GB1559001A

GB1559001A - Hydrophilic textiles coloured with azo dyes and a process for their colouration

Info

Publication number: GB1559001A
Application number: GB12734/76A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1976-03-30
Filing date: 1976-03-30
Publication date: 1980-01-09
Also published as: OA05620A

Description

(54) HYDROPHILIC TEXTILES COLOURED WITH AZO DYES AND A PROCESS FOR THEIR COLOURATION (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London, SW1P 3JF a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to textile materials particularly those of a hydrophilic nature and especially cellulosic textile materials, and to their colouration with azo dyestuffs.

According to the invention we provide a hydrophilic textile material coloured with a dyestuff of the formula: wherein

U is the residue of a diazo or tetrazo component; Rl is a hydrogen atom or an alkyl, chloro, acetamido, benzamido, carbamoyl or an Nsubstituted carbamyl, for example -CONHBr, group or, preferably, a cyano R2 is an alkyl group, especially methyl, optionally substituted with a chlorine atom, a phenyl group, optionally substituted with an alkyl or alkoxy group, or a carboxylic acid or carboxylic acid ester group; or R, and R2 together with the carbon atoms in the 3- or Sposition of the pyridone ring may form an alicyclic or aromatic ring system so that, for example, R, and R2 together may be a trior tetra-methylene group forming with the pyridone of penteno [c] or hexeno (c] pyrid2-one, or Rl and R2 may form together with the adjacent carbon atoms of the pyridone ring a benzene ring giving a benz [cJ pyrid-2one; R, is an aryl group carrying one or more substituents selected from -NO, -S02R1, - COR', -COOR', -CF, or -CN, wherein R1 is an optionally substituted alkyl or aryl group; and is is an integer which may be 1 or 2.

Preferred dyestuffs are those derived from the coupling components 1 - (2' or 3' or 4' nitrophenyl) - 3 - cyano - 4 - methyl - 6 hydroxypyrid - 2 - one.

It will be appreciated that the coupling components and hence the dyestuffs used in the invention can exist in a number of tautomeric forms. While, for convenience, only one tautomeric form is shown, it is to be understood that this specification relates to dyestuffs in any of the possible tautomeric forms.

Any suitable diazo or tetrazo component may be used in the invention including those derived from amines of the anthraquinone and naphthalene series and from heterocyclic amines. Particularly useful, however, are diazo and tetrazo components derived from amines of the benzene series so that D is preferably a phenyl radical which may be substituted by one or more chlorine or bromine atoms, hydroxyl, cyano, nitro, alkyl, especially methyl and ethyl, trifluoromethyl, alkoxy, especially methoxy and ethoxy, carboxylic acid ester, optionally substituted phenyl, anilino, benzaamido, phenylazo or substituted phenylazo groups, especially methylphenylazo, nitrophenylazo and nilino phenylazo, or D is a divalent radical derived from diamines of the benzene series in which one of the amino groups may be attached to a substituent of the benzene ring.

As specific examples of suitable amines of the benzene series we mention 3,5 - trifluoromethyl - aniline, 2 - trifluoromethyl - 4 chloroaniline, 2 - chloroaniline, 3 chloro- aniline, 2,5 - dichloroaniline, 2 - nitro 4 - methoxyaniline, 2 - methoxy - 5 chloroaniline, 2,5 - dimethoxy - 4 - cyanoaniline, the ,B' - ethoxyethylester of p aminobenzoic acid, 2 - methoxy - 4 benzamido - 5 - methylaniline, 2,5 - dimethoxy - 4 - benzamidoaniline - 2,4 - diethoxy - 4 - benzamidoaniline, 3 - methoxy 4 - aminodiphenylamine, 2,2' - dimethyl 4,4' - diaminodiphenylamine, 4methoxy 4 - methoxy 4' - aminodiphenylamine, 3 methyl - 4 (3' - methyl - phenylazo) aniline, 2,5 - dimethoxy - 4 - (4' - nitrophenylazo)aniline, 2 methoxy - 4 - (2' - nitro - 4' - methylphenyl- azo) - 5 - methylaniline, 2 - ethoxy - 4 - (p - amino - 4' - anilinophenylazo) - 5 - methyl- aniline and sulphanilamide.

As specific examples of suitable amines of the anthraquinone series we mention, in particular, 1- and 2-aminoanthraquinones.

The hydrophilic textile materials which are coloured with the azo dyestuffs as hereinbefore defined may be in the form of thread, yarn or woven or knitted fabric. Preferably they are cellulosic textile materials such as viscose rayon which may be in admixture with other types of materials such as hydrophobic synthetic materials.

Conveniently the textile materials are coloured by forming the azo dyestuffs in situ on the fibre.

Thus according to a further feature of the invention we provide a process for the colouration of hydrophilic textile materials or unions of hydrophilic and hydrophobic textile materials, which comprises applying to the textile material an alkaline solution of a 6 hydroxypyrid - 2 - one of the formula wherein

R,, R and R, have the meanings hereinbefore defined and R4 is hydrogen or a carbamoyl group, and thereafter coupling the pyridone with a diazo or tetrazo component in an acidic medium.

The preferred pyridones and diazo or tetrazo components used in the process are those already defined hereinbefore.

Any alkali which has a solubilising effect on the hydroxypyridone can be used in the process of the invention, for example, sodium hydroxide, sodium carbonate or sodium acetate or the equivalent potassium salts which will give the soluble alkali metal salt of the hydroxypyridone. The alkaline solution may be applied to the textile material by any known technique, for example, by "padding" the material in the solution which may also contain additives to assist impregnation such as the commonly used wetting agents.

Optionally the impregnated material is dried before being treated with a solution, suspension or paste of the diazo or tetrazo component which may be in the form of a stable salt such as a complex with zinc chloride. If, for example, the material is to be completely coloured in one shade drying may be unnecessary before the impregnated material is immersed in a diazo or tetrazo solution. If, however, the material is to be printed in one or more shades using a diazo or tetrazo paste, predrying of the material is preferable.

In a further embodiment of the process the diazo or tetrazo component may first be converted to a stable derivative such as a diazoamino compound which may be applied to the textile material in admixture with the coupling component, the dyestuff then being generated in situ on the material by a subsequent acidic treatment or by neutral steaming.

In yet another embodiment of the process the pyridone is applied in conjunction with sodium nitrite, both the diazo and tetrazo and the dyestuff being generated in situ on the material by the application of the acidified amine precursor.

Where the pyrid-2-one has a carbamoyl group in the 5-position, the coupling reaction takes place more slowly than with the corresponding pyrid-2-ene in which the 5-position is unsubstituted, as would be expected.

Finally, the coloured material is dried and usually given a clearing treatment in water to remove any unused pyridone or loose dyestuff from the surface of the material.

The pyridone coupling components can themselves be obtained by a number of methods such as are described, for example, in "Heterocyclic compounds - Pyridine and its derivatives - Part 3" which was edited by Klingsberg and published by Interscience Publishers in 1962. Typical methods include, for example (i) condensing together compounds of the formula KCOCH,COO alkyl and Rl,CH2COO alkyl in the presence of an excess of an amine of the formula R3-NH2; (ii) cyclisation of an e-disubstituted glutaconamide of the formula: :

which is itself obtained by condensing together in the presence of a basic catalyst compounds of the formula R,COCH,COO alkyl and R1CH2CONHR,; or (iii) cyclisation of an e-ss-disubstituted glutaconamide of the formula

which is itself obtained by condensing together compounds of the formula WCOCOCH.CONHR, and R,CH,COO alkyl. They are conveniently prepared by the process described in our copending UK Patent Annllcation No. 46360/75 (Serial No.

1,559,780).

Benz[c]pyrid-2-ones can be prepared by condensing homophthalic anhydride with an amine, and penteno or hexeno [c] pyrid-2ones by reacting together 2-carboethoxy cyclopentanone or hexanone, ethylcyanoacetate and an amine followed by hydrolysis. 5-Carbamoyl pyrid-2-ones are prepared by partially hydrolysing the 5-cyano derivative.

The diazo or tetrazo components used in the invention can be readily obtained by well known conventional techniques for the diazo tisation and tetrazotisation of primary amines of the type hereinbefore defined. Usually a solution of the hydrochloride salt of the amine is first formed and sodium nitrite then added in the presence of an excess of hydrochloric acid at low temperature. Generally these components are unstable and are prepared immediately prior to their use. However, they may be stabilised as previously mentioned and in fact stabilised diazo or tetrazo components in the form of powders are commercially available.

The invention provides a comprehensive range of coloured textile materials and moreover a wide range of coloured textiles can be prepared from a single pyridine coupling component. Thus, for instance, having impregnated a length of fabric with the selected pyridone, it can then be printed with different diazo or tetrazo components thereby generating a variety of colours on the same length of fabric. The process of the invention is particularly useful for the colouration of both mercerised, unmercerised and causticised cotton and of viscose rayon causticised and uncausticised, and with the particular pyridone coupling components of the invention strong colour yields of dyestuff, i.e. heavy depths of shade, are obtainable.

The dyestuffs of the invention may be used in combination with other dyestuffs to provide an even greater range of shades. For example, in dyeing cellulosic materials, a phthalocyanine precursor may be applied together with the diazo or tetrazo component thus modifying the shade of the resulting pyridone dyestuff.

Particularly atuactive is the ease with which both unused pyridone and unfixed surface dye is removed from the developed material, thus giving outstandingly good contract between printed and unprinted areas and very low levels of cross-staining of unprinted or ground shade areas.

It will be understood by those practised in the art that such a process may also be used to overprint already coloured fabric to provide prints with a good ground shade alternative to white.

It will also be understood that such a process may be used to continuously colour cellulose in a single shade by judicious choice of amines, stabilised diazo salts or mixtures thereof each with the other or mixtures of each.

The dyestuffs of the invention will also dye hydrophobic materials, such as synthetic polyamide, cellulose triacetate and polyester materials. This may be used to advantage in the dyeing of unions of hydrophilic and hydrophobic materials for example 50:50, 67:33.

and 80:20 polyester/cotton fabric. Dyeing may be carried out by any one of the processes hereinbefore described except that after generation of the dyestuff on the fibre, the coloured material is dried and then subjected to a fixation treatment, for example, dry heat thermofixation, high temperature steaming or pressure steaming to "fix" the pigment onto the hydrophobic fibres. The material is then given a clearing treatment with water in the normal way. Thus one or more dyestuffs of the invention generated from one or more pyridones may be used to dye both components of a mixed fabric. Alternatively, the dyestuffs of the invention may be used in combination with other dyestuffs more commonly used for the dyeing of hydrophobic materials, which may be other azoic-type pyridone dyes.

The invention is illustrated but not limited by the following example in which parts and percentages are by weight.

Example Mercerised cotton material is padded in a hot solution comprising 20 parts of 1 - (3' nitrophenyl) - 3 cyano - 4 - methyl - 6 hydroxypyrid - 2 - one, 20 parts of crystalline sodium acetate and 1000 parts of water, and then dried. Alternatively, tetrasodium pyro- phosphate is used in place of the sodium acetate or, the pyridone may be dissolved in caustic soda followed by the addition of an equivalent of acetic acid to buffer the system, and the cotton material can then be padded in cold solution.

A diazo or tetrazo print paste is prepared from a mixture comprising 40 parts of one of the diazotised or tetrazotised gamines listed below, and 500 parts of a 3% paste of "Indalca PA/1" (Registered Trade Mark) which is a mannogalactan thickening agent obtained from Cesalpinia Spa, Italy, and including 45 parts of 40% acetic acid, which is made up to 1,000 parts with cold water.

The padded textile is then printed with the print paste and dried and washed. The colour of the print obtained is indicated below against the particular amine used in the preparation of the print paste.

Colour of Print Amine Obtained 2 - chloroaniline yellow 1 - aminoanthraquinone golden-yellow 2,5 - dimethoxy - 4 cyanoaniline orange/red 2 - methoxy - 4 - benz- amido - 5 - methyl aniline red 2,5 - diethoxy - 4 benzamido aniline rubine/brown 2,2' - dimethyl - 4,4' diaminodiphenylamine navy blue 2,5 - dimethoxy - 4 (4' - nitrophenylazo) aniline brown WHAT WE CLAIM IS: 1.A hydrophilic textile material coloured with a dyestuff of the formula:

wherein D is the residue of a diazo or tetrazo component; R1 is a hydrogen atom or an alkyl, chloro, acetamido, benzamido, carbamoyl or an Nsubstituted carbamoyl or a cyano group; R2 is an alkyl group, optionally substituted with a chlorine atom, a phenyl group, optionally substituted with an alkyl or alkoxy group, or a carboxylic acid or carboxylic acid ester group; or Rl and R2 together with the carbon atoms in the 3- or 4-position of the pyridone ring may form an alicyclic or aromatic ring system; R3 is an aryl group carrying one or more substituents selected from -NO2, -SOR', -COR1, -COOR% -CF, or --GN, wherein R1 is an optionally substituted alkyl or aryl group; and n is an integer which may be 1 or 2.

2. A hydrophilic textile material as claimed in claim 1 wherein R1 is cyano.

3. A hydrophilic textile material as claimed in claim 1 or 2 wherein R2 is methyl.

4. A hydrophilic textile material as claimed in claim 1 wherein R1 and R2 together form a tri- or tetramethylene group.

5. A hydrophilic textile material as claimed in claim 1 wherein R1 and R form together with the adjacent carbon atoms of the pyridone ring a benzene ring.

6. A hydrophilic textile material as claimed in any one of claims 1 to 5 wherein R, is a nitro substituted aryl group.

7. A hydrophilic textile material as claimed in claim 1 wherein the dyestuff is derived from 1 - (2' or 3' or 4' - nitrophenyfl - 3 cyano - 4 - methyl - 6 - hydroxypyrid - 2 one.

8. A hydrophilic textile material as claimed in any one of the Dreceding claims wherein D is a nhenyl radical which is optionally substituted by one or more chlorine or bromine atoms, hydroxyl, cyano, nitro, alkyl trifluoromethyl, alkoxy, carboxylic acid esters, optionally substituted phenyl, anilino, benzamido, phenylazo or substituted phenylazo groups, or D is a divalent radical derived from diamines of the benzene series in which one of the amino groups is optionally attached to a substituent of the benzene ring.

9. A hydrophilic textile material as claimed in any one of the preceding claims which is a cellulosic material.

10. A hydrophilic textile material as claimed in any one of the preceding claims which is in admixture with other types of material.

11. A process for the colouration of hydrophilic textile materials or unions of hydrophilic and hydrophobic textile materials, which comprises applying to the textile material an alkaline solution of a 6 - hydroxypyrid - 2 one of the formula:

wherein R1, R2 and R, have the meanings hereinbefore defined and R is hydrogen or a carbamoyl group, and thereafter coupling the pyridone with a diazo or tetrazo component in an acidic medium.

12. A process as claimed in claim 11 wherein the diazo or tetrazo component is in the form of a stable derivative which is applied to the textile material in admixture with the coupling component, the dyestuff then being generated in situ on the material by a subsequent acidic treatment or by neutral steaming.

13. A process as claimed in claim 11 wherein the pyridone is applied in conjunction with sodium nitrite, both the diazo or tetrazo component and the dyestuff being generated in situ on the fibre by the application of the acidified amine precursor.

14. A process as claimed in any one of claims 11 to 13 wherein the hydrophilic textile material is a cellulosic material.

15. A process as claimed in any one of

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Colour of Print Amine Obtained

2 - chloroaniline yellow 1 - aminoanthraquinone golden-yellow 2,5 - dimethoxy - 4 cyanoaniline orange/red 2 - methoxy - 4 - benz- amido - 5 - methyl aniline red 2,5 - diethoxy - 4 benzamido aniline rubine/brown 2,2' - dimethyl - 4,4' diaminodiphenylamine navy blue 2,5 - dimethoxy - 4 (4' - nitrophenylazo) aniline brown WHAT WE CLAIM IS: 1.A hydrophilic textile material coloured with a dyestuff of the formula:

wherein D is the residue of a diazo or tetrazo component; R1 is a hydrogen atom or an alkyl, chloro, acetamido, benzamido, carbamoyl or an Nsubstituted carbamoyl or a cyano group; R2 is an alkyl group, optionally substituted with a chlorine atom, a phenyl group, optionally substituted with an alkyl or alkoxy group, or a carboxylic acid or carboxylic acid ester group; or Rl and R2 together with the carbon atoms in the 3- or 4-position of the pyridone ring may form an alicyclic or aromatic ring system; R3 is an aryl group carrying one or more substituents selected from -NO2, -SOR', -COR1, -COOR% -CF, or --GN, wherein R1 is an optionally substituted alkyl or aryl group; and n is an integer which may be 1 or 2.
2. A hydrophilic textile material as claimed in claim 1 wherein R1 is cyano.
3. A hydrophilic textile material as claimed in claim 1 or 2 wherein R2 is methyl.
4. A hydrophilic textile material as claimed in claim 1 wherein R1 and R2 together form a tri- or tetramethylene group.
5. A hydrophilic textile material as claimed in claim 1 wherein R1 and R form together with the adjacent carbon atoms of the pyridone ring a benzene ring.
6. A hydrophilic textile material as claimed in any one of claims 1 to 5 wherein R, is a nitro substituted aryl group.
7. A hydrophilic textile material as claimed in claim 1 wherein the dyestuff is derived from 1 - (2' or 3' or 4' - nitrophenyfl - 3 cyano - 4 - methyl - 6 - hydroxypyrid - 2 one.
8. A hydrophilic textile material as claimed in any one of the Dreceding claims wherein D is a nhenyl radical which is optionally substituted by one or more chlorine or bromine atoms, hydroxyl, cyano, nitro, alkyl trifluoromethyl, alkoxy, carboxylic acid esters, optionally substituted phenyl, anilino, benzamido, phenylazo or substituted phenylazo groups, or D is a divalent radical derived from diamines of the benzene series in which one of the amino groups is optionally attached to a substituent of the benzene ring.
9. A hydrophilic textile material as claimed in any one of the preceding claims which is a cellulosic material.
10. A hydrophilic textile material as claimed in any one of the preceding claims which is in admixture with other types of material.
11. A process for the colouration of hydrophilic textile materials or unions of hydrophilic and hydrophobic textile materials, which comprises applying to the textile material an alkaline solution of a 6 - hydroxypyrid - 2 one of the formula:

wherein R1, R2 and R, have the meanings hereinbefore defined and R is hydrogen or a carbamoyl group, and thereafter coupling the pyridone with a diazo or tetrazo component in an acidic medium.
12. A process as claimed in claim 11 wherein the diazo or tetrazo component is in the form of a stable derivative which is applied to the textile material in admixture with the coupling component, the dyestuff then being generated in situ on the material by a subsequent acidic treatment or by neutral steaming.
13. A process as claimed in claim 11 wherein the pyridone is applied in conjunction with sodium nitrite, both the diazo or tetrazo component and the dyestuff being generated in situ on the fibre by the application of the acidified amine precursor.
14. A process as claimed in any one of claims 11 to 13 wherein the hydrophilic textile material is a cellulosic material.
15. A process as claimed in any one of

Claims 11 to 13 wherein the union is a 50:50, 67: 33 or a 80:20 polyester/cotton fabric.
16. A process for the colouration of a hydrophilic textile material substantially as herein described with reference to the Example.