Bleaching and dyeing; fluid treatment and chemical modification – Reactive dye composition – process – or product
Reexamination Certificate
1999-03-31
2001-11-20
Shah, Mukund J. (Department: 1624)
Bleaching and dyeing; fluid treatment and chemical modification
Reactive dye composition, process, or product
C008S436000, C008S544000, C008S917000, C008S918000, C008S924000, C544S076000, C544S075000, C544S077000, C106S031470
Reexamination Certificate
active
06319289
ABSTRACT:
The invention relates to novel triphendioxazine dyes, a novel process for their preparation and to their use for the dyeing of organic substrates.
Triphendioxazine dyes are known both as anionic and as cationic dyes for the dyeing of a wide range of substrates. They are also used as reactive dyes and as pigments.
It has now been found that a novel process makes it possible to prepare unilaterally substituted triphendioxazine dyes which contain a discretionarily substituted sulfone group and may serve both as acid dyes and as reactive dyes.
The invention accordingly provides compounds of formula (I)
wherein A is hydrogen or a discretionary substituent and R is a discretionary radical, the manner of the substitution of this radical or the substituents A being determining for the nature of the end products. Neutral or anionic substituents provide acidic dyes for the dyeing of wool, silk and synthetic polyamides; and also for leather, paper and for preparing inks for the inkjet process, and the presence of reactive groups provides reactive dyes for the dyeing of cellulose. These are merely exemplary suggestions, which may be added to at one's discretion, because the novel inventive process makes it possible to introduce discretionary radicals R and the substituents A can likewise be discretionary in nature.
A is preferably hydrogen or a discretionarily substituted alkyl or aryl radical, these substituents preferably being identical. However, it is also possible to introduce a discretionarily substituted triazine group in a targeted manner on one side of the molecule only.
However, preferred dyes for the dyeing of wool, silk and synthetic polyamides contain only single, unsubstituted C
1-12 2
alkyl or phenyl radicals as substituent A or, most preferably, are unsubstituted, i.e. contain two primary amino groups.
If, on the other hand, reactive dyes are desired, the reactive group(s) required for this purpose is(are) preferably introduced as correspondingly substituted radical A, it being possible for the molecule to be provided either symmetrically with two identical radicals A or unilaterally with one radical A. Examples of such radicals are known from a wide range of dye classes and may be used discretionarily provided it is possible to introduce them by substitution of a primary amino group.
The novel triphendioxazine dyes contain at a given location a discretionarily substituted sulfone group which is introduced using a novel process. This process according to the invention is characterized in that a triphendioxazine of the formula (II)
is reacted with a discretionarily substituted sulfinic acid or its salt in the presence of an oxidizing agent. This reaction is already known and is described, for example for dyes, in Berichte 28 (1895), 1315-1318.
However, this reaction has hitherto never been used for the unilateral substitution of the triphendioxazine molecule and it is surprising that this asymmetric substitution using discretionarily substituted sulfinic acids succeeds in quantitative yield.
The radical R may therefore be a discretionarily substituted alkyl, cycloalkyl or aryl radical and it is also possible to use heterocyclic sulfinic acids. Preference is given to the available aliphatic and particularly aromatic sulfinic acids as described in a wide range of general articles. Examples of preferred radicals R are C
1-12
alkyl, phenyl, naphthyl and, in particular, substituted phenyl or naphthyl, these substituents possibly being C
1-12
alkyl, halogen, C
1-12
alkoxy and, in particular, substituted amino or sulfonic acid groups. Particularly preferred radicals R are phenyl and naphthyl groups carrying an amide radical, which is for its part discretionarily substituted and may be either an amino group reacted with sulfonic acid or carboxylic acid or an amidated sulfonic acid or carboxyl group. These radicals R may for their part also carry dye radicals such as anthraquinone radicals or triphendioxazine radicals.
Particularly preferred dyes of the formula (I) have the structure
wherein X is a radical —NH—CO—Y, —SO
2
—NH—Y, —CO—NH—Y or —NH—SO
2
—Y and Y is a discretionary radical.
This radical Y is preferably a discretionarily substituted C
1-12
alkyl, phenyl or naphthyl group or, in the case of —SO
2
—NH—Y or —CO—NH—Y, hydrogen.
The process for the preparation of the compounds of the formula (I) according to the invention may be carried out under the known conditions as have been described for reacting phenylenediamine with sulfinic acids. Depending on the choice of the oxidizing agent, the pH maintained is alkaline or acidic and the reaction takes place at higher or lower temperatures. Examples of suitable oxidizing agents are: iron(III) salts, peroxodisulfates (persulfates), permanganates, manganese dioxide, chromic acid, peroxides, peracids, dichromate, chlorates, bromates, iodates, silver oxide, lead oxide, lead tetraacetate, with peroxodisulfates and iron(III) salts being preferred.
The starting compounds of the formula (II) and the sulfinic acids used are known compounds or can be prepared from known compounds analogously to known preparative processes.
The dyes of the formula (I) can be isolated from the reaction medium by known processes, for example by salting out with an alkali metal salt, filtration and drying, optionally in vacuo at slightly elevated temperature.
Depending on the reaction and/or isolation conditions, the dyes of the formula (I) can be obtained as free acid, as salt or as mixed salt which contains for example one or more cations selected from alkali metal ions, for example the sodium ion, or an ammonium ion or alkylammonium cation, for example mono-, di- or trimethyl- or -ethyl-ammonium cations. The dye can be converted by conventional techniques from the free acid into a salt or into a mixed salt or vice versa or from one salt form into another.
The dyes of the formula (I) and their salts are particularly suitable for dyeing or printing fibrous material consisting of natural or synthetic polyamides in blue shades.
The invention therefore provides from another aspect for the use of the dyes of the formula (I), their salts and mixtures for the dyeing or printing of fibrous materials which consist of natural or synthetic polyamides.
The dyeing is carried out according to known processes, for example the dyeing processes described in Ullmanns Encyklopädie der technischen Chemie, 4th edition, 1982, Volume 22, pages 658-673 or in the book by M. Peter and H. K. Rouette, Grundlagen der Textilveredlung, 13th edition, 1989, pages 535-556 and 566-574. Dyeing preferably takes place in the exhaust process at a temperature of 30 to 100° C., particularly preferably 80 to 100° C., and a liquor ratio of 40:1.
The substrate to be dyed can be present for example in the form of yarn, woven fabric, knitted fabric or carpet. Fully-fashioned dyeings are also very satisfactorily possible on delicate substrates, for example lamb's wool, cashmere, alpaca and mohair.
The dyes according to the present invention and their salt possess good compatibility with known acid dyes. Accordingly, the dyes of the formula (I), their salts or mixtures can be used alone in a dyeing or printing process or else as component in a combination dyeing or printing composition together with other acid dyes of the same class, i.e., with acid dyes which possess comparable dyeing properties, for example fastness properties and exhaustion rates from the dyebath to the substrate. The dyes of the present invention can in particular be used together with certain other dyes having suitable chromophores. The ratio in which the dyes are present in a combination dyeing or printing composition is dictated by the hue to be obtained.
The novel dyes of the formula (I), as stated above, are highly suitable for the dyeing of natural and synthetic polyamides, i.e., of wool, silk and all nylon types, on which dyeings having high fastness level, especially good lightfastness and good wetfastnesses (wash 50° C., alkaline perspiration) are obtained. The dyes of the formula (I) and their salts provide high
Clariant Finance (BVI) Limited
Hanf Scott E.
Patel Sudhaker B
Shah Mukund J.
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