EP0181836B1 - Procédé d'amélioration de la solidité à la lumière de cuirs teints - Google Patents

Procédé d'amélioration de la solidité à la lumière de cuirs teints Download PDF

Info

Publication number
EP0181836B1
EP0181836B1 EP85810512A EP85810512A EP0181836B1 EP 0181836 B1 EP0181836 B1 EP 0181836B1 EP 85810512 A EP85810512 A EP 85810512A EP 85810512 A EP85810512 A EP 85810512A EP 0181836 B1 EP0181836 B1 EP 0181836B1
Authority
EP
European Patent Office
Prior art keywords
group
copper
formula
radical
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85810512A
Other languages
German (de)
English (en)
Other versions
EP0181836A1 (fr
Inventor
Alois Dr. Püntener
Gerhard Dr. Back
Josef Koller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0181836A1 publication Critical patent/EP0181836A1/fr
Application granted granted Critical
Publication of EP0181836B1 publication Critical patent/EP0181836B1/fr
Expired legal-status Critical Current

Links

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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/10—After-treatment with compounds containing metal
    • 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
    • D06P1/6423—Compounds containing azide or oxime groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • 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
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/67341—Salts or hydroxides of elements different from the alkaline or alkaline-earth metals or with anions containing those elements
    • 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
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins

Definitions

  • the present invention relates to a process for improving the light fastness of leather dyed with anionic chromium or cobalt complex dyes, which is characterized in that the leather is treated with a compound of the copper before, during or after the dyeing.
  • salts of inorganic acids such as. B. copper chloride, sulfate, phosphate or nitrate
  • Salts of organic acids such as. B. copper acetate, tartrate or salicylate, mixtures of different copper salts or mixtures of a copper salt and another acid, for. B. mixtures of copper acetate and salicylic acid
  • Copper salts of salicylic acid derivatives or mixtures of the above-mentioned copper salts of inorganic or organic acids with salicylic acid derivatives are also suitable.
  • Useful salicylic acid derivatives are e.g. B. 2-hydroxy-5-sulfobenzoic acid or compounds of formula I.
  • W and W 2 are independently hydrogen, C, -C 4 alkyl, hydroxy-C, -C 4 alkyl or phenyl optionally substituted by sulfo or carboxy.
  • Bisazomethines of aromatic aldehydes and ketones are understood to mean Schiff bases of aliphatic or aromatic diamines, the aldehydes and ketones having an OH group in the o-position to the formyl or acyl radical.
  • the bond with the metal atom takes place via these two OH groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands.
  • the ligands preferably contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.
  • benzene rings A and B can also, independently of one another, be substituted or also have further fused rings. In addition, the benzene rings A and B can also be heterocyclic rings.
  • R denotes an optionally substituted alkyl radical
  • the cyclohexyl radical can also be used, which can also be substituted, for example by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
  • R 1 is an optionally substituted aryl radical
  • a phenyl or naphthyl radical is particularly suitable, which can be substituted by C 1 -C 4 -alkyl, such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C, -C 4 -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as Fluorine, chlorine and bromine, C 2 -C 5 alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • C 1 -C 4 -alkyl such as methyl, ethyl, propyl, Is
  • Y is an alkylene radical, it is primarily a C 2 to C 4 alkylene radical, in particular a ⁇ CH 2 ⁇ CH 2 bridge.
  • a C 2 to C 8 alkylene chain which is interrupted by oxygen or, in particular, nitrogen is also suitable, in particular the - (CH 2 ) 3 ⁇ NH ⁇ (CH 2 ) 3 bridge.
  • Y is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C 1 to C 4 alkyl or C 1 to C 4 alkoxy.
  • Possible substituents for the benzene rings A and B are: C 1 to C 4 alkyl, C 1 to C 4 alkoxy, halogen, such as fluorine, chlorine or bromine, and also the cyano or nitro group.
  • the copper complexes of the formula 1 are used in the present process, in which R 1 is hydrogen, Y is the ethylene or o-phenylene bridge and n is 2, the two sulfo groups being in the benzene rings A and B, and especially here the complexes in which the sulfo groups are each arranged in p-position to the oxygen.
  • the sulfo group-containing copper complexes of acylhydrazones of aromatic aldehydes and ketones are primarily complexes of the formula III wherein R 1 has the meaning given above under formula II, Q is oxygen or NH and n is zero or 1, and R 2 is hydrogen or an optionally substituted alkyl or aryl radical.
  • R 1 has the meaning given above under formula II
  • Q is oxygen or NH and n is zero or 1
  • R 2 is hydrogen or an optionally substituted alkyl or aryl radical.
  • the symbol Me in turn denotes copper.
  • R 2 is an alkyl radical, this can be branched. or be unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms.
  • Suitable substituents are halogen, such as fluorine, chlorine or bromine, C 1 to C 4 alkoxy, such as methoxy or ethoxy, further phenyl or carboxyl, C, to C 4 alkoxycarbonyl, such as. B. acetyl or hydroxy, mono- or dialkylamino.
  • R 2 is an optionally substituted aryl radical, a phenyl or naphthyl radical, which can be substituted by C 1-4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert .-butyl, C 1-4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen such as fluorine, chlorine and bromine, C 2 - 5 alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
  • C 1-4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and
  • Complexes of the formula III are preferably used in which R 1 is hydrogen and R 2 is hydrogen, methyl or in particular the phenyl radical and which contain copper as metal, especially the complexes in which the sulfo group in turn is in the p-position to the oxygen located.
  • Copper complexes of semicarbazones or thiosemicarbazones are primarily understood to mean complexes of the formula IV wherein R 1 has the meaning already given in connection with formula 1 and X represents oxygen or sulfur. Me denotes copper.
  • the ligands of which are derived from sulfosalicylaldehyde or the corresponding phenyl ketones, z. B. also those in which instead of mononuclear, multinuclear aromatic aldehydes and ketones, such as. B. 2-hydroxy-1-naphthaldehyde sulfonic acids were used to build up the ligand.
  • Suitable alkyl radicals are those with 1 to 4 carbon atoms.
  • Suitable cycloalkyl radicals are cyclohexyl and methylcyclohexyl radicals.
  • Suitable substituents in ring A are e.g. As methyl, methoxy or chlorine. However, this ring is preferably unsubstituted.
  • rings A and B can be substituted by C, -C 4 alkyl, cycloalkyl, C, -C 4 alkoxy, halogen or OH or also further fused rings can have.
  • rings A and B can also be heterocyclic rings.
  • the complex compounds mentioned which have sulfo groups, are preferably used as the alkali, especially sodium, or amine salt.
  • the preferred compounds for the process according to the invention are copper (II) chloride, sulfate, nitrate or acetate and mixtures of these salts with tartaric acid or salicylic acid.
  • the metal compounds are expediently applied from an aqueous bath in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of the leather.
  • the treatment with the metal compound can take place before, during or after the coloring.
  • an aftertreatment is preferably carried out in a fresh, aqueous liquor containing the metal compound and, if appropriate, acids and / or salts to adjust a certain pH.
  • the treatment takes place e.g. B. at a pH between 3 and 7 at 20 to 100 ° C for about 10 to 60 minutes.
  • the dyeings of the leather can be produced in a conventional manner with the usual anionic chromium or cobalt complex leather dyes.
  • the anionic chromium or cobalt complex dyes are, for example, salts of chromium or cobalt-containing mono-, dis- or polyazo dyes including the azomethine and formazan dyes as well as the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes.
  • the anionic character of these dyes can be caused by metal complex formation alone and by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups, alkylsulfone, sulfonamido or sulfonic acid groups.
  • the 1: 1 or 1: 2 metal complex dyes are preferred.
  • the 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. In particular, they contain chromium as metal.
  • the 1: 2 metal complex dyes contain a cobalt or in particular a chromium atom as the central atom. Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. The two dye molecules involved in the complex formation can be the same or different from one another.
  • the 1: 2 metal complex dyes can e.g. B. contain two azomethine molecules, an azo and an azomethine dye or two azo dyes, which dyes can be substituted with further arylazo and / or arylazoaryleno groups.
  • Aryl here means above all benzene or naphthalene residues, which may be substituted, e.g. B.
  • the azo or azomethine dye molecules can have water solubilizing groups such as. B. acid amide, alkylsulfonyl or the above acid groups. Preference is given to 1 2-cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or sulfonic acid groups.
  • Z independently of one another is nitrogen or a CH group
  • a and C independently of one another each a residue of the benzene or naphthalene series which contains a hydroxyl or carboxy group in the o-position to the azo or azomething group,
  • the coupling component in the o- or a-position to the azo group contains the group X, or independently the rest of an o-hydroxyaldehyde if Z is the CH group represents
  • X 1 independently of one another each represent oxygen or a group of the formula -NR S -, in which R s represents hydrogen or a C 1 -C 4 alkyl group,
  • Suitable dyes of the formula VII are both symmetrical and asymmetrical 1: 2 azo or 1: 2 azomethine complexes and 1: 2 complexes which contain an azo and an azomethine dye bonded to the metal.
  • dyes of the formula VII those in which X is oxygen are preferably used.
  • dyes of the formula VII have several groups Y, these can be the same or different. However, preferably all Y S0 represent 3 H groups.
  • dyes of the formula VII in which p is 1 and those in which m is 1 to 3, preferably 2, are preferably used.
  • radicals A and C can also be further substituted by groups Y, in particular with C i -C 4 alkyl or alkoxy, chlorine or nitro.
  • Suitable diazo components A and C are e.g. E.g .: anthranilic acid, 4- or 5-sulfoanthranilic acid, 2-amino-1-hydroxybenzene, 4-chloro- and 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5-nitro-2-amino- 1-hydroxybenzene, 4-chloro and 4-methyl-6-nitro-2-amino-1-hydroxybenzene, 6-chloro-4-nitro-2-amino-1-hydroxybenzene, 4-cyano-2-amino-1 -hydroxybenzoi, 4-methoxy-2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene, 4-chloro-5-nitro -2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-
  • a and C preferably each independently represent the radical of a 1-hydroxy-2-aminobenzene, which is optionally substituted one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl or methoxy, and in particular the radical a 1-hydroxy-2-aminobenzene which carries a nitro group in the 4- or 5-position or the remainder of a 1-hydroxy-2-aminobenzene which carries a nitro group in the 4-position and a sulfo group in the 6-position, or the Residue of a 1-hydroxy-2-aminobenzene, which carries a sulfo group in the 4-position and a nitro group in the 6-position.
  • the radicals B and D are preferably derived from the following groups of coupling components: phenols which are optionally substituted by low molecular weight alkyl or alkoxy, amino or acylamino and which are coupled in the o-position, where acylamino is C 1 -C 4 -alkanoylamino-, C 1 -C 4 -Alkylsulfonylamino-, C, -C 4 -Alkoxycarbonylamino-, Aroylamino- or Arylsulfonylaminoreste means resorcinol, m-phenyienediamine, optionally substituted in the 4-position by sulfo, chlorine, methyl or methoxy, naphthols, optionally with C 1 -C 4 -Alkyl or alkoxy, chlorine, amino, acylamino or sulfo are substituted, where acylamino has the same meaning as given above, 5-pyrazolones or 5-a
  • Acetoacetic acid amides, acetoacetic acid anilides and benzoylacetic acid anilides which may be substituted in the anilide core with chlorine, C, -C 4 alkyl or alkoxy or sulfo groups, or 6-hydroxy-3-cyano or 6-hydroxy-3-carbonamido-4- alkyl-2-pyridones, which are in the 1-position by optionally substituted C 1 -C 4 -alkyl, e.g. B.
  • Examples of such coupling components are: 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 1-naphthol, 1-acetylamino-7-naphthol, 1-propionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1- Carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-4,8-disulfonic acid, 1-naphthol-3,8-disulfonic acid, 2-n
  • B or D is preferably a 1- or 2-naphthol, optionally substituted with a sulfo group, m-phenylenediamine, resorcinol, p-alkyl (C 1 -C 4 ) phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, where the phenyl group in the latter two compounds can be substituted by C 1 -C 4 alkyl, C, -C 4 alkoxy, chlorine or sulfo.
  • B or D represents the residue of an o-hydroxyaldehyde, preferably an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde.
  • Suitable aldehydes are, for example: 2-hydroxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-benzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5- Butyl-2-hydroxybenzaldehyde, 5-chloro or 5-bromo-2-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde, 3-methyl-5 -chloro-2-hydroxybenzaldehyde, 5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-s
  • the dyes used are preferably symmetrical 1: 2 metal complexes with 2 sulfo groups, and dyes which are of the formula VIII are particularly preferred correspond to what
  • Z independently of one another is a CH group or preferably nitrogen
  • a 'and C' each represent the residue of a 1-hydroxy-2-aminobenzene which carries a nitro group in the 4- or 5-position, or the residue of a 1-hydroxy-2-aminobenzene which has a nitro group in the 4-position and bears a sulfo group in the 6 position or the remainder of a 1-hydroxy-2-aminobenzene which bears a nitro group in the 6 position and a sulfo group in the 4 position,
  • B 'and D' each independently represent the remainder of one of the following coupling components if Z is nitrogen: 1- or 2-naphthol optionally substituted with a sulfo group, m-phenylenediamine, resorcinol, p-alkyl (C 1 -C 6 ) - Phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, it being possible for the phenyl group in the latter two compounds to be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chlorine or sulfo, or, if Z is the CH group, the remainder of an o- Hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which can be substituted by phenylazo or sulfophenylazo,
  • Ka ⁇ means a cation.
  • Particularly preferred dyes correspond to formula IX wherein q is an integer from 0 to 2, Me 1 cobalt or chromium, Ka ⁇ is a cation and Y is methyl, ⁇ CONH 2 or -CO-NHR, where R is an alkyl group having 1 to 4 carbon atoms, or the formula X wherein X 2 is hydrogen, chlorine, methyl or methoxy, Me 1 cobalt or chromium and Ka ⁇ is a cation, or the formula XI in which q is an integer from 0 to 2 and Ka ⁇ is a cation,
  • X s is hydrogen, chlorine or nitro
  • Ka ⁇ is a cation and A, the rest of 1-hydroxynaphthalene or 2-hydroxynaphthalene.
  • the dyeings on leather with the dyes described above are improved in lightfastness, e.g. B. by evaluating the light fastness according to SNV No. 95.809 by approx. 1 to 2 notes.
  • the process according to the invention is particularly suitable for improving the light fastness of leather dyeings which have been obtained with a mixture of a yellow, a red and a blue dye of the type indicated above (i.e. with a trichrome).
  • tanning agent A formaldehyde condensation product of phenolic sulfonic acids
  • tanning agent B condensation product of a urea derivative with phenolic sulfonic acids
  • the leather is then rinsed and then neutralized in a fresh liquor of 200 parts of water, 2 parts of a neutralizing agent based on ammonium salts of aromatic sulfonic acids and aliphatic dicarboxylic acids and 2.5 parts of sodium bicarbonate at 30 ° for a total of 60 minutes.
  • the dyed leather is then post-treated for 30 minutes in a new post-treatment bath consisting of 200 parts of water at 50 ° and 3 parts of a mixture of copper acetate and salicylic acid in a molar ratio of 1: 2, adjusted to pH 4.5 with formic acid. It is then finished as usual and a section of the aftertreated dyeing together with a section of a similar but not aftertreated dyeing is exposed in a Xenotest 450 from the quartz lamp company Hanau (FRG) for 200 hours. The light fastness is assessed with the aid of an ISO blue scale, which is also exposed at the same time, with 8 colorations graded in light fastness. It can be seen that the coloring aftertreated with the copper compound has a significantly improved light fastness.
  • the retanned furniture leather is dyed in a manner analogous to that in Example 1, but using 0.7 part of the dye of the formula instead of the yellow dye 1: 2 cobalt complex can be used.
  • the yellow-brown color is then aftertreated with 3 parts of copper tartrate as described in Example 1 and then exposed in the Xenotest 450 to determine the light fastness.
  • the lightfastness of the aftertreated dye is significantly better than the lightfastness of the nontreated dye.
  • the black coloring used for this example is produced as follows:
  • a dyeing liquor is prepared from 200 parts of water at 50 °, 1 part of ammonia 24% and 1 part of the neutralizing agent mentioned above.
  • the neutralized leather is left to run for 10 minutes in this liquor. Then 0.9 parts of the black dye of the formula
  • alkylaminopolyglycol ether-type leveling agent 0.5 parts of alkylaminopolyglycol ether-type leveling agent are added.
  • a fatty compound mixture consisting of 2 parts of sulfited marine oil, 2 parts of sulfited fatty acid esters and animal fatty substances and 2 parts of a formulation based on sulfated hydrocarbons, fatty acids and their derivatives is added.
  • 4 parts of white tanning agent condensation product of a urea derivative with phenolic sulfonic acids
  • 1.25 parts of 85% formic acid are added.
  • the liquor is drained off and replaced by a new one consisting of 0.4 part of the black dye listed above and 200 parts of water at 50 °. It is dyed for another 20 minutes. Then 2 parts of fatliquor based on natural and modified oils and fats as well as n-alkyl derivatives and 1.5 parts of a grip improver consisting of a fatty acid-polyamide condensation product are added. After a further 20 minutes, the mixture is acidified with 1 part of 85% formic acid and then further stained for another 20 minutes.
  • the black leather dyeing is then treated as described in Example 1 in a fresh bath with 3 parts of the mixture of copper acetate and salicylic acid at 50 °. Then the leather is finished as usual and exposed in the Xenotest.
  • the lightfastness of the aftertreated dye is significantly better than the lightfastness of a nontreated dye.
  • 100 parts of non-intermediate-dried furniture leather are retanned for 90 minutes in a fleet consisting of 200 parts of water at 50 ° and 8 parts of a condensation product of formaldehyde and phenolic sulfonic acids.
  • the leather is then washed in 500 parts of water at 30 ° for 15 minutes and then in a liquor composed of 300 parts of water at 30 ° and 1.5 parts of sodium formate, to which 2.5 parts of sodium bicarbonate are also added after 10 minutes, 80 Neutralized for minutes. Following neutralization, there is again a 10-minute washing operation in 500 parts of 40 ° water.
  • the leather treated in this way is then dyed in a liquor consisting of 200 parts of water, 2 parts of 24% ammonia and 1.0 part of the yellow dye used in Example 1 for 30 minutes at 40 °. Then a coloring agent mixture consisting of 8 parts of a formulation of sulfited hydrocarbons, fatty acids and their derivatives and 4 parts of sulfited oil and, after a further 90 minutes, 3 parts of 85% formic acid are added to the dye liquor. The dyeing is then continued for 30 minutes at the same temperature.
  • the dyed and greased leather is then in a new aftertreatment bath adjusted to pH 5 with formic acid, consisting of 200 parts of water at 50 ° and 1.0 part of the copper compound of the formula
  • the aftertreatment is not carried out in a new bath as described above but immediately after dyeing and greasing in the dye bath itself, a similar improvement in light fastness is obtained.
  • the pH of the treatment liquor is approximately 4 and the temperature is 40 °, due to the dyeing process.
  • the copper compound of the above formula is made as follows:

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)

Claims (21)

1. Procédé pour l'amélioration de la solidité à la lumière d'un cuir teint à l'aide de colorants anioniques, à complexe de chrome ou de cobalt, caractérisé en ce qu'on traite le cuir, avant, pendant ou après la teinture, avec un composé du cuivre.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme composé du cuivre un sel de cuivre d'un acide inorganique ou organique, éventuellement en mélange avec un autre acide carboxylique organique.
3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise du chlorure, du sulfate, du nitrate, de l'acétate, du tartrate ou du salicylate de cuivre.
4. Procédé selon la revendication 2, caractérisé en ce qu'on utilise du chlorure, du sulfate, du nitrate ou de l'acétate de cuivre, en mélange avec un acide hydroxycarboxylique organique, en particulier l'acide tartrique ou l'acide salicylique.
5. Procédé selon la revendication 1, caractérisé en ce qu'on traite le cuir avec un complexe de cuivre, contenant éventuellement des groupes sulfo, de bisazométhines, d'acylhydrazones, de semicarbazones ou de thiosemicarbazones d'aldéhydes ou de cétones aromatiques.
6. Procédé selon la revendication 5, caractérisé en ce qu'on utilise, pour améliorer la solidité à la lumière, un complexe métallique de bisazométhine de formule Il
Figure imgb0047
dans laquelle R1 est un hydrogène ou un radical alkyle ou aryle éventuellement substitué, Y est un radical alkylène ou arylène éventuellement substitué et Me est le cuivre, n = 1 à 3, et les radicaux benzéniques A et B sont non substitués, ou portent comme substituants supplémentaires des radicaux alkyle en C1-C4, alcoxy en C,-C4, halogéno, cyano ou nitro.
7. Procédé selon la revendication 5, caractérisé en ce qu'on utilise pour améliorer la solidité à la lumière un complexe métallique d'acylhydrazone de formule III
Figure imgb0048
dans laquelle R1 et Me ont les significations données pour la formule II, R2 est un hydrogène ou un radical alkyle ou aryle éventuellement substitué, Q est un oxygène ou NH, et n vaut 0 ou 1.
8. Procédé selon la revendication 5, caractérisé en ce qu'on utilise pour améliorer la solidité à la lumière un complexe de formule IV
Figure imgb0049
dans laquelle R1 et Me ont les significations données pour la formule II, et X est l'oxygène ou le soufre.
9. Procédé selon la revendication 5, caractérisé en ce qu'on utilise pour améliorer la solidité à la lumière un complexe de cuivre de composés de formule V
Figure imgb0050
dans laquelle R3 est un hydrogène, le radical OH, un radical alkyle ou cycloalkyle, et où le noyau A est non substitué, ou porte comme substituants supplémentaires des radicaux sulfo, sulfonamido, méthyle, méthoxy ou chloro.
10. Procédé selon la revendication 5, caractérisé en ce qu'on utilise pour améliorer la solidité à la lumière un complexe de formule VI
Figure imgb0051
dans laquelle R4 est un radical alkyle en C1-C18 ou cycloalkyle, et les noyaux A et B peuvent être substitués par des radicaux alkyle en C1-C4, cycloalkyle, alcoxy en C1-C4, halogéno ou OH, ou peuvent aussi comporter des noyaux condensés supplémentaires, ou peuvent être remplacés par des noyaux hétérocycliques.
11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce qu'on utilise le composé métallique destiné à améliorer la solidité à la lumière en une quantité de 0,1 à 10% en poids, de préférence de 0,5 à 5 % en poids, par rapport au poids du cuir.
12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que le cuir, après la teinture, est traité par un sel de cuivre pour améliorer sa solidité à la lumière.
13. Procédé selon la revendication 1, caractérisé en ce qu'on utilise comme colorant anionique un colorant mono-, di- ou polyazoïque, azométhine, formazan, anthraquinone, xanthène, nitro, triphénylméthane, naphtoquinonimine ou phtalocyanine, contenant du chrome ou du cobalt.
14. Procédé selon la revendication 13, caractérisé en ce qu'on utilise un complexe de cobalt ou de chrome 1 : 2 d'un colorant azoïque ou azométhine.
15. Procédé selon la revendication 14, caractérisé en ce qu'on utilise un colorant de formule VII
Figure imgb0052
dans laquelle
les radicaux Z, indépendamment les uns des autres, sont chacun un atome d'azote ou un groupe CH.
A et C, indépendamment l'un de l'autre, sont chacun un résidu de la série du benzène ou du naphtalène, contenant en position ortho par rapport au groupe azoïque ou azométhine un groupe hydroxy ou carboxy,
B et D, indépendamment l'un de l'autre, représentent chacun le résidu d'un composant de copulation, quand Z est un atome d'azote, auquel cas le composant de copulation comporte le groupe X en position ortho ou a par rapport au groupe azoïque, ou bien encore, indépendamment l'un de l'autre, représentent chacun le résidu d'un ortho-hydroxyaldéhyde quand Z est le groupe CH,
les radicaux X1, indépendamment l'un de l'autre, sont chacun un oxygène ou un groupe de formule -NR5-, dans laquelle R5 est un hydrogène bu un groupe alkyle en C,-C4,
Me1 représente le chrome ou le cobalt,
Y représente le groupe S03H, COOH, P03H2 ou S02-V, ou V est un radical alkyle en C1-C4 éventuellement substitué par un halogène ou un groupe vinyle amino, N-mono- ou N, N-dialkylamino,
p vaut 1 ou 2, et
m est un nombre entier de 0 à 6.
16. Procédé selon la revendication 15, caractérisé en ce qu'on utilise un colorant de formule VIII
Figure imgb0053
dans laquelle
les radicaux Z, indépendamment l'un de l'autre, représentent chacun un groupe CH ou de préférence un azote,
A' et C', indépendamment l'un de l'autre, représentent chacun le résidu d'un 1-hydroxy-2-aminoben- zène, lequel porte en position 4 ou 5 un groupe nitro, ou encore le résidu d'un 1-hydroxy-2-aminobenzène, lequel porte en position 4 un groupe nitro et en position 6 un groupe sulfo, ou encore le résidu d'un 1-hydroxy-2-aminobenzène, lequel porte en position 6 un groupe nitro et en position 4 un groupe sulfo,
B' et D', indépendamment l'un de l'autre, représentent chacun le résidu de l'un des composants de copulation suivants, quand Z est l'azote : 1- ou 2-naphtol, éventuellement substitué par un groupe sulfo, m-phénylènediamine, résorcinol, p-(alkyle en C1-C6)-phénol, 1-phényl-3-méthyl-5-pyrazolone, acétoacé- tanilide, le groupe phényle, dans les deux derniers composés ci-dessus, pouvant être substitués par un radical alkyle en C,-C4, alcoxy en C,-C4, chloro ou sulfo, ou encore, quand Z est le groupe CH, le résidu d'un o-hydroxybenzaldéhyde ou d'un o-hydroxynaphtaldéhyde, qui peuvent être substitués par des radicaux phénylazo ou sulfophénylazo,
Me1 est le cobalt ou le chrome, et
Ka- représente un cation.
17. Procédé selon la revendication 14, caractérisé en ce qu'on utilise l'un des colorants ayant les formules suivantes (Voir Formules page 24)
Figure imgb0054
où q est un nombre entier de 0 à 2, Me1 est le cobalt ou le chrome, Ka+ est un cation et Y est un radical méthyle, -CONH2 ou ―CO―NHR, R représentant un groupe alkyle ayant de 1 à 4 atomes de carbone, ou la formule X
Figure imgb0055
dans laquelle X2 est un hydrogène ou un radical chloro, méthyle ou méthoxy, Me1 est le cobalt ou le chrome et Ka⊕ est un cation, ou la formule XI
Figure imgb0056
dans laquelle q est un nombre entier de 0 à 2 et Ka- est un cation, ou la formule XII
Figure imgb0057
dans laquelle
A1 est le résidu du 1-hydroxynaphtalène ou du 2-hydroxynaphtalène,
R6 est un hydrogène ou le radical chloro ou méthyle,
R7 est un hydrogène ou le radical nitro ou chloro, et
Ka+ est un cation, et
des substituants X3, X4 et X5, l'un est un groupe S03 et les deux autres représentent chacun un hydrogène, X5 étant un hydrogène quand R6 est le chlore et R7 un hydrogène, ou la formule XIII
Figure imgb0058
dans laquelle X6 est un hydrogène ou un radical chloro ou nitro, et Ka+ est un cation, et où le groupe sulfo, dans le colorant pyrazolone, est disposé dans le noyau A ou B, et le groupe nitro dans le noyau A de ce colorant, en position 4, 5 ou 6 du 1-hydroxy-2-aminobenzène, ou la formule XIV (Voir Formule XIV page 26)
Figure imgb0059
dans laquelle X6 est un hydrogène ou le radical chloro ou nitro, Ka+ est un cation et A1 est le résidu du 1-hydroxynaphtalène ou du 2-hydroxynaphtalène.
EP85810512A 1984-11-09 1985-11-04 Procédé d'amélioration de la solidité à la lumière de cuirs teints Expired EP0181836B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH538984 1984-11-09
CH5389/84 1984-11-09

Publications (2)

Publication Number Publication Date
EP0181836A1 EP0181836A1 (fr) 1986-05-21
EP0181836B1 true EP0181836B1 (fr) 1988-12-21

Family

ID=4292743

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85810512A Expired EP0181836B1 (fr) 1984-11-09 1985-11-04 Procédé d'amélioration de la solidité à la lumière de cuirs teints

Country Status (10)

Country Link
US (1) US4818246A (fr)
EP (1) EP0181836B1 (fr)
JP (1) JPS61119785A (fr)
BR (1) BR8505624A (fr)
CA (1) CA1281508C (fr)
DE (1) DE3566915D1 (fr)
ES (1) ES8802331A1 (fr)
MX (1) MX168486B (fr)
PT (1) PT81460B (fr)
ZA (1) ZA858604B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3622864A1 (de) * 1986-07-08 1988-01-21 Bayer Ag Verfahren zur verbesserung der lichtechtheit von polyamidfaerbungen
IT1224686B (it) * 1987-08-08 1990-10-18 Sandoz Ag Procedimento per la tintura o lastampa di pelli
EP1602779A1 (fr) * 2004-06-04 2005-12-07 Clariant International Ltd. Complexes de cuivre en tant que photostabilisants pour textiles
CN116875080B (zh) * 2023-07-07 2024-03-01 约克夏(浙江)染化有限公司 酱红色酸性染料组合物、酱红色酸性染料及其制备方法和用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0183078A1 (fr) * 1984-11-09 1986-06-04 Hoechst Aktiengesellschaft Procédé d'amélioration de la solidité à la lumière de cuirs teints

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US837105A (en) * 1905-01-21 1906-11-27 Francis J Oakes Process for dyeing leather.
US1716218A (en) * 1922-11-25 1929-06-04 Escaich Auguste Dyeing process
DE417209C (de) * 1924-05-28 1925-08-08 Kalle & Co Akt Ges Verfahren zum Faerben von Leder
US1536725A (en) * 1924-11-22 1925-05-05 Anilin Fabrikation Ag Process for dyeing furs, skins, hairs, feathers, or the like
US2090396A (en) * 1936-12-15 1937-08-17 Edward S Chapin Fixing composition and method of aftertreating dyed materials
CH261948A (de) * 1947-07-09 1949-06-15 Ciba Geigy Färbepräparat.
US2741535A (en) * 1952-11-15 1956-04-10 Gen Aniline & Film Corp Aftertreatment of dyeings and compositions therefor
DE1079248B (de) * 1954-06-19 1960-04-07 Cassella Farbwerke Mainkur Ag Verfahren zur Herstellung von substantiven Tris- und Polyazofarbstoffen
US2908543A (en) * 1956-06-29 1959-10-13 Gen Aniline & Film Corp Aftertreatment of leather dyeings
US3075821A (en) * 1960-08-18 1963-01-29 Shulton Inc Process of dyeing keratinous fibers
CH478951A (de) * 1967-07-07 1969-06-13 Ciba Geigy Verfahren zum Färben von Wolle mit 1:2-Metallkompexfarbstoffen
US4116952A (en) * 1975-05-14 1978-09-26 Ciba-Geigy Corporation Unsymmetrical azo - azo methine 1:2 chromium complex dyes
SU614142A1 (ru) * 1976-09-30 1978-07-05 Всесоюзный Научно-Исследовательский Институт Меховой Промышленности Состав дл обработки кожевой ткани меховых шкур
JPS54128085A (en) * 1978-03-29 1979-10-04 Aida Eng Ltd Blank tank-out device for zigzag punch
PT70999A (en) * 1979-03-28 1980-04-01 Ciba Geigy Ag Process for the preparation of a 1:2 metal complex dye
US4253843A (en) * 1979-04-25 1981-03-03 Crompton & Knowles Corporation Method for improving the light fastness of nylon dyeings using copper phosphate
DE3041153A1 (de) * 1980-10-31 1982-06-16 Bayer Ag, 5090 Leverkusen Verfahren zur verbesserung der lichtechtheit von polyamidfaerbungen
DE3247051A1 (de) * 1982-12-20 1984-06-20 Bayer Ag, 5090 Leverkusen Verfahren zur verbesserung der lichtechtheit von polyamidfaerbungen
EP0162811B1 (fr) * 1984-05-22 1989-10-11 Ciba-Geigy Ag Procédé de stabilisation photochimique de matériaux textiles contenant des fibres en polyamide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0183078A1 (fr) * 1984-11-09 1986-06-04 Hoechst Aktiengesellschaft Procédé d'amélioration de la solidité à la lumière de cuirs teints

Also Published As

Publication number Publication date
EP0181836A1 (fr) 1986-05-21
DE3566915D1 (en) 1989-01-26
MX168486B (es) 1993-05-27
ES8802331A1 (es) 1988-05-01
JPS61119785A (ja) 1986-06-06
PT81460A (en) 1985-12-01
PT81460B (pt) 1987-12-30
ZA858604B (en) 1986-06-25
BR8505624A (pt) 1986-08-12
ES549314A0 (es) 1988-05-01
US4818246A (en) 1989-04-04
CA1281508C (fr) 1991-03-19

Similar Documents

Publication Publication Date Title
EP0061670B1 (fr) Procédé de teinture de cuir et de peaux avec des mélanges de colorants
DE2520526C2 (de) Neue Chromkomplexfarbstoffe, deren Herstellung und Verwendung
EP0181836B1 (fr) Procédé d'amélioration de la solidité à la lumière de cuirs teints
EP0005207B1 (fr) Colorants de chrome bis-1:2 disazo-bisazométhiniques, leur préparation et leur utilisation pour la teinture du cuir
EP0110825B1 (fr) Colorants à complexe de chrome 1:2 asymétrique contenant un composé azoique et un composé azométhinique
EP0082117B1 (fr) Complexes de chrome de colorants polyazoiques
EP0009466B1 (fr) Colorants 1 : 2-bis-complexes de chrome de composés polyazo- ou disazo-azométhiniques, leur préparation et leur utilisation
EP0231147B1 (fr) Procédé de teinture de cuir en trois couleurs
EP0648816B1 (fr) Teinture du cuir avec des mélanges de colorants
EP0079858B1 (fr) Colorants azoiques, complexes de métaux de ces colorants, leur préparation et leur utilisation
EP0148121B1 (fr) Colorants 1:2 complexes de chrome asymétriques
EP0048693B1 (fr) Colorants disazoiques, leurs complexes métalliques, leur préparation et leur utilisation
EP0019851B1 (fr) Colorants complexes de chrome 1:2 de la série azométhine et/ou azoique, leur préparation et utilisation pour la teinture et l'impression de matériaux en polyamide ou cellulose
EP0148120B1 (fr) Colorants 1:2 complexes de chrome asymétriques
EP0150676B1 (fr) Colorants 1:2 complexes de chrome
EP0100297B1 (fr) Bi-complexes de chrome 1:2 de colorants disazoiques, leur préparation et leur utilisation
DE3703361A1 (de) Unsymmetrische 1:2-chromkomplexfarbstoffe
EP0037377B1 (fr) Colorants azoiques métallisés, leur préparation et leur utilisation
EP0151369B1 (fr) Complexes de chrome 1:2 asymétriques contenant un composé azoîque et un composé azométhinique
CH664763A5 (de) Unsymmetrische chromkomplexfarbstoffe.
EP0087715B1 (fr) Complexes de colorants métallifères dépourvus de groupes amino et sulfonamide
DE3703343A1 (de) Unsymmetrische 1:2-chromkomplexfarbstoffe
DE2457590A1 (de) Neue metallkomplexe, deren herstellung und verwendung
DE3512078A1 (de) Chromkomplexfarbstoffe, deren herstellung und verwendung
DE3516421A1 (de) Chromkomplexfarbstoffe, deren herstellung und verwendung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB IT LI

17P Request for examination filed

Effective date: 19851106

17Q First examination report despatched

Effective date: 19870722

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REF Corresponds to:

Ref document number: 3566915

Country of ref document: DE

Date of ref document: 19890126

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19921214

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930924

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19931007

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19931018

Year of fee payment: 9

ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19931130

Ref country code: CH

Effective date: 19931130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19941104

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST