Bleaching and dyeing; fluid treatment and chemical modification – Nontextile – dyeing process or product – including inorganic... – Inorganic substrate
Reexamination Certificate
1999-11-24
2001-04-03
Einsmann, Margaret (Department: 1751)
Bleaching and dyeing; fluid treatment and chemical modification
Nontextile, dyeing process or product, including inorganic...
Inorganic substrate
C008S506000, C008S685000, C534S700000, C534S713000, C534S721000, C534S724000, C534S725000
Reexamination Certificate
active
06210448
ABSTRACT:
Structures, articles or parts made of aluminium or aluminium alloys and provided with a protective oxide layer, in particular an oxide layer produced electrochemically by anodization, are nowadays increasingly used in engineering and construction as, for example, a component and/or for the decoration of buildings or means of transport or for utility or artistic articles. For the aesthetic design of such structures, articles or parts they or their oxide layers are frequently dyed. It is therefore desirable for the dyed layers to retain their coloured design for as long as possible and, consequently, for them to have very high levels of fastness to environmental influences, especially to the action of sunlight.
CH-A 396256 discloses heavy-metal complexes of monoazo dyes containing phosphonic acid groups which are used, inter alia, to dye anodic oxide layers on aluminium. Example 10 of CH-A 396256 describes a yellow chromium complex of the monazo dye made from 2-aminophenol-4,6-disulphonic acid → 3-acetoacetylaminobenzenephosphonic acid.
It has now been found that the 1:2 chromium complex dyes defined below are outstandingly suitable as yellow dyes for such oxide layers, especially for anodized aluminium or anodized aluminium alloys, and are notable for their surprisingly high light fastness.
The invention relates to the defined 1:2 chromium complex dyes, to their production and to their use for dyeing oxide layers produced artificially (principally galvanically) on aluminium or aluminium alloys, and to preparations which comprise these dyes. The invention therefore firstly provides 1:2 chromium complex dyes of the formula:
in which R signifies c
1-9
-alkyl or a radical of the formula:
The alkyl radicals occurring in the formula (I) may be linear or, if they contain three or more carbon atoms, may also be branched, or, if they contain six or more carbon atoms, can also be cyclic.
In the definition of R
1
the lower-molecular alkyl radicals are preferred, in particular ethyl and above all methyl.
Among the alkyl radicals in the definition of R the branched and the cyclic are preferred, especially C
4-8
-isoalkyl, secondary C
3-8
-alkyl, unsubstituted cyclohexyl and cyclohexyl which carries from one to three methyl groups as substituents. According to one embodiment of the invention preferred alkyl radicals in the definition of R are those which contain at least 4 carbon atoms.
In the radicals of the formula (a) the respective substituents can be located in any desired positions on the phenyl radical; if R
2
is a sulpho group —SO
3
M, this group is preferably located in meta position or para position; if R
3
is methyl or methoxy, and/or if R
4
is methyl, methoxy or chloro, these substituents can be located in any of the available positions, with preferably at least one of the two ortho positions of the phenyl radical being unsubstituted. With particular preference both R
3
and R
4
are hydrogen.
The free bond on the sulpho-substituted naphthalene radical (b) can be located arbitrarily in &agr; or &bgr; position, the a position being preferred. For n=1 to 3 the n sulpho groups in the formula (b) can be located in n arbitrary available positions, the vicinal positions to the bond to —NH— preferably being unsubstituted. Mention may be made in particular of &agr;-naphthyl and the following naphthylsulphonic acid radicals of the formula (b): 2-naphthyl-4,6,8-tri-sulphonic acid, 1-naphthyl-3,6-disulphonic acid, 1-naphthyl-3,7-disulphonic acid, 1-naphthyl-4,6-di-sulphonic acid, 1-naphthyl-4,7-disulphonic acid, 2-naphthyl-4,8-disulphonic acid, 2-naphthyl-5,7-di-sulphonic acid, 2-naphthyl-6,8-disulphonic acid, 1-naphthyl-3-, -4-, -5-, -6- or -7-sulphonic acid and 2-naphthyl-5- or -6-sulphonic acid. Among these radicals, preference is given to those in which n=1, especially 1-naphthyl-4- or -5-sulphonic acid.
Particular preference in the definition of R is given to isooctyl, sulphophenyl or, in particular, unsubstituted phenyl.
The sulphonic acid groups can be in the form of the free acid or, preferably, in the form of salts of non-chromophoric cations.
M and Kat
+
can each be hydrogen or a non-chromophoric cation. Hydrogen as ion is present as the hydronium ion. Examples of suitable non-chromophoric cations are alkali metal cations, ammonium cations and alkaline earth metal cations. As alkaline earth metal cations mention may be made, for example, of calcium and magnesium. As ammonium cations mention may be made of unsubstituted ammonium or also ammonium ions of low-molecular amines, primarily mono-, di- or tri-C
1-2
-alkyl- and/or -&bgr;-hydroxy-C
2-3
-alkyl-ammonium, examples being mono-, di- or tri-isopropanolammonium, mono-, di- or triethanolammonium, N-methyl-N-ethanol-ammonium. Suitable alkali metal cations are customary such cations, examples being lithium, sodium and/or potassium ions. Among these cations the alkali metal cations and ammonium cations are preferred. In one embodiment of the invention some of the symbols M and Kat
+
are hydrogen and the rest of them are alkali metal cations and/or ammonium cations.
The 1:2 chromium complex dyes of the formula (I) can be symmetrical or also asymmetrical complexes; i.e., apart from the definitions of M and Kat
+
, the two radicals R can have the same definition as or different definitions to one another, and/or the two radicals R
1
can have the same definition as or different definitions to one another. Preference is given to symmetrical chromium complexes of the formula (I); i.e., to those in which the two radicals R have the same definition and in which the two radicals R
1
also have the same definition.
The 1:2 chromium complex dyes of the formula (I) can be prepared in analogy to chromation reactions which are known per se. In particular, the process for preparing the 1:2 chromium complex dyes of the formula (I) is characterized in that at least one metallizable compound which corresponds in one of its tautomeric forms to the formula:
is reacted with a chromium donor compound.
The compounds of the formula (II) can be prepared by coupling the diazo compound of 2-amino-1-hydroxybenzene-4,6-disulphonic acid to a coupling component which corresponds in one of its tautomeric forms to the formula:
The compounds of the formula (III) are known or can be prepared in analogy to known methods by acylating an amine of the formula R—NH
2
with an acylacetic halide of the formula R
1
—CO—CH
2
—CO—Hal under dehydrohalogenating conditions, for example, at pH values within the range from 3 to 8, in particular from 4 to 6, and at mild temperatures, for example, within the range from 0 to 70° C., in particular from 20 to 60° C., or, if R is aromatic, alternatively by reacting the respective arylamines with corresponding acylacetic esters of low-molecular alcohols (preferably methyl or ethyl esters) at temperatures above 100° C., or, in a preferred variant, if R
1
, is methyl, by reacting diketene:
optionally as an acetone adduct, with corresponding amines of the formula R—NH
2
, in solution (e.g., in water or acetone) at temperatures, for example, within the range from 40° C. up to reflux.
The diazotization of 2-amino-1-hydroxybenzene-4,6-disulphonic acid can be carried out in a manner known per se, in particular with sodium nitrite in an acidic medium (preferably at a pH of 1 to 3) and at a low temperature, preferably within the range from −5 to +15° C. The coupling of the diazonium compound to a coupling component of the formula (III) can be carried out in a manner known per se, advantageously at temperatures within the range from −5 to +30° C., preferably below 25° C., and with particular preference within the range from 0 to 10° C., and under distinctly alkaline conditions, advantageously within the pH range from 8 to 12, preferably from 9 to 11. The reactions may be carried out in an aqueous medium or also in an aqueous/organic medium, the organic medium preferably being a water-miscible inert solvent (e.g., an alcohol or dioxane).
For the chromation of the compounds of the for
Clariant Finance (BVI) Limited
Einsmann Margaret
Hanf Scott E.
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