Bleaching and dyeing; fluid treatment and chemical modification – Dye or potential dye composition – additive – treatment,... – Azo – acridone – or quinone dye
Reexamination Certificate
1999-12-14
2001-10-30
Wong, Edna (Department: 1741)
Bleaching and dyeing; fluid treatment and chemical modification
Dye or potential dye composition, additive, treatment,...
Azo, acridone, or quinone dye
C008S686000, C008S687000, C008S692000, C008S693000, C106S453000, C204S508000, C204S510000, C205S333000, C205S202000
Reexamination Certificate
active
06309427
ABSTRACT:
Structures, articles or parts made of aluminium or aluminium alloys and provided with a protective oxide layer, in particular an oxide layer produced electro-chemically 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.
GB-A 703949 discloses copper and cobalt complexes of moroazo dyes of the 2-aminophenol-4,6-disulphonic acid→1-phenyl-3-methyl-5-pyrazolone type, which are used, inter alia, to dye anodic oxide layers on aluminium.
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 monoazo 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 orange 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 dyeing of oxide layers produced artificially (principally galvanically) on aluminium or aluminium alloys with the 1:2 chromium complex dyes defined below, and to preparations of these 1:2 chromium complex dyes that are particularly suitable for this purpose.
The invention therefore firstly provides a method of dyeing oxide layers produced artificially on aluminium or aluminium alloys, which is characterized in that the dye employed comprises at least one 1:2 chromium complex dye of the formula
in which
R signifies C
1-9
-alkyl or a radical of the formula
R
1
signifies C
1-4
-alkyl, —COOM, —COOR
5
or —CONH
2
,
R
2
signifies hydrogen or —SO
3
M,
R
3
signifies hydrogen, methyl or methoxy,
R
4
signifies hydrogen, methyl, methoxy or chloro,
n signifies from 0 to 3,
M signifies hydrogen or a non-chromophoric cation and
Kat
+
signifies hydrogen or a non-chromophoric cation.
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
and R
5
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 naphthalene radical of the formula (b) can be located arbitrarily in &agr; or &bgr; position, the &agr; 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 the pyrazole ring preferably being unsubstituted. Mention may be made in particular of &agr;-naphthyl, &bgr;-naphthyl and the following naphthylsulphonic acid radicals of the formula (b): 2-naphthyl-4,6,8-trisulphonic acid, 1-naphthyl-3,6-disulphonic acid, 1-naphthyl-3,7-disulphonic acid, 1-naphthyl-4,6-disulphonic acid, 1-naphthyl-4,7-disulphonic acid, 2-naphthyl-4,8-disulphonic acid, 2-naphthyl-5,7-disulphonic 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 sulphophenyl or, in particular, unsubstituted phenyl.
The carboxylic and 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, e.g., 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 of the formula (I), in which R
1
is methyl and R is unsubstituted phenyl, is disclosed in “Chemical Abstracts” as the tetra- and pentasodium salt under the Registry Numbers 68541-69-5 and 68239-48-5.
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 optionally acetylated hydrazine of the formula R—NH—NH
2
with corresponding 1,3-dicarbonyl compounds, especially with corresponding acylacetic esters of low-molecular alcohols (e.g., methyl or ethyl esters) or with acylacetamide, and carrying out ring closure to give the corresponding pyrazolinone, for example, in aqueous, aqueous/organic or organic solution, at mild temperatures, for example, in the range from 0 to 70° C., in particular from 20 to 60° C., for the acylation, and at higher temperatures, for example, from 50° C. to reflux, for the ring closure.
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 acidi
Clariant Finance (BVI) Limited
Hanf Scott E.
Pang Andrew
Wong Edna
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