Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/651—Compounds without nitrogen
  • D06P1/65106—Oxygen-containing compounds
  • D06P1/65112—Compounds containing aldehyde or ketone groups

Definitions

• the present invention relates to a method for improving the light fastness of colored and uncolored leather.
• leather dyeings generally have a lower lightfastness than comparable dyeings on textile fiber materials, e.g. from B. Magerkurth, The Leather Manufacturer, January 1987, pages 10-26: Identical dyes gave a lightfastness rating of 6-7 when dyed nylon, a lightfastness rating reduced by 1 grade on wool and a maximum of 4 on leather, each according to ISO -Blue scale measured.
• the carboxy and sulfor radicals can generally be used as a free acid or as a salt, e.g. as an alkali metal, earth alkali metal, ammonium or amine salt.
• R2 or any other substituents are C1-C4alkoxy, they represent, for example, methoxy, ethoxy, n- or iso-propoxy, or n-, iso-, sec- or tert-butoxy.
• 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.
• C1-C4-alkoxy groups e.g. straight or branched pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy or dodecyloxy in question.
• 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.
• R6 or any other substituents are C1-C12-alkyl, in addition to the aforementioned C1-C Alkyl-alkyl radicals e.g. a linear or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl radical in question.
• C1-C Alkyl-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.
• aralkyl R6 or any other variables are preferably phenylethyl or in particular benzyl.
• 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 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 above formula (2a) 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 hydrogen and R'8 C1-C4 alkyl or sulfo.
• 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'-Hydr
• 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
• R9 and R10 independently of one another each preferably represent phenyl which is unsubstituted or substituted by sulfo, hydroxy, chlorine and / or C1-C4-alkyl and particularly preferably unsubstituted or substituted by C1-C4-alkyl, hydroxy or sulfo Phenyl; particularly preferred meanings of R9 and R10 are phenyl, o-, m- or p-methylphenyl, tert-butylphenyl, 2,4-dimethylphenyl or o-, m- or p-sulfophenyl.
• radicals R9 and R10 can be different or, preferably, the same.
• R11 preferably represents a Sulforest.
• the phenyl radical (A) preferably has no further substituents or is further substituted by chlorine, methyl or methoxy.
• UV absorbers of the formula (3a) are preferred, wherein R11 sulfo or 2-hydroxy-3-sulfo-n-propoxy, R12 is hydrogen, chlorine, methyl or methoxy, and R13, R14, R15 and R16 each independently represent hydrogen, hydroxy C1-C4-alkyl or sulfo.
• UV absorbers of the formula (3) or (3a) are: 2- (2'-hydroxy-4'-methoxy-5'-sulfophenyl) -4,6-diphenyl-s-triazine, 2- (2'-hydroxy-5'-sulfophenyl) -4,6-diphenyl-s-triazine, 2- (2'-hydroxy-5'-sulfophenyl) -4,6-bis- (2 ⁇ , 4 ⁇ -dimethylphenyl) -s-triazine, 2- [2'-Hydroxy-4 '- (2-hydroxy-3-sulfo-n-propoxy -) - phenyl] -4,6-diphenyl-s-triazine.
• improving lightfastness means preventing or at least reducing yellowing.
• the inventive method is advantageously carried out so 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.
• a temperature e.g. 20 to 100 ° C, preferably 40 to 60 ° C.
• 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.
• the dye bath can optionally contain other generally customary additives, e.g. Wetting agents, leveling agents, color deepening agents and / or fatty agents are added.
• Wetting agents e.g. Acidified with formic acid for better bath exhaustion and let it run for some time.
• the dyed leather is finished in a manner known per se.
• customary anionic dyes as are known, for example, from the Color Index, are used to dye the leather.
• Anionic dyes that can be used are all dyes usually 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.
• anionic dyes can also be used.
• 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 nit 0.5 to 4.0 wt .-%, based on the weight of the leather, of a UV absorber of the formula 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.
• 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
• the method according to the invention is suitable for all types of grain, rough and suede leather, for example chrome leather, retanned leather or suede leather from goat, sheep, beef and pork.
• 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 leather treated in this way is now in a from 300 parts of water, 1 part of dye of the formula and 2 parts of UV absorber of the formula existing fresh liquor stained 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 is continued for a further 30 minutes at unchanged temperature and the dyed leather is made after Rinse done as usual. A level red coloration is obtained with a light fastness which is greatly improved compared to a color depth of the same color without UV absorber.
• the neutralizing liquor is supplemented with 2 parts of the UV absorber of the formula 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 existing fresh liquor stained 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 is continued for a further 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.
• a fatliquor preparation based on sulfonated chlorinated paraffin
• chrome cowhide 100 parts 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 fomaldehyde and urea) and 2 parts of the UV absorber used in Example 1 treated 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 0.67 part of the red dye used in Example 1 and 0.67 part of the blue dye of the formula colored.
• Example 3 100 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.
• a color-deepening auxiliary polyquaternary amine-ethylene oxide adduct
• Example 1 After a treatment period of 15 minutes, one 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 light fastness in comparison to a dyeing of the same color depth without UV absorber.
• Example 1 100 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 absorber listed in Example 1 Treated for 60 minutes. This is followed by a 15-minute washing process 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 characterized by a greatly improved leather compared to 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.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)

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Citations (3)

• 1992
  • 1992-04-22 EP EP19920810292 patent/EP0512946B1/fr not_active Expired - Lifetime
  • 1992-04-22 DE DE59203628T patent/DE59203628D1/de not_active Expired - Fee Related
  • 1992-05-01 JP JP4112671A patent/JPH05272076A/ja not_active Withdrawn

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