Claims
- 1. An azo dye (Z) which contains at least one azo group and at least one chromophoric radical wherein at least one chromophoric radical comprises a radical of a dye (S) and which is obtainable by reacting at least one azo group-containing diazonium compound (Dz) with at least one dye (S) and/or by coupling the diazonium compound of at least one diazotizable dye (S), optionally over at least one middle component (Mk), to at least one coupling component (B) and optionally subjecting the product of said reacting or said coupling to a further modification reaction, each said dye (S) being an optionally modified, optionally (pre)reduced sulfur dye, or a mixture of such azo dyes (Z).
- 2. A metal complex of at least one metallizable azo dye (Z) according to claim 1, or a mixture thereof.
- 3. A process for dyeing a substrate dyeable with sulphur dyes or azo dyes which comprises dyeing said substrate with a dye according to claim 2.
- 4. A process according to claim 3 wherein the substrate is leather.
- 5. A process for producing an azo dye (Z) containing at least one azo group and at least one chromophoric radical wherein at least one chromophoric radical comprises a radical of an optionally modified, optionally (pre)reduced sulphur dye (S) or a mixture thereof, which process comprises
- a) coupling the diazonium compound of at least one optionally modified, optionally (pre)reduced sulphur dye (S.sub.1), optionally over at least one middle component (Mk), to at least one coupling component (B) and optionally further modifying the resulting product, or
- b) reacting at least one azo-group-containing diazonium compound (Dz) with at least one optionally modified, optionally (pre)reduced sulphur dye (S.sub.2) and optionally further modifying the resulting product.
- 6. A process according to claim 5 wherein the optionally (pre)reduced sulphur dye (S) is a dye of the general formula (I)
- D--.paren open-st.(XH).sub.y (I)
- in which X signifies --O--, --S-- or --NH--,
- D is the y-valent radical of the dye (S)
- and
- y signifies a figure from 1 to the maximum functionality of the optionally (pre)reduced sulphur dye of formula (I), and
- a) the diazonium compound of the dye (S.sub.1) is a product of diazotizing a dye of said general formula (I) having at least one diazotizable amino group, or
- b) the dye (S.sub.2) contains at least one reactive group capable of reacting with the diazonium compound (Dz).
- 7. A process according to claim 6 wherein the diazotizable amino group is a primary amino group and the dye (S.sub.2) contains at least one substituent capable of reacting with a diazonium compound to form a (thio)ether bridge with cleavage of the nitrogen of the diazonium compound.
- 8. A process according to claim 7 wherein the dye (S.sub.2) contains at least one oxalate or thiolate group which reacts with the diazonium compound (Dz).
- 9. A process according to claim 14 wherein the dye (S) is selected from the group consisting of C.I. Leuco Sulphur Blacks 1, 2, 11 and 18, C.I. Leuco Sulphur Reds 10 and 18, C.I. Leuco Sulphur Blues 3, 7, 11, 13, 15 and 20, C.I. Reduced Vat Blue 43, C.I. Leuco Sulphur Greens 2, 16, 35 and 36, C.I. Leuco Sulphur Browns 1, 3, 10, 21, 26, 31, 37, 52, 95 and 96, C.I. Leuco Sulphur Orange 1, C.I. Leuco Sulphur Yellows 9 and 22 and the corresponding non-reduced or non-leuco dyes.
- 10. An azo dye (Z) obtainable by the process of claim 6.
- 11. An azo dye (Z) obtainable by the process of claim 5.
- 12. A process for dyeing a substrate dyeable with sulphur dyes or azo dyes which comprises dyeing said substrate with an azo dye (Z) according to claim 11.
- 13. A process according to claim 12 wherein the substrate is leather.
- 14. A hydrosoluble azo dye (Z) obtainable by the process of claim 5.
- 15. A process according to claim 6 wherein the dye (S) is a (pre)reduced sulphur dye.
- 16. A process according to claim 6 wherein, when the dye (S.sub.1) or (S.sub.2) is a modified dye, the modification comprises the introduction of a hydrophilizing group.
- 17. A process according to claim 16 wherein the modification comprises introduction of a substituent containing a sulpho, carboxy or amide group by alkylation and/or arylation.
- 18. A process according to claim 5 which comprises coupling the diazonium compound of a diazo component comprising at least one optionally modified, optionally (pre)reduced diazotizable amino group-containing sulphur dye (S.sub.1).
- 19. An azo dye (Z), or mixture thereof, obtainable by the process of claim 18 wherein at least one is an amino group-containing, optionally modified, optionally (pre)reduced sulphur dye (S.sub.1).
- 20. A process according to claim 5 wherein the resulting product from a) or b) is further modified by reaction with a reactant (E).
- 21. A hydrosoluble azo dye (Z) obtainable by the process of claim 20.
- 22. A process according to claim 6 wherein the dyes (S.sub.1) and (S.sub.2) are modified with a hydrophilizing substituent.
- 23. A hydrosoluble azo dye (Z) obtainable by the process of claim 22.
- 24. A process according to claim 6 wherein the azo group-containing diazonium compound (Dz) is selected from the group consisting of
- 1. the product of coupling the diazo compound of a diazo component (A) to one middle component (Mk) or sequentially to more middle components (Mk) and finally diazotizing the terminal amino group;
- 2. the product of coupling the diazo compound of a diazo component (A), optionally over at least one middle component (Mk), to a bis-coupling component (Bb) and then coupling selectively thereto one diazonium group of a component (Aa) which is a bis-diazotized bis-diazo component or a component containing one diazotizable amino group and one substituent that can be converted afterwards to an amino group;
- 3. the product of coupling a diazotized bis-diazo component (Aa) at one side to a coupling component (B), optionally over at least one middle component (Mk), converting any protected amino group or nitro group to primary amino which is diazotized and optionally coupling the resulting diazonium compound to a middle component (Mk) or sequentially to more middle components (Mk), the terminal amino group of which is then diazotized; or
- 4. diazotized sulphur dye (S.sub.1),
- wherein (A) is a diazotizable amine of the benzene or naphthalene series, (B) is the radical of a coupling component H--B of the benzene, naphthalene, heterocyclic or open-chain methylene-active series, (Bb) is an aminonaphthole containing one or two sulpho groups, resorcine, metaaminophenol or metaphenylenediamine and (Mk) is an aminonaphthalene or aminonaphthole, optionally containing one or two sulpho groups, or a bicyclic compound of the formula (mk.sub.1) ##STR27## in which L.sub.2 is a group --Q.sub.1 --L, R.sub.y is a homocyclic or heterocyclic radical capable of a coupling reaction,
- Q.sub.1 is --CO--, --SO.sub.2 -- or the direct bond and
- L is --O--, --NH-- or the direct bond.
- 25. An azo dye (Z) obtainable by the process of claim 24.
- 26. A process according to claim 24 wherein (A) contains at least one sulpho group, carboxy group, carbarnoyl group or sulphamoyl group, the coupling compound H--B contains at least one substituent that activates the compound H-B for coupling and which is an aromatically bound or enolic, optionally etherified hydroxy group or an optionally substituted amino group.
- 27. A process according to claim 24, wherein (A) is a compound of the formula ##STR28## wherein R.sub.1 signifies hydrogen, nitril, trifluoromethyl, nitro, --SO.sub.3 M, --SO.sub.2 NR.sub.4 R.sub.5, --COOM or --CONR.sub.4 R.sub.5,
- R.sub.2 signifies hydrogen, nitro, --SO.sub.3 M, --SO.sub.2 NR.sub.4 R.sub.5, trifluoromethyl, nitril, --COOM, --CONR.sub.4 R.sub.5, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, halogen or C.sub.1-2 -mercaptoalkyl,
- R.sub.3 signifies hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, halogen, C.sub.1-2 -mercaptoalkyl, --NH--Ac, --NH--CO--O--CH.sub.3 or a radical of formula ##STR29## R.sub.4 signifies hydrogen, C.sub.1-4 -alkyl, C.sub.1-3 -alkylene-R' or C.sub.2-3 -hydroxyalkyl,
- R.sub.5 signifies hydrogen, C.sub.1-4 -alkyl, C.sub.1-3 -alkylene-R', C.sub.2-3 -hydroxyalkyl, benzyl or a radical of formula ##STR30## R' signifies nitril, carbamoyl or --COOM, R.sub.6 signifies hydrogen, nitro or --SO.sub.3 M.
- R.sub.7 signifies hydrogen, methyl, chlorine, nitro, --COOM or --SO.sub.3 M,
- R.sub.8 signifies hydrogen, halogen, nitro, --SO.sub.3 M, --SO.sub.2 NR.sub.4 R.sub.5, methylsulphonyl, C.sub.1-4 -alkyl or --NH--Ac,
- R.sub.9 signifies hydrogen, halogen, nitro, --SO.sub.3 M, --SO.sub.2 NR.sub.4 R.sub.5, methylsulphonyl, C.sub.1-4 -alkyl or --NH--Ac,
- R.sub.10 signifies nitro, --SO.sub.3 M or --SO.sub.2 NR.sub.4 R.sub.5,
- R.sub.11 signifies hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, hydroxy, --NH.sub.2 or --NH--Ac,
- R.sub.12 signifies the radical of a diazocomponent deriving from the diazotization of an amine of formula (a.sub.1), (a.sub.2), (a.sub.3), (a.sub.4) or (a.sub.7),
- Ac signifies an aliphatic acyl group,
- M signifies hydrogen or an alkali metal cation,
- p signifies 0 or 1,
- q signifies 0, 1 or 2,
- r signifies 0 or 1
- and
- s signifies 0 or 1;
- (Aa) is an amine of formula (a.sub.1), (a.sub.2), (a.sub.3) or (a.sub.7) containing a nitro group, or of formula (a.sub.1), (a.sub.2), (a.sub.5) or (a.sub.7) containing a group --NH--Ac, or of formula (Aa.sub.1) ##STR31## wherein L.sub.1 signifies a heteroatomic bridging member or a methylene bridge,
- R.sub.x signifies primary amino, acetylamino or nitro,
- and
- z signifies 0 or 1; and
- H--B is a compound of the formula ##STR32## wherein R.sub.13 signifies hydrogen, --OR.sub.17 or --NHR.sub.17,
- R.sub.14 signifies --OR.sub.17 or --NHR.sub.17,
- R.sub.15 signifies hydrogen, --SO.sub.3 M, --SO.sub.2 NR.sub.4 R.sub.5, --COOM or --CONR.sub.4 R.sub.5,
- R.sub.16 signifies hydrogen, --SO.sub.3 M, --SO.sub.2 N.sub.4 R.sub.5, --COOM or --CONR.sub.4 R.sub.5,
- R.sub.17 signifies hydrogen, C.sub.1-4 -alkyl, Ac' or a radical of formula ##STR33## Ac' signifies the acyl radical of an aliphatic carboxylic acid, Q.sub.1 signifies --CO--, --SO.sub.2- or the direct bond,
- R.sub.18 signifies hydrogen, methyl, --NH--Ac, --COOM or --NO.sub.2 or, if in formula (b') Q.sub.1 signifies --CO-- or --SO.sub.2-, also --NH.sub.2,
- R.sub.19 signifies --OH or --NH.sub.2,
- R.sub.20 signifies hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, --OH, --NR"R'" or --NH--Ac,
- R.sub.21 signifies hydrogen, C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy,
- R" and R'", independently, signify hydrogen, C.sub.1-2 -alkyl or C.sub.2-3,hydroxy-alkyl,
- R.sub.22 signifies hydrogen, sulphonaphthyl or a radical of formula ##STR34## W.sub.1 signifies hydrogen, halogen, methyl, methoxy or --COOM, W.sub.2 signifies hydrogen, halogen, trifluoromethyl, nitril, nitro, --COOM, --SO.sub.3 M or --SO.sub.2 NR.sub.4 R.sub.5,
- R.sub.23 signifies C.sub.1-4 -alkyl, phenyl, --COOM, --CONR.sub.4 R.sub.5, --COOCH.sub.3 or --COOC.sub.2 H.sub.5,
- R.sub.24 signifies .dbd.O or .dbd.NH,
- R.sub.25 signifies hydrogen, unsubstituted amino, phenylamino, sulphonaphthyl, open-chain C.sub.1-8 -alkyl, C.sub.6-9 -cycloalkyl, carboxy-(C.sub.1-4 -alkyl), C.sub.2-4 -alkyl substituted with hydroxy, methoxy, ethoxy or a sulpho group in one of the positions .beta. to .omega., or a radical of formula (b").
- R.sub.26 signifies hydrogen, nitril, acetyl, --COOM, carbamoyl, --SO.sub.3 M, pyridinio or 2-methyl-pyridinio,
- R.sub.27 signifies hydrogen, hydroxy, methyl, carboxy, phenyl, sulphomethyl or carbamoyl,
- R.sub.28 signifies hydroxy, primary amino, nitrilamino, thiol or a radical of formula ##STR35## R.sub.29 signifies hydroxy or primary amino, R.sub.30 signifies hydroxy or primary amino,
- R.sub.31 signifies hydrogen, methyl, chlorine , chloromethyl or chloroacetyl,
- L signifies --O--, --NH-- or the direct bond,
- R.sub.32 signifies naphthyl, sulphonaphthyl, disulphonaphthyl or a radical of formula (b"),
- R.sub.33 signifies C.sub.1-4 -alkyl,
- W.sub.3 signifies hydrogen, hydroxy, C.sub.1-4 -alkoxy, --NHAc, --NH.sub.2, di-(C.sub.1-4 alkyl)-amino or carboxymethylamino
- and
- W.sub.4 signifies hydrogen or methyl,
- and, where in formula (b.sub.4) R.sub.26 stands for pyridinio or orthomethylpyridinio, any carboxy or sulpho group present in ib molecule may be in the form of the anion --SO.sub.3.sup.- or --COO.sup.- to form the counterion in the form of the inner salt.
- 28. A process according to claim 27 wherein the sulphur dye (S) is a dye (S.sub.1) which has at least one diazotizable amino group and which has been modified by reaction of at least one thiol or hydroxy group of the dye (S.sub.1) with a reactant (E) or it is a dye (S.sub.2) which has been modified by reaction of an amino group or at least thiol or hydroxy group of the dye (S.sub.2) with a reactant (E), wherein said reactant (E) is a reactant (E.sub.1) of the formula ##STR36## wherein Hal signifies halogen,
- Q.sub.2 signifies --CO-- or --SO.sub.2-,
- "alkylene" in formula (e.sub.1) is a C.sub.1-3 -alkylene bridge,
- G signifies butylene-1,3 or -1,4, naphthylene-1,8 or tolylene-.alpha., 2,
- G.sub.1 signifies an optionally further substituted benzene radical,
- G.sub.2 signifies an optionally further substituted benzene or naphthalene radical,
- G.sub.3 signifies an optionally further substituted benzene radical,
- m1 signifies 1 or 2,
- k signifies 1 to 3,
- R.sub.a signifies hydrogen, methyl or --COOM,
- R.sub.b signifies hydrogen or, if R.sub.a signifies hydrogen, also methyl,
- M signifies hydrogen or an alkali metal cation,
- E signifies C.sub.1-4 -alkyl, benzyl, --(C.sub.1-4 -alkylene)--Q.sub.2 --NR.sup.iv R.sup.v, ##STR37## R.sup.iv signifies hydrogen, C.sub.1-4 -alkyl or phenyl, R.sup.v signifies hydrogen or C.sub.1-4 -alkyl,
- m2 signifies 0, 1 or 2,
- R.sub.f signifies --CONR.sup.iv R.sup.v,
- W signifies a leaving group or atom,
- Y signifies an aliphatic or araliphatic bridging group and
- Z signifies a primary, secondary or tertiary amino group of basic character or its protonated derivative or a quaternary ammonium group or an optionally quaternized oligamine radical.
- 29. An azo dye (Z) obtainable by the process of claim 28.
- 30. A process according to claim 6 which comprises producing an azo dye (Z) containing at least one azo group and at least one chromophoric radical wherein at least one chromophoric radical comprises a radical of an optionally modified, optionally (pre)reduced sulphur dye (S) or mixture thereof, by
- a) coupling the diazonium compound of at least one optionally modified, optionally (pre)reduced sulphur dye (S.sub.1), optionally over at least one middle component (Mk), to at least one coupling component (B) and further modifying the resulting product by reacting it with a reactant (E), or
- b) reacting at least one azo group-containing diazonium compound (Dz) with at least one optionally modified, optionally (pre)reduced sulphur dye (S.sub.2) and further modifying the resulting product by reacting it with a reactant (E),
- wherein said reactant (E) is a reactant (E.sub.1) providing substituents which do not contain any azo groups and are of anionic, cationic, basic or non-ionic character or a reactant (E.sub.2) which is suitable for modifying said resulting product.
- 31. A process according to claim 30 wherein the reactant (E.sub.1) is as defined in claim 28 and reactant (E.sub.2) is a complex-forming metal compound, a reducing agent or an oxidizing agent.
- 32. An azo dye (Z) obtainable by the process of claim 30.
- 33. A process according to claim 30 wherein the reactant (E.sub.1) is selected from the group consisting of
- i) reactants (E.sub.11) providing anionic substituents and selected from the group consisting of
- a) compounds of formula
- W--Y--(Z.sub.1).sub.m (II)
- in which
- W signifies a reactive substituent,
- Y signifies an aromatic, araliphatic or aliphatic bridging group,
- Z.sub.1 signifies --COOM or --SO.sub.3 M,
- m signifies the number of substituents Z.sub.1 linked to each group Y and is at least
- and M signifies hydrogen or an alkali metal cation,
- and functional derivatives thereof,
- b) a combination of a low molecular aliphatic aldehyde and alkali metal sulphite or bisulphite or SO.sub.2 in the presence of alkali metal hydroxide and
- c) ethylenically unsaturated carboxylic or sulphonic acids or their salts,
- ii) reactants (E.sub.12) which provide non-ionic substituents and are of the formula
- W--E (e.sub.10)
- in which
- W is as defined above and
- E signifies a non-ionic substituent,
- and iii) reactants (E.sub.13) which provide basic or cationic substituents and are of the formula
- W--Y--Z.sub.2 (III)
- in which
- W and Y are as defined above and
- Z.sub.2 signifies a primary, secondary or tertiary group of basic character or its protonated derivative or a quaternary amnonium group or an optionally quaterttzed oligamine radical
- and the reactant (E.sub.2) is a complex-forming metal compound, a reducing agent or an oxidizing agent.
- 34. An azo dye (Z) obtainable by the process of claim 33.
- 35. A process according to claim 6 wherein the sulphur dye (S) is a dye (S.sub.1) which has at least one diazotizable amino group and which has been modified by reaction of at least one thiol or hydroxy group of the dye (S.sub.1) with a reactant (E) or it is a dye (S.sub.2) which has been modified by reaction of an amino group or at least one thiol or hydroxy group of the dye (S.sub.2) with a reactant (E) and wherein said reactant (E) is selected from the group consisting of reactants (E.sub.1) providing substituents which do not contain any azo groups and are of anionic, cationic or non-ionic character.
- 36. An azo dye (Z) obtainable by the process of claim 35.
- 37. A process according to claim 35 wherein the reactant (E) is selected from the group consisting of
- i) reactants (E.sub.11 ) providing anionic substituents and selected from the group consisting of
- a) compounds of formula
- W--Y--(Z.sub.1).sub.m (II)
- in which
- W signifies a reactive substituent,
- Y signifies an aromatic, araliphatic or aliphatic bridging group,
- Z.sub.1 signifies --COOM or --SO.sub.3 M,
- m signifies the number of substituent Z.sub.1 linked to each group Y and is at least 1
- and M signifies hydrogen or an alkali metal cation,
- and functional derivatives thereof,
- b) a combination of a low molecular aliphatic aldehyde and alkali metal sulphite or bisulphite or SO.sub.2 in the presence of alkali metal hydroxide and
- c) ethylenically unsaturated carboxylic or sulphonic acids or their salts,
- ii) reactants (E.sub.12) which provide non-ionic substituents and are of the formula
- W--E (e.sub.10)
- in which
- W is as defined above and
- E signifies a non-ionic substituent,
- and iii) reactants (E.sub.13) which provide basic or cationic substituents and are of the formula
- W--Y--Z.sub.2 (III)
- in which
- W and Y are as defined above and
- Z.sub.2 signifies a primary, secondary or tertiary group of basic character or its protonated derivative or a quaternary ammonium group or an optionally quaternized oligamine radical.
- 38. An azo dye (Z), or mixture thereof, obtainable by reacting at least one azo group-containing diazonium compound (Dz) with at least one optionally modified, optionally (pre)reduced sulphur dye (S.sub.2) according to the process of claim 10.
- 39. A process according to claim 12, wherein watersoluble dyes (Z) are employed for the dyeing of substrates dyeable with watersoluble dyes.
- 40. An azo dye (Z) obtainable by the process of claim 19.
- 41. A process which comprises diazotizing an optionally modified, optionally (pre)reduced sulphur dye which contains at least one aromatically linked --NH.sub.2 group to form a diazo compound and coupling said diazo compound to a compound capable of a coupling reaction.
Priority Claims (1)
Number |
Date |
Country |
Kind |
9504870 |
Mar 1995 |
GBX |
|
Parent Case Info
This a continuation division of application Ser. No. 08/613,573, filed Mar. 11, 1996 now abandoned.
US Referenced Citations (4)
Foreign Referenced Citations (6)
Number |
Date |
Country |
573831 |
May 1944 |
GBX |
2201165 |
Aug 1988 |
GBX |
2228490 |
Aug 1990 |
GBX |
2255981 |
Nov 1992 |
GBX |
2273103 |
Jun 1994 |
GBX |
WO 9307221 |
Apr 1993 |
WOX |
Non-Patent Literature Citations (3)
Entry |
Chem. Abstr. vol. 81, No. 26, Osman et al., 171322h, Dec. 30, 1974. |
Rath and Wagner, "Palette", Pt. l, 19-22, 1959. |
Rath and Wagner, "Palette", Pt. II, 23-28, 1959. |
Continuations (1)
|
Number |
Date |
Country |
Parent |
613573 |
Mar 1996 |
|