EP0417040A1 - Dyeing process for wool - Google Patents

Dyeing process for wool Download PDF

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Publication number
EP0417040A1
EP0417040A1 EP90810646A EP90810646A EP0417040A1 EP 0417040 A1 EP0417040 A1 EP 0417040A1 EP 90810646 A EP90810646 A EP 90810646A EP 90810646 A EP90810646 A EP 90810646A EP 0417040 A1 EP0417040 A1 EP 0417040A1
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
sulfo
hydroxy
absorber
Prior art date
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EP90810646A
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German (de)
French (fr)
Inventor
Gerhard Dr. Reinert
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Novartis AG
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Ciba Geigy AG
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Publication of EP0417040A1 publication Critical patent/EP0417040A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk

Definitions

  • the present invention relates to a method for dyeing wool for producing lightfast, highly pure, brilliant color shades.
  • Process (a) provides the best bleaching effects (whiteness), but is very time-consuming.
  • Process (b) is short bleaching, which leads to a lower degree of whiteness, combined with a significantly redder shade.
  • the object on which the present invention is based is to provide a dyeing process for wool in order to achieve stable bleaching effects and to produce bright and brilliant shades with good lightfastness properties.
  • the present invention accordingly relates to a process for dyeing wool with anionic dyes, which is characterized in that the wool is dyed in the presence of a UV absorber and bleached oxidatively and then in one new bathroom bleaches reductively.
  • the dyeing process and the oxidative bleaching process are preferably carried out in the same bath.
  • Suitable UV absorbers are water-soluble UV absorbers, which e.g. in WO 86/03528, WO 88/00942 and in US-A-4 770 667.
  • the compounds of the formulas (1) and (2) can be prepared by methods known per se, e.g. in US-A-3,468,938, US-A-3,696,077 and US-A-4,698,064, respectively.
  • the compounds of formula (3) can be prepared in a manner known per se, e.g. following the procedures described in US-A-4,698,064.
  • the UV absorber is expediently added to the dyebath. It can be added before, during or after the coloring step. It is also possible to apply the UV absorber during the oxidative bleaching process.
  • the UV absorbers are used in an amount of 0.01 to 7.5, preferably 0.25 to 4.0 and particularly 0.5 to 2.0 percent by weight, based on the weight of the wool material.
  • wool for dyeing anionic dyes are used, which are known for example from the Color Index.
  • the anionic dyes are, for example, salts of metal-containing or metal-free mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes.
  • the anionic character of these dyes can be caused by metal complex formation alone and / or preferably by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or sulfonic acid groups.
  • These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored. Acidic, metal-free dyes having a single sulfonic acid group or reactive dyes which preferably have at least two sulfonic acid groups are preferred.
  • mixtures of the anionic dyes can also be used.
  • dye mixtures of at least 2 or 3 components can be used.
  • the oxidative bleaching process is carried out according to methods known per se and is described for example in textile industry 67 , 723f (1963).
  • active oxygen-releasing compounds such as performic acid, peracetic acid or in particular hydrogen peroxide are used as bleaching agents. 35% hydrogen peroxide is preferably used.
  • the amount used is 1 to 75 ml / l, preferably 5 to 30 ml / l, based on the wool material to be bleached.
  • the optimal pH of this bleach is from 5 to 5.5.
  • the oxidative bleaching agent can be used before, during or after dyeing.
  • the bleaching agent is preferably added to the dye bath immediately after the dyeing stage. This procedure has the advantage that products to be applied to the fiber, such as dyes, UV absorbers, etc., can be applied to unbleached wool, the affinity of which has not been changed, or pre-bleached wool.
  • the preferred single-bath dyeing and bleaching is preferably carried out by the exhaust process at liquor ratios of 1: 5 to 1: 250, preferably 1:10 to 1:50% by weight.
  • Dyeing and bleaching can also be carried out continuously using low-fleet application systems or hot application systems.
  • the reductive bleaching process follows the single-bath oxidative bleaching and dyeing process in a new bath.
  • Sodium bisulfite is preferably used as the reductive bleaching agent.
  • the amounts of sodium bisulfite are between 0.25 and 10 percent by weight, in particular between 1 and 5 percent by weight, based on the wool material used.
  • the reductive bleaching process is preferably carried out in a long liquor.
  • the reductive bleaching agent can also be applied continuously using low-liquor application systems or hot application systems.
  • Both the oxidative dyeing / bleaching baths and the reductive bleaching baths can contain mineral acids, such as sulfuric acid or phosphoric acid, organic acids, expediently lower, aliphatic carboxylic acids, such as formic, acetic or oxalic acids and / or salts, such as ammonium acetate, ammonium sulfate or sodium acetate. These compounds serve above all to adjust the pH of the liquors, which is generally between 1.5 and 7, preferably between 3 and 5.
  • the baths also contain commercially available stabilizers and activators and can also contain other auxiliaries customary in dyeing technology, e.g. Dispersing agents, leveling agents, electrolytes, wetting agents, defoamers, anti-foaming agents, thickeners or wool protection agents.
  • the wool material can be in a wide variety of processing forms. For example, the following can be considered: flake, sliver, fabric, knitted fabric, nonwovens, yarn or piece goods.
  • the process of the present invention in which a combined dyeing / bleaching process in the presence of a UV absorber is proposed, makes it possible to produce excellent lightfast, pure pastel shades.
  • Example 1 4 samples of 10 g of a wool fabric are treated in an open dyeing machine, for example an ®AHIBA, with a liquor ratio of 1:30, first at 40 ° in 10 minutes in 4 equal liquors, each contain. It is treated for 10 minutes at this temperature and the pH is again corrected with acetic acid. Then you take the samples from the fleets.
  • an open dyeing machine for example an ®AHIBA
  • the individual samples are further processed in the fleets 1-4 as follows:
  • Sample 1 (fleet 1): The following dyes are added to the fleet in dissolved form: in dissolved form.
  • the sample is treated at 40 ° for 10 minutes, then heated to 85 ° at 1.5 ° / minute and dyed for 45 minutes.
  • the mixture is then cooled to 800 and oxidation bleaching is carried out with the addition of the following compounds: 2 g / l of a stabilizer consisting of 43 parts of crystalline citric acid 46 parts of secondary sodium phosphate and 11 parts of ethylenediaminetetraacetic acid sodium salt and 15 ml / l 35% hydrogen peroxide.
  • the bleaching bath contains the following additives: 1.5 g / l sodium bisulfite 2% 96% sulfuric acid.
  • the samples are rinsed cold after the treatment, centrifuged and dried at 70 ° in a forced air oven.
  • Pattern 2 (fleet 2): The procedure is the same as for pattern 1, with the difference that dyeing is carried out in this fleet without the addition of the UV absorber of the formula (101).
  • Pattern 3 (fleet 3): The procedure is the same as pattern 1, with the difference that the treatment is stopped after dyeing. After dyeing, the sample is rinsed cold, centrifuged and dried at 70 ° in a forced air oven.
  • Pattern 4 (fleet 4): The procedure is the same as pattern 3, with the difference that dyeing is carried out without the addition of the UV absorber of the formula (101).
  • Example 2 Prepare three 10 g samples of an unbleached and three 10 g samples of one with an acidic pre-bleach in combination with a reductive bleach using sodium dithionite-pre-bleached wool-sère fabric. These are pre-wetted in an open dyeing machine, for example an ®AHIBA, at a liquor ratio of 1:30. 6 identical fleets are prepared with the following additives:
  • Sample 1 After removing the sample from the fleet, the following are set Dyes in dissolved form to:
  • the sample is treated at 50 ° for a further 10 minutes, then heated to 95 ° at 1.5 ° / minute. Treat at this temperature for 30 minutes.
  • the pattern is then bleached oxidatively and reductively, as described in Example 1.
  • Pattern 2 (fleet 2): The procedure is the same as pattern 1, with the difference that dyeing is carried out without the addition of the UV absorber of the formula (102).
  • Sample 3 (Fleet 3): The procedure is the same as for Sample 1, with the difference that no dye is added to the liquor. The treatment in this liquor corresponds to blind coloring.
  • Pattern 4 (fleet 4): The procedure is the same as pattern 1, with the difference that the treatment is stopped after dyeing. After dyeing, the liquor is cooled to 70 °, rinsed with cold water and dried at 70 ° in a convection oven.
  • Pattern 5 (fleet 5): The procedure is the same as pattern 4, with the difference that no UV absorber of the formula (102) is used.
  • Pattern 6 (fleet 6): The procedure is the same as pattern 4, with the difference that no dye and no UV absorber are used. The process in this fleet corresponds to blind dyeing.
  • Example 3 The procedure is as in Example 1, with the difference that the following dye combination is used: 0.0025% of the dye of the formula 0.0100% of the dye of formula I and 0.0025% of the dye of formula II.
  • Example 4 4 samples of 10 g each of a wool fabric are treated in an open dyeing machine, for example an ®AHIBA, at a liquor ratio of 1:30 and 40 ° within 10 minutes in dye liquors, each containing 10% 80% acetic acid, 5% Glaüberalz and 1% of a leveling agent included. The pH is then corrected to 5.5, if necessary, then the samples are taken from the liquors and treated as follows:
  • the dye liquor 1 contains no other additives.
  • the dye liquor 2 becomes 1% of the compound of the formula added in dissolved form, the dye liquor 3 0.75% of the compound of formula and the dye liquor 4 0.75% of the compound of the formula
  • the dyeing is carried out as described in Example 1. After the dyeing process is complete, the mixture is cooled to 70 ° and the liquor is mixed with 5 ml / l of a bleach stabilizer, e.g. ®Prestogen W liquid (BASF) and 20 ml / l hydrogen peroxide 35% and bleached for one hour. After the samples have been rinsed, as described in Example 1, they are reductively bleached with sodium bisulfite and finished.
  • a bleach stabilizer e.g. ®Prestogen W liquid (BASF)
  • BASF ®Prestogen W liquid
  • Example 5 6 samples (No. 1 to 6) of 10 g each of a woolen fabric are prepared. While samples 1 to 4 are still white, samples 5 and 6 are pretreated using the combination bleaching process, which is composed as follows:
  • the bleach is started at a pH of 8.5 at 45 ° with a falling temperature and left to stand overnight. It is then rinsed.
  • the patterns are then evaluated colorimetrically.
  • the degree of bleaching is determined as a yellow number according to DIN 6167, on the other hand the amount of the compound of formula (102) on the fiber by means of the so-called K / S values.
  • K / S Kubelka-Munk function.
  • the values are determined using a Perkin-Elmer Lambda 9 with a 6 cm Ulbrich sphere of 698 and 280 nm.
  • Table 5 Treatment Yellow number K / S value Pattern 1 28.80 20.8 Pattern 2 21.00 21.5 Pattern 3 16.9 22.0 Pattern 4 16.1 3.9 Pattern 5 13.8 3.2 Pattern 6 14.9 16.6 Wool, unbleached 27.9 3.0 Wool, pre-bleached 11.3 -

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  • Textile Engineering (AREA)
  • Coloring (AREA)
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Abstract

There is described a process for dyeing wool with anionic dyes, which is characterised in that the wool is dyed and oxidatively bleached in the presence of a UV absorber and then reductively bleached in a new bath. <??>This process makes it possible to prepare very clean, brilliant shades.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Färben von Wolle zur Herstellung lichtechter, hochreiner, brillanter Farbnuancen.The present invention relates to a method for dyeing wool for producing lightfast, highly pure, brilliant color shades.

Beim Färben von Wolle ist es oft erforderlich, das zu färbende Wollgut einem Bleich­prozess zu unterziehen, damit die Farbstoffe voll zur Wirkung kommen können.When dyeing wool, it is often necessary to subject the wool to be dyed to a bleaching process so that the dyes can take full effect.

Das Bleichen von Wolle wird dabei nach 2 verschiedenen Verfahren vorgenommen:

  • (a) als zweistufige Kombinationsbleiche mit alkalischem Peroxid und anschliessender reduktiver Bleiche oder
  • (b) als einstufige schwachsaure Peroxidbleiche unter Mltverwendung eines speziellen Aktivators.
The bleaching of wool is carried out according to two different processes:
  • (a) as a two-stage combination bleaching with alkaline peroxide and subsequent reductive bleaching or
  • (b) as a one-step weakly acidic peroxide bleach using a special activator.

Das Verfahren (a) liefert die besten Bleicheffekte (Weissgrad), ist allerdings sehr zeitaufwendig. Das Verfahren (b) ist eine Kurzbleiche, die zu einem niedrigeren Weissgrad führt, verbunden mit einer deutlich röteren Nuance.Process (a) provides the best bleaching effects (whiteness), but is very time-consuming. Process (b) is short bleaching, which leads to a lower degree of whiteness, combined with a significantly redder shade.

Die mit beiden Verfahren erzielten Bleicheffekte werden in der Regel unter dem Einfluss des Färbeprozesses schlechter, da die Einwirkung von Hitze zur Vergilbung der Faser führt. Nachteilig wirkt sich dies besonders dann aus, wenn Pastellfärbungen erstellt werden sollen oder nuanciert werden muss.The bleaching effects achieved with both processes generally become worse under the influence of the dyeing process, since the action of heat leads to yellowing of the fiber. This is particularly disadvantageous when pastel colors are to be created or nuanced.

Die der vorliegenden Erfindung zu Grunde liegende Aufgabe besteht darin, ein Färbeverfabren für Wolle zur Erzielung stabiler Bleicheffekte und zur Herstellung von hellen und brillanten Nuancen mit guten Lichtechtheitseigenschaften bereitzustellen.The object on which the present invention is based is to provide a dyeing process for wool in order to achieve stable bleaching effects and to produce bright and brilliant shades with good lightfastness properties.

Gegenstand der vorliegenden Erfindung ist demnach ein Verfahren zum Färben von Wolle mit anionischen Farbstoffen, das dadurch gekennzeichnet ist, dass man die Wolle in Anwesenheit eines UV-Absorbers färbt und oxidativ bleicht und anschliessend in einem neuen Bad reduktiv bleicht.The present invention accordingly relates to a process for dyeing wool with anionic dyes, which is characterized in that the wool is dyed in the presence of a UV absorber and bleached oxidatively and then in one new bathroom bleaches reductively.

Vorzugsweise wird der Färbeprozess und der oxidative Bleichprozess in dem gleichen Bad vorgenommen.The dyeing process and the oxidative bleaching process are preferably carried out in the same bath.

Als UV-Absorber eignen sich wasserlösliche UV-Absorber, die z.B. in WO 86/03528, WO 88/00942 und in der US-A-4 770 667 beschrieben sind.Suitable UV absorbers are water-soluble UV absorbers, which e.g. in WO 86/03528, WO 88/00942 and in US-A-4 770 667.

Es können z.B. folgende Verbindungen eingesetzt werden:

  • a) 2-Hydroxybenzophenone der Formel (1)
    Figure imgb0001
     worin
    R₁ Wasserstoff, Hydroxy, C₁-C₁₄-Alkoxy oder Phenoxy,
    R₂ Sulfo,
    R₃ Wasserstoff, Hydroxy oder C₁-C₄-Alkoxy und
    R₄ Wasserstoff, Hydroxy oder Carboxy
    bedeuten,
    wie z.B. das 4-Hydroxy, 4-Methoxy, 4-Octyloxy, 4-Decyloxy, 4-Dodecyloxy, 4-Methoxy-2′-carboxy-, 4,2′,4′-Trihydroxy-, 4,4′-Dimethoxy-2′-hydroxy-, 4-Methoxy-5-sulfo-, 2′-Hydroxy-4,4′-dimethoxy-5-sulfo-, 4-Benzyloxy- und 5-Chlor-Derivat;
  • b) 2-(2′-Hydroxyphenyl)-benzotriazole der Formel (2)
    Figure imgb0002
     worin
    R₁ Wasserstoff, Chlor, C₁-C₁₂-Alkyl, C₅-C₆-Cycloalkyl, sulfoniertes C₇-C₉-Arylalkyl oder Sulfo,
    R₂ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Hydroxy oder Sulfo,
    R₃ C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl, C₂-C₉-Alkoxycarbonyl, Carboxyethyl, sulfoniertes C₇-C₉-Arylalkyl oder Sulfo,
    R4 Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder Sulfo und
    R₅ Wasserstoff oder Chlor
    bedeuten und mindestens einer der Reste R₃ oder R₄ Sulfo sein muss.
  • c) 2-(2′-Hydroxyphenyl)-s-triazine der Formel (3)
    Figure imgb0003
     worin R Wassestoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
    R₁ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy,
    R₂ Sulfo und
    R₃ und R₄, unabhängig voneinander, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl bedeuten, wobei die Sulfogruppen in freier Form oder in Salzform, z.B. als Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalze vorliegen können.
  • d) s-Triazinverbindungen der Formel
    Figure imgb0004
     worin mindestens einer der Substituenten R₁, R₂ und R₃ ein Rest der Formel
    Figure imgb0005
     ist, worin
    R₆ Wasserstoff oder Hydroxy,
    M Natrium, Kalium, Calcium, Magnesium, Ammonium oder Tetra-C₁-C₄-Alkylammonium und
    m 1 oder 2 ist, und der übrige Substituent bzw. die übrigen Substituenten unabhängig voneinander C₁-C₁₂-Alkyl, Phenyl, durch Sauerstoff, Schwefel, Imino oder C₁-C₁₁-Alkylimino an den Triazinylrest gebundenes C₁-C₁₂-Alkyl oder Phenyl sind, wie z.B. das Kaliumsalz der Verbindung der Formel (4), worin
    R₁ Phenyl und
    R₂ und R₃ je den Rest der Formel (5) bedeuten oder das Natriumsalz der Verbindung der Formel (4), worin R₁ p-Chlorphenyl und R₂ und R₃ je den Rest der Formel (5) bedeuten. Weitere Verbindungen sind in der EP-A-165608 beschrieben.
For example, the following connections can be used:
  • a) 2-hydroxybenzophenones of the formula (1)
    Figure imgb0001
     wherein
    R₁ is hydrogen, hydroxy, C₁-C₁₄ alkoxy or phenoxy,
    R₂ sulfo,
    R₃ is hydrogen, hydroxy or C₁-C₄ alkoxy and
    R₄ is hydrogen, hydroxy or carboxy
    mean,
    such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-methoxy-2'-carboxy-, 4,2 ', 4'-trihydroxy-, 4,4'-dimethoxy -2'-hydroxy, 4-methoxy-5-sulfo, 2'-hydroxy-4,4'-dimethoxy-5-sulfo, 4-benzyloxy and 5-chloro derivatives;
  • b) 2- (2'-hydroxyphenyl) benzotriazoles of the formula (2)
    Figure imgb0002
     wherein
    R₁ is hydrogen, chlorine, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, sulfonated C₇-C₉-arylalkyl or sulfo,
    R₂ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy or sulfo,
    R₃ C₁-C₁₂-alkyl, chlorine, C₅-C₆-cycloalkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₂-C₉-alkoxycarbonyl, carboxyethyl, sulfonated C₇-C₉-arylalkyl or sulfo,
    R4 is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and
    R₅ is hydrogen or chlorine
    mean and at least one of the radicals R₃ or R₄ must be sulfo.
  • c) 2- (2'-hydroxyphenyl) -s-triazines of the formula (3)
    Figure imgb0003
     wherein R is hydrogen, halogen, C₁-C₄ alkyl or sulfo,
    R₁ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
    R₂ sulfo and
    R₃ and R₄, independently of one another, are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy, the sulfo groups in free form or in salt form, for example can be present as alkali metal, alkaline earth metal, ammonium or amine salts.
  • d) s-triazine compounds of the formula
    Figure imgb0004
     wherein at least one of the substituents R₁, R₂ and R₃ is a radical of the formula
    Figure imgb0005
     is what
    R₆ is hydrogen or hydroxy,
    M sodium, potassium, calcium, magnesium, ammonium or tetra-C₁-C₄-alkylammonium and
    m is 1 or 2, and the remaining substituent or substituents are, independently of one another, C₁-C₁₂-alkyl, phenyl, C₁-C₁₂-alkyl or phenyl which are bonded to the triazinyl radical by oxygen, sulfur, imino or C₁-C₁₁-alkylimino, such as the potassium salt of the compound of formula (4), wherein
    R₁ phenyl and
    R₂ and R₃ each represent the rest of formula (5) or the sodium salt of the compound of formula (4), wherein R₁ p-chlorophenyl and R₂ and R₃ each represent the rest of formula (5). Further compounds are described in EP-A-165608.

Die Verbindungen der Formel (1) und (2) können nach an sich bekannten Verfahren, wie sie z.B. in der US-A-3 468 938,US-A-3,696,077 bzw. US-A-4,698,064 beschrieben sind, hergestellt werden.The compounds of the formulas (1) and (2) can be prepared by methods known per se, e.g. in US-A-3,468,938, US-A-3,696,077 and US-A-4,698,064, respectively.

Die Verbindungen der Formel (3) können nach an sich bekannter Weise hergestellt werden, z.B. nach den in US-A-4,698,064 beschriebenen Verfahren.The compounds of formula (3) can be prepared in a manner known per se, e.g. following the procedures described in US-A-4,698,064.

Den UV-Absorber gibt man zweckmässigerweise dem Färbebad zu. Er kann dabei vor, während oder nach der Färbestufe zugefügt werden. Es ist also auch möglich, den UV-Absorber beim oxidativen Bleichprozess zu applizieren.The UV absorber is expediently added to the dyebath. It can be added before, during or after the coloring step. It is also possible to apply the UV absorber during the oxidative bleaching process.

Es ist aber auch möglich, den UV-Absorber dem reduktiven Bleichbad zuzugeben.However, it is also possible to add the UV absorber to the reductive bleaching bath.

Die UV-Absorber werden in einer Menge von 0,01 bis 7,5, vorzugsweise 0,25 bis 4,0 und besonders 0,5 bis 2,0 Gewichts-Prozent, bezogen auf das Gewicht des Wollmaterials, eingesetzt.The UV absorbers are used in an amount of 0.01 to 7.5, preferably 0.25 to 4.0 and particularly 0.5 to 2.0 percent by weight, based on the weight of the wool material.

Für das erfindungsgemässe Verfahren werden zum Färben der Wolle ausgewählte anionische Farbstoffe verwendet, die zum Beispiel aus dem Colour Index bekannt sind.For the method according to the invention, wool is selected for dyeing anionic dyes are used, which are known for example from the Color Index.

Bei den anionischen Farbstoffen handelt es sich beispielsweise um Salze metallhaltiger oder metallfreier Mono-, Dis- oder Polyazofarbstoffe einschliesslich der Formazanfarb­stoffe sowie der Anthrachinon-, Xanthen-, Nitro-, Triphenylmethan-, Naphthochinonimin- und Phthalocyaninfarbstoffe. Der anionische Charakter dieser Farbstoffe kann durch Metallkomplexbildung allein und/oder vorzugsweise durch saure, salzbildende Sub­stituenten, wie Carbonsäuregruppen, Schwefelsäure- und Phosphonsäureestergruppen, Phosphonsäuregruppen oder Sulfonsäuregruppen bedingt sein. Diese Farbstoffe können im Molekül auch sogenannte reaktive Gruppierungen, welche mit dem zu färbenden Material eine kovalente Bindung eingehen, aufweisen. Bevorzugt sind saure, metallfreie, eine einzige Sulfonsäuregruppe aufweisende Farbstoffe oder auch Reaktivfarbstoffe, welche vorzugsweise mindestens zwei Sulfonsäuregruppen aufweisen.The anionic dyes are, for example, salts of metal-containing or metal-free mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes. The anionic character of these dyes can be caused by metal complex formation alone and / or preferably by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or sulfonic acid groups. These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored. Acidic, metal-free dyes having a single sulfonic acid group or reactive dyes which preferably have at least two sulfonic acid groups are preferred.

Es können auch Mischungen der anionischen Farbstoffe eingesetzt werden. Beispielsweise können Farbstoffmischungen von mindestens 2 oder 3 Komponenten verwendet werden.Mixtures of the anionic dyes can also be used. For example, dye mixtures of at least 2 or 3 components can be used.

Der oxidative Bleichprozess wird nach an sich bekannten Methoden durchgeführt und ist beispielsweise in Textilindustrie 67, 723f (1963) beschrieben. Bei dem erfindungs­gemässen bevorzugten einbadigen Bleich- und Färbeverfahren werden als Bleichmittel aktiven Sauerstoff freisetzende Verbindungen wie Perameisensäure, Peressigsäure oder insbesondere Wasserstoffperoxid eingesetzt. Vorzugsweise wird 35%-iges Wasser­stoffperoxid verwendet. Die dabei eingesetzte Menge liegt bei 1 bis 75 ml/l, vorzugsweise 5 bis 30 ml/l, bezogen auf das zu bleichende Wollmaterial. Der optimale pH-Wert dieser Bleiche liegt bei einem pH-Wert von 5 bis 5,5.The oxidative bleaching process is carried out according to methods known per se and is described for example in textile industry 67 , 723f (1963). In the preferred single-bath bleaching and dyeing process according to the invention, active oxygen-releasing compounds such as performic acid, peracetic acid or in particular hydrogen peroxide are used as bleaching agents. 35% hydrogen peroxide is preferably used. The amount used is 1 to 75 ml / l, preferably 5 to 30 ml / l, based on the wool material to be bleached. The optimal pH of this bleach is from 5 to 5.5.

Das oxidative Bleichmittel kann vor, während oder nach dem Färben eingesetzt werden. Vorzugsweise wird das Bleichmittel unmittelbar nach der Färbestufe dem Färbebad zugefügt. Dieses Vorgehen hat den Vorteil, dass auf die Faser zu applizierende Produkte wie Farbstoffe, UV-Absorber usw. auf ungebleichter, nicht in ihrer Affinität veränderter, oder vorgebleichter Wolle aufgebracht werden können.The oxidative bleaching agent can be used before, during or after dyeing. The bleaching agent is preferably added to the dye bath immediately after the dyeing stage. This procedure has the advantage that products to be applied to the fiber, such as dyes, UV absorbers, etc., can be applied to unbleached wool, the affinity of which has not been changed, or pre-bleached wool.

Das bevorzugte einbadige Färben und Bleichen erfolgt vorzugsweise nach dem Ausziehverfahren bei Flottenverhältnissen von 1:5 bis 1:250, vorzugsweise 1:10 bis 1:50 Gew.%. Das Färben und Bleichen kann aber auch kontinuierlich mittels Niedrig­flottenauftragsystemen oder Heissapplikationssystemen erfolgen.The preferred single-bath dyeing and bleaching is preferably carried out by the exhaust process at liquor ratios of 1: 5 to 1: 250, preferably 1:10 to 1:50% by weight. Dyeing and bleaching can also be carried out continuously using low-fleet application systems or hot application systems.

Das reduktive Bleichverfahren erfolgt im Anschluss an das einbadige oxidative Bleich-Färbeverfahren in einem neuen Bad. Als reduktives Bleichmittel wird dabei vorzugsweise Natriumbisulfit verwendet. Die Mengen des Natriumbisulfits liegen dabei zwischen 0,25 und 10 Gewichtsprozent, insbesondere zwischen 1 bis 5 Gew.%, bezogen auf das eingesetzte Wollmaterial. Der reduktive Bleichprozess wird vorzugsweise in langer Flotte durchgeführt. Das reduktive Bleichmittel kann aber ebenso auch kontinuierlich mittels Niedrigflottenauftragssystemen oder Heissapplikationssystemen appliziert werden.The reductive bleaching process follows the single-bath oxidative bleaching and dyeing process in a new bath. Sodium bisulfite is preferably used as the reductive bleaching agent. The amounts of sodium bisulfite are between 0.25 and 10 percent by weight, in particular between 1 and 5 percent by weight, based on the wool material used. The reductive bleaching process is preferably carried out in a long liquor. However, the reductive bleaching agent can also be applied continuously using low-liquor application systems or hot application systems.

Sowohl die oxidativen Färbe/Bleichbäder als auch die reduktiven Bleichbäder können Mineralsäuren, wie Schwefelsäure oder Phosphorsäure, organische Säuren, zweckmässig niedere, aliphatische Carbonsäuren, wie Ameisen-, Essig- oder Oxalsäuren und/oder Salze, wie Ammoniumacetat, Ammoniumsulfat oder Natriumacetat enthalten. Diese Verbindungen dienen vor allem der Einstellung des pH-Wertes der Flotten, der in der Regel zwischen 1,5 bis 7, vorzugsweise zwischen 3 bis 5, liegt. Die Bäder enthalten auch handelsübliche Stabilisatoren und Aktivatoren und können ausserdem noch weitere in der Färbereitechnik üblichen Hilfsmittel enthalten, z.B. Dispergiermittel, Egalisiermittel, Elektrolyte, Netzmittel, Entschäumer, Schaumverhütungsmittel, Verdicker oder Wollschutzmittel.Both the oxidative dyeing / bleaching baths and the reductive bleaching baths can contain mineral acids, such as sulfuric acid or phosphoric acid, organic acids, expediently lower, aliphatic carboxylic acids, such as formic, acetic or oxalic acids and / or salts, such as ammonium acetate, ammonium sulfate or sodium acetate. These compounds serve above all to adjust the pH of the liquors, which is generally between 1.5 and 7, preferably between 3 and 5. The baths also contain commercially available stabilizers and activators and can also contain other auxiliaries customary in dyeing technology, e.g. Dispersing agents, leveling agents, electrolytes, wetting agents, defoamers, anti-foaming agents, thickeners or wool protection agents.

Das Wollmaterial kann in den verschiedensten Verarbeitungsformen vorliegen. Beispielsweise kommen in Betracht: Flocke, Kammzug, Gewebe, Gewirke, Vliesstoffe, Garn oder Stückware.The wool material can be in a wide variety of processing forms. For example, the following can be considered: flake, sliver, fabric, knitted fabric, nonwovens, yarn or piece goods.

Mit dem Verfahren der vorliegenden Erfindung, bei der ein kombiniertes Färbe/Bleichverfahren in Anwesenheit eines UV-Absorbers vorgeschlagen wird, lassen sich ausgezeichnet lichtechte, reine Pastellnuancen herstellen.The process of the present invention, in which a combined dyeing / bleaching process in the presence of a UV absorber is proposed, makes it possible to produce excellent lightfast, pure pastel shades.

Die folgenden Beispiele veranschaulichen die Erfindung. Teile bedeuten Gewichtsteile, Prozente Gewichtsprozente. Die Temperaturen sind in °C angegeben.The following examples illustrate the invention. Parts mean parts by weight, percentages by weight. The temperatures are given in ° C.

Beispiel 1: 4 Muster à 10 g eines Wollgewebes werden in einem offenen Färbeapparat, z.B. einem ®AHIBA, bei einem Flottenverhältnis von 1:30 zunächst bei 40° innerhalb 10 Minuten in 4 gleichen Flotten behandelt, die jeweils

Figure imgb0006
enthalten. Man behandelt 10 Minuten bei dieser Temperatur und korrigiert nochmals den pH-Wert mit Essigsäure.
Anschliessend entnimmt man die Muster den Flotten. Example 1: 4 samples of 10 g of a wool fabric are treated in an open dyeing machine, for example an ®AHIBA, with a liquor ratio of 1:30, first at 40 ° in 10 minutes in 4 equal liquors, each
Figure imgb0006
 contain. It is treated for 10 minutes at this temperature and the pH is again corrected with acetic acid.
Then you take the samples from the fleets.

Die einzelnen Muster werden in den Flotten 1-4 wie folgt weiterbehandelt:The individual samples are further processed in the fleets 1-4 as follows:

Muster 1 (Flotte 1): Man setzt der Flotte folgende Farbstoffe in gelöster Form zu:

Figure imgb0007
in gelöster Form zu. Sample 1 (fleet 1): The following dyes are added to the fleet in dissolved form:
Figure imgb0007
 in dissolved form.

Man behandelt das Muster 10 Minuten bei 40°, erhitzt dann mit 1,5°/Minute auf 85° und färbt 45 Minuten. Anschliessend kühlt man auf 800 ab und führt unter Zusatz der folgenden Verbindungen eine Oxidationsbleiche durch:
2 g/l eines Stabilisators, bestehend aus
43 Teilen kristalliner Citronensäure
46 Teilen sekundärem Natriumphosphat und
11 Teile Ethylendiamintetraessigsäure-Natriumsalz und
15 ml/l 35%-iges Wasserstoffperoxid.The sample is treated at 40 ° for 10 minutes, then heated to 85 ° at 1.5 ° / minute and dyed for 45 minutes. The mixture is then cooled to 800 and oxidation bleaching is carried out with the addition of the following compounds:
2 g / l of a stabilizer consisting of
43 parts of crystalline citric acid
46 parts of secondary sodium phosphate and
11 parts of ethylenediaminetetraacetic acid sodium salt and
15 ml / l 35% hydrogen peroxide.

Man bleicht 60 Minuten bei absinkender Temperatur. Danach wird kalt gespült und in einem neuen Bad bei einem Flottenverhältnis von 1:30 bei 60° 45 Minuten reduktiv ge­bleicht. Das Bleichbad enthält folgende Zusätze:
1,5 g/l Natriumbisulfit
2% 96%-ige Schwefelsäure.It is bleached for 60 minutes at a falling temperature. It is then rinsed cold and reductively bleached in a new bath at a liquor ratio of 1:30 at 60 ° for 45 minutes. The bleaching bath contains the following additives:
1.5 g / l sodium bisulfite
2% 96% sulfuric acid.

Die Muster werden nach der Behandlung kalt gespült, zentrifugiert und bei 70° in einem Umluftofen getrocknet.The samples are rinsed cold after the treatment, centrifuged and dried at 70 ° in a forced air oven.

Muster 2 (Flotte 2): Man verfährt wie bei Muster 1 mit dem Unterschied, dass in dieser Flotte ohne Zusatz des UV-Absorbers der Formel (101) gefärbt wird. Pattern 2 (fleet 2): The procedure is the same as for pattern 1, with the difference that dyeing is carried out in this fleet without the addition of the UV absorber of the formula (101).

Muster 3 (Flotte 3): Man verfährt wie mit Muster 1 mit dem Unterschied, dass die Behandlung nach dem Färben abgebrochen wird. Das Muster wird nach dem Färben kalt gespült, zentrifugiert und bei 70° im Umluftofen getrocknet. Pattern 3 (fleet 3): The procedure is the same as pattern 1, with the difference that the treatment is stopped after dyeing. After dyeing, the sample is rinsed cold, centrifuged and dried at 70 ° in a forced air oven.

Muster 4 (Flotte 4): Man verfährt wie mit Muster 3 mit dem Unterschied, dass ohne Zusatz des UV-Absorbers der Formel (101) gefärbt wird. Pattern 4 (fleet 4): The procedure is the same as pattern 3, with the difference that dyeing is carried out without the addition of the UV absorber of the formula (101).

Alle Muster werden anschliessend auf ihre Lichtechtheiten nach SN-ISO 105-BO2(=­XENON) und DIN 75.202 (=FAKRA) geprüft.All samples are then tested for light fastness according to SN-ISO 105-BO2 (= XENON) and DIN 75.202 (= FAKRA).

Die Ergebnisse sind in Tabelle 1 aufgeführt:

Figure imgb0008
The results are shown in Table 1:
Figure imgb0008

Beispiel 2: Man bereitet drei 10 g Muster eines ungebleichten und drei 10 g Muster eines mit einer sauren Vorbleiche in Kombination mit einer reduktiven Bleiche mittels Natrium-dithionit vorgebleichten Woll-Sèrgegewebes. Diese werden in einem offenen Färbeapparat, z.B. einem ®AHIBA, bei einem Flottenverhältnis von 1:30 vorgenetzt. Man bereitet dazu 6 gleiche Flotten mit folgenden Zusätzen:

Figure imgb0009
Example 2: Prepare three 10 g samples of an unbleached and three 10 g samples of one with an acidic pre-bleach in combination with a reductive bleach using sodium dithionite-pre-bleached wool-sère fabric. These are pre-wetted in an open dyeing machine, for example an ®AHIBA, at a liquor ratio of 1:30. 6 identical fleets are prepared with the following additives:
Figure imgb0009

Die Muster der ungebleichten Wolle werden in den Flotten 1-3, die der vorgebleichten Wolle in den Flotten 4-6 10 Minuten bei 50° behandelt. Danach wird der pH-Wert mit Essigsäure korrigiert. Die einzelnen Muster werden wie folgt weiterbehandelt:The samples of unbleached wool are treated in fleets 1-3, those of pre-bleached wool in liquors 4-6 for 10 minutes at 50 °. Then the pH is corrected with acetic acid. The individual samples are processed as follows:

Muster 1 (Flotte 1): Nach Entnahme des Musters aus der Flotte setzt man folgende Farbstoffe in gelöster Form zu:

Figure imgb0010
Sample 1 (fleet 1): After removing the sample from the fleet, the following are set Dyes in dissolved form to:
Figure imgb0010

Das Muster wird weitere 10 Minuten bei 50° behandelt, danach erwärmt man mit 1,5°/Minute auf 95°. Bei dieser Temperatur behandelt man 30 Minuten.The sample is treated at 50 ° for a further 10 minutes, then heated to 95 ° at 1.5 ° / minute. Treat at this temperature for 30 minutes.

Anschliessend wird das Muster, wie in Beispiel 1 beschrieben, oxidativ und reduktiv ge­bleicht.The pattern is then bleached oxidatively and reductively, as described in Example 1.

Muster 2 (Flotte 2): Man verfährt wie mit Muster 1 mit dem Unterschied, dass ohne Zusatz des UV-Absorbers der Formel (102) gefärbt wird. Pattern 2 (fleet 2): The procedure is the same as pattern 1, with the difference that dyeing is carried out without the addition of the UV absorber of the formula (102).

Muster 3 (Flotte 3): Man verfährt wie mit Muster 1 mit dem Unterschied, dass der Flotte kein Farbstoff zugesetzt wird. Die Behandlung in dieser Flotte entspricht einer Blind­färbung. Sample 3 (Fleet 3): The procedure is the same as for Sample 1, with the difference that no dye is added to the liquor. The treatment in this liquor corresponds to blind coloring.

Muster 4 (Flotte 4): Man verfährt wie mit Muster 1, mit dem Unterschied, dass die Behandlung nach dem Färben abgebrochen wird. Die Flotte wird nach dem Farben auf 70° gekühlt, mit kaltem Wasser gespült und bei 70° im Umluftofen getrocknet. Pattern 4 (fleet 4): The procedure is the same as pattern 1, with the difference that the treatment is stopped after dyeing. After dyeing, the liquor is cooled to 70 °, rinsed with cold water and dried at 70 ° in a convection oven.

Muster 5 (Flotte 5): Man verfährt wie mit Muster 4 mit dem Unterschied, dass kein UV-Absorber der Formel (102) verwendet wird. Pattern 5 (fleet 5): The procedure is the same as pattern 4, with the difference that no UV absorber of the formula (102) is used.

Muster 6 (Flotte 6): Man verfährt wie mit Muster 4 mit dem Unterschied, dass kein Farbstoff und kein UV-Absorber verwendet wird. Der Prozess in dieser Flotte entspricht einer Blindfärbung.

Figure imgb0011
Pattern 6 (fleet 6): The procedure is the same as pattern 4, with the difference that no dye and no UV absorber are used. The process in this fleet corresponds to blind dyeing.
Figure imgb0011

Beispiel 3: Man verfährt wie in Beispiel 1 mit dem Unterschied, dass man folgende Farbstoffkombination einsetzt:
0,0025 % des Farbstoffes der Formel

Figure imgb0012
0,0100 % des Farbstoffes der Formel I und
0,0025 % des Farbstoffes der Formel II. Example 3: The procedure is as in Example 1, with the difference that the following dye combination is used:
0.0025% of the dye of the formula
Figure imgb0012
 0.0100% of the dye of formula I and
0.0025% of the dye of formula II.

Die Ergebnisse der Lichtechtheitsbestimmung sind aus der Tabelle 3 ersichtlich.

Figure imgb0013
The results of the light fastness determination are shown in Table 3.
Figure imgb0013

Die Bewertung der Lichtechtheiten, dargestellt in den Tabellen 1-3 zeigt deutlich, dass in den Beispielen 1-3 das jeweils erfindungsgemäss behandelte Muster 1 die besten Lichtechtheiten aufweist bei gleichzeitiger Erzielung von reinen Farbtönen.The evaluation of the light fastness, shown in Tables 1-3, clearly shows that in Examples 1-3, the pattern 1 treated in each case according to the invention has the best light fastness while at the same time achieving pure shades.

Beispiel 4: 4 Muster von je10 g eines Wollgewebes werden in einem offenen Färbeapparat, z.B. einem ®AHIBA, bei einem Flottenverhältnis von 1:30 und 40° innerhalb von 10 Minuten in Färbeflotten behandelt, die jeweils 10 % 80 %ige Essigsäure, 5 % Glaübersalz und 1 % eines Egalisiermittels enthalten. Danach korrigiert man den pH-Wert, falls erforderlich, auf den Wert 5,5.Anschliessend entnimmt man die Muster den Flotten und behandelt wie folgt weiter: Example 4: 4 samples of 10 g each of a wool fabric are treated in an open dyeing machine, for example an ®AHIBA, at a liquor ratio of 1:30 and 40 ° within 10 minutes in dye liquors, each containing 10% 80% acetic acid, 5% Glaüberalz and 1% of a leveling agent included. The pH is then corrected to 5.5, if necessary, then the samples are taken from the liquors and treated as follows:

Jedes Bad versetzt man mit 0,03 % des grünen Farbstoffes der Formel (VI) in gelöster Form:

Figure imgb0014
Each bath is mixed with 0.03% of the green dye of the formula (VI) in dissolved form:
Figure imgb0014

Die Färbeflotte 1 enthält keine weiteren Zusätze. Der Färbeflotte 2 wird 1 % der Verbindung der Formel

Figure imgb0015
in gelöster Form zugesetzt, der Färbeflotte 3 0,75 % der Verbindung der Formel
Figure imgb0016
 und der Färbeflotte 4 0,75 % der Verbindung der Formel
Figure imgb0017
 The dye liquor 1 contains no other additives. The dye liquor 2 becomes 1% of the compound of the formula
Figure imgb0015
 added in dissolved form, the dye liquor 3 0.75% of the compound of formula
Figure imgb0016
 and the dye liquor 4 0.75% of the compound of the formula
Figure imgb0017

Man färbt wie in Beispiel 1 beschrieben. Nach Beendigung des Färbeprozesses kühlt man auf 70° ab und versetzt die Flotte mit 5 ml/l eines Bleichstabilisators, z.B. ®Prestogen W flüssig (BASF) und 20 ml/l Wasserstoffperoxid 35 % und bleicht eine Stunde. Nach dem Spülen der Muster wird, wie in Beispiel 1 beschrieben, noch mit Natriumbisulfit reduktiv gebleicht und fertiggestellt.The dyeing is carried out as described in Example 1. After the dyeing process is complete, the mixture is cooled to 70 ° and the liquor is mixed with 5 ml / l of a bleach stabilizer, e.g. ®Prestogen W liquid (BASF) and 20 ml / l hydrogen peroxide 35% and bleached for one hour. After the samples have been rinsed, as described in Example 1, they are reductively bleached with sodium bisulfite and finished.

Die Muster 1 bis 4 werden auf ihre Lichtechtheiten nach SN-ISO 105-B02 (= XENON) geprüft mit fogenden Ergebnissen: Tabelle 4: Färbung Nr. Lichtechtheit "XENON" 1 4 2 5 3 5-6+ 4 5-6 Samples 1 to 4 are tested for their light fastness according to SN-ISO 105-B02 (= XENON) with the following results: Table 4: Coloring no. Lightfastness "XENON" 1 4th 2nd 5 3rd 5-6 + 4th 5-6

Beispiel 5: Es werden 6 Muster (Nr. 1 bis 6) von je 10 g eines Wollgewebes bereitet. Während die Muster 1 bis 4 noch weiss sind, werden Musters 5 und 6 nach dem Kombinationsbleichverfahren vorbehandelt, die sich wie folgt zusammensetzt: Example 5: 6 samples (No. 1 to 6) of 10 g each of a woolen fabric are prepared. While samples 1 to 4 are still white, samples 5 and 6 are pretreated using the combination bleaching process, which is composed as follows:

a. Alkalische oxidative Bleiche:a. Alkaline oxidative bleach:

15 g/l H₂O₂ 35%15 g / l H₂O₂ 35%

2 g/l Tetra-Natriumpyrophosphat2 g / l tetra sodium pyrophosphate

0.5 g/l eines Wasch-und Netzmittels0.5 g / l of a detergent and wetting agent

Man beginnt die Bleiche bei einem pH-Wert von 8,5 bei 45° mit absinkender Temperatur und lässt über Nacht stehen. Anschliessend wird gespült.The bleach is started at a pH of 8.5 at 45 ° with a falling temperature and left to stand overnight. It is then rinsed.

b. Reduktive Bleiche:b. Reductive bleach:

3 g/l stabilisiertes Natriumdithionit3 g / l stabilized sodium dithionite

0.5 g/l eines Wasch-und Netzmittels.0.5 g / l of a detergent and wetting agent.

Man bleicht bei 60° während 90 Minuten. Anschliessend wird gespült, zentrifugiert und getrocknet.It is bleached at 60 ° for 90 minutes. It is then rinsed, centrifuged and dried.

Die einzelnen Muster werden wie folgt weiterbehandelt, indem man wie in Beispiel 1 vorgeht.

  • Muster 1: man behandelt mit 1 % des UV-Absorbers der Formel (102) ohne Farbstoffzusatz ("Blindfärbeprozess").
  • Muster 2: man behandelt wie Muster 1 nach dem Blindfärbeprozess und führt anschliessend, wie in Beispiel 1 beschrieben, eine saure Oxidationsbleiche durch.
  • Muster 3: man behandelt wie Muster 2 und führt zusätzlich im Anschluss an die Oxidationsbleiche wie in Beispiel 1 beschrieben, eine Reduktionsbleiche durch.
  • Muster 4: man behandelt wie Muster 3, jedoch ohne den Zusatz der Verbindung der Formel (102).
  • Muster 5: man behandelt wie Muster 1, jedoch ohne den Zusatz der Verbindung der Formel (102)
  • Muster 6: man behandelt wie Muster 1 und setzt dabei 0,75 % der Verbindung der Formel (102) ein.
The individual samples are treated as follows, using the same procedure as in Example 1.
  • Sample 1: treatment with 1% of the UV absorber of the formula (102) without addition of dye ("blind dyeing process").
  • Pattern 2: treated like pattern 1 after the blind dyeing process and then, as described in example 1, an acidic oxidation bleaching is carried out.
  • Pattern 3: treatment is carried out as pattern 2 and, in addition to the oxidation bleaching as described in example 1, a reduction bleach is carried out.
  • Pattern 4: Treated as Pattern 3, but without the addition of the compound of formula (102).
  • Pattern 5: treated as Pattern 1, but without the addition of the compound of the formula (102)
  • Pattern 6: you treat as pattern 1 and set 0.75% of the connection of the Formula (102).

Alle Muster werden anschliessend kalt gespült, zentrifugiert und bei Zimmertemperatur getrocknet.All samples are then rinsed cold, centrifuged and dried at room temperature.

Die Muster werden sodann farbmetrisch ausgewertet. Einerseits wird der Bleichgrad als Gelbzahl nach DIN 6167 ermittelt, andererseits die auf der Faser befindliche Menge der Verbindung der Formel (102) mittels der sogenannten K/S-Werte. (K/S = Kubelka-Munk-Funktion). Die Werte werden mittels eines Perkin-Elmer Lambda 9 mit 6 cm Ulbrichtscher Kugel von 698 und 280 nm bestimmt. Die Ergebnisse sind in Tabelle 5 aufgeführt: Tabelle 5: Behandlung Gelbzahl K/S-Wert Muster 1 28,80 20,8 Muster 2 21,00 21,5 Muster 3 16,9 22,0 Muster 4 16,1 3,9 Muster 5 13,8 3,2 Muster 6 14,9 16,6 Wolle, ungebleicht 27,9 3,0 Wolle, vorgebleicht 11,3 - The patterns are then evaluated colorimetrically. On the one hand the degree of bleaching is determined as a yellow number according to DIN 6167, on the other hand the amount of the compound of formula (102) on the fiber by means of the so-called K / S values. (K / S = Kubelka-Munk function). The values are determined using a Perkin-Elmer Lambda 9 with a 6 cm Ulbrich sphere of 698 and 280 nm. The results are shown in Table 5: Table 5: treatment Yellow number K / S value Pattern 1 28.80 20.8 Pattern 2 21.00 21.5 Pattern 3 16.9 22.0 Pattern 4 16.1 3.9 Pattern 5 13.8 3.2 Pattern 6 14.9 16.6 Wool, unbleached 27.9 3.0 Wool, pre-bleached 11.3 -

Die Ergebnisse zeigen, dass durch die Kombination der sauren Peroxid-Bleiche mit einer schwachen Reduktionsbleiche entsprechend dem erfindungsgemässen Verfahren (Muster 3) ein deutlich besserer Bleichgrad erzielt wird. Der Zusatz des UV-Absorbers der Formel (102) bewirkt dabei eine nur unwesentliche Verschlechterung des Bleichgrades (Vergleich Muster 3 mit Muster 4), während der Blindfärbeprozess der mittels einer Kombinationsbleiche vorgebleichten Wolle den Bleichgrad der Wolle sowohl bei Verwendung mit als auch ohne UV-Absorber der Formel (102) deutlich verschlechtert (Vergleich Wolle vorgebleicht mit Muster 5, bzw. Muster 6). Beim Vergleich der WS-Werte der Muster 1-3 und Muster 6 wird offensichtlich, dass die Verbindung (102) bei vergleichbaren Bedingungen besser durch ungebleichte als durch gebleichte Wolle aufgenommen wird, d.h. durch die alkalische Vorbleiche erleidet die Wolle einen Affinitätsverlust.The results show that the combination of the acidic peroxide bleaching with a weak reduction bleaching in accordance with the method according to the invention (sample 3) achieves a significantly better degree of bleaching. The addition of the UV absorber of the formula (102) causes only an insignificant deterioration in the degree of bleaching (comparison of pattern 3 with pattern 4), while the blind dyeing process of the wool pre-bleached by means of combination bleaching reduces the degree of bleaching of the wool both when used with and without UV. Absorber of the formula (102) deteriorated significantly (Comparison of wool pre-bleached with pattern 5 or pattern 6). When comparing the WS values of Patterns 1-3 and Pattern 6, it becomes apparent that the compound (102) is better absorbed by unbleached than by bleached wool under comparable conditions, ie the wool suffers a loss of affinity through the alkaline pre-bleaching.

Claims (18)

1. Verfahren zum Färben von Wolle mit anionischen Farbstoffen, dadurch gekennzeichnet, dass man die Wolle in Anwesenheit eines UV-Absorbers färbt und oxidativ bleicht und anschliessend in einem neuen Bad reduktiv bleicht.1. A method for dyeing wool with anionic dyes, characterized in that the wool is dyed in the presence of a UV absorber and bleached oxidatively and then bleached reductively in a new bath. 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet dass man die Wolle in demselben Bad färbt und oxidativ bleicht.2. The method according to claim 1, characterized in that the wool is dyed in the same bath and bleached oxidatively. 3. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass man als UV-Absorber ein 2-Hydroxybenzophenon der Formel
Figure imgb0018
 verwendet, worin
R₁ Wasserstoff, Hydroxy, C₁-C₁₄-Alkoxy oder Phenoxy,
R₂ Sulfo,
R₃ Wasserstoff, Hydroxy oder C₁-C₄-Alkoxy und
R₄ Wasserstoff, Hydroxy oder Carboxy
bedeuten.3. The method according to any one of claims 1 or 2, characterized in that a 2-hydroxybenzophenone of the formula is used as the UV absorber
Figure imgb0018
 used where
R₁ is hydrogen, hydroxy, C₁-C₁₄ alkoxy or phenoxy,
R₂ sulfo,
R₃ is hydrogen, hydroxy or C₁-C₄ alkoxy and
R₄ is hydrogen, hydroxy or carboxy
mean. 4. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass man als UV-Absorber ein 2-(2′-Hydroxyphenyl)-benzotriazol der Formel
Figure imgb0019
 verwendet, worin
R₁ Wasserstoff, Chlor, C₁-C₁₂-Alkyl, C₅-C₆-Cycloalkyl, sulfoniertes C₇-C₉-Arylalkyl oder Sulfo,
R₂ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Hydroxy oder Sulfo,
R₃ C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl,
C₂-C₉-Alkoxycarbonyl, Carboxyethyl, sulfoniertes C₇-C₉-Arylalkyl oder Sulfo,
R₄ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder Sulfo und
R₅ Wasserstoff oder Chlor
bedeuten und mindestens einer der Reste R₃ oder R₄ Sulfo sein muss.4. The method according to any one of claims 1 or 2, characterized in that a 2- (2'-hydroxyphenyl) benzotriazole of the formula is used as the UV absorber
Figure imgb0019
 used where
R₁ is hydrogen, chlorine, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, sulfonated C₇-C₉-arylalkyl or sulfo,
R₂ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy or sulfo,
R₃ C₁-C₁₂-alkyl, chlorine, C₅-C₆-cycloalkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl,
C₂-C₉-alkoxycarbonyl, carboxyethyl, sulfonated C₇-C₉-arylalkyl or sulfo,
R₄ is hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and
R₅ is hydrogen or chlorine
mean and at least one of the radicals R₃ or R₄ must be sulfo. 5. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass man als UV-Absorber ein 2-(2′-Hydroxyphenyl)-s-triazin der Formel
Figure imgb0020
 verwendet, worin
R Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
R₁ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy,
R₂ Sulfo und
R₃ und R₄ unabhängig voneinander C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl bedeuten.5. The method according to any one of claims 1 or 2, characterized in that a 2- (2'-hydroxyphenyl) -s-triazine of the formula is used as the UV absorber
Figure imgb0020
 used where
R is hydrogen, halogen, C₁-C₄-alkyl or sulfo,
R₁ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy,
R₂ sulfo and
R₃ and R₄ independently of one another are C₁-C₄-alkyl, C₁-C₄-alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy. 6. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass man als UV-Absorber eine s-Triazinverbindung der Formel
Figure imgb0021
 verwendet, worin mindestens einer der Substituenten R₁, R₂ und R₃ ein Rest der Formel
Figure imgb0022
 ist, worin
R₆ Wasserstoff oder Hydroxy,
M Natrium, Kalium, Calcium, Magnesium, Ammonium oder Tetra-C1-C₄-alkylammonium und m 1 oder 2 ist, und der übrige Substituent bzw. die übrigen Substituenten, unabhängig voneinander, C₁-C₁₂-Alkyl, Phenyl, durch Sauerstoff, Schwefel, Imino oder C₁-C₁₁-Alkylimino an den Triazinylrest gebundenes C₁-C₁₂-Alkyl oder Phenyl ist.6. The method according to any one of claims 1 or 2, characterized in that an s-triazine compound of the formula is used as the UV absorber
Figure imgb0021
 used, wherein at least one of the substituents R₁, R₂ and R₃ is a radical of the formula
Figure imgb0022
 is what
R₆ is hydrogen or hydroxy,
M is sodium, potassium, calcium, magnesium, ammonium or tetra-C1-C₄-alkylammonium and m is 1 or 2, and the remaining substituent or substituents, independently of one another, C₁-C₁₂ alkyl, phenyl, by oxygen, sulfur , Imino or C₁-C₁₁-alkylimino is C₁-C₁₂-alkyl or phenyl bonded to the triazinyl radical. 7. Verfahren gemäss einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man den UV-Absorber dem Färbebad zugibt.7. The method according to any one of claims 1 to 6, characterized in that the UV absorber is added to the dyebath. 8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass man den UV-Absorber dem reduktiven Bleichbad zugibt.8. The method according to any one of claims 1 to 7, characterized in that the UV absorber is added to the reductive bleaching bath. 9. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man den UV-Absorber in einer Menge von 0,01 bis 7,5 Gew.%, bezogen auf das Wollmaterial einsetzt.9. The method according to any one of claims 1 to 8, characterized in that the UV absorber is used in an amount of 0.01 to 7.5 wt.%, Based on the wool material. 10. Verfahren gemäss einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man als anionische Farbstoffe Säurefarbstoffe einsetzt.10. The method according to any one of claims 1 to 9, characterized in that acid dyes are used as anionic dyes. 11. Verfahren gemäss einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man zum oxidativen Bleichen eine sauerstoff freisetzende Verbindung verwendet.11. The method according to any one of claims 1 to 10, characterized in that an oxygen-releasing compound is used for the oxidative bleaching. 12. Verfahren gemäss Anspruch 11, dadurch gekennzeicnet, dass man zum oxidativen Bleichen Wasserstoffperoxid verwendet.12. The method according to claim 11, characterized in that hydrogen peroxide is used for the oxidative bleaching. 13. Verfahren gemäss einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass man das oxidative Bleichmittel nach dem Färben zugibt.13. The method according to any one of claims 1 to 12, characterized in that the oxidative bleaching agent is added after dyeing. 14. Verfahren gemäss einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass das oxidative Bleichen und Färben nach dem Ausziehverfahren erfolgt.14. The method according to any one of claims 1 to 13, characterized in that the oxidative bleaching and dyeing is carried out by the exhaust process. 15. Verfahren gemäss einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass der reduktive Bleichprozess mit Natrium-Bisulfit durchgeführt wird.15. The method according to any one of claims 1 to 14, characterized in that the reductive bleaching process is carried out with sodium bisulfite. 16. Verfahren gemäss Anspruch 15, dadurch gekennzeichhnet, dass das Natrium-Bisulfit in einer Menge von 0,25 bis 10 Gew.%, bezogen auf das Wollmaterial, eingesetzt wird.16. The method according to claim 15, characterized in that the sodium bisulfite is used in an amount of 0.25 to 10% by weight, based on the wool material. 17. Verfahren gemäss einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass der reduktive Bleichprozess in langer Flotte durchgeführt wird.17. The method according to any one of claims 1 to 17, characterized in that the reductive bleaching process is carried out in a long liquor. 18. Das gemäss der Ansprüche 1 bis 17 behandelte Wollmaterial.18. The wool material treated according to claims 1 to 17.
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