insoluble alkaline earth metal salts of component c) of the etchant mixture can be brought into a finely divided form by grinding (dry and preferably wet grinding in the presence of a dispersant) and optionally sieving the ground material.
  • the particle size of the water-insoluble salts is preferably below the clear width of the screens of the printing stencils, ie below 0.15 mm, preferably in the range from 0.01 to 0.15 mm.
  • Carbohydrates or their derivatives are used as component d) of the etchant used according to the invention.
  • Mono- or disaccharides are particularly suitable as carbohydrates and ascorbic acid in particular as carbohydrate derivatives.
  • the monosaccharides are e.g. B. tetrosis, such as erythrosis, especially pentoses, such as xylose, arabinose, ribose and in particular hexoses, such as glucose, fructose, sorbose, gulose, rhamnose, galactose, mannose and fucose. Lactose, maltose, cellobiose and reducing dextrin types are particularly suitable as disaccharides.
  • Glucose both 1-glucose and d-glucose, also called dextrose, d-fructose, lactose, maltose, cellobiose, dextrin and ascorbic acid and their mixture are preferred.
  • dextrose adenosine triphosphate
  • d-fructose lactose
  • maltose maltose
  • cellobiose cellobiose
  • dextrin dextrin
  • ascorbic acid e.g. B. from fructose and glucose.
  • the printing paste with which the etchant mixture is printed on the textile material usually contains thickeners to adjust the viscosity. It is preferred to use natural thickeners, such as powdered meal ether, starch-tragacanth thickeners and alginates.
  • 1,000 parts by weight of the printing paste containing caustic contains 10 to 400 parts by weight of the caustic mixture and 20 to 100 parts by weight of the natural thickener.
  • synthetic thickeners which are known to be sensitive to electrolytes, but because of the electrolyte content of the etching printing paste, higher amounts are usually required than usual.
  • Suitable synthetic thickeners are, for example, high molecular weight polycarboxylic acids, e.g. As polyacrylic acid, crosslinking agents crosslinked polyacrylic acid and copolymers of ethylene and acrylic acid or copolymers of styrene or ethylene and maleic anhydride.
  • the synthetic thickeners develop their effectiveness in the pH range above 6. It is also possible to use mixtures of natural and synthetic thickeners.
  • 1,000 parts by weight of the printing pastes contain 0.5 to 50 parts by weight of a disperse dye or a mixture of disperse dyes.
  • the printing pastes containing the etchant may also have other additives, e.g. B. foam damper, fixative, urea, etching aids such. B. anthraquinone, solvents such as. B. biscyanethylformamide, thiodiglycol, glycerol or polyalkylene glycols or substances that either generate an alkaline pH in the printing paste, such as. B. alkali hydroxides, alkali carbonates or hydrogen carbonates, ammonia, triethanolamine or urotropin or alkali donors, d. H. Agents that release alkali during the fixing process, such as. B. the sodium salt of trichloroacetic acid.
  • the pH of the printing pastes containing caustic is usually between 7.5 and 13, preferably between 8 and 12.5.
  • the process according to the invention is characterized in that even when a small amount of an etch-resistant dye is printed on together with the etchant on a deep-colored fund, clearer nuances of the illuminating dye are obtained than was previously the case.
  • the process according to the invention also gives sharp prints.
  • the printed fiber materials, especially polyester, suffer little or no fiber damage.
  • the pH of the padding liquor is adjusted to 5.5 with tartaric acid.
  • the fleet intake is 90%.
  • the fabric is dried at a temperature in the range from 90 to 100 ° C. and then printed with a printing paste which has the following composition:
  • the printed material is dried and then treated for 10 minutes at a temperature of 170 ° C. with superheated steam under normal pressure.
  • the material is then rinsed and reductively cleaned as usual. You get a yellow print on a black background.
  • the print is characterized by a clear color and sharp contours.
  • the fabric treated in this way is printed with a printing paste which has the following composition:
  • the printed material is then dried and then treated for 8 minutes at a temperature of 175 ° C. with superheated steam under normal pressure. Then it is rinsed and cleaned reductively as usual. You get a clear blue print on a black background.
  • the printed material is dried and then treated for 12 minutes at a temperature of 175 ° C. with superheated steam under normal pressure. After that, the material is used as usual rinsed and reductively cleaned. A clear yellow, sharply defined print is obtained on a black background.
  • a polyester fabric is padded, as described in Example 1, with a liquor containing 50 g / l of the blue dye of the formula contains. After drying at 90 to 100 ° C, printing is carried out with a printing paste which has the following composition:
  • the printed material is dried and then treated for 10 minutes at a temperature of 170 ° C. with superheated steam under normal pressure.
  • the material is then rinsed and reductively cleaned as usual. You get a sharp pink print on a blue background.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Claims (5)

1. Procédé d'impression de fibres de synthèse, en polyester, triacétate, acétate, polyamide ou leurs mélange entre elles, avec des colorants de dispersion selon le procédé d'enlevage ou au rongeant- réserve avec des mélanges contenant de l'hydroxyméthansulfinate comme rongeant ou procédé de rongeage en blanc avec utilisation exclusive du rongeant, caractérisé par le fait que l'on utilise comme rongeant un mélange de
a) 5 à 100 parties en poids d'au moins un composé de formule
Figure imgb0034
éventuellement en mélange avec un thiocyanate alcalin ou d'ammonium,
R1 désignant, dans la formule l, hydrogène, alkyle en Ci à C4 ou alkylène en CI-C4-COOM
R2, hydrogène, méthyle, méthoxy ou
Figure imgb0035
M, un cation alkalin ou ammonium et n, 0, 1 ou 2.
b) 5 à 95 parties en poids d'un hydroxyméthan-sulfinate d'ammonium ou alcalin, hydroxyéthansul- finate alcalin ou d'ammonium ou un dérivé d'ammoniaque qui possède au moins une fois le reste d'un sel alcalin ou d'ammonium de l'acide méthan- ou éthansulfinique
c) 5 à 90 parties en poids d'un sel alcalino-terreux insoluble dans l'eau d'un composé de formule
Figure imgb0036
dans laquelle R est mis pour H ou un groupe alkyle en C1 à C3, et
d) 0 à 50 parties en poids d'un hydrate de carbone à action réductrice.
2. Procédé selon la revendication 1, caractérisé par le fait que le rongeant contient, comme composant a), un sel alcalin ou d'ammonium de l'acide anthranilique et/ou de la phénylglycine.
3. Procédé selon la revendication 1, caractérisé par le fait que le rongeant contient, comme composant a), un mélange d'un sel alcalin ou d'ammonium de l'acide thiocyanique avec un sel alcalin ou d'ammonium de l'acide anthranilique et/ou de la phénylglycine.
4. Procédé selon la revendication 1, caractérisé par le fait que le rongeant contient, comme composant b), un sel alcalin ou d'ammonium de l'acide anthranilo-N-méthansulfinique ou de l'acide N-phényl-glycino-N-méthansulfinique.
5. Procédé selon la revendication 1, caractérisé par 'le fait que le rongeant contient, comme composant b) un hydroxyméthansulfinate alcalin ou d'ammonium, un sel alcalin ou d'ammonium de l'acide aminométhansulfinique, de l'acide iminométhandisulfinique ou l'acide nitrométhantrisulfinique.
EP84115523A 1984-01-18 1984-12-15 Procédé d'impression de fibres synthétiques Expired EP0150405B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3401500 1984-01-18
DE19843401500 DE3401500A1 (de) 1984-01-18 1984-01-18 Verfahren zum bedrucken von synthesefasern

Publications (3)

Publication Number Publication Date
EP0150405A2 EP0150405A2 (fr) 1985-08-07
EP0150405A3 EP0150405A3 (en) 1987-02-04
EP0150405B1 true EP0150405B1 (fr) 1989-06-07

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Family Applications (1)

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EP84115523A Expired EP0150405B1 (fr) 1984-01-18 1984-12-15 Procédé d'impression de fibres synthétiques

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DE (2) DE3401500A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19743759A1 (de) * 1997-10-02 1999-04-08 Brueggemann L Kg Sulfinsäurederivate und deren Herstellung und Verwendung
WO2007107310A2 (fr) * 2006-03-21 2007-09-27 Henkel Ag & Co. Kgaa Décoloration réductive
ITFI20120163A1 (it) * 2012-08-07 2014-02-08 Francesco Casati Processo ecologico di stampa a corrosione su materiali tessili

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB402037A (en) * 1932-02-15 1933-11-23 British Celanese Improvements in or relating to the colouration of materials
BE794898A (fr) * 1972-02-04 1973-08-02 Montedison Fibre Spa Procede ameliore d'impression par decoloration ou decharge de fibres et de produits formes de telles fibres
DE3128984A1 (de) * 1980-07-25 1982-03-18 CIBA-GEIGY AG, 4002 Basel "aetzreservedruckverfahren zum bedrucken von polyester enthaltenden fasermaterialien unter einsatz eines reduzierenden kohlenhydrate enthaltenden aetzmittels"
DE3113732A1 (de) * 1981-04-04 1982-10-21 Basf Ag, 6700 Ludwigshafen Verfahren zum bedrucken von synthesefasern
DE3246788A1 (de) * 1982-12-17 1984-06-20 Basf Ag, 6700 Ludwigshafen Verfahren zum bedrucken von synthesefasern

Also Published As

Publication number Publication date
EP0150405A3 (en) 1987-02-04
DE3478624D1 (en) 1989-07-13
DE3401500A1 (de) 1985-07-25
EP0150405A2 (fr) 1985-08-07

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