United States Patent 15) Bitterli CANA AA 'US00S123930A (1) Patent Number: 5,123,930 l4s]_Date of Patent: Jun. 23, 1992 [54] 1:2 CHROMIUM AND COBALT COMPLEXES ‘(OF MONOAZO COMPOUNDS FOR DRYING POROUS OXIDE LAYERS ON ALUMINUM AND ALUMINUM ALLOY SUBSTRATES {75} Inventor: Peter Bitter, Reinach, Switzerland [73] Assignee: Sandoz Ltd, Basel, Switzerland [21] Appl. No: $70,940 [22] Filed: Aug. 21, 1990 Related US. Application Data {60} Continuation of Ser. No. 438,148, Nov. 16, 198, ban- R ‘SNHR__Me_Aldyeing o OF cocks 7 ca on SosHt “ a 3k « —cocitts 2 Ga % z 5 Gg a oo @ 6 o q 7 2 @ 8 ry . 2G 0 on 2 8 ow’ 31 ~cocls 3 Gt 2 a 2&8 5 cont SoG 5 2 E 3&8 ss 2 a8 <0) In accordance with the method as described the 1:2 metal complexes of Examples 2 to 55 like the complex of Example 1 are obtained in sodium salt form. They may be converted into other salt forms or even mixed salt forms containing one or more cations indicated in the description above in accordance with known meth- ods. EXAMPLE 56 440 Parts of the monoazo dyestuff obtained from diazotised I-amino-2-hydroxy-S-nitrobenzene and 2- acetamido-8-hydroxynaphthalene-6-sulphonic acid are Converted into the 1:2 chromium complex according to the method described in Example I and the chromium ‘complex is separated by filtration. The wet filtercake is dissolved at room temperature in a mixture of 19 parts of crystalline sodium acetate, 30 parts of water and 115, parts of diethylene glycol monoethy| ether. 240 Parts of a stable liquid homogeneous dyestuff preparation are ‘obtained. Such preparation does not show any precipi tation of dyestuff after prolonged storage at tempera- tures below 0° and gives a clear solution in a matter of seconds when added to water. In the following examples the application of the 1:2 ‘metal complexes of this invention is illustrated. APPLICATION EXAMPLE A. A degreased and deoxidised workpiece of pure alumi- ‘num is anodically oxidised for 30 minutes at a tempera- ture of 18° to 20° with a potential of 15 to 16 volts and with a direct current of density 1.5 amperes/dm? in an aqueous solution containing 18 to 22 parts sulphuric 4 3s 65 acid and 1.2 to 7.5 parts of aluminum sulphate per 100 parts. An oxide layer of approximately 12 thickness is obtained. ‘Afier rinsing with water, the workpiece is immersed for a period of 15 mimutes at 60° in a solution containing 5 parts of the chromium complex produced in accor- dance with Example | in 1000 parts of deionised water the pH of which is adjusted to ca 5.5 by means of acetic acid and sodium acetate. The dyed workpiece is rinsed with water and then sealed in deionised water for 30 minutes at 98° to 100". A pure black coloration is ob- tained having good resistance to heat and also to fading on exposure to light. If the sealing is carried out under otherwise identical conditions in a solution containing 3 parts of nickel acetate in 1000 parts of water, a coloration of compara- ble quality is obtained. APPLICATION EXAMPLE B 10 Parts of the dyestuff produced according to Exam- ple | are dissolved in 500 parts of water and stirred to form a highly viscous mixture with a solution compris- ing 400 parts of water and 100 parts of methylcellulose of a medium degree of polymerisation and 1.5 degrees substitution. The printing ink so obtained is applied by a silk-screen process to a dry oxidised aluminum sheet obtained by anodising an aluminum alloy of the type AI/Mg/Si (0.5) for 30 minutes in a solution of 100 parts of chromic anhydride in 1000 parts of water at 53° and a current density of 1.2 amperes/dm?. The printed alu- minum alloy sheet is immersed in boiling water for 105,123,930 13 minutes and then rinsed thoroughly in cold water. A ‘black pattern on a pale greyish background is obtained. Similarly, the complexes of Examples 2 to 55 may be employed in accordance with Application Example A or B; for the process of Application Example A it is also possible to employ a liquid dye preparation of the dye~ stuffs of Examples 1 to 55 (according to Example 56). ‘What is claimed is: 1. A process for dyeing an artificially produced po- rous oxide layer on an aluminum or aluminum alloy substrate comprising contacting an aluminum or alumi- ‘num alloy substrate having an artifically produced po- rous oxide layer thereon with a solution of a complex of the formula Moss, oar al Bs aS wei" 3 a SoM each of R; and Rsis independently hydrogen or sitro, with the proviso that when a ring has two nitro groups, they are meta to each other, each of Ry and Rais independently hydrogen, chloro or —SOaM, each of Rs and Re is independently —COR;, —CONHRs or —SO2Rs, wherein Rr is Cr-ealkyl, C1-salkoxy, phenyl(C\-ralky) or phenyl(C)-aalky!) the phenyl group of which is substituted by 1 oF 2 substituents selected from halo, Ci-ralkyl, Ci-alkoxy, nitro, amino, —COOM, —S03M and acetamido, Re is hydrogen; Ci.salkyl; phenyl; phenyl substi- tuted by 1 or 2 substituents selected from halo, Craalkyl, Ciaalkory, nitro, amino, —COOM, —SO3M and acetamido; naphthyl or naphthyl monosubstituted by chloro, amino, phenylamino, acetamido, benzamido or —SO:M, and Reis Cy-calkyl, phenyl or phenyl substituted by 1 (of 2 substituents selected from halo, Cy-salkyl, Cisalkory, nitro, amino, —COOM, —SO:M and acetamido, and Me is chromium or cobalt, wherein each M and M® is independently hydrogen or a non-chromophoric cation, with the proviso that the —NHRs group is in the 2- or 3-position of Ring A and the —NHRs group isin the 2- ‘oF 3-position of Ring B, whereby said substrate is dyed. 2. A process according to claim 1 comprising con- tacting an aluminum or aluminum alloy substrate hav- ing an artfcally produced porous oxide layer thereon with a solution of a complex of the formula Me 25 38 4s 5s Mo ates ‘SOM te or a mixture thereof, having a concentration of 0.01-10 ‘grams/liter of said complex or mixture of complexes at a pH of 3-8 and a temperature ranging from room tem- perature to the boiling point of the solution for 1 to 30 ‘minutes and subsequently sealing the dyed substrate. 3. A process according to claim 1 comprising con- tacting an aluminum or aluminum alloy substrate hav- ing an artifically produced porous oxide layer thereon with a solution of a complex of the formula © oss. on N 0. Ne. 4. A process according to claim 3 wherein each of Rs and Rg is independently COR», CONTR or —SOaRon wherein Rrpis Ci-zalkyl, C,-alkoxy, phenyl(Cy-z-alkyD or phenyl(Ci-zalky!) the phenyl group of which is monosubstituted by chloro, methyl or methoxy, Ragis hydrogen, phenyl or phenyl monosubstituted ’y chloro, methyl or methoxy, and” opis C1-zalkyl, phenyl or phenyl monosubstituted by chloro, methyl or methoxy. 5. A process according to claim 4 wherein each of Rs and Re is independently —CORre —CONHRa. or —SO2Ro, wherein Ric is Ci-zalkyl or Ci-zalkoxy, Ric is hydrogen or phenyl, and Rocis phenyl or methylphenyl 6. A process according to claim § wherein each of Rs and Rg is independently —CORrw or —CONH,, wherein Rrgis methyl or ethyl 7.4 process according to claim 3 wherein Rs and Re are identical 8. A process according to claim 3 wherein each M and MS is independently hydrogen, lithium, sodium, potassium, ammonium, methylammonium, dimethylammonium, trimethylammonium, tetra. methylammonium, triethylammonium, ethanolam- monium, diethanolammonium, _ triethanolam- ‘onium, isopropanolammonium, disopropanolam- onium or trisopropanolammonium,5,123,930 15 9. A process according to claim 8 wherein each M and M@ is independently hydrogen, lithium, sodium, potassium or ammonium. 10. A process according to claim 9 wherein each M and M@ is lithium, sodium, potassium or 5 ammonium, each M and M@ being identical 11, A process according to claim 10 wherein each M and M@ is sodium, 12. A process according to claim 3 wherein Rings C and D are identical, 1B. A process according to claim 12 wherein the complex is a complex of the formula RL OR e > Moss. A $ 0. KE E we we, om No sas DICE TB No, i , SOM a Ry when each of Ry and Ry is hydrogen or nitro, with the proviso that when a ring has two nitro groups, they 20 are meta to each other, each of Ro and Rs is hydrogen, chloro or —SOsM, each of Rss and Res is —COR7., —CONHRsc or SORsq wherein Ricis Ci-zalkyl or C1-zalkoxy, Racis hydrogen or phenyl, and Recis phenyl or methyiphenyl, and Me is chromium or cobalt, wherein each M and M® is independently hydrogen or a non-chromophoric cation, ‘with the provisos that (1) the NHR group is in the 2- or 3-position of Ring A and the —NHR«s group is in the 2- or 3:position of Ring B, (2) Rings C and D are identical, and (3) Rsp and Rep are identical 1d. A process according to claim 13 wherein each of Rss and Rep is —CORrg or —CONH:, wherein Rrzis methyl or ethyl. 15. A process according to claim 14 wherein each of Rsp and Res is —CORra, wherein Ria is methyl or ethyl. 16. A process according to claim 18 wherein each of Rsp and Rep is —COCHs, with the proviso that each —NHCOCH; group is in the 3-position of the ring to which itis attached. 17. A process according to claim 16 wherein 38 4s 0 5s 6s 16 Me is chromium. 18. A process according to claim 17 wherein each of Ro and Ry is hydrogen. 19. A process according (0 claim 18 wherein the complex is the complex of the formula ‘NOz ° oe e0 OL DQ} TY} taicoct <7 Set ne 20. A process according to claim 18 wherein the ‘complex is the complex of the formula RN - NHcocHs c aa oncom 9 9 lode “or OO "'SO3Na 21. A process according to claim 15 wherein the complex is the complex of the formula M8. Nor oN 2 op ‘cuCOHN 8. Nop SON No: