Claims
- 1. Process for improving the light-fastness of leather dyed with an anionic cobalt or chrome complex dye, which process comprises treating the leather before, during or after dyeing with a composition consisting essentially of a light-fastness improving amount of a compound of copper selected from the group consisting of (1) a copper salt of an inorganic or organic acid, (2) a copper salt of an inorganic or organic acid in admixture with a further organic carboxylic acid, (3) an acylhydrazone copper complex of the formula ##STR22## wherein R.sub.1 and R.sub.2 are each, independent of the other, hydrogen or an unsubstituted or substituted alkyl or aryl radical, Me is copper, Q is oxygen or NH and n is zero or 1, (4) a copper complex of the formula ##STR23## wherein R.sub.1 and Me are as defined above, and X is oxygen or sulfur, and (5) a copper complex of a compound of the formula ##STR24## wherein R.sub.3 is hydrogen, OH, alkyl or cycloalkyl, and wherein the ring A is unsubstituted or is further substituted by sulfo or sulfonamido.
- 2. Process according to claim 1, wherein the copper compound is selected from the group consisting of a copper salt of an inorganic or organic acid, and a copper salt of an inorganic or organic acid in admixture with a further organic carboxylic acid.
- 3. Process according to claim 2, wherein the copper compound is selected from the group consisting of copper chloride, copper sulfate, copper nitrate, copper acetate, copper tartrate and copper salicylate.
- 4. Process according to claim 2, where the copper compound is selected from the group consisting of copper chloride, copper sulfate, copper nitrate or copper acetate in admixture with an organic hydroxy carboxylic acid.
- 5. Process according to claim 1, wherein the compound of copper is an acylhydrazone copper complex of the formula ##STR25## wherein R.sub.1, R.sub.2, Me, Q and n are as defined in claim 1.
- 6. Process according to claim 1, wherein the compound of copper is a copper complex of the formula ##STR26## wherein R.sub.1, Me and X are as defined in claim 1.
- 7. Process according to claim 1, wherein the compound of copper is a copper complex of a compound of the formula ##STR27## wherein R.sub.3 and the ring A are as defined in claim 1.
- 8. Process according to claim 1, wherein the compound of copper is used in an amount of 0.1 to 10% by weight relative to the weight of the leather.
- 9. Process according to claim 8, wherein the amount employed is 0.5 to 5% by weight relative to the weight of the leather.
- 10. Process according to claim 1, wherein the leather, after dyeing, is treated with a salt of copper for improving the fastness to light.
- 11. Process according to claim 1, wherein the anionic dye is a cobalt or chrome-containing mono-, di- or polyazo, azomethine, formazan, anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine or phthalocyanine dye.
- 12. Process according to claim 1, wherein the anionic dye is a 1:2-cobalt or 1:2-chrome complex of an azo or azomethine dye.
- 13. Process according to claim 1, wherein the anionic dye is a dye of the formula ##STR28## wherein Z independently of one another are each nitrogen or a CH group,
- A and C independently of one another are each a radical of the benzene or naphthalene series, which radical contains in the o-position with respect to the azo or azomethine group a hydroxyl or carboxyl group,
- B and D independently of one another are each the radical of a coupling component when Z is nitrogen, the coupling component containing in the o- or .alpha.-position with respect to the azo group the group X, or independently of one another are each the radical of an o-hydroxyaldehyde when Z is the CH group,
- X.sub.1 independently of one another are each oxygen or a group of the formula --NR.sub.5 --, in which R.sub.5 is hydrogen or a C.sub.1 -C.sub.4 -alkyl group,
- Me.sub.1 is chromium or cobalt,
- Y is the SO.sub.3 H, COOH, PO.sub.3 H.sub.2 or SO.sub.2 -V group, in which V is C.sub.1 -C.sub.4 -alkyl, unsubstituted or substituted by halogen, vinyl, amino, N-mono- or N,N-dialkylamino,
- p is 1 or 2, and
- m is an integer from 0 to 6.
- 14. Process according to claim 13, wherein the anionic dye is a dye of the formula ##STR29## wherein Z independently of one another are each a CH group or nitrogen,
- A' and C' are each the radical of a 1-hydroxy-2-aminobenzene which carries in the 4- or 5- position a nitro group, or the radical of a 1-hydroxy-2-aminobenzene which carries in the 4-position a nitro group and in the 6-position a sulfo group, or the radical of a 1-hydroxy-2-aminobenzene which carries in the 6-position a nitro group and in the 4-position a sulfo group,
- B' and D' independently of one another are each the radical of one of the following coupling components, when Z is nitrogen: 1- or 2-naphthol which is unsubstituted or substituted by a sulfo group, m-phenylenediamine, resorcinol, p-alkyl(C.sub.1 -C.sub.6)-phenol, 1-phenyl-3-methyl-5-pyrazolone or aceto-acetic acid anilide, and the phenyl group in the two last-mentioned compounds can be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine or sulfo, or when Z is the CH group: the radical of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which can each be substituted by phenylazo or sulfophenylazo,
- Me.sub.1 is cobalt or chromium, and
- Ka.sup..sym. is a cation.
- 15. Process according to claim 12, wherein the anionic dye is one of the dyes of the following formulae: ##STR30## wherein q is an integer from O to 2, Me.sub.1 is cobalt or chromium, Ka.sup..sym. is a cation, and Y is methyl, --CONH.sub.2 or --CO--NHR, in which R is an alkyl group having 1 to 4 C atoms; ##STR31## or of the formula ##STR32## wherein X.sub.2 is hydrogen, chlorine, methyl or methoxy, Me.sub.1 is cobalt or chromium, and Ka.sup..sym. is a cation; or of the formula ##STR33## wherein q is an integer from 0 to 2, and Ka.sup..sym. is a cation; or of the formula ##STR34## wherein A.sub.1 is the radical of 1-hydroxynaphthalene or 2-hydroxynaphthalene,
- R.sub.6 is hydrogen, chlorine or methyl,
- R.sub.7 is hydrogen, nitro or chlorine, and
- Ka.sup..sym. is a cation, and of the substituents X.sub.3, X.sub.4 and X.sub.5, one is an SO.sub.3 group and the two others are hydrogen, X.sub.5 being hydrogen when R.sub.6 is chlorine and R.sub.7 hydrogen; or of the formula ##STR35## wherein X.sub.6 is hydrogen, chlorine or nitro, and Ka.sup..sym. is a cation, and wherein the sulfo group in the pyrazolone dye in the ring A or B and the nitro group in the ring A of this dye are arranged in the 4-, 5- or 6-position of the 1-hydroxy-2-aminobenzene; or of the formula ##STR36## wherein X.sub.6 is hydrogen, chlorine or nitro, Ka.sup..sym. is a cation, and A.sub.1 is the radical of 1-hydroxynaphthalene or 2-hydroxynaphthalene.
- 16. A process according to claim 4, wherein the organic hydroxy carboxylic acid is tartaric acid or salicylic acid.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 5389/84 |
Nov 1984 |
CHX |
|
Parent Case Info
This application is a continuation of now abandoned application Ser. No. 796,446, filed Nov. 8, 1985, abandoned.
The present invention relates to a process for improving the light-fastness of leather dyed with anionic dyes, which process comprises treating the leather, before, during or after dyeing, with a compound of nickel, cobalt or copper.
Suitable compounds of nickel, cobalt or copper are for example salts of inorganic or organic acids, and also compounds which contain the stated metals in complexed form. Also suitable are mixtures of these compounds.
Preferably used are compounds of copper, for example the following: salts of inorganic acids, such as copper chloride, copper sulfate, copper phosphate or copper nitrate; salts of organic acids, for example copper acetate, copper tartrate or copper salicylate; and there can also be used mixtures of various copper salts, or mixtures of one copper salt and a further acid, for example mixtures of copper acetate and salicylic acid.
Suitable also are copper salts of salicylic acid derivatives, or mixtures of the above-mentioned copper salts of inorganic or organic acids with salicylic acid derivatives. Applicable salicylic acid derivatives are for example 2-hydroxy-5-sulfobenzoic acid or compounds of the formula I ##STR1## wherein W.sub.1 and W.sub.2 independently of one another are each hydrogen, C.sub.1 -C.sub.4 -alkyl, hydroxy-C.sub.1 -C.sub.4 -alkyl, or phenyl unsubstituted or substituted by sulfo or carboxyl.
Suitable complex compounds are for example copper, cobalt or nickel complexes of bisazomethines, acylhydrazones, semicarbazones and thiosemicarbazones of aromatic aldehydes or ketones, which complexes can optionally contain sulfo groups.
By bisazomethines of aromatic aldehydes and ketones are meant here Schiff bases of aliphatic or aromatic diamines, the aldehydes and ketones having in the o-position with respect to the formyl or acyl radical an OH group. The bond with the metal atom occurs by way of these two OH groups and the two nitrogen atoms in the bisazomethine moiety. It is accordingly a case here of tetradentate ligands. The ligands preferably contain one or more sulfo groups, which are in the aldehyde or ketone moiety and/or in the bisazomethine bridge.
There are used for example bisazomethine metal complexes of the formula II ##STR2## wherein R.sub.1 is hydrogen or an unsubstituted or substituted alkyl or aryl radical, Y is an unsubstituted or substituted alkylene or arylene radical, Me is copper, cobalt or nickel, and n is 1 to 3. The benzene rings A and B can likewise be substituted, independently namely of one another, or can also contain further fused-on rings. There can moreover be in place of the benzene rings A and B also heterocyclic rings.
When R.sub.1 is an unsubstituted or substituted alkyl radical, it is preferably a C.sub.1 -C.sub.8 -alkyl radical, in particular a C.sub.1 -C.sub.4 -alkyl radical, which can be either branched-chain or straight-chain, and can be substituted by halogen, such as fluorine, chlorine or bromine, or by C.sub.1 -C.sub.4 -alkyoxy, such as methoxy or ethoxy, by a phenyl or carboxyl radical, by C.sub.1 -C.sub.4 -alkoxycarbonyl, such as by the acetyl radical, or by hydroxyl or a mono- or dialkylated amino group. It can furthermore be the cyclohexyl radical, which can likewise be substituted, for example by C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy.
When R.sub.1 is an unsubstituted or substituted aryl radical, it is especially by a phenyl or naphthyl radical whcih can be substituted by C.sub.1 -C.sub.4 -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C.sub.1 -C.sub.4 -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C.sub.2 -C.sub.5 -alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.
When Y is an alkylene radical, it is particularly a C.sub.2 -C.sub.4 -alkylene radical, especially a --CH.sub.2 --CH.sub.2 -- bridge. Also applicable however is a C.sub.2 -C.sub.8 -alkylene chain interrupted by oxygen and in particular by nitrogen, above all the --(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.3 -- bridge.
When Y is an arylene radical, it is primarily a phenylene radical, particularly an o-phenylene radical. This can likewise be substituted by C.sub.1 -C.sub.4 -alkyl, or by C.sub.1 -C.sub.4 -alkoxy.
Substituents for the benzene rings A and B are: C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, or halogen, such as fluorine, chlorine or bromine, also the cyano or nitro group.
There are used in particular in the present process the copper complexes of the formula I wherein R.sub.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 the complexes in which the sulfo groups are in each each arranged in the p-position with respect to the oxygen atom.
In the case of the copper, cobalt and nickel complexes of acylhydrazones of aromatic aldehydes and ketones, which complexes contain sulfo groups, they are in the first place complexes of the formula III ##STR3## wherein R.sub.1 has the meaning defined in the foregoing under the formula II, Q is oxygen or NH, and n is zero or 1, and R.sub.2 is hydrogen or an unsubstituted or substituted alkyl or aryl radical. The symbol Me again denotes copper, cobalt or nickel.
When R.sub.2 is an alkyl radical, this can be branched-chain or straight-chain, and has a chain-length of preferably 1 to 8, especially 1 to 4, C atoms. Applicable substituents are halogen, such as fluorine, chlorine or bromine, C.sub.1 -C.sub.4 -alkoxy, such as methoxy or ethoxy, also phenyl or carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, for example acetyl or hydroxyl, or mono- or dialkylamino.
When R.sub.2 is an unsubstituted or substituted aryl radical, it is in particular a phenyl or naphthyl radical which can be substituted by C.sub.1 -C.sub.4 -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C.sub.1 -C.sub.4 -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine C.sub.2 -C.sub.5 -alkanoylamino, such as acetylamino, propionylamino and butyrylamino, nitro, cyano or sulfo, or a mono- or dialkylated amino group.
There are preferably used complexes of the formula III in which R.sub.1 is hydrogen, and R.sub.2 is hydrogen, methyl or especially the phenyl radical, and in which the metal contained is copper, above all the complexes wherein the sulfo group again is in the p-position with respect to the oxygen atom.
By copper, cobalt and nickel complexes of semicarbazones or thiosemicarbazones in the present process are meant in the first place complexes of the formula IV ##STR4## wherein R.sub.1 has the meaning already defined in connection with the formula I, and X is oxygen or sulfur. Me denotes copper, cobalt or nickel.
Besides the transition-metal complexes of the formulae III and IV, of which the ligands are derived from sulfosalicylaldehyde or from the corresponding phenylketones, there are applicable for example also those in the case of which there have been used for the build-up of the ligands, instead of mononuclear, polynuclear aromatic aldehydes and ketones, such as 2-hydroxy-1-naphthaldehydesulfonic acids. Reference is moreover made to the fact that the fourth coordination position of the metal atom in the complex of the formulae III and IV is occupied by for example water as neutral ligand.
Also applicable in the process according to the invention are the copper, cobalt or nickel complexes of compounds of the formula V ##STR5## wherein R.sub.3 is H, OH, alkyl or cycloalkyl, and wherein the ring A can optionally contain further substituents, for example sulfo or sulfonamide groups.
Suitable alkyl radicals are those having 1 to 4 C atoms. Cycloalkyl radicals which are suitable are cyclohexyl and methylcyclohexyl radicals. And suitable substituents in the ring A are for example methyl, methoxy or chlorine. This ring is however preferably unsubstituted.
Also suitable for the process according to the invention are compounds of the formula IV ##STR6## wherein R.sub.4 is C.sub.1 -C.sub.18 -alkyl or cycloalkyl, and the rings A and B can be substituted by C.sub.1 -C.sub.4 -alkyl, cycloalkyl, C.sub.1 -C.sub.4 -alkoxy, halogen or OH, or can also contain further fused-on rings. Furthermore, there can be in place of the rings A and B also heterocyclic rings.
The stated complex compounds which contain sulfo groups are preferably used as alkali metal salt, in particular sodium salt, or as amine salt.
The preferred compounds for the process according to the invention are: copper(II) chloride, -sulfate, -nitrate or -acetate, and also mixtures of these salts with tartaric acid or salicylic acid.
The metal compounds are advantageously applied from an aqueous bath, and in an amount of 0.1 to 10 % by weight, preferably 0.5 to 5% by weight, relative to the weight of the leather.
The treatment with the metal compound can be carried out before, during or after dyeing. With the use of salts of nickel, cobalt or copper, there is preferably performed after the dyeing and rinsing of the leather an aftertreatment in a fresh aqueous liquor containing the metal compound as well as optionally acids and/or salts to obtain a specific pH value.
The treatment is performed for example at a pH value of between 3 and 7 at 20.degree. to 100.degree. C. for about 10 to 60 minutes.
The dyeings of the leather can be produced in the customary manner with the usual anionic leather dyes.
In the case of the anionic dyes, they are for example salts of heavy-metal-containing or metal-free 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 brought about by metal-complex formation alone and/or by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid ester groups 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 contain one or two sulfonic acid groups. They contain as metal a heavy-metal atom, for example copper, nickel, iron and especially chromium.
The 1:2 metal complex dyes contain as central atom a heavy-metal atom, for example an iron, cobalt or in particular a chromium atom. With the central atom are linked two complex-forming components, of which at least one is a dye molecule; preferably however both are dye molecules. The two dye molecules concerned in the complex formation can be identical or different from one another. The 1:2 metal complex dyes can contain for example two azomethine molecules, an azo and an azomethine due or two azo dyes; and these dyes can be substituted by further arylazo and/or arylazoaryleneazo groups. By aryl are meant here particularly benzene or naphthalene radicals, which are unsubstituted or substituted by for example: nitro, sulfo, halogen, alkyl or alkoxy. The azo or azomethine dye molecules can contain water-solubilising groups, for example acid amide, alkylsulfonyl or the above-mentioned acid groups. The 1:2 cobalt or 1:2 chrome complexes of monoazo dyes which contain the acid amide, alkylsulfonyl or sulfonic acid groups are preferred.
The cationic dyes concerned are metal-free or metal-containing dyes. These dyes can belong to various classes of dyes. They are in particular salts, for example chlorides, sulfates, onium chlorides or metal halides, for example zinc chloride salts or azo dyes, such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine or azomethine dyes, ketonimine, cyanine, azine, oxazine or thiazine dyes.
Particularly suitable dyes correspond to the formula VII ##STR7## wherein Z independently of one another are each nitrogen or a CH group;
Suitable dyes of the formula VII are both symmetrical and asymmetrical 1:2 azo or 1:2 azomethine complexes, and also 1:2 complexes which contain an azo and an azomethine dye bound to the metal.
Of the dyes of the formula VII, there are preferably used those in which X is oxygen.
When dyes of the formula VII contain several groups Y, these can be identical or different. Preferably, however, all groups Y are SO.sub.3 H groups.
Further dyes of the formula VII preferably used are those in which p is 1, as well as those in which m is 1 to 3, preferably 2.
The radicals A and C can in addition be further substituted by groups Y, especially by C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, chlorine or nitro.
Suitable diazo components A and C are for example: 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-hydroxybenzene, 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-hydroxybenzene, 2-amino-1-hydroxybenzene-4- or -5-sulfonic acid, 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid, 5-nitro- or 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 6-chloro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino- 1-hydroxybenzene-4,6-disulfonic acid, 1-amino-2-hydroxybenzene-4-sulfonic acid amide, 4-methylsulfonyl-2-amino-1-hydroxybenzene, 4-(2'-, 3'- or 4'-sulfophenylazo)-2-amino-1-hydroxybenzene, 4-(3'-sulfonamidophenylazo)-2-amino-1-hydroxybenzene, 4-(4'-phenylazophenylazo)-2-amino-1-1-hydroxybenzene, 1-amino-2-hydroxy-5-sulfonic acid anthranilide and 1-amino-2-hydroxy-5-(2'sulfo)-sulfonic acid anilide.
Preferably, A and C independently of one another are in each case the radical of a 1-hydroxy-2-aminobenzene, which is unsubstituted or mono- or polysubstituted by identical or different substituents from the group comprising nitro, sulfo, chlorine, methyl or methoxy; and especially the radical of a 1-hydroxy-2-aminobenzene, which carries in the 4- or 5-position a nitro group; or the radical of a 1-hydroxy-2-aminobenzene, which carries in the 4-position a nitro group and in the 6-position a sulfo group; or the radical of a 1-hydroxy-2-aminobenzene, which carries in the 4-position a sulfo group and in the 6-position a nitro group.
The radicals B and D are derived preferably from the following groups of coupling components: phenols which couple in the o-position and which are unsubstituted or substituted by low-molecular alkyl or alkoxy, amino or acylamino, where acylamino is C.sub.1 -C.sub.4 -alkanoylamino, C.sub.1 -C.sub.4 -alkylsulfonylamino, C.sub.1 -C.sub.4 -alkoxycarbonylamino, aroylamino or arylsulfonylamino radicals, resorcinol, m-phenylenediamine, unsubstituted or substituted in the 4-position by sulfo, chlorine, methyl or methoxy, naphthols, which are unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl or alkoxy, chlorine, amino, acylamino or sulfo, where acylamino has the same meaning as that given in the foregoing, 5-pyrazolones or 5-aminopyrazoles, which contain in the 1-position a phenyl or naphthyl radical unsubstituted or substituted by chlorine, nitro, C.sub.1 -C.sub.4 -alkyl or alkoxy groups or sulfo groups, and which contain in the 3-position a C.sub.1 -C.sub.4 -alkyl group, especially a methyl group; acetoacetic acid amides, acetoacetic acid anilides and benzoylacetic acid anilides, which can be substituted in the anilide nucleus by chlorine, C.sub.1 -C.sub.4 -alkyl or alkoxy or sulfo groups, or 6 -hydroxy-3-cyano- or 6-hydroxy-3-carbonamido-4-alkyl-2-pyridones, which are substituted in the 1-position by unsubstituted or substituted C.sub.1 -C.sub.4 -alkyl, for example methyl, isopropyl, .beta.-hydroxyethyl, .beta.-aminoethyl or .gamma.-isopropoxypropyl, or by phenyl, and which can carry in the 4-position a C.sub.1 -C.sub.4 -alkyl group, particularly methyl.
Examples of such coupling components are: 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 1-naphthol, 1-acetyl-amino-7-naphthol, 1-propionylamino-7-naphthol, 1-carbo-methoxyamino-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 aid, 1-naphthol-3,8-disulfonic acid, 2-naphthol-3,6-disulfonic acid, 4-methyl-1-naphthol, 4-methoxy-1-naphthol, 4-acetyl-1-naphthol, 5,8-dichloro-1-naphthol, 5-chloro-1-naphthol, 2-naphthylamine, 2-naphthylamino-1-sulfonic acid, 1-naphthylamino-4- or -5-sulfonic acid, 2-aminoaphthalene-6- or -5-sulfonic acid, 1-phenyl-3-methylpyrazol-5-one, 1-phenyl-5-pyrazolone-3-carboxylic acid amide, 1-(2'-,3-, or 4'-methylphenyl)-3-methylpyrazol-5-one, 1-( 2',3'- or 4'-sulfophenyl)-3-methylpyrazol-5-one, 1-(2'-chloro-5-sulfophenyl)-3-methylpyrzaol-5-one, 1-(2- or 4-methoxyphenyl-3-methylpyrazol-5-one, 1-(2-, 3- or 4-chlorophenyl)-3 1-(2'-, 3'- or 4'-nitrophenyl)-3-methylpyrazol-5-one, 1-(2'-,5'- or 3',4'-dichlorophenyl)-3-methylpyrazol-5-one, 1-(2',5'-dichloro-4'-sulfophenyl)-3-methylpyrazol-5-one, 1-(2',3'or 4'-sulfophenyl)-3-methyl-5-aminopyrazole, 1-(2'-chloro-5'-sulfophenyl)-3-methyl-5-aminopyrazole, acetoacetanilide, acetoacetanilide-2-, -3- or -4-sulfonic acid, acetoacet-o-anisidine, acetoacet-o-toluidide, acetoacet-o-chloroanilide, acetoacet-m-xylidide, tetralol, 4-methylphenol, 3-dialkyl-aminophenol, especially 3-dimethylamino- and 3-diethyl-aminophenol, 4-butylphenol, 4-amylphenol, particularly 4-t-amylphenol, 2-isopropyl-4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methylphenol, 2 -ethoxycarbonylamino-4-methylphenol and 3,4-dimethylphenol, resorcinol, 1-ethyl-3-cyano-4-methyl-6-hydroxypyridone, 1-methyl-3-cyano-4-methyl-6-hydroxypyridone and 1-phenyl-3-carbonamido-4-methyl-6-hydroxypyridone.
The coupling components B and/or D are preferably a 1- or 2-naphthol which is unsubstituted or substituted by a sulfo group, m-phenylenediamine, resorcinol, p-alkyl-(C.sub.1 -C.sub.4)-phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetic acid anilide, and the phenyl group in the two last-mentioned compounds can be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine or sulfo.
When Z is the --CH- group, B and/or D are the radical 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-hydroxybenzaldehyde, 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'-sulfophenylazo)-2-hydroxybenzaldehyde, 5-(6'-sulfonaphthyl-1'azo)-2-hydroxbenzaldehyde and 5-(4"-sulfo-4'-phenylazo)-phenylazo-2-hydroxybenzaldehyde.
The employed dyes are preferably in each case symmetrical 1:2 metal complexes having 2 sulfo groups, and particularly preferred are the dyes corresponding to the formula VIII ##STR8## wherein Z independently of one another are each a CH group or preferably nitrogen,
Particularly preferred dyes correspond to the formula IX ##STR9## wherein q is an integer from 0 to 2, Me.sub.1 is cobalt or chromium, Ka.sup..sym. is a cation, and Y is methyl, --CONH.sub.2 or --CO--NHR, in which R is an alkyl group having 1 to 4 C atoms; or to the formula X ##STR10## wherein X.sub.2 is hydrogen, chlorine, methyl or methoxy, Me.sub.1 is cobalt or chromium, and Ka.sup..sym. is a cation; or to the formula XI ##STR11## wherein q is an integer from 0 to 2, and Ka.sup..sym. is a cation; or to the formula XII ##STR12## wherein A.sub.1 is the radical of 1-hydroxynaphthalene or 2-hydroxynaphthalene,
As a result of treatment with the metal compounds, the dyeings on leather produced with the dyes described in the foregoing are improved with respect to their fastness to light; for example, by about 1 or 2 ratings on the basis of the evaluation of the fastness to light according to SNV No. 95,809.
The process according to the present invention is particularly suitable for improving the light-fastness of leather dyeings obtained with a mixture of a yellow, of a red and of a blue dye of the type defined in the foregoing (that is to say, with a trichromic effect).
The following Examples serve to further illustrate the invention. The term `parts` denotes parts by weight, and percentages are per cent by weight.
US Referenced Citations (13)
Foreign Referenced Citations (6)
| Number |
Date |
Country |
| 0018775 |
Nov 1980 |
EPX |
| 417209 |
Aug 1925 |
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Apr 1960 |
DEX |
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Mar 1979 |
JPX |
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Sep 1949 |
CHX |
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Jun 1978 |
SUX |
Non-Patent Literature Citations (5)
| Entry |
| Venkataraman, The Chemistry of Synthetic Dyes vol. VIII, pp. 37, 38, 39 Academic Pres 1978. |
| Encyclopedia of Chemical Technology vol. 8, p. 331, Wiley New York 1979. |
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Continuations (1)
|
Number |
Date |
Country |
| Parent |
796446 |
Nov 1985 |
|
Patent Grant
4818246
