GB2115433A

GB2115433A - Monoazo disperse dyes

Info

Publication number: GB2115433A
Application number: GB08205231A
Authority: GB
Inventors: Keith Bramham
Original assignee: Yorkshire Chemicals Ltd
Current assignee: Yorkshire Chemicals Ltd
Priority date: 1982-02-23
Filing date: 1982-02-23
Publication date: 1983-09-07
Also published as: GB2115433B

Abstract

There are disclosed blue monoazo disperse dyes free from carboxylic acid and sulphonic acid groups which is of the general formula:- <IMAGE> wherein: R<1> is an alkyl or aralkyl group, R<2> is a group of formula -C2H4COOR<4> R<3> is an alkyl group and R<4> is an alkyl or alkoxyalkyl group and wherein all alkyl and alkylene groups contain 1 to 4 carbon atoms. There are also disclosed methods for their preparation and their use in the colouration of hydrophobic fibres, especially polyester fibres.

Description

SPECIFICATION Blue monoazo disperse dyes This invention relates to blue monoazo disperse dyes which are valuable for colouring synthetic textile materials, in particular, polyester textile materials.

G.B. Patent Specification No. 1125683 discloses dyestuffs of the general formula:

in which A denotes an aromatic-carbocyclic radical in which the CN group is in an ortho position to the azo group, and K is the radical of a coupling component.

These dyestuffs are described as being suitable for the dyeing of hydrophobic materials and the colourations obtained vary from red to violet, through various shades of red, blue and violet.

Within the general formula given above, blue azo disperse dyes are known which have the general formula

wherein Y1 andY2 are optionally substituted lower alkyl or aralkyl groups, Y3 iS a lower alkyl group and Z is a nitro or a cyano group. Typically, these dyes are prepared by the diazotisation of an amine of general formula:

where Hal is a halogen atom and coupling it to a compound of general formula:

followed by treatment with cuprous cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound to replace the halogen atom with a cyano group.

Particularly important dyes for application to polyester fibres are those in which Y1 and Y2 are unsubstituted, because they produce clear mid to greenish blue hues. Where both Y1 and Y2 are substituted the resultant dyes tend to be redder blues or bluish violets which have less wide application. Where only one of Y1 or Y2 iS substituted, the hues tend to be acceptable mid blues but in many of these dyes, the introduction of only one substituted group Y1 or Y2 during the manufacture of the coupling component Ill is difficult to control and frequently resuits in products which need purification before preparation of the final dye.

In general, those dyes of formula I in which Z is a nitro group are to be preferred to those where Z is a cyano group, because the latter when dyed in admixture with certain other dyes, especially certain yellow dyes, tend to give dyeings which show unexpectedly low light fastness, (sometimes referred to as anomalous or catalytic fading).

Until dyes of this type were developed, disperse dyes with clear mid-blue shades were normally based on anthraquinone structures. The azo dyes were found to be more economical to produce and to have a greater tinctorial strength than anthraquinone dyes of similar hue. In general, however, the blue anthraquinone dyes have the advantage of superior dyeing properties. That is, they dye more rapidly and exhaust well at lower temperatures than the blue azo dyes.

Dyes with good dyeing properties are particularly suited for use in machines designed for rapid dyeing, which incorporate the facility for high rates of rise in temperatue during the heating up stage of the dyeing, coupled with particularly efficient liquor circulation around or through the material to be dyed. On polyester fibres, for example, dyes with good dyeing properties, especially with respect to good exhaustion within practical dyeing times at temperatures significantly below the 1 300C frequently employed to dye this fibre, can not only save on dyeing time but on energy usage.

They minimise or eliminate the effects of temperature variations which can occur due to control problems with the dyeing machines. They can be used on texturised or other materials which may be adversely affected by dyeing at too high temperatures.

We-have now surprisingly found that dyes of general formula I where Z is a nitro group and one of Y1 and Y2 iS an alkyl group and the other is an alkoxy-carbonylethyl group, which dyes are not specifically disclosed in G.B. Specification No. 1125 683, are clear mid blue dyes which have certain advantages. They do not suffer from unexpectedly low light fastness in admixture with certain other dyes as do many of the dyes where Z is a cyano group, and have coupling components of general formula Ill which are economically prepared by a readily controlled reaction and so do not require purification before use.In addition to these advantages we have been surprised to find that on polyester fibres these dyes have especially good dyeing properties, particularly with reference to sensitivity to temperature of dyeing and show notable advantages in this respect in comparison with those dyes in which Y1 and Y2 are unsubstituted and with those in which Z is a cyano group.

According to the present invention therefore, there are provided blue monoazo disperse dyes free from carboxylic acid and sulphonic acid groups which have the general formula:

wherein: R1 is an alkyl or aralkyl group, R2 is a group of formula -C2H4COOR4 R3 is an alkyl group and R4 is an alkyl or alkoxyalkyl group and wherein all alkyl and alkylene groups contain 1 to 4 carbon atoms.

The preferred dyes are those where: R1 is an alkyl group of 1 to 4 carbon atoms R2 is a group offormula -C2H4COOR4 R3 is an alkyl group of 1 or 2 carbon atoms, and R4 is an alkyl group of 1 to 3 carbon atoms.

As examples of group R1 may be mentioned, methyl ethyl, propyl, iso-propyl, n-butyl, benzyl and phenyl-propyl, whilst examples of group R3 are methyl, ethyl and propyl and examples of R4 are methyl, ethyl, propyl, methoxyethyl, ethoxyethyl, ethoxymethyl, propoxyethyl and butoxyethyl.

The dyes of the present invention can be obtained by known methods such as that described, for example, in our British Patent Application 81 26755. The preferred process, comprises reacting a compound of general formula:

wherein Hal is a halogen atom, preferably chlorine or bromine, and R1, R2 and R3 have the meanings given above, with cuprus cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound in an organic solvent, organic solvent/aqueous or aqueous medium.

The compound of formula V is prepared by diazotising an amine of formula:

and coupling this to a coupling component of general formula:

where Hal, R1, R2 and R3 have the meanings given above.

Specific examples of coupling components of general formula VII are: 3:acetylamino-N-methyl-N-(ss-methoxywarbonylethyl) aniline 3-acetylamino-N-ethyl-N-(ss-methoxywarbonylethyl) aniline 3-acetylamino-N-n-propyl-N-(ss-methoxycarbonylethyl) aniline 3-acetylamino-N-iso-propyl-N-(ss-methoxywarbonylethyl) aniline 3-acetylamino-N-n-butyl-N-(ss-methoxywarbonylethyl) aniline 3-acetylamino-N-methyl-N-(ss-ethoxywarbonylethyl) aniline 3-acetylamino-N-n-propyl-N-(ss-ethoxywarbonylethyl ) aniline 3-acetylamino-N-n-butyl-N-(f3-ethoxycarbonylethyl) aniline 3-acetylamino-N-methyl-N-[ss-(ss-methoxyethoxy)carbonylethyl] aniline 3-acetyiamino-N-ethyl-N-[ss-(ss'methoxyethoxy)carbonylethyl] aniline 3-acelamino-N-isoprnpyI-N-[4-methoxyethoxy)carbonyIethyl] aniline 3-acetylamino-N-ethyl-N-[ss-(ss'-ethoxyethoxy)carbonylethyl]anil ine 3-acetylamino-N-n-butyl-N [P-(p'-methoxyethoxy)carbonylethyl] aniline 3-acetylamino-N-methyl-N-(ss-propoxycarbonylethyl ) aniline 9-acetylami no-N-ethyl-N-(P-isopropoxycarbonylethyl) aniline 3-propionylamino-N-ethyl-N-(P-methoxyca rbonylethyl) aniline 3-propionyla mino-N-n-propyi-N-(ss-methoxycarbonylethyl) aniline 3-propionylamino-N-n-butyl-N-(p-methoxycarbonylethyl) aniline 3-acetylamino-N-benzyl-N-((3-methoxycarbonylethyl) aniline 3-acetylamino-N-benzyl-N-(-ethoxycarbonyIethyl) aniline 3-propionylamino-N-benzyl-N-(ss-methoxycarbonylethyl) aniline 3-acetylam ino-N-benzyl-N-ss-[ss'-(methoxyethoxy)carbonylethyl] aniline 3-acetylamino-N-phenylpropyl-N-(P-methoxycarbonylethyl) aniline 3-propionylamino-N-phenylpropyl-N-(ss-methoxyearbonylethyl) aniline 3-acetylamino-N-ethyl-N-(ss-n-propoxywa rbonylethyl) aniline 3-acetylamino-N-ethyl-N-(ss-n-butoxycarbonylethyl) aniline The invention also includes a process for the dyeing and printing of hydrophobic fibres, especially polyesterfibres in which the dye used is an azo dye of general formula IV.

Specific examples of hydrophobic fibres are cellulose acetate fibres such as 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 SL.

Dyeing may be carried out on polyester fibres from, for example, an aqueous bath at 95-100"C containing a carrier, e.g. an emulsion of 2-phenylphenol such as that sold as "Optinol B" or in pressurised vessels at 100-140"C. 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 160-220" for 30-90 seconds or by heating at 170-180"C for 4-8 minutes with high temperature (superheated) steam.The dyes may also be applied by dyeing or printing on to secondary cellulose acetate, triacetate, polyamide and polyacrylonitrile fibres by the typical methods of application to these fibres described in the Colour Index, Third Edition, 1971 (published by the Society of Dyers & Colourists, Bradford, England).

The prints and dyeings produced have good fastness to light and sublimation and very good fastness to wet treatments, especially when applied to polyester fibres.

We have been surprised to find that the dyes which are subject of the invention have particularly good dyeing properties, especially on polyester fibres. Consequentiy, they are particularly suitable for application to polyester fibres in machinery designed for rapid dyeing cycles which feature a rapid rate of rise of temperature during the heating upstage of the dyeing, coupled with particularly efficient liquor circulation around or through the material being dyed. They are also suitable for application to texturised material as they may be applied at temperatures below 125"C to preserve the textured effect. In all types of dyeing machinery, their insensitivity to temperature variation enables reproducible shades to be obtained without critical control of dyeing temperature.

Because of these good dyeing properties they can be considered for use in areas of application traditionally occupied by certain less economical anthraquinone based dyes.

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

Example 1 This Example illustrates the type of process which may be employed to prepare dyes of general formula IV according to the invention.

6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at300C by external cooling. The temperature is then raised to 70"C before cooling to 300C. 26.2 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 of 26.4 parts of 3-acetylamino-N ethyl:N-(ss-methoxywarbonylethyl) aniline in 40 parts of 100% sulphuric acid and 500 parts of iced water at 0 C. The mixture is stirred for one hour when the precipitated dye of formula:

is filtered off, washed acid free and dried.

48.4 parts of the above dye are dissolved in 70 parts dimethylformamide and the solution is added to a slurry of 1.14 parts of cuprous cyanide in 20 parts of dimethylformamide.

The mixture is stirred for four hours at 70-80"C, cooled and filtered. The dye, precipitated by the addition of water to the filtrate and filtered off, treated with aqueous ferric chloride solution to remove copper salts, washed with water and dried has the formula:

One part of the above dyestuff and two parts of Dyapol SL are added to 20 parts of water and milled in a ball mill until the average particle size of the dye is reduced to 1-5 Fm, before dilution 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 1300C and maintained for one hour in a pressurised dyeing machine.

After this time the yarn is removed, rinsed and dried. The polyester fibres are dyed blue shades of very good fastness to light, washing and sublimation.

Example 2 One part of the dye of formula

and two parts of Dyapol SL are added to 20 parts of water and milled in a ball mill until the average particle size of the dye is reduced to 1-5 Rm. This is then added to a mixture of 5 parts of a galactomannan thickening agent, such as that sold as "Indalca PA3", 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 blue print so obtained has very good fastness to light, washing and sublimation.

Example 3 The dyes within the scope of the invention have particularly good dyeing properties, especially in respect of sensitivity to temperature variations in dyeing. A convenient way of demonstrating the effect of temperature on the dyeing of disperse dyes on polyester is to produce a number of dyeings of the dye under examination, which differ from one another only in the final temperature of dyeing.

In this example the dyes concerned are applied to polyester piece at percentage shades which give 2/1 standard depths when dyed at 1 300C for 45 minutes at pH 4.5. Dyeings at these percentages are made for 45 minutes at the following temperatures:- 110 C, 115 C, 1 200C and 1 30"C. In each case the temperature is raised to the dyeing temperature as quickly as the machine allows. Cooling at the end of the dyeing period is also as rapid as possible. The dyeings are removed from the liquors and squeezed. These liquors are then used to dye fresh polyester pieces at 1300C for 45 minutes as an indication of the dye remaining in the bath at the end of the first dyeing.

Visual comparison of these two sets of dyeings with dyeings of the same dye produced at a range of depths at 130"C for 45 minutes enable approximate comparative percentage exhaustion figures to be produced for the first set of dyeings at the different temperatures.

In the table below, % exhaustion figures from the above experiment are given for a series of dyes. Of these only structure (a) is a dye of general Formula IV according to the invention. The remainder are related dyes included by way of comparison.

Structure Approximate % exhaustion of 2/1 (see above) standard depth dyeing after 45 mins at temperature:- R2 1300C 1200C 115"C llO"C a -C2H4COOCH3 99 99 98 97 b (CH2)3CsH5 99 98 93 68 c -C2H5 99 98 86 51 d -C2H40COCH3 99 99 96 60 These results clearly show that the dye of the invention (Structure (a)) in which R2 is an alkoxycarbonylethyl group, dyes much more rapidly at temperatures in the region of 1 10"C or 11 5"C than do those dyes where R2 is an alkyl group (Structure (c)) or an aralkyl group (Structure (b)). It is also superior to structure (d) in which R2 is an alkylcarbonyloxyethyl group, a group found in many azo disperse dyes.

Example 4

Two dyes one a dye of general formula IV according to the invention, in which R in the above structure is a nitro group and one in which R is a cyano group is dyed on polyester piece at 2/1 standard depths as in the previous example. The percentage exhaustion of each dye is estimated as in the previous example and is recorded in the following table.

Structure Approximate % exhaustion of 2/1 standard depth dyeing after 45 mins.

at temperature: R 1300C 120"C 115"C llO"C a -NO2 99 99 97 96 b -CN 99 89 72 45 These results clearly show the advantages of the dye in which R is a nitro group compared to the dye where R is a cyano group.

Example 5 Two dyes are dyed onto polyester fabric at 130"C for 1 hour. One dye is a dye of general formula IV according to the invention in which R in the above formula is a nitro group and the other dye is one in which R is a cyano group. Both give similar mid blues which when examined as self-shades are both found to have very good light fastness. They are then dyed in admixture with C.I. Disperse Yellow 126, also a dye of good light fastness. The bright greens based on the dye of the invention (R = - NO2) have very good light fastness, much as would be expected from such a mixture, but those based on the dye where R is a cyano group have poor light fastness, fading to a blue shade, the yellow dye being rapidly destroyed in the presence of the blue dye.

Example 6 1.5g of the dye from Preparation 1 is milled with 1.5g dispersing agent (Dyapol SL) as in Example 1. The resulting milled paste is added to a 6 litre dyebath set with 0.3 ml/l acetic acid and 1 ml/l Dyapol SL in a small scale circulation dyeing machine. The machine is loaded with a 5009 cheese of textured polyesteryarn and dyeing commenced at 65"C. The temperature is raised at 5 C/minute to 1200C where it is maintained for 25 minutes. After cooling rapidly, the cheese is rinsed well and dried.

The yarn is dyed to a full bright mid blue shade having good fastness to light, sublimation and washing.

The yarn fully maintains its textured effect during the dyeing process.

The mid blue dyes of general formula IV shown in the following table also have very good dyeing properties and fastness properties together with freedom from unexpectedly poor light fastness in admixture with certain other dyes, especially certain yellow dyes. They may be prepared according to the method described in Example 1 and used according to the methods described in any of the foregoing examples.

Ex. R' R3 R4 No. R1 R3 R4 7 -CH2CH2CH3 -CH3 -CH3 8 -CH(CH3)2 -CH3 -CH3 9 -CH3 -CH3 -CH2CH3 10 -CH2CH2CH3 -CH3 -CH2CH3 11 -CH2CH2CH2CH3 -CH3 -CH2CH3 12 -CH3 -CH3 -CH2CH20CH3 13 -CH2CH3 -CH3 -CH2CH20CH3 14 -CH2CH3 -CH3 -CH2CH20CH2CH3 15 -CH(CH3)2 -CH3 -CH2CH20CH3 16 -CH2CH2CH2CH3 -CH3 -CH2CH20CH3 17 -CH3 -CH3 -CH2CH2CH3 18 -CH2CH3 -CH3 -CH(CH3)2 19 -CH2CH3 -CH2CH3 -CH3 20 -CH2CH2CH3 -CH2CH3 -CH3 21 -CH2CH2CH2CH3 -CH2CH3 -CH3 22 -CH2C6H5 -CH3 -CH3 23 -CH2C6H5 -CH3 -CH2CH3 24 -CH2C6H5 -CH2CH3 -CH 25 -CH2C6Hs -CH3 -CH2CH2OCH3 26 -CH2CH2CH2C6H5 -CH3 -CH 27 -CH2CH2CH2C6H5 -CH2CH3 -CHs 28 -CH2CH3 -CH3 -CH2CH2CH3 29 -CH2CH3 -CH3 -CH2CH2CH2CH3 CLAIMS (filed on 25.1.83) 1. A blue monoazo disperse dye free from carboxylic acid and sulphonic acid groups which is of the general formula:

2. A dye as claimed in claim 1, in which R1 is an alkyl group of 1 to 4 carbon atoms R2 is a group of formula -C2H4COOR4 R3 is an alkyl group of 1 or 2 carbon atoms, and R4 is an alkyl group of 1 to 3 carbon atoms.

3. A dye as claimed in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.

4. A process for the preparation of a dye of the general formula I as defined in claim 1, which comprises reacting a compound of general formula:

wherein Hal is a halogen atom, and R1, R2 and R3 have the meanings given in claim 1, with cuprous cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound in an organic solvent, organic solvent/aqueous or aqueous medium.

5. A process as claimed in claim 4, in which Hal is chlorine or bromine.

6. A process as claimed in claim 4 or 5, in which R', R2, R3 and R4 have the meanings given in claim 2.

7. A process for the preparation of a dye of general formula I as defined in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.

8. A process for the dyeing and/or printing of hydrophobic fibres, in which the dye used is an azo dye as claimed in any one of claims 1 to 3.

9. A process as claimed in claim 8, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyacrylonitrile fibres or polyester fibres.

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

Claims

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

20 -CH2CH2CH3 -CH2CH3 -CH3

21 -CH2CH2CH2CH3 -CH2CH3 -CH3

22 -CH2C6H5 -CH3 -CH3

23 -CH2C6H5 -CH3 -CH2CH3

24 -CH2C6H5 -CH2CH3 -CH 25 -CH2C6Hs -CH3 -CH2CH2OCH3

26 -CH2CH2CH2C6H5 -CH3 -CH 27 -CH2CH2CH2C6H5 -CH2CH3 -CHs

28 -CH2CH3 -CH3 -CH2CH2CH3

29 -CH2CH3 -CH3 -CH2CH2CH2CH3 CLAIMS (filed on 25.1.83) 1.A blue monoazo disperse dye free from carboxylic acid and sulphonic acid groups which is of the general formula:

wherein: R1 is an alkyl or aralkyl group, R2 is a group of formula -C2H4COOR4 R3 is an alkyl group and R4 is an alkyl or alkoxyalkyl group and wherein all alkyl and alkylene groups contain 1 to 4 carbon atoms.
2. A dye as claimed in claim 1, in which R1 is an alkyl group of 1 to 4 carbon atoms R2 is a group of formula -C2H4COOR4 R3 is an alkyl group of 1 or 2 carbon atoms, and R4 is an alkyl group of 1 to 3 carbon atoms.
3. A dye as claimed in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.
4. A process for the preparation of a dye of the general formula I as defined in claim 1, which comprises reacting a compound of general formula:

wherein Hal is a halogen atom, and R1, R2 and R3 have the meanings given in claim 1, with cuprous cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound in an organic solvent, organic solvent/aqueous or aqueous medium.
5. A process as claimed in claim 4, in which Hal is chlorine or bromine.
6. A process as claimed in claim 4 or 5, in which R', R2, R3 and R4 have the meanings given in claim 2.
7. A process for the preparation of a dye of general formula I as defined in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.
8. A process for the dyeing and/or printing of hydrophobic fibres, in which the dye used is an azo dye as claimed in any one of claims 1 to 3.
9. A process as claimed in claim 8, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyacrylonitrile fibres or polyester fibres.
10. A process as claimed in claim 8 or 9, in which the dye is dispersed by grinding with water and a

dispersing agent.
11. A process as claimed in any one of claims 8 to 10, in which polyester fibres are dyed from an aqueous bath at 95-100"C containing a carrier, or in a pressurised vessel at 100-140"C.
12. A process as claimed in any one of claims 8 to 10, in which the dye dispersion 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.
13. A process for the colouration of hydrophobic fibres substantially as hereinbefore described in any one of the foregoing Examples.