EP0634517B1 - Process for dying for pelts with oxidation dyes - Google Patents

Process for dying for pelts with oxidation dyes Download PDF

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Publication number
EP0634517B1
EP0634517B1 EP94110399A EP94110399A EP0634517B1 EP 0634517 B1 EP0634517 B1 EP 0634517B1 EP 94110399 A EP94110399 A EP 94110399A EP 94110399 A EP94110399 A EP 94110399A EP 0634517 B1 EP0634517 B1 EP 0634517B1
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EP
European Patent Office
Prior art keywords
mordant
metal
acid
liquor
glyoxylic acid
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EP94110399A
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German (de)
French (fr)
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EP0634517A1 (en
Inventor
Hubert Dipl.-Ing. Herdt
Josef Hurt
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Hoechst AG
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Hoechst AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/30—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts
    • D06P3/3041—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts using vat, sulfur or indigo 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
    • Y10S8/93—Pretreatment before dyeing

Definitions

  • the fur is usually treated with a pickling solution before coloring with oxidation dyes.
  • the purpose of the stain is to make the dyeings light, washable, storable and sublimation-free.
  • the stains on a stain are much more intense and vivid.
  • Metal salts mainly chromium and iron salts, in rare cases copper salts, are used as pickling agents.
  • the present invention relates to a process for dyeing fur skins with oxidation dyes, in which the fur skins are first pretreated and then dyed, which is characterized in that the fur skins are pretreated with a metal stain containing glyoxylic acid.
  • Metal salts mainly chromium or iron salts, are used as pickling agents.
  • the dichromate concentration is usually between 0.1 and 7 g / l pickling liquor, the pH of the stain being in the range between 3 and 5. It has been shown that at higher pH values between pH 5 and 7, only a little dichromate is absorbed, even if the concentration is chosen to be relatively strong. If the pH values are lower than 3, the hair already hardens. The amount of dichromate to be applied to the hair can therefore be regulated by the pH value and also by the dichromate concentration.
  • a mild pickling effect is achieved on the one hand with a quantity of dichromate of 2 to 5 g / l pickling liquor if the acid addition is low and on the other hand with a quantity of dichromate of 0.3 to 0.5 g / l pickling liquor at a pH of 3.5 to 4.
  • a strong pickling effect is achieved with 0.5 to 1 g dichromate per liter pickling liquor at a low pH.
  • Glyoxylic acid is used to adjust the pH, but the addition of other acids, e.g. Formic acid, acetic acid or glycolic acid is conceivable.
  • the content of glyoxylic acid per liter of pickling liquor depends on the desired pH and is between 1 and 7 g / l pickling liquor.
  • the amount of acid is about 1.5 to 3 g glyoxylic acid per liter pickling liquor. If the addition of acid is too low, uneven colorations are obtained, and if the addition of acid is too high, the coloring becomes weaker than with normal addition of acid.
  • the acid addition also plays a special role in iron pickling. Iron stains with too little acid tend to oxidize. The baths become cloudy due to the formation of yellow-brown basic ferrisulfate and ferrihydroxide and, when standing, deposit brown sludge. A sufficient amount of acid, preferably glyoxylic acid, in the stain can prevent the formation of the poorly soluble iron compounds. Usually 1.5 to 3 g of glyoxylic acid, based on one liter of pickling liquor, are added to the iron stain.
  • stains which contain combinations of the metal salts with one another are also suitable. These include: the copper-iron stain, the chrome-copper stain, the iron-chrome alum stain and the copper-chrome alum stain.
  • the mordants used according to the invention usually contain a certain amount of degreasing agent.
  • Preferred degreasing agents are fatty alcohol polyglycol ethers with 5 to 12 EO units, for example ® Remolgan CX, ® Genapol UD O50, ® Genapol UD O80 (manufacturer: Hoechst AG).
  • the glyoxylic acid is usually added to the pickling liquor in the form of an aqueous solution, preferably 40-50% by weight.
  • the pickling process is generally carried out in reels, fur turns or closed vessels (drum, barrel).
  • the temperature is advantageously 20 to 40 ° C, while the duration varies between 3 and 24 hours.
  • the skins are rinsed briefly, if necessary, then spun well and finally come to the dye bath. Thorough rinsing is never beneficial, as otherwise some of the pickling salts that are absorbed will be washed out again.
  • the purpose of rinsing is only to remove excess metal salts and acids. Are the stains, e.g. Dichromate stain, applied with little acid, so rinsing can be avoided. It is sufficient to centrifuge the skins well.
  • a total of 8.0 ml of H 2 O 2 (30% by weight) / l of dye liquor are used for the oxidation.
  • the dyeing takes place at 35 ° C for a total of 6 hours.
  • the undercoat had a brown tinge. Recolouring was necessary here.
  • the dichromate content is 527 mg / l pickling liquor.
  • the leather side of the fur skins stained with glyoxylic acid is incomparably softer and more tear-resistant than that of those treated by the conventional method.
  • a total of 8.0 ml of H 2 O 2 (30% by weight) / l of dye liquor are used for the oxidation.
  • the dyeing takes place at 35 ° C for a total of 6 hours.
  • a total of 5.0 ml H 2 O 2 (30% by weight) / l dyeing liquor is used for the oxidation.
  • a total of 3 1/2 hours are stained at 35 ° C.
  • the leather side of the fur skins stained with glyoxylic acid is significantly softer and more tear-resistant than that of those treated with the conventional method.
  • a total of 5.0 ml H 2 O 2 (30% by weight) / l dyeing liquor is used for the oxidation.
  • a total of 3 1/2 hours are stained at 35 ° C.
  • the dichromate content after finishing the pickling is 478 mg / l pickling liquor.

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

Description

Vor der eigentlichen Färbung mit Oxidationsfarbstoffen müssen die Pelzfelle in geeigneter Weise vorbehandelt werden, denn es hat sich gezeigt, daß das Haar der Pelzfelle die Oxidationsfarbstoffe sonst nur ungleichmäßig aufnimmt. Bisher war es üblich den Arbeitsgang des Färbens mit einem Prozeß zu beginnen, den man als Haaraufschluß oder Tötung (des Haares) bezeichnet. Diese Tötung soll eine weitgehende Reinigung des Haares bewirken, also überschüssiges Fett und Schmutz beseitigen, schädliche Säuren neutralisieren und außerdem das Haar in geeigneter Weise aufschließen. Bei dem Vorgang der Tötung kennt der Fachmann in der Hauptsache zwei verschiedene Formen:

  • a) Tauchtötung und
  • b) Streichtötung.
Before the actual coloring with oxidation dyes, the fur skins must be pretreated in a suitable manner, because it has been shown that the hair of the fur skins otherwise only absorbs the oxidation dyes unevenly. So far, it has been customary to begin the dyeing process with a process known as hair unlocking or killing (of the hair). This killing is said to result in extensive cleaning of the hair, i.e. removing excess grease and dirt, neutralizing harmful acids and also opening the hair in a suitable manner. In the process of killing, the specialist knows two main forms:
  • a) diving killing and
  • b) Streak killing.

Nachdem das Haar durch eine Tötung genügend aufgeschlossen ist, werden die Felle vor dem Färben mit Oxidationsfarbstoffen meist noch mit einer Beizlösung behandelt. Die Beize hat den Zweck, die Färbungen licht-, wasch-, lager- und sublimierechter zu machen. Außerdem fallen die Färbungen auf einer Vorbeize viel intensiver und farbkräftiger aus. Als Beize werden Metallsalze, und zwar vorwiegend Chrom- und Eisensalze, in seltenen Fällen Kupfersalze, verwendet.After the hair is sufficiently disrupted by killing, the fur is usually treated with a pickling solution before coloring with oxidation dyes. The purpose of the stain is to make the dyeings light, washable, storable and sublimation-free. In addition, the stains on a stain are much more intense and vivid. Metal salts, mainly chromium and iron salts, in rare cases copper salts, are used as pickling agents.

Nach der Beize werden die Felle, wenn erforderlich, kurz gespült, dann gut geschleudert und kommen schließlich in das Färbebad. Die vorstehend beschriebene Arbeitsweise war bisher üblich und kann der gängigen Fachliteratur, z.B. Dr. W. Pense "Rauchwaren", Handbuch der Gerbereichemie und Lederfabrikation, 3. Band, Teil 2, 1955, entnommen werden.After pickling, the skins are rinsed briefly, if necessary, then spun well and finally come to the dye bath. The method of operation described above was previously common and can be found in the usual specialist literature, eg Dr. W. Pense "Rauchwaren", Handbook of tanning chemistry and leather manufacturing, Volume 3, Part 2, 1955.

Überraschenderweise hat sich gezeigt, daß eine Vorbehandlung der Pelzfelle mit Metallbeizen, die Glyoxylsäure enthalten, den bisher üblichen Vorgang des Tötens überflüssig macht.Surprisingly, it has been shown that pretreatment of the fur skins with metal stains which contain glyoxylic acid makes the previously usual process of killing superfluous.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben von Pelzfellen mit Oxidationsfarbstoffen, bei dem die Pelzfelle zunächst vorbehandelt und anschließend gefärbt werden, das dadurch gekennzeichnet ist, daß die Pelzfelle mit einer Metallbeize enthaltend Glyoxylsäure vorbehandelt werden.The present invention relates to a process for dyeing fur skins with oxidation dyes, in which the fur skins are first pretreated and then dyed, which is characterized in that the fur skins are pretreated with a metal stain containing glyoxylic acid.

Als Beizmittel werden Metallsalze, und zwar vorwiegend Chrom- oder Eisensalze verwendet. Bei Anwendung der Chrombeize liegt die Dichromat-Konzentration üblicherweise zwischen 0,1 und 7 g/l Beizflotte, wobei der pH-Wert der Beize im Bereich zwischen 3 und 5 liegt. Es hat sich gezeigt, daß bei höheren pH-Werten zwischen pH 5 und 7 nur wenig Dichromat aufzieht, selbst wenn die Konzentration verhältnismäßig stark gewählt wird. Liegen die pH-Werte niedriger als 3, so tritt schon eine Verhärtung des Haares auf. Die Menge an Dichromat, die auf das Haar gebracht werden soll, kann also durch den pH-Wert und auch durch die Dichromatkonzentration geregelt werden. Eine milde Beizwirkung wird einerseits bei einer Dichromatmenge von 2 bis 5 g/l Beizflotte erzielt, wenn der Säurezusatz gering ist und andererseits mit einer Dichromatmenge von 0,3 bis 0,5 g/l Beizflotte bei einem pH-Wert von 3,5 bis 4. Umgekehrt erzielt man eine starke Beizwirkung schon mit 0,5 bis 1 g Dichromat pro Liter Beizflotte bei niedrigem pH-Wert. Zur Einstellung des pH-Wertes dient Glyoxylsäure, wobei aber auch der Zusatz anderer Säuren, z.B. Ameisensäure, Essigsäure oder Glykolsäure denkbar ist. Der Gehalt an Glyoxylsäure pro Liter Beizflotte richtet sich nach dem gewünschten pH-Wert und liegt zwischen 1 und 7 g/l Beizflotte.Metal salts, mainly chromium or iron salts, are used as pickling agents. When using the chrome stain, the dichromate concentration is usually between 0.1 and 7 g / l pickling liquor, the pH of the stain being in the range between 3 and 5. It has been shown that at higher pH values between pH 5 and 7, only a little dichromate is absorbed, even if the concentration is chosen to be relatively strong. If the pH values are lower than 3, the hair already hardens. The amount of dichromate to be applied to the hair can therefore be regulated by the pH value and also by the dichromate concentration. A mild pickling effect is achieved on the one hand with a quantity of dichromate of 2 to 5 g / l pickling liquor if the acid addition is low and on the other hand with a quantity of dichromate of 0.3 to 0.5 g / l pickling liquor at a pH of 3.5 to 4. Conversely, a strong pickling effect is achieved with 0.5 to 1 g dichromate per liter pickling liquor at a low pH. Glyoxylic acid is used to adjust the pH, but the addition of other acids, e.g. Formic acid, acetic acid or glycolic acid is conceivable. The content of glyoxylic acid per liter of pickling liquor depends on the desired pH and is between 1 and 7 g / l pickling liquor.

Bei Verwendung von Kupferbeizen beträgt die Säuremenge etwa 1,5 bis 3 g Glyoxylsäure pro Liter Beizflotte. Bei zu geringem Säurezusatz erhält man ungleichmäßige Färbungen und bei zu hohem Säurezusatz wird die Färbung jedoch schwächer als bei normalem Säurezusatz.When using copper pickling, the amount of acid is about 1.5 to 3 g glyoxylic acid per liter pickling liquor. If the addition of acid is too low, uneven colorations are obtained, and if the addition of acid is too high, the coloring becomes weaker than with normal addition of acid.

Auch bei der Eisenbeize spielt der Säurezusatz eine besondere Rolle. Eisenbeizen mit zu geringen Säuremengen neigen leicht zum Oxidieren. Die Bäder werden durch die Bildung von gelbbraunem basischem Ferrisulfat und Ferrihydroxid trüb und setzen beim Stehen braunen Schlamm ab. Eine genügende Säuremenge, bevorzugt Glyoxylsäure, in der Beize kann aber die Bildung der schwerlöslichen Eisenverbindungen verhindern. Üblicherweise werden der Eisenbeize 1,5 bis 3 g Glyoxylsäure, bezogen auf einen Liter Beizflotte, zugesetzt.The acid addition also plays a special role in iron pickling. Iron stains with too little acid tend to oxidize. The baths become cloudy due to the formation of yellow-brown basic ferrisulfate and ferrihydroxide and, when standing, deposit brown sludge. A sufficient amount of acid, preferably glyoxylic acid, in the stain can prevent the formation of the poorly soluble iron compounds. Usually 1.5 to 3 g of glyoxylic acid, based on one liter of pickling liquor, are added to the iron stain.

Neben den vorstehend genannten Beizen eignen sich auch Beizen, die Kombinationen der Metallsalze untereinander enthalten. Hierbei sind zu nennen: die Kupfer-Eisen-Beize, die Chrom-Kupfer-Beize, die Eisen-Chromalaun-Beize und die Kupfer-Chromalaun-Beize.In addition to the abovementioned stains, stains which contain combinations of the metal salts with one another are also suitable. These include: the copper-iron stain, the chrome-copper stain, the iron-chrome alum stain and the copper-chrome alum stain.

Die erfindungsgemäß verwendeten Beizen enthalten üblicherweise neben dem Metallsalz oder einer Kombination von Metallsalzen und Glyoxylsäure eine gewisse Menge an Entfettungsmittel. Bevorzugte Entfettungsmittel sind Fettalkoholpolyglykolether mit 5 - 12 EO-Einheiten, z.B. ®Remolgan CX, ®Genapol UD O50, ®Genapol UD O80 (Hersteller: Hoechst AG).In addition to the metal salt or a combination of metal salts and glyoxylic acid, the mordants used according to the invention usually contain a certain amount of degreasing agent. Preferred degreasing agents are fatty alcohol polyglycol ethers with 5 to 12 EO units, for example ® Remolgan CX, ® Genapol UD O50, ® Genapol UD O80 (manufacturer: Hoechst AG).

Der bisher übliche Zusatz von starken Säuren, wie Ameisensäure und/oder Essigsäure ist nicht erforderlich aber denkbar. Bei Einsatz derartiger Säuren beträgt das Verhältnis Glyoxylsäure zu starker Säure üblicherweise 9:1. Die in der Praxis gebräuchliche Zusammensetzung der Metallbeize ist nachfolgend aufgeführt

  • 0,5 g bis 3 g mindestens eines Metallsalzes, bevorzugt Kaliumdichromat
  • 1,5 g bis 3 g Glyoxylsäure und
  • 0,5 g bis 1 g Entfettungsmittel, bezogen auf ein Liter Beizflotte.
The usual addition of strong acids such as formic acid and / or acetic acid is not necessary but is conceivable. When using such acids, the ratio of glyoxylic acid to strong acid is usually 9: 1. The composition of the metal stain that is used in practice is listed below
  • 0.5 g to 3 g of at least one metal salt, preferably potassium dichromate
  • 1.5 g to 3 g glyoxylic acid and
  • 0.5 g to 1 g of degreasing agent, based on one liter of pickling liquor.

Die Glyoxylsäure wird üblicherweise in Form einer wässrigen Lösung, bevorzugt 40 - 50 gew.-%ig, der Beizflotte zugesetzt.The glyoxylic acid is usually added to the pickling liquor in the form of an aqueous solution, preferably 40-50% by weight.

Der Beizprozeß wird im allgemeinen in Haspeln, Fellwenden oder geschlossenen Gefäßen (Trommel, Faß) durchgeführt. Die Temperatur beträgt zweckmäßigerweise 20 bis 40°C, während die Dauer zwischen 3 und 24 Stunden schwankt. Nach der Beize werden die Felle - falls erforderlich - kurz gespült, dann gut geschleudert und kommen schließlich in das Färbebad. Ein gründliches Spülen ist niemals günstig, da sonst ein Teil der aufgenommenen Beizsalze wieder ausgewaschen wird. Das Spülen hat lediglich den Zweck Überschüsse an Metallsalzen und Säuren zu entfernen. Sind die Beizen, z.B. Dichromatbeize, mit wenig Säure angesetzt, so kann ein Spülen unterbleiben. Es genügt hier, die Felle gut zu zentrifugieren.The pickling process is generally carried out in reels, fur turns or closed vessels (drum, barrel). The temperature is advantageously 20 to 40 ° C, while the duration varies between 3 and 24 hours. After pickling, the skins are rinsed briefly, if necessary, then spun well and finally come to the dye bath. Thorough rinsing is never beneficial, as otherwise some of the pickling salts that are absorbed will be washed out again. The purpose of rinsing is only to remove excess metal salts and acids. Are the stains, e.g. Dichromate stain, applied with little acid, so rinsing can be avoided. It is sufficient to centrifuge the skins well.

Im Anschluß an das Beizen werden die Pelzfelle mit Hilfe bekannter Färbeverfahren mit Oxidationsfarbstoffen, z.B. Tauchfärbung oder Streichfärbung gefärbt. Durch den Einsatz von Glyoxylsäure in der Metallbeize entsprechend dem erfindungsgemäßen Verfahren werden bei der Färbung von Pelzfellen mit Oxidationsfarbstoffen zahlreiche Vorteile erzielt, die nachfolgend genannt werden:

  • es wird eine bessere Grannendeckung bei der Färbung erreicht;
  • der natürliche Glanz des Pelzhaares wird gesteigert;
  • der in der Metallbeize verbleibende Rest an Dichromat wird erheblich reduziert;
  • eine Verhärtung des chromgegerbten Leders bei Färbungen mit hohem Oxidationsmittel-Einsatz, z.B. Schwarz und Dunkelbraun-Färbungen, wird weitgehend verhindert;
  • das Pelzleder chromgegerbter Pelzfelle besitzt eine um mindestens 30 bis 50 % höhere Reißfestigkeit gegenüber den auf herkömmliche Weise chromgebeizten Pelzfellen;
  • es wird eine deutliche Farbtonvertiefung bei den gefärbten Pelzfellen erreicht.
Following the pickling, the fur skins are dyed with the aid of known dyeing processes using oxidation dyes, for example immersion dyeing or brush dyeing. The use of glyoxylic acid in metal pickling in accordance with the process according to the invention gives numerous advantages in the coloring of fur skins with oxidation dyes, which are mentioned below:
  • better awning coverage during coloring is achieved;
  • the natural shine of the fur hair is increased;
  • the residual dichromate remaining in the metal pickling is considerably reduced;
  • hardening of the chrome-tanned leather in the case of dyeings with a high use of oxidizing agents, for example black and dark brown dyeings, is largely prevented;
  • the fur leather of chrome-tanned fur has a tear strength that is at least 30 to 50% higher than that of chrome-stained fur;
  • there is a significant deepening of the color of the colored fur skins.

Anwendungsbeispiele:Examples of use: Beispiel 1:Example 1: Schwarz auf Mutations-NerzBlack on mutation mink (Nerzleder mit 0,5 % Cr2O3-Gehalt nach Zurichtung)(Mink leather with 0.5% Cr 2 O 3 content after finishing)

Flotte 1:20, bezogen auf Trockengewicht der Felle

Tötung:
entfällt
Beize:
2,0 g/l Kaliumdichromat
1,5 ml/l Glyoxylsäure (®Feliderm CS)
0,5 g/l Entfettungsmittel (®Remolgan CX)
35°C, über Nacht im Bad belassen, zentrifugieren
Färbung:
3,0 g/l Pelzfarbstoff-Grau (®Nako-Grau BK)
2,0 g/l Pelzfarbstoff (®Nako H)
2,0 g/l Pelzfarbstoff-Gelb (®Nako-Gelb 3GA)
1,0 g/l Pelzfarbstoff (®Nako TEG)
Fleet 1:20, based on the dry weight of the skins
Killing:
not applicable
Stain:
2.0 g / l potassium dichromate
1.5 ml / l glyoxylic acid ( ® Feliderm CS)
0.5 g / l degreasing agent ( ® Remolgan CX)
35 ° C, leave in the bath overnight, centrifuge
Coloring:
3.0 g / l fur dye gray ( ® Nako gray BK)
2.0 g / l fur dye ( ® Nako H)
2.0 g / l fur dye yellow ( ® Nako yellow 3GA)
1.0 g / l fur dye ( ® Nako TEG)

Zur Oxidation werden insgesamt 8,0 ml H2O2 (30 gew.-%ig)/l Färbeflotte eingesetzt. Gefärbt wird bei 35°C insgesamt 6 Stunden.A total of 8.0 ml of H 2 O 2 (30% by weight) / l of dye liquor are used for the oxidation. The dyeing takes place at 35 ° C for a total of 6 hours.

Ergebnis:Result:

Im Vergleich zur Färbung mit vorangegangener Tötung und herkömmlicher Beize erfolgt komplette Grannendeckung. Die Unterwolle der Pelzfelle ist voll Schwarz.Compared to the dyeing with previous killing and conventional stain, there is complete awning coverage. The undercoat of the fur skins is completely black.

Bei herkömmlicher Methode mit gleicher Dichromatmenge und gleichem Farbstoffangebot hatte die Unterwolle einen Braunstich.
Hier war eine Nachfärbung notwendig.
Nach Beendigung der Beize beträgt der Dichromatgehalt 527 mg/l Beizflotte.With a conventional method with the same amount of dichromate and the same range of dyes, the undercoat had a brown tinge.
Recolouring was necessary here.
When the pickling is complete, the dichromate content is 527 mg / l pickling liquor.

Die Lederseite der mit Glyoxylsäure gebeizten Pelzfelle ist ungleich weicher und reißfester als diejenige der nach herkömmlicher Methode behandelten.The leather side of the fur skins stained with glyoxylic acid is incomparably softer and more tear-resistant than that of those treated by the conventional method.

Vergleichsbeispiel 1:Comparative Example 1: Schwarz auf MutationsnerzBlack on mutation mink (Nerzleder mit 0,5 % Cr2O3-Gehalt nach Zurichtung)(Mink leather with 0.5% Cr 2 O 3 content after finishing)

Flotte 1:20, bezogen auf Trockengewicht der Felle

Tötung:
2,0 g/l Soda calc.
2,0 ml/l Ammoniak (25 gew.-%ig)
0,8 g/l Entfettungsmittel (®Remolgan CX)
32°C, 2 Stunden, gut spülen, zentrifugieren
Beize:
2,0 g/l Kaliumdichromat
1,0 ml/l Glykolsäure 57 %
35°C, über Nacht im Bad belassen, zentrifugieren
Färbung:
3,0 g/l Pelzfarbstoff-Grau (®Nako-Grau BK)
2,0 g/l Pelzfarbstoff (®Nako H)
2,0 g/l Pelzfarbstoff-Gelb (®Nako-Gelb 3GA)
2,0 g/l Pelzfarbstoff-Schwarz (®Nako-Schwarz RN)
1,0 g/l Pelzfarbstoff (®Nako TEG)
Fleet 1:20, based on the dry weight of the skins
Killing:
2.0 g / l soda calc.
2.0 ml / l ammonia (25% by weight)
0.8 g / l degreasing agent ( ® Remolgan CX)
32 ° C, 2 hours, rinse well, centrifuge
Stain:
2.0 g / l potassium dichromate
1.0 ml / l glycolic acid 57%
35 ° C, leave in the bath overnight, centrifuge
Coloring:
3.0 g / l fur dye gray ( ® Nako gray BK)
2.0 g / l fur dye ( ® Nako H)
2.0 g / l fur dye yellow ( ® Nako yellow 3GA)
2.0 g / l fur dye black ( ® Nako black RN)
1.0 g / l fur dye ( ® Nako TEG)

Zur Oxidation werden insgesamt 8,0 ml H2O2 (30 gew.-%ig)/l Färbeflotte eingesetzt. Gefärbt wird bei 35°C insgesamt 6 Stunden.A total of 8.0 ml of H 2 O 2 (30% by weight) / l of dye liquor are used for the oxidation. The dyeing takes place at 35 ° C for a total of 6 hours.

Ergebnis:Result:

Granne nicht genügend gedeckt, Unterwolle leicht braunstichig.
Der Dichromatgehalt nach Beendigung der Beize beträgt 1250 mg/l Beizflotte.Awn not sufficiently covered, underwool slightly brownish.
The dichromate content after finishing the pickling is 1250 mg / l pickling liquor.

Beispiel 2:Example 2: Dunkelbraun auf BlaufuchsDark brown on blue fox (Fuchsleder mit 0,58 % Cr2O3-Gehalt nach Zurichtung)(Fox leather with 0.58% Cr 2 O 3 content after finishing)

Flotte 1:40, bezogen auf Trockengewicht der Felle

Tötung:
entfällt
Beize:
1,0 g/l Kaliumdichromat
1,5 ml/l Glyoxylsäure (®Feliderm CS)
0,5 g/l Entfettungsmittel (®Remolgan CX)
35°C, über Nacht im Bad belassen, zentrifugieren
Färbung:
2,0 g/l Pelzfarbstoff-Braun (®Nako-Braun GG)
1,6 g/l Pelzfarbstoff-Grau (®Nako-Grau BK)
1,0 g/l Pelzfarbstoff-Braun (®Nako-Braun R)
0,8 g/l Pelzfarbstoff (®Nako H)
Fleet 1:40, based on the dry weight of the skins
Killing:
not applicable
Stain:
1.0 g / l potassium dichromate
1.5 ml / l glyoxylic acid ( ® Feliderm CS)
0.5 g / l degreasing agent ( ® Remolgan CX)
35 ° C, leave in the bath overnight, centrifuge
Coloring:
2.0 g / l fur dye brown ( ® Nako brown GG)
1.6 g / l fur dye gray ( ® Nako gray BK)
1.0 g / l fur dye brown ( ® Nako brown R)
0.8 g / l fur dye ( ® Nako H)

Zur Oxidation werden insgesamt 5,0 ml H2O2 (30 gew.-%ig)/l Färbeflotte eingesetzt. Gefärbt wird bei 35°C insgesamt 3 1/2 Stunden.A total of 5.0 ml H 2 O 2 (30% by weight) / l dyeing liquor is used for the oxidation. A total of 3 1/2 hours are stained at 35 ° C.

Ergebnis:Result:

Im Vergleich zur Färbung mit vorangegangener Tötung und herkömmlicher Beize erfolgt komplette Grannendeckung.
Bei herkömmlicher Methode mit gleicher Dichromatmenge und gleichem Farbstoffangebot ist die Färbung nicht kräftig genug.
Nach Beendigung der Beize beträgt der Dichromatgehalt 11 mg/l Beizflotte.Compared to the dyeing with previous killing and conventional stain, there is complete awning coverage.
With a conventional method with the same amount of dichromate and the same range of dyes, the coloring is not strong enough.
When the pickling is complete, the dichromate content is 11 mg / l pickling liquor.

Die Lederseite der mit Glyoxylsäure gebeizten Pelzfelle ist deutlich weicher und reißfester als diejenige der nach herkömmlicher Methode behandelten.The leather side of the fur skins stained with glyoxylic acid is significantly softer and more tear-resistant than that of those treated with the conventional method.

Vergleichsbeispiel 2:Comparative Example 2: Dunkelbraun auf BlaufuchsDark brown on blue fox (Fuchsleder mit 0,58 % Cr2O3-Gehalt nach Zurichtung)(Fox leather with 0.58% Cr 2 O 3 content after finishing)

Flotte 1:40, bezogen auf Trockengewicht der Felle

Tötung:
3,0 g/l Soda calc.
3,0 ml/l Ammoniak (25 gew.-%ig)
0,8 g/l Entfettungsmittel (®Remolgan CX)
32°C, 2 Stunden, gut spülen, zentrifugieren
Beize:
1,0 g/l Kaliumdichromat
1,5 ml/l Glykolsäure 57 %
35°C, über Nach im Bad belassen, zentrifugieren
Färbung:
2,0 g/l Pelzfarbstoff-Braun (®Nako-Braun GG)
1,6 g/l Pelzfarbstoff-Grau (®Nako-Grau BK)
1,0 g/l Pelzfarbstoff-Braun (®Nako-Braun R)
0,8 g/l Pelzfarbstoff (®Nako H)
Fleet 1:40, based on the dry weight of the skins
Killing:
3.0 g / l soda calc.
3.0 ml / l ammonia (25% by weight)
0.8 g / l degreasing agent ( ® Remolgan CX)
32 ° C, 2 hours, rinse well, centrifuge
Stain:
1.0 g / l potassium dichromate
1.5 ml / l glycolic acid 57%
35 ° C, leave overnight in the bath, centrifuge
Coloring:
2.0 g / l fur dye brown ( ® Nako brown GG)
1.6 g / l fur dye gray ( ® Nako gray BK)
1.0 g / l fur dye brown ( ® Nako brown R)
0.8 g / l fur dye ( ® Nako H)

Zur Oxidation werden insgesamt 5,0 ml H2O2 (30 gew.-%ig)/l Färbeflotte eingesetzt. Gefärbt wird bei 35°C insgesamt 3 1/2 Stunden.A total of 5.0 ml H 2 O 2 (30% by weight) / l dyeing liquor is used for the oxidation. A total of 3 1/2 hours are stained at 35 ° C.

Ergebnis:Result:

Färbung zu hell, Grannendeckung nicht komplett.
Der Dichromatgehalt nach Beendigung der Beize beträgt 478 mg/l Beizflotte.Coloring too light, awn coverage not complete.
The dichromate content after finishing the pickling is 478 mg / l pickling liquor.

Claims (13)

  1. A process for dyeing fur skins with oxidation dyes following a pretreatment, which comprises pretreating the fur skins with a metal mordant that contains glyoxylic acid.
  2. The process of claim 1, wherein the metal mordant used is an iron mordant, chromium mordant, copper mordant, copper-iron mordant, chromium-copper mordant, iron-chrome alum mordant or copper-chrome alum mordant.
  3. The process of claim 1 or 2, wherein the metal salts used in the chromium mordant are potassium and/or sodium dichromate.
  4. The process of any one of claims 1 to 3, wherein the metal mordant contains 0.1 to 7 g of metal salt, based on one liter of mordanting liquor.
  5. The process of claim 3, wherein the chromium mordant contains 0.1 to 7 g of dichromate, based on one liter of mordanting liquor.
  6. The process of any one of claims 1 to 5, wherein the metal mordant contains a degreasing agent, preferably a fatty alcohol polyglycol ether.
  7. The process of any one of claims 1 to 6, wherein the pH of the metal mordant lies within the range between 3 and 5.
  8. The process of any one of claims 1 to 7, wherein the metal mordant contains 1 to 7 g of glyoxylic acid, based on one liter of mordanting liquor.
  9. The process of any one of claims 1 to 8, wherein the glyoxylic acid is added to the mordanting liquor in the form of an aqueous solution, preferably 40 - 50% strength by weight.
  10. The process of any one of claims 1 to 9, wherein the mordant, as well as glyoxylic acid, contains further acids, preferably formic acid, acetic acid and/or glycolic acid.
  11. The process of claim 10, wherein the ratio of glyoxylic acid to further acids is 9:1.
  12. The process of any one of claims 1 to 11, wherein the pretreatment is carried out at a temperature from 20 to 40°C and over a duration from 3 to 24 hours.
  13. The process of any one of claims 1 to 12, further comprising hydroextracting the fur skins after the mordanting, if desired rinsing them beforehand with water and then introducing them into the dyebath.
EP94110399A 1993-07-10 1994-07-04 Process for dying for pelts with oxidation dyes Expired - Lifetime EP0634517B1 (en)

Applications Claiming Priority (2)

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DE4323123A DE4323123A1 (en) 1993-07-10 1993-07-10 Process for dyeing fur skins with oxidation dyes
DE4323123 1993-07-10

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EP0634517B1 true EP0634517B1 (en) 1996-06-12

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EP (1) EP0634517B1 (en)
JP (1) JPH07138887A (en)
CN (1) CN1100765A (en)
CA (1) CA2127648A1 (en)
DE (2) DE4323123A1 (en)
ES (1) ES2091073T3 (en)
FI (1) FI943248A (en)
GR (1) GR3020231T3 (en)
RU (1) RU2130984C1 (en)

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Publication number Priority date Publication date Assignee Title
CN1061724C (en) * 1996-12-24 2001-02-07 中国科学院新疆化学研究所 Method for bleaching special fur by organic solvent
CN103669032A (en) * 2012-09-19 2014-03-26 浙江中辉皮草有限公司 Recycling method of fur oxidation dyeing chrome mordant dye liquor
CN104372694B (en) * 2014-10-30 2016-08-24 北京泛博化学股份有限公司 A kind of arctic fox ginned cotton look processing method
CN104448895B (en) * 2014-11-10 2017-01-11 北京泛博化学股份有限公司 Novel environment-friendly acid blue-light red dye applied to furs and synthesis method of dye
FR3037240B1 (en) * 2015-06-12 2018-11-23 L'oreal MULTI-STAGE HAIR COLORING PROCESS USING AT LEAST ONE TITANIUM SALT AND SYNTHETIC DIRECT COLOR
CN105754368A (en) * 2016-02-16 2016-07-13 北京泛博清洁技术研究院有限公司 Red dye and synthesis method thereof, dyeing solution and dyeing method for fur
CN112376299A (en) * 2020-11-26 2021-02-19 华斯控股股份有限公司 Environment-friendly fur dyeing process

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DE936863C (en) * 1954-04-27 1955-12-22 Schloemann Ag Device for braking and straightening the rolling stock entering a strip reel
US4348201A (en) * 1979-05-11 1982-09-07 Seitetsu Kagaku Co., Ltd. Tanning process and tanning compositions
DE3022849C2 (en) * 1980-06-19 1983-06-09 Riedel-De Haen Ag, 3016 Seelze Process for disinfecting and preserving raw hides
SU969728A1 (en) * 1981-02-20 1982-10-30 Джамбулский технологический институт легкой и пищевой промышленности Method for preparing depilated hide for chrome tanning
SU1240810A1 (en) * 1984-10-31 1986-06-30 Всесоюзный Заочный Институт Советской Торговли Method of testing fur pelts prior to dyeing with oxidative dyes
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DE4009805C1 (en) * 1990-03-27 1991-12-05 Dr. Th. Boehme Kg Chem. Fabrik Gmbh & Co, 8192 Geretsried, De

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CN1100765A (en) 1995-03-29
US5466263A (en) 1995-11-14
CA2127648A1 (en) 1995-01-11
ES2091073T3 (en) 1996-10-16
FI943248A0 (en) 1994-07-07
RU2130984C1 (en) 1999-05-27
DE59400347D1 (en) 1996-07-18
JPH07138887A (en) 1995-05-30
EP0634517A1 (en) 1995-01-18
RU94026294A (en) 1997-04-27
DE4323123A1 (en) 1995-01-12
GR3020231T3 (en) 1996-09-30

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