Claims
- 1. A process for preparing a mixed aluminium-heavy metal dyestuff complex in which the heavy metal is present in an amount of 10-98 mole % and the aluminium is present in an amount of 2 to 90 mole %, said mole % based on 1 mole of said mixed aluminum-heavy metal dyestuff complex, wherein said process comprises
- i) reacting the metal free dyestuff with less than a stoichiometric amount of a heavy metal compound to form a mixture, said stoichiometric amount calculated based on the metal-free dyestuff or all the metal present in the complex, and
- ii) adding to said mixture an aluminium compound in an amount sufficient to produce a stoichiometric excess of metal (calculated on all the metal present in the dyestuff complex) to form the mixed aluminium-heavy metal complex.
- 2. A process according to claim 1 in which the heavy metal compound is selected from the group consisting of a cobalt compound, a copper compound, a chromium compound and nickel compound.
- 3. A process according to claim 2 in which
- a) the chromium compound is an alkali dichromate;
- b) the cobalt compound is selected from a cobalt chloride and a cobalt sulphate;
- c) the nickel and copper compounds are selected from nickel and copper halides, sulphates and acetates; and
- d) the aluminium compound is an aluminium sulphate.
- 4. A process according to claim 1 in which the amount of heavy metal compound for a 1:1 dye:metal complex is 10 to 98 mole % per mole of metal-free dyestuff and for a 2:1 dye:metal complex is 10 to 98 mole % per 2 moles of metal-free dyestuff.
- 5. A process according to claim 1 in which the mount of aluminium compound added to the mixture for a 1:1 dye:metal complex is 10 to 120 mole % per mole of metal-free dyestuff and for a 2:1 dye:metal complex is 10 to 120 mole % per two moles of metal-free dyestuff.
- 6. A process according to claim 1 in which in the metal-free dyestuff is selected from the group consisting of water-soluble dyestuffs, solvent-soluble dyestuffs and insoluble dyestuffs and pigments.
- 7. A process according to claim 6 in which the metal-free dyestuff is a solvent soluble, water-insoluble dyestuff.
- 8. A process according to claim 1 in which the complex is a 2:1 azo dye: mixed aluminium-heavy metal dyestuff complex.
- 9. A process according to claim 1 in which the complex is one of formula I and I' ##STR21## in which each group R.sub.1, together with the two carbon atoms independently to which R.sub.1 is attached, form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxy, aminocarbonyl, monoC.sub.1-4 alkylaminocarbonyl, di-(C.sub.1-4 alkyl)aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, di-(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, C.sub.1-3 alkoxycarbonyl, aminosulphonyl, monoC.sub.1-4 alkylaminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl and 4,6-bis-(bis(2',4'-dimethylphenyl) triazinyl-2;
- both groups R.sub.2, independently are selected from C.sub.3-20 alkyl, C.sub.1-4 alkoxy-C.sub.2-8 alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxy, aminocarbonyl, monoC.sub.1-4 alkylaminocarbonyl, di(C.sub.1-4 alkyl)aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, di(C.sub.2-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, C.sub.1-3 alkoxycarbonyl, aminosulphonyl, monoC.sub.1-4 alkylaminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl and di(C.sub.2-4 alkoxy- C.sub.2-4 alkyl)aminosulphonyl;
- group R.sub.A together with the two carbon atoms independently to which R.sub.A is attached form a phenyl or naphthyl radical which is unsubstituted or further substituted by one or two groups independently selected from hydrogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, C.sub.1-4 alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, monoC.sub.1-4 alkyl-aminocarbonyl, di(C.sub.1-4 alkyl)aminocarbonyl, mono (C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, phenylaminocarbonyl, aminosulphonyl, monoC.sub.1-4 alkylaminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl) amino- sulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl and phenylaminosulphonyl;
- Me is 10 to 98 mole % of a metal selected from chromium, copper, cobalt and nickel and 20 to 90 mole % aluminium; and
- X.sup.+ is a cation.
- 10. A process according to claim 1 in which the complex is one of formula Ia, Ib or Ic ##STR22## in which each R.sub.3 ' independently is selected from nitro or --SO.sub.3 NHR.sub.7, where R.sub.7 is selected from hydrogen, C.sub.1-2 alkyl, C.sub.1-2 alkoxy-C.sub.2-3 alkyl and phenyl;
- each R.sub.6 is hydrogen, halogen, C.sub.1-2 alkyl or C.sub.1-2 alkoxy;
- each R.sub.2 ' is 2-ethylhexyl or phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo and methyl or one to two substituents selected from chloro, bromo and methyl, ethyl, C.sub.1-4 alkoxy and acetyl;
- Me is 25 to 95 mole % Cr or Co and 5 to 75 mole % Al;
- X.sup.2+ is selected from sodium, potassium, ammonium, C.sub.1-10 alkylammonium, 4-amino-2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions and
- each R.sub.10 and each R.sub.11 independently are selected from the group consisting of hydrogen, halogen, hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, acetyl, benzoyl and 4,6-bis(2',4'-dimethylphenyl) triazinyl-2; or
- collectively, R.sub.10 and R.sub.11 together with the phenyl ring to which they are both attached form a naphthyl group, preferably attached in the 5' and 6' position, said naphthyl group being substituted in the 4- or 5-position with R.sub.3 '.
- 11. A process according to claim 2 wherein said heavy metal is chromium.
- 12. A process according to claim 11 wherein said complex comprises from 80 to 98 mole % of chromium and 2 to 20 mole % of aluminium.
- 13. A process according to claim 12 wherein an organic reducing compound is added to the mixture in i) prior to adding the aluminium compound.
- 14. A mixed aluminium-heavy metal dyestuff complex of the formulae I and I' ##STR23## wherein each R.sub.1 together with the two carbon atoms independently to which R.sub.1 is attached form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from the group consisting of hydroxy, c.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxy, aminocarbonyl, mono(C.sub.1-4 alkyl) aminocarbonyl, di(C.sub.1-4 alkyl)-aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminocarbonyl, C.sub.1-3 alkoxycarbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminosulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, and 4,6-bis(2',4'-dimethylphenyl)triazinyl-2; both groups R.sub.2, independently are selected from the group consisting of C.sub.3-20 alkyl, C.sub.1-4 alkoxy-C.sub.2-8 alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from the group consisting of hydroxy, C.sub.1-4 alkyl, C.sub.1-4 -alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxyl, aminocarbonyl, mono(C.sub.1-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkyl)aminocarbonyl, mono- (C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, C.sub.1-3 alkoxycarbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)-aminosulphonyl, di(C.sub.1-4 alkyl)-aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, and di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminosulphonyl; group R.sub.A together with the two carbon atoms independently to which R.sub.A i attached form a phenyl or naphthyl radical which is unsubstituted or further substituted by one or two groups independently selected from the group consisting of hydrogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, C.sub.1-4 alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, mono(C.sub.1-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkyl)-aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminocarbonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminocarbonyl, phenylaminocarbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkoxyC.sub.2-4 alkyl)aminosulphonyl and phenylaminosulphonyl;
- Me is 10 to 98 mole % of a metal selected from the group consisting of chromium, copper, cobalt and nickel and 20 to 90 mole % aluminium; and
- X.sup.+ is a cation selected from the group consisting of mono(C.sub.1-12 alkyl)-ammonium, di(C.sub.1-12 alkyl)ammonium, tri(C.sub.1-12 alkyl)ammonium, 4-amino-2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions.
- 15. A mixed aluminium-heavy metal dyestuff complex of the formulae Ia, Ib and Ic ##STR24## wherein each R.sub.3 ' is independently selected from the group consisting of nitro and --SO.sub.3 NHR.sub.7 ; R.sub.7 is selected from the group consisting of hydrogen, C.sub.1-2 alkyl, C.sub.2-3 alkoxy-C.sub.2-3 alkyl and phenyl; each R.sub.6 is selected from the group consisting of hydrogen, halogen, C.sub.1-2 alkyl and C.sub.1-2 alkoxy;
- each R.sub.2 ' is selected from the group consisting of 2-ethylhexyl and phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo, and methyl or one or two substituents selected from chloro, bromo, methyl, ethyl, C.sub.1-4 alkoxy and acetyl; Me is 25 to 90 mole % chromium or cobalt and 5 to 75 mole % aluminium; X.sup.2+ is selected from the group consisting of C.sub.1-10 alkylammonium, 4-amino-2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions; and
- each R.sub.10 and each R.sub.11 independently are selected from the group consisting of hydrogen, halogen, hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, acetyl, benzoyl, and 4,6-bis(2',4'-dimethylphenyl)triazinyl-2, or collectively R.sub.10 and R.sub.11 together with the phenyl ring to which they are attached form a naphthyl group, preferably attached in the 5' and 6' position, said naphthyl group being substituted in the 4- or 5-position with R.sub.3 '.
- 16. A complex according to claim 14 wherein said Me comprises from 80 to 98 mole % of chromium and 2 to 20 mole % aluminium.
- 17. A complex according to claim 14 wherein said Me comprises from 25 to 98 mole % of cobalt and 2 to 75 mole % of aluminium.
- 18. A mixed aluminium-heavy metal dyestuff complex in which the heavy metal is present in an amount of 10 to 98 mole % and aluminium is present in an amount of 2 to 90 mole %, said mole % based on one mole of said aluminium-heavy metal dyestuff complex, the complex prepared by
- i) reacting a metal free dyestuff with less than a stoichiometric amount (calculated based on the metal free dyestuff or all the metal present in the complex) of a heavy metal compound to form a mixture, and
- ii) adding to said mixture an aluminium compound in an amount sufficient to produce a stoichiometric excess of metal (calculated based on all the metal present in the dyestuff complex) to form the mixed aluminium-heavy metal dyestuff complex.
- 19. A complex according to claim 18 in which the heavy metal compound is selected from the group consisting of a cobalt compound, copper compound, chromium compound and nickel compound.
- 20. A complex according to claim 18 wherein
- a) the chromium compound is an alkali dichromate;
- b) the cobalt compound is a cobalt chloride or a cobalt sulphate;
- c) the nickel and copper compounds are selected from a nickel or copper halide, sulphate or acetate; and
- d) the aluminium compound is aluminium sulphate.
- 21. A complex according to claim 18 in which the amount of heavy metal compound for a 1:1 dye:metal complex is 10 to 98 mole % per mole of metal-free dyestuff and for a 2:1 dye:metal complex is 10 to 98 mole % per two moles of metal-free dyestuff.
- 22. A complex according to claim 18 in which the amount of aluminium compound added to the mixture for a 1:1 dye:metal complex is 10 to 120 mole % per mole of metal-free dyestuff and for a 2:1 dye:metal complex is 10 to 120 mole % per two moles of metal-free dyestuff.
- 23. A complex according to claim 18 in which the metal-free dyestuff is selected from the group consisting of a water soluble dyestuff, a solvent soluble dyestuff and an insoluble dyestuff and pigment.
- 24. A complex according to claim 23 in which the metal-flee dyestuff is a solvent soluble, water insoluble dyestuff.
- 25. A complex according to claim 18 in which the complex is a 2:1 azo dye: mixed aluminium-heavy metal dyestuff complex.
- 26. A complex according to claim 18 in which the complex is one of formula I and I' ##STR25## wherein each R.sub.1 together with the two carbon atoms independently to which R.sub.1 is attached form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from the group consisting of hydroxy, c.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxy, aminocarbonyl, mono(C.sub.1-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkyl)-aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminocarbonyl, C.sub.1-3 alkoxycarbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminosulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, and 4,6-bis-(bis)(2',4'-dimethylphenyl)triazinyl-2; both groups R.sub.2, independently are selected from the group consisting of C.sub.3-20 alkyl, C.sub.1-4 alkoxy-C.sub.2-8 alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from the group consisting of hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, cyano, nitro, rhodan, C.sub.1-4 alkylcarbonyl, benzoyl, C.sub.1-3 alkylcarbonyloxy, aminocarbonyl, mono(C.sub.1-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkyl)aminocarbonyl, mono- (C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, C.sub.1-3 alkoxy-carbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)-aminosulphonyl, di(C.sub.1-4 alkyl)amino-sulphonyl, mono(C.sub.1-4 alkoxyC.sub.2-4 alkyl)aminosulphonyl, and di(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminosulphonyl; group R.sub.A together with the two carbon atoms independently to which R.sub.A is attached form a phenyl or naphthyl radical which is unsubstituted or further substituted by one or two groups independently selected from the group consisting of hydrogen, C.sub.1-4 alkyl. C.sub.1-4 alkoxy, cyano, nitro, C.sub.1-4 alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, mono(C.sub.1-4 alkyl)aminocarbonyl, di(C.sub.1-4 alkyl)-aminocarbonyl, mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)-aminocarbonyl, di(C.sub.1-4 alkoxy-C.sub.1-4 alkyl)-aminocarbonyl, phenylaminocarbonyl, aminosulphonyl, mono(C.sub.1-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkyl)aminosulphonyl; mono(C.sub.1-4 alkoxy-C.sub.2-4 alkyl)aminosulphonyl, di(C.sub.1-4 alkoxyC.sub.2-4 alkyl)aminosulphonyl and phenylaminosulphonyl;
- Me is 10 to 98 mole % of a metal selected from the group consisting of chromium, copper, cobalt and nickel and 20 to 90 mole % aluminium; and
- X.sup.+ is a cation.
- 27. A complex according to claim 18 of the formula Ia, Ib and Ic ##STR26## wherein each R.sub.3 ' is independently selected from the group consisting of nitro and --SO.sub.3 NHR.sub.7 ;
- R.sub.7 is selected from the group consisting of hydrogen, C.sub.1-2 alkyl, C.sub.1-2 alkoxy-C.sub.2-3 alkyl and phenyl;
- each R.sub.6 is selected from the group consisting of hydrogen, halogen, C.sub.1-2 alkyl and C.sub.1-2 alkoxy;
- each R.sub.2 ' is selected from the group consisting of 2-ethylhexyl and phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo, and methyl or one or two substituents selected from chloro, bromo, methyl, ethyl, C.sub.1-4 alkoxy and acetyl;
- Me is 25 to 90 mole % chromium or cobalt and 5 to 75 mole % aluminium;
- X.sup.2+ is selected from the group consisting of sodium, potassium, ammonium, C.sub.1-10 alkylammonium, 4-amino-2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions; and
- each R.sub.10 and each R.sub.11 independently are selected from the group consisting of hydrogen, halogen, hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, acetyl, benzoyl, and 4,6-bis(2',4'-dimethylphenyl) triazinyl-2, or collectively R.sub.10 and R.sub.11 together with the phenyl ring to which they are attached form a naphthyl group, preferably attached in the 5'- and 6'- position, said naphthyl group being substituted in the 4- or 5-position with R.sub.3 '.
- 28. A complex according to claim 15 comprising 25 to 98 mole % of chromium and 2 to 75 mole % of aluminium.
- 29. A complex according to claim 15 comprising 25 to 98 mole % of cobalt and 2 to 75 mole of aluminium.
Parent Case Info
This application is a continuation-in-part of U.S. Ser. No. 08/155,979, filed Nov. 19, 1993, now abandoned.
US Referenced Citations (8)
Foreign Referenced Citations (4)
Number |
Date |
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0861677 |
Feb 1941 |
FRX |
0637404 |
May 1950 |
GBX |
2259305 |
Mar 1993 |
GBX |
2272702 |
May 1994 |
GBX |
Continuation in Parts (1)
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Number |
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Parent |
155979 |
Nov 1993 |
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