GB2134130A

GB2134130A - Disperse azo dyes

Info

Publication number: GB2134130A
Application number: GB08301601A
Authority: GB
Inventors: Keith Bramham; John Frederic Dawson; Malcolm Stewart Jackson
Original assignee: Yorkshire Chemicals Ltd
Current assignee: Yorkshire Chemicals Ltd
Priority date: 1983-01-21
Filing date: 1983-01-21
Publication date: 1984-08-08
Also published as: GB8301601D0

Abstract

There are disclosed disperse dyestuffs of the formula: <IMAGE> wherein X represents a chlorine or bromine atom R<1> represents a hydrogen atom or an alkoxy group containing from 1-4 carbon atoms. R<2> represents an alkyl group containing from 1-4 carbon atoms R<3> represents an alkyl group containing from 1-8 carbon atoms and R<4> represents an alkyl group containing from 5-8 carbon atoms. There are also disclosed mixtures of such dyes with other disperse dyes, methods of production of the dyes of this mixture and the mixtures of the invention, and also their use in dyeing hydrophobic fibres especially polyester fibres.

Description

SPECIFICATION Blue monoazo disperse dyes The invention relates to disperse azo dyes, their preparation and uses and to mixtures of such dyes with other dyes, to the preparation of such mixtures and their use.

Disperse dyestuff mixtures are known whereby a reddish blue to violet dye of general structure:

where Y represents a chlorine or bromine atom.

Q1, Q2 and Q3 are alkyl groups containing 1-L4 carbon atoms is mixed with a greenish blue dye of general structure

wherein Y, Q1, Q2 and Q3 have the meaning above the Q4 is an alkoxy group containing 1-4 carbon atoms.

Such mixtures can be used, by varying the proportions of each component of the mixture, to produce economical blues ranging in hue from reddish blue to greenish blue. These mixtures generally dye more rapidly and have less sensitivity to variations in dyeing temperature than related homogeneous dyes of similar hue in which Q3 and Q4 are as defined above and at least one of Q1 and Q2 are substituted alkyl groups.

The improved properties which these mixtures show over similarly hued homogeneous dyes are particularly important when dyeing polyester fibres by exhaust dyeing processes under high temperature conditions, especially when using the so called rapid dyeing equipment which employs high rates of liquor circulation and rapid rates of temperature rise.

Also under these conditions, it is advantageous for any mixtures of dyes to be compatible, that is, under the conditions employed, all components of any mixture should exhibit similar dyeing rates thus giving one-tone build up. (references: Blackburn D., J. Society of Dyers and Colourists, 96 (1 980), 237-245: Siegrist, Review of Progress in Colouration, 8 (1977), (24). Mixtures of any given disperse dyes are only compatible when applied in a certain ratio. Deviation from this ratio can result in an incompatible mixture. Consequently, whilstthe known mixtures described above may give hues in the range from reddish to greenish blues, not all such mixtures will be compatible mixtures.

These known mixtures contain dyes in which substituents Q' and Q2 are alkyl groups containing 1-4 carbon atoms.

We have now found that dyes of similar structure in which longer alkyl chains are employed enable dyes to be produced economically and with similar hues to the known products but with significantly different rates of dyeing and sensitivities to temperature variations in the dyebath. By the careful selection of these dyes, used in admixture with one another or in admixture with known dyes of related structure, it has been found possible to produce compatible mixtures over a much wider hue range between reddish blue and greenish blue than is obtainable with the known mixtures. We were particularly surprised to find that the mixtures in which they were used showed excellent build up and high tinctorial strength, in spite of the greater molecular size of these new dyes.

According to the present invention thereof, there are provided disperse dyestuffs of the formula:

wherein X represents a chlorine or bromine atom R1 represents a hydrogen atom or an alkoxy group containing from 1-4 carbon atoms.

R2 represents an alkyl group containing from 1-4 carbon atoms R3 represents an alkyl group containing from 1-8 carbon atoms and R4 represents an alkyl group containing from 5-8 carbon atoms.

By the term alkyl is meant straight or branched chain alkyl or cycloalkyl.

Preferred dyes are those in which R4 represents a branched chain alkyl group. Especially preferred dyes are those in which R1 represents a hydrogen atom or a methoxy group, R2 represents a methyl group, R3 represents an alkyl group containing 1-4 carbon atoms and R4 is a branched chain alkyl group containing 5-8 carbon atoms.

The invention also includes a process for the manufacture of disperse dyes of formula I which comprises coupling a diazotised amine of formula:

with a coupling component of formula:

wherein X, R', R2, R3 and R4 have the meanings given above.

In a preferred process, R4 represents a branched chain alkyl group containing 5-8 carbon atoms.

In an especially preferred process, R' represents a hydrogen atom or a methoxy group, R2 represents a methyl group, R3 represents an alkyl group containing 1-4 carbon atoms and R4 represents a branched chain alkyl group.

Also according to the present invention there are provided mixtures of at least one disperse dyestuff to general formula I as defined above with at least one dyestuff of general formula:

wherein X represents a chlorine or bromine atom R5 represents a hydrogen atom or an alkoxy group containing 1-4 carbon atoms R6 represents an alkyl group containing 1-4 carbon atoms R7 and RS each independently represent alkyl groups containing 1-8 carbon atoms and in which mixture, when R' represents a hydrogen atom, R5 must represent an alkoxy group or when R1 represents an alkoxy group, R5 must represent a hydrogen atom.

The preferred mixtures are those in which R7 and R8 contain 1-4 carbon atoms, Especially preferred mixtures are those in which R2 and R6 represent methyl groups, R3, R7 and R8 contain 1-4 carbon atoms, R4 represents a branched chain alkyl group containing 5-8 carbon atoms and R' represents a hydrogen atom when R5 represents a methoxy group or R' represents a methoxy group when R5 represents a hydrogen atom.

The invention further includes a process of manufacture of a mixture of disperse dyes of formulae I and IV in which a diazotised amine of general formula II as defined above is coupled to a mixture of coupling components containing at least one coupling component of formula:

and at least one coupling component of formula:

wherein R1, R2, R3, R4, R5, B, B7 and B8 have the meanings given above and in which mixture, when R' represents a hydrogen atom, R5 must represent an alkoxy group or when R1 represents an alkoxy group, R5 must represent a hydrogen atom.

In preferred mixtures, R7 and R8 contain 1-4 carbon atoms and in especially preferred mixtures, R2 and B6 represent methyl groups, R3, R7 and B8 contain 1-4 carbon atoms, R4 represents a branched chain alkyl group of 5-8 carbon atoms and when R1 represents a hydrogen atom, R5 represents a methoxy group or R' represents a methoxy group and R5 represents a hydrogen atom.

The mixtures of the invention may also be prepared by admixure of disperse dyes of general formulae I and IV subsequent to their manufacture.

The invention is not restricted to mixtures containing one component of general formula I and one component of the general formula IV. By including more than one component in which R' represents a hydrogen atom and R5 represents an alkoxy group or R1 represents an alkoxy group and R5 represents a hydrogen atom, the range of compatible shades which can be obtained is extended to cover the whole greenish blue to reddish blue area.

The mixtures of the invention are of particular interest when applied to polyester fibres as dark blues and as the basic of heavy shades, especially blacks. It is in these areas of application that the good dyeing properties of these products shown particular advantages.

The amines of general formula II which may be used for preparing the diazo components are: 2bromo-4,6-dinitro-aniline and 2-chloro-4,6=dinitroaniline.

Specific examples of amines of general formula Ill and V which may be used as coupling components are: 3-acetylamino-N-methyl-N-3-methylbutyaniline 3-acetylamino-N-methyl-N-2-methylbutylaniline 3-acetylamino-N-methyl-N-1 -methylbutylaniline 3-acetylamino-N-ethyl-N-pentylaniline 3-acetylamino-N-ethyl-N-2-methylbutylaniline 3-acetylamino-N-éthyl-N-3-methylbutylaniline 3-acetylamino-N-ethyl-N-1 -methylbutylaniline 3-acetylamino-N-ethyl-N-2-ethylbutylaniline 3-acetylamino-N-ethyl-n-hexylaniline 3-propionylamino-N-propyl-N-2-methylpentylaniline 3-acetylamino-N-ethyl-N-3-methylpentylaniline 3-acetylamino-N-ethyl-N-1 -methylpentylaniline 3-butyrylamino-N-butyl-N-3-methylbutylaniline 3-acetyla mino-N,N-di-3-methylbutylaniline 3-acetyiamino-N,N-dipentylaniline 3-acetylamino-N,N-di-1 -methylbutylaniline 3-acetyla mino-N,N-di-2-methylbutylaniline 3-acetylamino-N,N-di-4-methylpentylaniline 3-propionylamino-N,N-di-5 -methylhexylaniline 3-acetylamino-N,N-dihexylaniline 2-methoxy-5-acetylamino-N-methyl-N-3-methylbutylaniline 2-methoxy-5-acetyla mino-N-methyl-N-2-methylbutylaniline 2-methoxy-5-acetylamino-N-methyl-N-1 -methylbutylaniline 2-methoxy-5-acetylamino-N-ethyl-N-pentylaniline 2-methoxy-5-acetyla mino-N-ethyl-N-2-methylbutylaniline 2-methoxy-5-acetylamino-N-ethyl-N-3-methylbutylaniline 2-methoxy-5-acetyla mino-N-ethyl-N-hexylaniline 2-methoxy-5-acetyla mino-N-ethyl-N-2-methyípentyíaniline 2-methoxy-5-acetyla mino-N-ethyl-N-4-methylpentylaniline 2-methoxy-5-acetylamino-N-methyl-N-1 -methylpentylaniline 2-methoxy-5-propionyla mino-N-ethyl-N-2-methyíbutylaniline 2-methoxy-5-propionyla mino-N-methyl-N-3-methylbutylaniline 2-ethoxy-5-acetyla mino-N-methyl-N-2-methylbutylaniline 2-methoxy-5-acetylamino-N,N- -di-2-methylbutylaniline 2-methoxy-5-acetylamino-N,N-di-3-methylbutylaniline 2-methoxy-5-acetyla mino-N-ethyl-N-cyclohexyl aniline 2-methoxy-5-acetylamino-N,N-dipentylaniline 2-methoxy-5-acetylamino-N,N-di-4-methylpentylaniline 2-methoxy-5-acetylamino-N,N-di-5-methylhexylaniline Specific examples of amines of general formula V which may be used as coupling components are:: 3-acetylamino-N,N-diethylaniline 3-acetylamino-N,N-dipropylaniline 3-acetylamino-N,N-diburylaniline 3-propionylamino-N,N-diethylaniline 3-butyrylamino-N,N-diethylaniline 3-acetylamino-N-ethyl-N-2-methylpropylaniline 3-acetylamino-N,N-di-2-methylpropylaniline 2-methoxy-5-acetylamino-N,N-diethylaniline 2-methoxy-5-acetylamino-N,N-dipropylaniline 2-ethoxy-5-acetylamino-N,N-diethylaniline 2-methoxy-5-acetylamino-N,N-dibutylaniline 2-methoxy-5-propionylamino-N,N-diethylaniline 2-methoxy-5-butyrylamino-N,N-diethylaniline 2-ethoxy-5-acetylamino-N-ethyl-N-2-methylpropylaniline The coupling components of general formula Ill and V may be prepared by conventional means.

The preferred coupling components of general formula III in which R4 represents a branched chain alkyl group may for example by prepared by the condensation of the corresponding branched chain alkyl bromide with an amine or formula

followed by aikylation of the resulting secondary amine wherein R' and R2 have the aforementioned meanings.

Products prepared by this technique tend not to be homogeneous but usually container other products, particularly the bis branched chain alkyl product. It is believed that these components contribute significantly to the build up of the dye.

The invention further includes a process for the dyeing and printing of hydrophobic fibres particularly polyester fibres with disperse dyes of general formula 1.

The invention further includes a process for the dyeing and printing of hydrophobic fibres, particularly polyester fibres with one or more compounds of general formula I in admixture with one or more compounds of general formula IV.

Dyes of formula I and mixtures of dyes of formulae I and IV are valuable components in the production of dark node shades particularly dark blue, navy and black shades on hydrophobic fibres, particularly polyester fibres.

Specific example of hydrophobic fibres are cellulose acetate fibres such a secondary cellulose acetate and cellulose triacetate, polyamide fibres, polyacrylonitrile fibres such as "COURTELLE" ("COURTELLE" is a Registered Trade Mark), and in particular polyester fibres such as "TERYLENE" ("TERYLENE" is a Registered Trade Mark).

The dyes are preferably dispersed by grinding with water and a suitable dispersing agent, e.g.

Dyapol PHS. Dyeing may be carried out on cellulose triacetate fibres at 95-11 50C optically in the presence of a carrier, e.g. an emulsion of diethyl phthalate such as that sold as "Optinol TR". Dyeing may be carried out on polyester fibres from an aqueous bath at 95-1 400C optionally in the presence of a carrier, for example, an emulsion of 2-phenylphenol such as that sold as "OPTINOL B". Alternatively the dye dispersion may be thickened with sodium alginate or other thickeners commonly used in textile printing and applied to polyester fabrics in the usual way by padding or printing with a roller or through a screen.After drying the fabric, the dye is fixed, for example by steaming at 1.0-1.7 bar pressure or by heating the fabric in dry air at 1 60-2200C for 30-90 seconds or by heating at 1 70-1 800C for 4-8 minutes with high temperature (superheated) steam. The dyes may also be applied by dyeing or printing on to secondary cellulose acetate, polyamide and polyacrylonitrile fibres by the typical methods of application to these fibres described in the Color Index, Third Edition, 1971 and its supplements, 1975 and 1982 (published by the Society of Dyers and Colourists, Bradford, England.) The dyes of the present invention provide reddish blue to greenish blue shades on hydrophobic fibres and particularly on polyester fibres of excellent build up and high tinctorial strength.By careful selection of these dyes, used in admixture with one another or in an admixture with known dyes of related structure compatible mixtures over the whole hue range can be obtained.

The invention will be more clearly understood by reference to the following examples in which parts and percentages are by weight.

EXAMPLE 1 6.9 parts of sodium nitrate are added with stirring to 70 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to 300C. 26.6 parts of 2-bromo-4,6-dinitroaniline are then added during 30 minutes and the mixture stirred for 3 hours at this temperature. The diazo solution so obtained is added to a solution prepared by dissolving 27.8 parts 5-acetylamino-2-methoxy-N-ethyl-N-3-methylbutylaniline prepared as in Preparation 1 below in 10 parts of 100% sulphuric acid and 500 parts of iced water at OOC and adjusted to pH 4 by the addition of anhydrous sodium acetate. The pH is maintained at 4 during the addition of the diazo component by the portionwise addition of anhydrous sodium acetate.The mixture is stirred for one hour and the dye in which the major component has the formula:

is filtered off, washed acid free and dried.

One part of this dye is added to 18 parts of water and 2 parts of Dyapol PHS and milled in a ball mill until the average particle size of the dye is reduced to 1.5,us.

20 parts of the resultant 5% aqueous dispersion is diluted to 1000 parts with water to form a dyebath. 100 parts of polyester yarn are introduced into the dyebath at room temperature and the temperature is then raised to 1 300C and maintained to one hour in a pressurised dyeing machine. After this time the yarn is removed, rinsed and dried. The polyester fibres are dyed greenish blue shades possessing very good buildup. Normally the build up of a dye is reduced by the introduction of a large alkyl group. Surprisingly the build up of this dye is of the same order as the related dye in which the 3 methyl butyl group is replaced by an ethyl group.

Preparation 1 The 5-acetylamino-2-methoxy-N-ethyl-N-3-methylbutylaniline used for the preparation of the above dye may be prepared as follows: A mixture of 1 8g 4-acetylamino-2-methoxyaniline, 1 5.1 g 3-methylbutyl bromide and 5.3g sodium carbonate is heated together at 1 200C until TLC shows the reaction to be complete. The mixture is added to 65 ml water and the pH adjusted to 9-10 by the addition of sodium hydroxide solution. The temperature is adjusted to 650C and 1 6.8g sodium bicarbonate are added. 30.8g Diethyl sulphate are added dropwise and the mixture stirred until the reaction is complete. After cooling to room temperature the product is isolated, washed with water and dried.

EXAMPLE 2 If the 27.8 parts of 5-acetylamino-2-methoxy-N-ethyl-N-3-methylbutylaniline used in Example 1 are replaced by 27.8 parts of 5-acetylamino-2-methoxy-N-ethyl-N-2-methylbutylaniline the major component of the dye obtained has the formula:

One part of this dye is added to 1 8 parts of water and 2 parts of Dyapol PHS and milled in a ball mill until the average particle size of the dye is reduced to 1-5 ym.

20 parts of the resultant 5% aqueous dispersion is added to a mixture of 5 parts of a galactomannon thickening agent, such as that sold as "Indalca PA 3" and 5 parts of urea in 50 parts of water to form a paste which is then printed through a screen onto polyester fabric. After drying, the print is fixed by steaming for 20 minutes at 1.4 bar pressure. After this time the fabric is removed, washed and dried. The greenish blue print has good fastness to light and washing.

The 5-acetylamino-2-methoxy-N-ethyl-N-2-N-methylbutylaniline may be prepared by condensing 5-acetylamino-2-methoxy-aniline with 2-methylbutyl bromide followed by ethylation according to the procedure described in Preparation 1.

EXAMPLE 3 If the 27.8 parts of 5-acetylamino-2-methoxy-N-ethyl-N-3-methylbutylaniline used in Example 1 are replaced by 24.8 parts of 3-acetylamino-N-ethyl-N-3-methylbutylaniline the main component of the dye obtained has the formula:

and dyes polyester fibres reddish blue shades of very good build up. In spite of the introduction of a large alkyl group the build up of this dye is very similar to the related dye in which the 3-methylbutyl group is replaced by an ethyl group.

The 3-acetylamino-N-ethyl-N-3-methylbutylaniline used in Example 3 may be prepared by condensing 3-acetylamino-aniline with 3-methylbutyl bromide followed by ethylation according to the procedure described in Preparation 1.

In the following table data are given referring to other monoazo dyes of the present invention corresponding to the general formula I which may be prepared and used in accordance with the general methods described previously in the examples.

Shade on Shade on Example X Rl R2 R3 R4 polyester fibres 4 Br OCH3 CH3 CH3 CH2CH2CH(CH3)CH3 Greenish blue 5 Br OCH3 CH3 CH3 CH2CH(CH3)CH2CH3 Greenish blue 6 Br OCH3 CH3 CH3 CH(CH3) CH2CH2CH3 Greenish blue 7 Br OCH3 CH3 O2H1 (CH2)4CH3 Greenish blue 8 C l OCH3 CH3 O2Hs CH2CH(CH3) CH2CH3 Greenish blue 9 Br 00H3 CH3 O2H1 (CH2) 5CH3 Greenish blue 10 Br OCH3 CH3 O2H1 CH2CH(CH3)CH2CH2CH3 Greenish blue 11 Br OCH3 CH3 O2H1 CH2CH2CH2CH(CH3)CH3 Greenish blue 12 CI OCH3 CH3 CH3 CH(CH3) CH2CH2CH2CH3 Greenish blue 13 Cl OC2Hs C2H1 O2H1 CH2CH2CH2CH(CH3) Greenish blue 14 0 l OOH3 CH3 O3H CH2CH2CH2CH(CH3) CH3 Greenish blue 15 CI OCH3 CH3 03H1 Greenish blue 16 Br H CH3 CH3 CH,CH,CH(CHdCH, Reddish blue 17 Br H CH3 CH3 CHi2CH(CH3)CH2CH3 Reddish blue 18 Br H CH3 CH3 CH(CH3)CH2CH2CH3 Reddish blue 19 CI H CH3 O2H5 (CH)4CH3 Reddish blue 20 Br H CH3 O3H1 CH2CH2CH(CH3) CH3 Reddish blue 21 CI H CH3 QHs CH2CH(CH3)CH2CH3 Reddish blue 22 Ci H CH3 O2Ha CH(CH3) CH2CH2CH3 Reddish blue 23 Cl H C2H1 C2H1 CH(CH3) CH2CH2CH3 Reddish blue 24 Cl H O2Hs O3Hs (CH2) ,CH3 Reddish blue 25 Br H CH3 O3H1 CH2CH2CH2CH(CH3)CH3 Reddish blue 26 Cl H O3H7 O3H1 CH2CH(CH3) CH2CH2CH3 Reddish blue 27 Br H CH3 C3H7 CH2CH2CH(CH3) CH3 Reddish blue 28 Br H CH3 O4H9 CH2CH2CH(CH3)CH3 Reddish blue 29 Br H CH3 O2H5 Reddish blue

The dyes described in examples 1-29 which conform to general formula I may be mixed with dyes of general formula IV in which mixtures R1 represents a hydrogen atom which R5 represents an alkoxy group or vice versa to produce reddish blue to greenish blue dyes possessing high tinctorial strength and good build up.

Since the dyes of general formula I encompass products of different dyeing rates, it is possible to select one or more of these, which when used in admixture with one or more suitable compounds of formula IV according to the invention, gives a compatible mixture, (i.e. one which builds up on tone).

Consequently it is possible to produce a compatible blue mixture according to the invention over a hue range from reddish blue to greenish blue, which builds up on tone. Although from a theoretical viewpoint for a given depth of shade the proportion of the components which produce a compatible mixture is fixed in practice small variations in the proportions of the components either side of this figure normally given acceptable results.

EXAMPLE 30 6.9 parts of sodium nitrite are added with stirring to 70 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to 300C. 26.2 parts of 2-bromo-4,6-dinitro aniline are then added during 30 minutes and the mixture stirred for 3 hours at this temperature. The diazo solution so obtained is added to a solution prepared by dissolving a mixture of 8.4 parts 5-acetylamine-2-methoxy-N-ethyl-N-3-methylbutylaniline and 1 4.4 parts of 3-acetylamino-N,N-diethylaniline in 10 parts of 100% sulphuric acid and 500 parts of iced water at OOC and adjusted to pH 4 by addition of anhydrous sodium acetate.The pH is maintained at 4 during the addition of the diazo component by the addition of anhydrous sodium acetate. The mixture is stirred for 1 hour and filtered off, washed acid free and dried.

One part of this dye mixture is added to 18 parts of water and 2 parts of Dyapol PHS and milled in a ball mill until the average particle size of the dye is reduced to 1-5 ym.

20 parts of the resultant 5% aqueous dispersion is diluted to 1000 parts with water to form a dyebath. 100 parts of polyester yarn are introduced into the dyebath at room temperature and the temperature is then raised to 1 300C and maintained for one hour in a pressurised dyeing maching. After this time the yarn is removed, rinsed and dried. The polyester fibres are dyed dark blue shades of very good build up and high tinctorial strength. The dye mixture exhibits the considerable advance of ontone build up.

The same mixture can also be produced by replacing the 20 parts of 5% aqueous dye dispersion above by a mixture comprising 6.6 parts of a 5% aqueous dispersion of the dye of Example 1 and 13.4 parts of a 5% aqueous dispersion of the dye of formula IV wherein X = Br, R5 = H, R6 = CH3 and R7 = C2H5, the latter being prepared in a manner analogous to that described in Example 1.

EXAMPLE 31 The 8.4 parts of 5-acetylamino-2-methoxy-N-ethyl-N-3-methylbutylaniline and 14.4 parts of 3acetylamino-N,N-diethylaniline used in Example 30 are replaced by 7.9 parts of 5-acetylamino-2methoxy-N,N-diethylaniline and 1 6.5 parts of 3-acetylamino-N-ethyl-N-3-methylbutyianiline.

One part of the resultant dye mixture is added to 1 8 parts of water and 2 parts of Dyapol PHS and milled in a ball mill until the average particle size of the dye is reduced to 15,um.

20 parts of the resultant 5% aqueous dispersion is diluted to 1000 parts with water to form a dyebath. 100 parts of polyester yarn are introduced into the dyebath at room temperature and the temperature is then raised to 130 C and maintained for one hour in a pressurized dyeing machine. The polyester fibres are dyed dark blue shades of very good build up and high tinctorial strength. The dye mixture exhibits on-tone build up.

The same mixture can also be formed by replacing the 20 parts of the 5% aqueous dispersion of the dye mixture above by a mixture of 1 3.4 parts of a 5% dispersion of the dye of Example 3 with 6.6 parts of a dye of general formula IV wherein X = Br, R5 = OCH3, R6 = CH3 and R7 = R8 = C2H5, the latter having been prepared by a method analogous to that described in Example 1.

EXAMPLES 32-57 The procedure described in example 31 is repeated whereby there is produced and used, a mixture of dyes A and B in accordance with the following table in which dye A corresponds to the general formula I and dye B corresponds to the general formula IV and in which R1 represents a hydrogen atom, R5 must represent an alkoxy group and when R1 represents an alkoxy group, R5 must represent a hydrogen atom.

DYE A DYE B Eg X R1 R2 R3 R4 X R5 R6 R7 R8 32 Br OCH3 CH3 CH3 CH2CH2CH(CH3)CH3 Br H CH3 C2H5 C2H5 33 Br OCH3 CH3 CH3 CH2CH(CH3)CH2CH3 Br H CH3 C2H5 C2H5 34 Br OCH3 CH3 CH3 CH(CH3)CH2CH2CH3 Br H CH3 C2H5 C2H5 35 Br OCH3 CH3 C2H5 (CH2)4CH3 Br H CH3 C3H7 C3H7 36 Cl OCH3 CH3 C2H5 CH2CH(CH3)CH2CH3 Br H CH3 C2H5 C2H5 37 Br OCH3 CH3 C2H5 (CH2)5CH3 Br H CH3 C2H5 C2H5 38 Br OCH3 CH3 C2H5 CH2CH(CH3)CH2CH2CH3 Cl H C2H5 C2H5 C2H5 39 Br OCH3 CH3 C2H5 CH2CH2CH2CH(CH3)CH3 Cl H C2H5 C2H5 C2H5 40 Cl OCH3 CH3 C2H5 CH(CH3)CH2CH2CH2CH3 Br H C3H5 C2H5 C2H5 41 Cl OCH3 CH3 C2H7 CH2CH2CH2CH(CH3)CH3 Br H CH3 C2H5 C2H5 42 Cl OC2H5 C2H5 C2H3 CH2CH2CH2CH(CH3)CH3 Br H CH3 nC4H9 nC4H9 43 C1 OCH3 CH3 C2H3 CH2CH2CH2(CH3)CH3 Br H CH3 C2H5 CH2CH(CH3)CH3 44 Cl OCH3 CH3 C2H5 CH2CH2CH(CH3)CH3 Br H CH3 CH2CH(CH3)CH3 CH2CH(CH3)CH3 45 Br OCH3 CH3 C2H5 CH2CH2CH(CH3)CH3 Br H CH3 (CH2)4CH3 (CH2)4CH3 46 Br H CH3 CH3 CH2CH2CH(CH3)CH3 Br OCH3 CH3 C2H5 C2H5 47 Br H CH3 CH3 CH2CH(CH3)CH2CH3 Br OCH3 CH3 C2H5 C2H5 48 Br H CH3 CH3 CH(CH3)CH2CH2CH3 Br OCH3 CH3 C3H7 C3H7

DYE A Eg X R1 R2 R3 R4 X R5 R6 R7 R8 49 Cl H CH3 C2H5 (CH2)4CH3 Cl OCH3 CH3 C2H5 C2H5 50 Br H CH3 C2H5 CH2CH2CH(CH3)CH3 Cl OC2H5 CH3 C2H5 C2H5 51 Cl H CH3 C2H5 CH(CH3)CH2CH2CH3 Cl OCH3 CH3 C2H5 C2H5 52 Cl H C2H9 C3H7 CH2CH(CH3)CH2CH2CH3 Br OCH3 CH3 nC4H9 nC4H9 53 Br H CH3 C2H5 (CH2)5CH3 Br OCH3 CH3 C2H5 C2H5 54 Cl H C3H7 C2H5 CH2CH(CH3)CH2CH2CH3 Cl OCH3 CH3 C2H5 C2H5 55 Br H CH3 C2H5 CH2CH2CH(CH3)CH3CH3 Cl OCH3 C3H7 C2H5 C2H5 56 Br H CH3 C2H5 CH(CH3)CH2CH2CH2CH3 Br OCH3 CH3 C2H5 CH2CH(CH3)CH2 57 Br H C3H7 C4H9 CH2CH2CH(CH3)CH3 Br OCH3 CH3 (CH2)4CH3 (CH2)4CH3

EXAMPLE 58 A mixture is prepared of 3.8 parts of a 5% dispersion of the dye of formula I (X = Br, R6 = OCH3, R2 = CH3, R3 = C2H5, R4 = CH2CH2CH(CH3)CH3), 3.8 parts of a 5% aqueous dispersion of the dye of formula I (X = Br, R1 = OCH3, R2 = CH3, R3 = C2H5, R4 = CH2CH(CH3)CH2CH3) and 12.4 parts of a 5% aqueous dispersion of the dye of formula IV (X = Br, R5 = H, R6- CH3, R7 = Era = C2H5) all three dyes having been made by a method analogous to that described in Example 1. This mixture when applied tot polyester by the method described in Example 1 gives dark blue shades of high tinctorial strength exhibiting a tone build up.

Claims

1. A disperse dyestuff of the formula:

wherein X represents a chlorine or bromine atom, R1 represents a hydrogen atom or an alkoxy group containing from 1-4 carbon atoms, R2 represents an alkyl group containing from 1-4 carbon atoms, R3 represents an alkyl group containing from 1-8 carbon atoms, and R4 represents an alkyl group containing from 5-8 carbon atoms.

2. A dyestuff as claimed in claim 1, in which R4 represents a branched chain alkyl group.

3. A dyestuff as claimed in claim 1 or 2, in which R1 represents a hydrogen atom or a methoxy group, R2 represents a methyl group, R3 represents an alkyl group containing 1-4 carbon atoms and R4 is a branched chain alkyl group containing 5-8 carbon atoms.

4. A dyestuff of the general formula I as defined in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.

5. A process for the manufacture of a disperse dye of formula I as defined in claim 1, which comprises coupling a diazotised amine of the formula:

with a coupling component of formula:

wherein X, R1, R2, R3 and R4 have the meanings given in claim 1.

6. A process as claimed in claim 5, in which R4 represents a branched chain alkyl group containing 5-8 carbon atoms.

7. A process as claimed in claim 5, in which R1 represents a hydrogen atom or a methoxy group, R2 represents a methyl group, R3 represents an alkyl group containing 1-4 carbon atoms and R4 represents a branched chain alkyl group.

8. A process for the manufacture of a disperse dye of formula I as defined in claim 1, substantially as herein before described in any one of the foregoing Examples.

9. A mixture of at least one disperse dyestuff as claimed in any one of claims 1 to 4, with at least one dyestuff of general formula:

wherein X represents a chlorine or bromine atom R5 repre,sents a hydrogen atom or an alkoxy group containing 1-4 carbon atoms R6 represents an alkyl group containing 1-4 carbon atoms R7 and R8 each independently represent alkyl groups containing 1-8 carbon atoms and in which mixture, when R1 represents a hydrogen atom, R5 must represent an alkoxy group or when R1 represents an alkoxy group, R5 must represent a hydrogen atom.

10. A mixture as claimed in claim 9, in which R7 and R8 contain 1-4 carbon atoms.

11. A mixture as claimed in claim 9 or 10, in which R2 and R6 represent methyl groups, R3, R7 and R8 contain 1-4 carbon atoms, R4 represents a branched chain alkyl group containing 5-8 carbon atoms and R1 represents a hydrogen atom when R5 represents a methoxy group or R1 represents a methoxy group when R5 represents a hydrogen atom.

12. A mixture as claimed in claim 9, substantially as hereinbefore described in any one of the foregoing Examples.

13. A process of manufacture of a mixture of disperse dyes of formulae I and IV in which a diazotised amine of general formula II as defined above is coupled to a mixture of coupling components containing at least one coupling component of formula:

and at least one coupling component of formula:

wherein R1, R2, R3 and R4 have the meanings given in claim 1 and R5, R6, R7 and R8 have the meanings given in claim 9, and in which mixture, when R1 represents a hydrogen atom, R5 represents an alkoxy group or when R1 represents an alkoxy group, R5 represents a hydrogen atom.

14. A process as claimed in any one of Claims 10 to 12, in which dyeing is carried out on polyester fibres from an aqueous bath at 95--1400C optionally in the presence of a carrier.

1 5. A process as claimed in any of claims 10 to 12, in which a dispersion of the dye or dye mixture is thickened with a thickener and applied to a polyester fabric by padding or printing with a roller or through a screen, the fabric is dried and the dye is fixed.

14. A Process as claimed in claim 13, in which R7 and R8 contain 1-4 carbon atoms.

1 5. A process as claimed in claim 1 3 or 14, in which R2 and R6 represent methyl groups, R3, R7 and R8 contain 1-4 carbon atoms, R4 represents a branched chain alkyl group of 5-8 carbon atoms and when R1 represents a hydrogen atom, R5 represents a methoxy group or R1 represents a methoxy group and R5 represents a hydrogen atom.

16. A process for the manufacture of a mixture as claimed in claim 9, which comprises admixing at least one disperse dye of general formulae I as defined in claim 1 and at least one disperse dye of general formula IV as defined in claim 9, subsequent to their manufacture.

17. A process for the manufacture of a mixture as claimed in claim 9, substantially as hereinbefore described in any one of the foregoing Examples.

18. A process for the dyeing and printing of hydrophobic fibres in which a disperse dye as claimed in any on of claims 1 to 4 is used.

19. A process for the dyeing and printing of hydrophobic fibres in which a mixture as claimed in any one of claims 9 to 12 is used.

20. A process as claimed in claim 18 or 19, in which the hydrophobic fibres are cellulose acetate fibres, such as secondary cellulose acetate and cellulose triacetate, poiyamide fibres. polyacrylonitrile fibres or polyester fibres.

21. A process as claimed in any one of claims 18 to 20, which the dye or dye mixture is dispersed by grinding with water and a suitable dispersing agent.

22. A process as claimed in any one of claims 1 8 to 21, in which dyeing is carried out on cellulose triacetate fibres at 95-11 50C optically in the presence of a carrier.

23. A process as claimed in any one of claims 18 to 21, in which dyeing is carried out on polyester fibres from an aqueous bath at 95-1 400C optionally in the presence of a carrier.

24. A process as claimed in any one of claims 1 8 to 21, in which a dispersion of the dye or dye mixture is thickened with a thickener and applied to a polyester fabric by padding or printing with a roller or through a screen, the fabric is dried and the dye is fixed.

Superseded claims 1-24 New or ammended claims:-- Claims 1-15

1. A mixture of at least one dyestuff of formula:

with at least one dyestuff of formula:

wherein X represents a chlorine or bromine atom R1 represents a hydrogen atom or an alkoxy group containing from 1-4 carbon atoms, R2 represents an alkyl group containing from 1-4 carbon atoms, R3 represents an alkyl group containing from 1-8 carbon atoms, R4 represents an alkyl group containing from 5-8 carbon atoms, R5 represents a hydrogen atom or an alkoxy group containing 1-4 carbon atoms, R8 represents an alkyl group containing 1-4 carbon atoms, R7 and R8 each independently represents alkyl groups containing 1-8 carbon atoms and in which mixture, when R1 represents a hydrogen atom, R5 must represent an alkyl group or when R1 represents an alkoxy group, R5 must represent a hydrogen atom.

2. A mixture as claimed in Claim 1, in which R7 and R8 contain 1-4 carbon atoms.

3. A mixture as claimed in Claim 1 or 2, in which R2 and R6 represent methyl groups R3, R7 and R8 contain 1-4 carbon atoms, R4 represents a branched chain alkyl group containing 5-8 carbon atoms and R1 represents a hydrogen atom when R5 represents a methoxy group or R1 represents a methoxy group when R5 represents a hydrogen atom.

4. A mixture as claimed in Claim 1, substantially as hereinbefore described in any one of the foregoing Examples.

5. A process of manufacture of a mixture of disperse dyes of formula I and Il in which a diazotised amine of general formula:

is coupled to a mixture of coupling components containing at least one coupling component of formula:

and at least one coupling component of formula:

wherein R1, R2, R3, R4, R5, R6, R7 and R8 have the meanings given in Claim 1, and in which mixture, when R1 represents a hydrogen atom, R5 represents an alkoxy group or when R1 represents an alkoxy group.

R5 represents a hydrogen atom.

6. A process as claimed in Claim 5, in which R7 and R5 contain 1-4 carbon atoms.

7. A process as claimed in Claim 5 or 6, in which R2 and R6 represent methyl groups. R3, R7 and R8 contain 1 4 carbon atoms, R4 represents a branched chain alkyl group of 5-8 carbon atoms and when R1 represents a hydrogen atom, R5 represents a methoxy group or R1 represents a methoxy group and R5 represents a hydrogen atom.

8. A process for the manufacture of a mixture as claimed in Claim 1, which comprises admixing at least one disperse dye of general formula I as defined in Claim 1 and at least one disperse dye of general formula II as defined in Claim 1, subsequent to their manufacture.

9. A process for the manufacture of a mixture as claimed in Claim 1, substantially as hereinbefore described in any one of the foregoing examples.

10. A process for the dyeing and printing of hydrophobic fibres in which a disperse dye mixture as claimed in any one of Claims 1 to 4 is used.

11. A process as claimed in Claim 10, in which the hydrophobic fibres are cellulose acetate fibres.

such as secondary cellulose acetate and cellulose triacetate, polyamide fibres, polyacrylonitrile fibres or polyester fibres.

12. A process as claimed in Claims 10 or 11 in which the dye or dye mixture is dispersed by grinding with water and a suitable dispersing agent.

13. A process as claimed in any one of Claims 10 to 12, in which dyeing is carried out on cellulose triacetate fibres at 95-11 1 500 optionally in the presence of a carrier.