EP0512946B1 - Process for improving the fastness to light of leather - Google Patents

Process for improving the fastness to light of leather Download PDF

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Publication number
EP0512946B1
EP0512946B1 EP19920810292 EP92810292A EP0512946B1 EP 0512946 B1 EP0512946 B1 EP 0512946B1 EP 19920810292 EP19920810292 EP 19920810292 EP 92810292 A EP92810292 A EP 92810292A EP 0512946 B1 EP0512946 B1 EP 0512946B1
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Prior art keywords
hydrogen
hydroxy
c1
sulfo
leather
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EP19920810292
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German (de)
French (fr)
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EP0512946A1 (en
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Kurt Dr. Burdeska
Alois Dr. Püntener
Campbell Dr. Page
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Ciba Geigy AG
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Ciba Geigy AG
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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642Compounds containing nitrogen
    • D06P1/6426Heterocyclic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651Compounds without nitrogen
    • D06P1/65106Oxygen-containing compounds
    • D06P1/65112Compounds containing aldehyde or ketone groups

Description

  • The present invention relates to a method for improving the light fastness of colored and uncolored leather.
  • The increased use of leather e.g. for the manufacture of car seats, furniture or articles of clothing has led to increasing demands being placed on the lightfastness of leather.
  • However, leather dyeings generally have a lower light fastness than comparable dyeings on textile fiber materials, e.g. from B. Magerkurth, The Leather Manufacturer, January 1987, page 10-26: Identical dyes gave a lightfastness rating of 6-7 when dyed nylon, a lightfastness rating lowered by 1 grade on wool and a maximum of 4 on leather, each according to ISO -Blue scale measured.
  • In the case of undyed leather, more or less yellowing occurs under the influence of light, which is usually undesirable.
  • There is therefore a need to improve dyed and undyed leather in its light fastness.
  • In US-A-3 444 164 and in EP-A-0 165 608 triazine derivatives are described as UV absorbers and EP-A-0 245 204 teaches that polyamide fiber material is stabilized with mixtures of UV absorbers and organic copper complexes can.
  • It has been shown that, surprisingly, leather with improved light fastness can be obtained if the leather is treated with specific UV absorbers.
  • The present application is therefore a process for improving the light fastness of leather, which is characterized in that the leather in the presence of a UV absorber selected from the group of
    • a) 2-hydroxybenzophenones of the formula (1)
      Figure imgb0001
      wherein
      R₁ is hydrogen, hydroxy, C₁-C₁₄ alkoxy or phenoxy,
      R₂ is hydrogen, hydroxy or C₁-C₄ alkoxy and
      R₃ is hydrogen, hydroxy or carboxy
      mean and
    • b) 2- (2'-hydroxyphenyl) benzotriazoles of the formula (2)
      Figure imgb0002
      wherein
      R₄ is hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₈-alkoxycarbonyl, carboxy or sulfo,
      R₅ is hydrogen or halogen,
      R₆ is hydrogen, halogen, C₁-C₁₂-alkyl, C₅-C₆-cycloalkyl, C₇-C₉-arylalkyl or sulfo,
      R₇ is hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy or sulfo, and
      R₈ is C₁-C₁₂-alkyl, halogen, C₅-C₆-cycloalkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₁-C₈-alkoxycarbonyl, carboxyethyl, C₇-C₉-aralkyl or sulfo and at least one of the radicals R₄ or R₈ must be sulfo treated.
  • The carboxy and sulfor radicals can generally be used as a free acid or as a salt, e.g. as an alkali metal, alkaline earth metal, ammonium or amine salt.
  • If R₂ or any other substituents are C₁-C₄alkoxy, they represent e.g. Methoxy, ethoxy, n- or iso-propoxy, or n-, iso-, sec.- or tert.-butoxy.
  • If R₁ is C₁-C₁₂-alkoxy, in addition to the above-mentioned C₁-C₄-alkoxy groups e.g. straight or branched pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy or dodecyloxy in question.
  • Examples of suitable UV absorbers of the formula (1) are 2-hydroxy-4-methoxy-5-sulfobenzophenone and 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone.
  • R₄ or any variables other than halogen are e.g. fluorine, bromine or preferably chlorine.
  • R₄ or any other variables for C₁-C₄-alkyl, here are the meanings methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl in question.
  • R₄ or R₈ as C₁-C₈ alkoxycarbonyl is preferably methoxycarbonyl or ethoxycarbonyl.
  • R₄ preferably represents hydrogen, chlorine, methyl, methoxy, methoxycarbonyl, Ethoxycarbonyl, carboxy or sulfo and particularly preferably for hydrogen or sulfo.
  • R₅ is preferably hydrogen.
  • If R₆ or any other substituents are C₁-C₁₂-alkyl, in addition to the aforementioned C₁-C₄-alkyl radicals e.g. a linear or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl radical in question.
  • R₆ or any variables other than C₅-C₆ cycloalkyl are e.g. cyclopentyl or preferably cyclohexyl.
  • As C₇-C₉-alalkyl R₆ or any other variables are preferably phenylethyl or in particular benzyl.
  • Preferred meanings of R₆ are hydrogen, chlorine, C₁-C₆-alkyl, benzyl, phenylethyl or sulfo. R₆ particularly preferably represents methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl or tert-amyl.
  • R₇ is preferably hydrogen, hydroxy or methoxy and particularly preferably hydrogen.
  • R₈ preferably represents hydrogen, chlorine, C₁-C₈-alkyl or sulfo, particularly preferably C₁-C₄-alkyl or sulfo and particularly preferably sulfo.
  • Preferred UV absorbers correspond to the formula
    Figure imgb0003

    wherein R'₄ is hydrogen, chlorine, methyl, methoxy, methoxycarbonyl, ethoxycarbonyl, carboxy or sulfo, R'₆ is hydrogen, chlorine, C₁-C₆-alkyl, benzyl, phenylethyl or sulfo, R'₇ is hydrogen, hydroxy or methoxy is and R'₈ is hydrogen, chlorine, C₁-C₈-alkyl or sulfo and at least one of the radicals R'₄ or R'₈ must be sulfo.
  • UV absorbers of the formula (2a) given above are particularly preferred, in which R'₄ is hydrogen or sulfo, R'₆ is methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl ( or tert-amyl, R'₇ is hydrogen and R'₈ is C₁-C₄alkyl or sulfo.
  • Examples of suitable UV absorbers of the formula (2) or (2a) are:
    2- (2'-hydroxy-3'-sulfo-5'-tert-octylphenyl) benzotriazole,
    2- (2'-hydroxy-3'-sulfo-5'-tert-butylphenyl) benzotriazole,
    2- (2'-hydroxy-3'-sulfo-5'-methylphenyl) benzotriazole,
    2- (2 ', 4'dihydroxy-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-4'-methoxy-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-5'-sulfophenyl) -5-chlorobenzotriazole,
    2- (2'-hydroxy-3'-methyl-5'-sulfophenyl) -5-chlorobenzotriazole,
    2- (2'-hydroxy-5'-methylphenyl) -5-sulfobenzotriazole,
    2- (2'-Hydroxy-3'-benzyl-5'-sulfophenyl) benzotriazole.
  • Examples of particularly preferred UV absorbers of the formula (2) or (2a) are:
    2- (2'-hydroxy-3'-tert-amyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-tert-butyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-sec-butyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-n-butyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-isobutyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-isopropyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-n-propyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-ethyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-methyl-5'-sulfophenyl) benzotriazole,
    2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-sulfobenzotriazole,
    2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-sulfobenzotriazole,
    2- (2'-hydroxy-3'-isopropyl-5'-tert-butylphenyl) -5-sulfobenzotriazole,
    2- (2'-Hydroxy-3'-tert-amyl-5'-methylphenyl) -5-sulfobenzotriazole.
  • In the case of uncoloured leather, improving lightfastness means preventing or at least reducing yellowing.
  • The process according to the invention is advantageously carried out in such a way that the leather initially subjected to pretreatment, for example retanning, neutralization and / or rolling.
  • The leather pretreated in this way is then, if desired, dyed by means of a known pull-out process using one or more dyes; for example, the leather is dyed in an aqueous solution at a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10 and a temperature of e.g. 20 to 100 ° C, preferably 40 to 60 ° C. Depending on the type of leather to be dyed, e.g. 0.25 to 15 wt .-%, preferably 1.0 to 10 wt .-%, based on the weight of the leather, dye. The dyeing time also depends on the type of leather to be dyed, but is generally e.g. 20 to 180 minutes.
  • The UV absorber can be added during the pretreatment, which is particularly useful for leather that should not be subsequently dyed. However, it can also be added to the dye bath before, during or after the dyeing process, i.e. the addition can take place during the pretreatment, during the actual coloring or only after the treatment. The UV absorber is preferably added after the dyeing process. Instead of a UV absorber, a mixture of different UV absorbers can also be used.
  • The UV absorbers are used in an amount of e.g. 0.25 to 7.5, preferably 0.5 to 4.0 and particularly 0.5 to 2.5% by weight, based on the weight of the leather, is used.
  • If necessary, the dye bath can be admixed with other commonly used additives, e.g. Wetting agents, leveling agents, color deepening agents and / or fatty agents are added. At the end of the dyeing process, e.g. Acidified with formic acid to improve bath exhaustion and let it run for some time. The dyed leather is finished in a manner known per se.
  • For the process according to the invention, customary anionic dyes, such as are known, for example, from the Color Index, are used for dyeing the leather. Anionic dyes that can be used are all dyes commonly used in leather dyeing; acid dyes and direct dyes, such as, in particular, sulfo-containing monoazo, disazo and polyazo dyes, and 1: 1 or 1: 2 metal complex dyes are preferred.
  • Mixtures of the anionic dyes can also be used. For example, dye mixtures of 2, 3, 4 or more components can be used.
  • A preferred embodiment of the present invention relates to a process for improving the light fastness of leather dyeings, characterized in that the leather is treated with 0.5 to 4.0% by weight, based on the weight of the leather, of a UV absorber of the formula
    Figure imgb0004

    wherein R'₄ is hydrogen, chlorine, methyl, methoxy, methoxycarbonyl, ethoxycarbonyl, carboxy or sulfo, R'₆ is hydrogen, chlorine, C₁-C₆-alkyl, benzyl, phenylethyl or sulfo, R'₇ is hydrogen, hydroxy or methoxy is and R'₈ is hydrogen, chlorine, C₁-C₈ alkyl or sulfo and at least one of the radicals R'₄ or R'₈ must be sulfo treated.
  • A particularly preferred embodiment of the present invention relates to a method for improving the lightfastness of leather dyeings, characterized in that after the dyeing process with 0.5 to 2.5% by weight, based on the weight of the leather, of a UV absorber Formula (2a) given above, in which R'₄ is hydrogen or sulfo, R'₆ is methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl or tert-amyl, R ' ₇ is hydrogen and R'₈ C₁-C₄ alkyl or sulfo treated.
  • The method according to the invention is suitable for all types of grain, suede and suede, for example chrome leather, retanned leather or suede from goat, sheep, beef and pork.
    When the process according to the invention is used in conjunction with a dyeing process, level, deep, well-covering dyeings with good general fastness properties are obtained, for example water, washing, welding, dry cleaning, acid, Alkali, solvent and diffusion fastness to soft PVC.
    The lightfastness of the leather obtainable according to the invention, which is greatly improved compared to a comparable method without UV absorber, deserves special mention.
  • The following examples illustrate the invention. Parts mean parts by weight, percentages by weight. The temperatures are given in ° C.
  • Example 1: 100 parts of chrome-tanned cowhide (fold weight) are washed for 15 minutes in 300 parts of water at 30 ° C. and then for 60 minutes in one of 300 parts of water, 2 parts of neutralizing agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) and 0. 5 parts of sodium bicarbonate existing liquor neutralized at 30 ° C. This is followed by a 15-minute washing operation in 300 parts of water at room temperature.
  • The leather treated in this way is now in a from 300 parts of water, 1 part of dye of the formula
    Figure imgb0005

    and 2 parts of UV absorber of the formula
    Figure imgb0006

    existing fresh liquor dyed at 50 ° C for 30 minutes. Then 3 parts of a fatliquor (preparation based on sulfonated chlorinated paraffin) are added to the dye liquor, and after a further 30 minutes 0.5 part of 85% formic acid is added. Dyeing continues for a further 30 minutes at unchanged temperature and the dyed leather is made after Rinse done as usual. A level red color is obtained with a light fastness that is greatly improved compared to a color depth of the same color without a UV absorber.
  • Example 2: 100 parts of chrome-tanned cowhide (fold weight) are washed for 15 minutes in 300 parts of water at 30 ° C. and then for 60 minutes in one of 300 parts of water, 2 parts of neutralizing agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) and 0. 5 parts of sodium bicarbonate existing liquor neutralized at 30 ° C.
  • The neutralizing liquor is supplemented with 2 parts of the UV absorber of the formula
    Figure imgb0007

    and let it run for 60 minutes. This is followed by a 15-minute washing operation in 300 parts of water at room temperature.
  • The leather treated in this way is now in a from 300 parts of water and 2 parts of dye of the formula
    Figure imgb0008

    existing fresh liquor dyed at 50 ° C for 30 minutes. Then 3 parts of a fatliquor (preparation based on sulfonated chlorinated paraffin) are added to the dyeing liquor and, after a further 30 minutes, 0.5 part of 85% formic acid is added. The dyeing is continued for 30 minutes at unchanged temperature and the dyed leather is finished as usual after rinsing . The result is a level red color with a light fastness that is greatly improved compared to a color depth of the same color without UV absorber.
  • Example 3: 100 parts of chrome cowhide (shaved weight) are neutralized as described in Example 1 and then at 30 ° C. in the same liquor with 7 parts of a liquid synthetic retanning agent (condensation products of polyphenolsulfonic acids with formaldehyde and urea) and 2 parts of that used in Example 1 UV absorber treated for another 60 minutes. This is followed by a 15-minute washing process in 300 parts of water at room temperature. This retanned chrome cowhide is then at 50 ° C in a liquor consisting of 300 parts of water and 2.01 parts of the dye mixture consisting of 0.67 parts of the yellow dye of the formula
    Figure imgb0009

    0.67 part of the red dye used in Example 1 and 0.67 part of the blue dye of the formula
    Figure imgb0010

    colored. After a dyeing time of 30 minutes, 3 parts of the synthetic fatliquor from Example 1 are added, and after a further 30 minutes, 1 part of 85% formic acid is added. After acidification, the treatment is continued for 30 minutes at 50 ° C. It is then rinsed in cold water and finished. The level brown dyeing obtained is distinguished from the dyeing of the same color depth without UV absorber by a significantly improved light fastness.
  • Example 4: 100 parts of chrome cowhide (shaved weight) are neutralized and retanned as described in Example 3 (without the UV absorber mentioned in Example 3) and then dyed in a liquor containing 300 parts of water and 1.5 parts of the dye mixture used in Example 3 at 50 ° C. for 30 minutes. After 30 minutes, 3 parts of the synthetic fatliquor from Example 1 are added, and after a further 30 minutes, 1 part of 85% formic acid is added. After acidification, the treatment is continued for 30 minutes at 50 ° C. The leather is then aftertreated in a fresh bath with 1 part of a color-deepening auxiliary (polyquaternary amine-ethylene oxide adduct) in 300 parts of water. After a treatment period of 15 minutes, a third of the above-mentioned dye mixture and 2 parts of the UV absorber used in Example 1 are added to the dyebath and then further dyeing at 50 ° C. for 15 minutes. Then 0.25 part of 85% formic acid is added. The coloring is complete after a further 20 minutes. It is then rinsed in cold water. The dyeing, which is finished as usual, is characterized by very good lightfastness in comparison to a dyeing of the same color depth without UV absorber.
  • Example 5: 100 parts of chrome cowhide (shaved weight) are neutralized as described in Example 1 and then at 30 ° C. in the same liquor with 7 parts of a liquid synthetic retanning agent (condensation products of naphthalenesulfonic acids with formaldehyde and urea) and 2 parts of that used in Example 1 UV absorber treated for a further 60 minutes. This is followed by a washing process of 15 minutes in 300 parts of water at room temperature. This retanned chrome cowhide is then dyed in a liquor containing 300 parts of water and 1.5 parts of the dye mixture used in Example 3 at 50 ° C. for 30 minutes. After 30 minutes, 3 parts of the synthetic fatliquor from Example 1 are added, and after a further 30 minutes, 1 part of 85% formic acid is added. After acidification, the treatment is continued for 30 minutes at 50 ° C. The leather is then aftertreated in a fresh bath with 1 part of a color-deepening auxiliary (polyquaternary amine-ethylene oxide adduct) in 300 parts of water for 15 minutes. After a treatment period of 15 minutes, a third of the dye mixture mentioned above is added to the dyebath and then further dyeing at 50 ° C. for 15 minutes. Then 0.25 part of 85% formic acid is added. The coloring is complete after a further 20 minutes. It is then rinsed in cold water. The result is a full brown color with a light fastness that is greatly improved compared to the color depth of the same color without UV absorber. This coloration shows a lower lightening effect compared to the leather treated according to Example 4.
  • Example 6: 100 parts of chrome leather (shaved weight) are neutralized and retanned as described in Example 3 (without the UV absorber mentioned in Example 3) and dyed with 2.0 or 4.0 parts of the red dye listed in Example 1. This finished crust leather is aftertreated by a fuel application with a solution containing 25 g of the UV absorber listed in Example 1, 100 g of methoxyisopropanol and 875 g of water. With this milky solution, the leather is sprayed 2 times crosswise and air-dried. The leather aftertreated with UV absorber shows very much improved light fastness compared to leather that has not been aftertreated.
  • Example 7: 100 parts of chrome-tanned cowhide (fold weight) are neutralized and dyed as described in Example 1, but 1 part of 2-hydroxy-4-methoxy-5-sulfobenzophenone is used instead of the UV absorber used there.
  • Compared to dyeing of the same color depth without UV absorber, the red color is characterized by a significantly improved light fastness.
  • Example 8: 100 parts of chrome cowhide (shaved weight) are neutralized as described in Example 1 and then at 30 ° C. in the same liquor with 4 parts of a synthetic retanning agent (formaldehyde condensation product of polyphenolsulfone and polynaphthalenesulfonic acid) and 2 parts of the UV listed in Example 1 -Absorbers treated another 60 minutes. This is followed by a washing process of 15 minutes in 300 parts of water at room temperature. The leather is then treated in a float of 300 parts of water and 3 parts of the synthetic fatliquor from Example 1 for 30 minutes at 50 ° C. After 30 minutes, 0.5 part of 85% formic acid is added and the treatment is continued for 30 minutes at 50 ° C. It is then rinsed in cold water and finished. The leather treated with UV absorber is markedly improved over leather treated in the same way but without UV absorber Lightfastness off, ie the leather with the UV absorber shows significantly less yellowing under the influence of light.
  • EXAMPLE 9 If the procedure is as described in Example 7, but 1 part of 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone is used as the UV absorber, a red coloration is obtained which differs from a coloration of the same color depth characterized by a significantly improved light fastness without UV absorber.

Claims (11)

  1. A process for improving the light fastness of leather, which comprises treating the leather with a UV absorber chosen from the group comprising
    2) 2-hydroxybenzophenones of the formula (1)
    Figure imgb0015
    in which R₁ is hydrogen, hydroxyl, C₁-C₁₄alkoxy or phenoxy, R₂ is hydrogen, hydroxyl or C₁-C₄alkoxy and R₃ is hydrogen, hydroxyl or carboxyl, and
    b) 2-(2'-hydroxyphenyl)-benzotriazoles of the formula (2)
    Figure imgb0016
    in which R₄ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy,
    C₁-C₈alkoxycarbonyl, carboxyl or sulfo, R₅ is hydrogen or halogen, R₆ is hydrogen, halogen, C₁-C₁₂alkyl, C₅-C₆cycloalkyl, C₇-C₉arylalkyl or sulfo, R₇ is hydrogen, halogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy or sulfo, and R₈ is C₁-C₁₂alkyl, halogen, C₅-C₆cycloalkyl, C₁-C₄alkoxy, phenyl,
    (C₁-C₈alkyl)phenyl, C₁-C₈alkoxycarbonyl, carboxyethyl, C₇-C₉aralkyl or sulfo, and at least one of the radicals R₄ or R₈ must be sulfo.
  2. A process according to claim 1, wherein a UV absorber of the formula (2) is used.
  3. A process according to claim 1 or 2, wherein a UV absorber of the formula
    Figure imgb0017
    in which R'₄ is hydrogen, chlorine, methyl, methoxy, methoxycarbonyl, ethoxycarbonyl, carboxyl or sulfo, R'₆ is hydrogen, chlorine, C₁-C₆alkyl, benzyl, phenylethyl or sulfo, R'₇ is hydrogen, hydroxyl or methoxy and R'₈ is hydrogen, chlorine, C₁-C₈alkyl or sulfo, and at least one of the radicals R'₄ or R'₈ must be sulfo, is used.
  4. A process according to claim 3, wherein a UV absorber of the formula (2a) in which R'₄ is hydrogen or sulfo, R'₆ is methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or tert-amyl, R'₇ is hydrogen and R'₈ is C₁-C₄alkyl or sulfo is used.
  5. A process according to one of claims 1 to 4, wherein
    2-(2'-hydroxy-3'-tert-amyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-tert-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-sec-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-n-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-iso-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-isopropyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-n-propyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-ethyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-methyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-sulfobenzotriazole,
    2-(2'-hydroxy-3',5'-dimethylphenyl)-5-sulfobenzotriazole,
    2-(2'-hydroxy-3'-isopropyl-5'-tert-butylphenyl)-5-sulfobenzotriazole or
    2-(2'-hydroxy-3'-tert-amyl-5'-methylphenyl)-5-sulfobenzotriazole
    is used as the UV absorber.
  6. A process according to one of claims 1 to 5, wherein
    2-(2'-hydroxy-3'-tert-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-sec-butyl-5'-sulfophenyl)-benzotriazole,
    2-(2'-hydroxy-3'-n-butyl-5'-sulfophenyl)-benzotriazole or
    2-(2'-hydroxy-3'-iso-butyl-5'-sulfophenyl)-benzotriazole
    is used as the UV absorber.
  7. A process according to one of claims 1 to 6, wherein the treatment with the UV absorber is carried out after a dyeing operation.
  8. A process according to one of claims 1 to 7, wherein the UV absorber is employed in an amount of 0.25 to 7.5, preferably 0.5 to 4.0 and in particular 0.5 to 2.5% by weight, based on the weight of the leather.
  9. A process for improving the light-fastness of a leather dyeing, which comprises treating the leather, after dyeing, with 0.5 to 4.0% by weight, based on the weight of the leather, of a UV absorber of the formula
    Figure imgb0018
    in which R'₄ is hydrogen, chlorine, methyl, methoxy, methoxycarbonyl, ethoxycarbonyl, carboxyl or sulfo, R'₆ is hydrogen, chlorine, C₁-C₆alkyl, benzyl, phenylethyl or sulfo, R'₇ is hydrogen, hydroxyl or methoxy and R'₈ is hydrogen, chlorine, C₁-C₈alkyl or sulfo, and at least one of the radicals R'₄ or R'₆ must be sulfo.
  10. A process according to claim 9, wherein 0.5 to 2.5% by weight, based on the weight of the leather, of a UV absorber of the formula (2a) defined in claim 9, in which R'₄ is hydrogen or sulfo, R'₆ is methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or tert-amyl, R'₇ is hydrogen and R'₈ is C₁-C₄alkyl or sulfo, is used.
  11. The leather treated according to claims 1 to 10.
EP19920810292 1991-05-02 1992-04-22 Process for improving the fastness to light of leather Expired - Lifetime EP0512946B1 (en)

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CH132191 1991-05-02
CH1321/91 1991-05-02

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EP0512946B1 true EP0512946B1 (en) 1995-09-13

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US5556973A (en) * 1994-07-27 1996-09-17 Ciba-Geigy Corporation Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
TW440633B (en) * 1996-09-27 2001-06-16 Kuraray Co Suede-like artificial leather and its preparation
GB0118156D0 (en) * 2001-07-25 2001-09-19 Pittards Plc Leather production
WO2008102822A1 (en) 2007-02-20 2008-08-28 Fujifilm Corporation Polymer material containing ultraviolet absorbent
EP2135911B1 (en) 2007-03-30 2014-05-28 FUJIFILM Corporation Ultraviolet ray absorber composition
KR101569220B1 (en) 2007-08-16 2015-11-13 후지필름 가부시키가이샤 Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent
JP5250289B2 (en) 2008-03-31 2013-07-31 富士フイルム株式会社 UV absorber composition
JP5244437B2 (en) 2008-03-31 2013-07-24 富士フイルム株式会社 UV absorber composition
JP2009270062A (en) 2008-05-09 2009-11-19 Fujifilm Corp Ultraviolet absorbent composition
US8691002B2 (en) 2009-01-19 2014-04-08 Basf Se Organic black pigments and their preparation
JP2011202144A (en) * 2010-03-01 2011-10-13 Fujifilm Corp Adhesive composition, adhesive tape or film using the same, surface protective film, laminated glass and solar cell module
EP3178947A4 (en) 2014-08-04 2018-05-30 Citizen Watch Co., Ltd. Leather or leather article and method for producing same, hexavalent chromium treatment agent, method for treating hexavalent chromium in crude leather or crude leather article

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CH478589A (en) * 1965-09-24 1969-09-30 Ciba Geigy Use of aryl-1,3,5-triazines as a stabilizer against ultraviolet radiation, heat outside the textile industry
EP0165608B1 (en) * 1984-06-22 1991-01-02 Ilford Ag Hydroxyphenyltriazines, process for their preparation and their use as uv absorbers
US4775386A (en) * 1986-05-05 1988-10-04 Ciba-Geigy Corporation Process for photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with other fibres: copper complex and light stabilizer treatment

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DE59203628D1 (en) 1995-10-19
JPH05272076A (en) 1993-10-19

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