GB2108141A

GB2108141A - Mixtures of disperse azo dyes

Info

Publication number: GB2108141A
Application number: GB08126775A
Authority: GB
Inventors: John Frederic Dawson; Keith Bramham; Andrew William Pitt
Original assignee: Yorkshire Chemicals Ltd
Current assignee: Yorkshire Chemicals Ltd
Priority date: 1981-09-04
Filing date: 1981-09-04
Publication date: 1983-05-11
Also published as: GB2108141B

Abstract

There is disclosed a mixture of two or more monoazo dyes of the formula: <IMAGE> wherein R represents a cyano or a nitro group, R<1> represents a hydrogen atom or an alkyl or alkanoylamino group, R<2> represents a substituted or unsubstituted alkyl or aralkyl group, R<3> represents a substituted or unsubstituted alkyl group; provided that the mixture contains at least one component in which R<1> is an alkanoylamino group and one component in which R<1> represents an alkyl group or a hydrogen atom. There are also disclosed processes for making such mixtures and their use in dyeing and printing hydrophobic fibres shades of blue.

Description

SPECIFICATION Mixtures of disperse azo dyes The invention relates to disperse azo dyes and more particularly to mixtures of two or more disperse monoazo dyes of closely related structure, to a process for the manufacture of the said mixtures and to the application of the said mixtures to hydrophobic fibres, particularly polyester fibres.

According to the present invention therefore there is provided a mixture of two or more monoazo dyes of the formula:

wherein R represents a cyano or a nitro group, R' represents a hydrogen atom or an alkyl or alkanoylamino group, R2 represents an optionally substituted alkyl or aralkyl group, R3 represents an optionally substituted alkyl group provided that the mixture contains at least one component in which R' is an alkanoylamino group and one component in which R1 represents an alkyl group or a hydrogen atom. The groups R2 and R3 in the two or more dyes are not necessarily the same.

The preferred dyes are those in which the alkyl groups contain 1-4 carbon atoms and are unsubstituted.

A specially preferred mixture of dyes according to the present invention is that comprising two dyes of formula I in one of which R is NO2, R1 is NHCO alkyl, R2 is C3H6 phenyl, R3 is alkyl and in the other of which R is NO2, R', R2 and R3 are independently alkyl respectively, the alkyl groups containing 1-4 carbon atoms.

When the mixture of dyes comprises only two components, then these components may be present in the'mixture in a ratio of from 95:5 to 5:95 parts by weight, preferably from 20:80 to 80:20 parts by weight.

The invention also includes a process for the manufacture of disperse dyes of formula I which comprises reacting a mixture of at least two dyes of formula:

wherein R1, R2 and R3 have the meanings given above, R4 represents a chlorine, bromine or iodine atom and R5 represents a chlorine, bromine or iodine atom or a cyano or nitro group, in known manner with cuprous cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound in an organic solvent or an aqueous medium.

The mixture of dyes of formula II may be obtained by coupling a mixture of at least two coupling components of formula:

wherein R', R2 and R3 have the meanings stated above with a diazonium compound obtained by the diazotisation of an amine of formula:

wherein R4 and R5 have the meanings given above.

In addition to preparing mixtures of dyes according to the invention from mixed coupling components the mixtures may clearly be obtained by mixing together the individually prepared component dyestuffs of the mixture obtained by conventional diazotisation, coupling and cyanisation reactions from an amine of formula IV and a coupling component of formula Ill.

Specific examples of amines of general formula IV which may be used for preparing the diazo components are: 2-bromo-4,6-dinitroaniline 2-bromo-4-nitro-6-cyanoani line 2,6-dibromo-4-nitroaniline 2-chloro-4,6-dinitroaniline 2-chloro-4-nitro-6-cyanoaniline 2,6-dichloro-4-nitroaniline 2-iodo-4,6-dinitroaniline Specific examples of amines of general formula III which may be used as coupling components are:: N-ethyl-N-y-phenylpropyl-3-methylaniline N,N-diethylaniline N,N-di-n-propylaniline N-ethyl-N-benzylaniline N-ethyl-N-y-phenylpropylaniline N,N-diethyl-3-methylaniline N,N-di-n-propyl-3-methylaniline N-ethyl-N-benzyl-3-methylaniline N-butyl-N-benzyl-3-methylaniline N-ethyl-N-y-phenylpropyl-3-acetylaminoaniline N-ethyl-N-y-phenylpropyl-3-propionylaminoaniline N,N-diethyl-3-acetylaminoaniline N,N-diethyl-3-propionylaminoaniline N,N-di-n-propyl-3-acetylaminoaniline N-ethyl-N-benzyl-3-acetylaminoaniline N-ethyl-N-P-acetoxyethyl-3-methylaniline N-butyl-N-p-ethoxycarbonyloxyethyl-3-methylaniline N-ethyl-N-/3-cyanoethylaniline-3-methylaniline N-ethyl-N-/3-acetoxyethyi-3-acetyla minoani line N-buWl-N--ethoxycarbonyloxyethyl-3-acetyIaminoaniline N-ethyl-N-,B-cyanoethyl-3-acetylaminoaniline The invention further includes a process for the dyeing and printing of hydrophobic fibres with mixtures of dyes corresponding to general formula I.

The dye mixtures of the present invention provide blue shades on hydrophobic fibres and particularly on polyester fibres which have very good build up properties and high tinctorial strength superior to the effect achieved by the application of any single component of the dye mixture on its own. The mixtures produce shades of similar brightness and hue to a number of anthraquinone dyes, for example Colour Index Disperse Blue 56 but offer the advantage over these dyes of higher tinctorial strength and economy of manufacture.

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 cellulose triacetate fibres from an aqueous bath at 95 100C containing 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, for example, an aqueous bath at 95-1 000C containing a carrier, e.g. an emulsion of 2-phenylphenol such as that sold as "Optinol B" or in pressurised vessels at 125-1 400 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 at 1.0-1.7 bar pressure or by heating the fabric in dry air at 1 60-2200C for 3090 seconds or by heating at 1 70-1 8O0C 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 Colour Index, Third Edition, 1971 (published by the Society of Dyers S Colourists, Bradford, England).

The preparation of certain preferred dyes for the preferred mixtures according to the present invention is described below, the parts and percentages being by weight.

Preparation 1 Diazotisation and coupling of 2-Bromo-4.6-dinitroaniline to N-t-phenylpropyl-N-ethyl-3- acetylaminoaniline 6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to 300 C. 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 29.6 parts of N-y-phenylpropyl-N-ethyl-3-acetylaminoaniline in 40 parts of 100% sulphuric acid and 500 parts of iced water at 00 C. the mixture is stirred for one hour when the precipitated dye of formula:

is filtered off, washed acid free and dried.

Preparation 2 Preparation of 2-Acetylamino-4-(N-y-phenylpropyl-N-ethyl)amino-2'-cyano-4',6'- dinitroazobenzene 5.69 parts of 2-acetylamino-4-(N-y-phenylpropyl-N-ethyl)amino-2'-bromo-4',6'- dinitroazobenzene 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 70-800C, cooled and filtered. The dye is 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.

Preparation 3 Preparation of 2-Methyl-4-(N,N-diethyl)amino-2'-cyano-4',6'-dinitroazobenzene 2-Bromo-4,6-dinitroaniline (26.2 parts) is diazotised and coupled with N,N-diethyl-3methylaniline (16.3 parts) and the product reacted with cuprous cyanide (1.14 parts) by an identical procedure to the one described above.

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

Example 1 One part of the dye of formula I in which R=NO7, R1=NHCOCH3,

and R3=C2H5. (Dye X) is added to 20 parts of water and 2 parts of Dyapol SL and milled in a bail mili until the average particle size of the dye is reduced to 15,um. One part of the dye of formula I in which R=NO2, R'=CH3, R2=R3=C2H5. (Dye Y) is similarly added to 20 parts of water and 2 parts of Dyapol SL and milled in a ball mill until the average particle size of the dye is reduced to 1-5 ym.

14.0 parts of the 5% aqueous dispersion of Dye X and 6.0 parts of the 5% aqueous dispersion of Dye Y are mixed and 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 machine. After this time the yarn is removed, rinsed and dried. The polyester fibres are dyed blue shades of very good build up and tinctorial strength.

Example 2 The dyeing procedure described in Example 1 is repeated except that the 14 parts of 5% aqueous dispersion of the dye X and the 6.0 parts of 5% aqueous dispersion of the dye Y are replaced by the following amounts: Ag. disp. of Ag. disk. of Dye X Dye Y (i) 19.00 1.00 (ii) 16.00 4.00 (iii) 10.00 10.00 (iv) 9.00 11.00 (v) 3.00 17.00 (vi) 1.00 19.00 Blue dyeings of high tinctorial strength are obtained on polyester material.

Examples 3 to 18 The dyeing procedure described in Example 1 is repeated using a mixture of 14 parts of a 5% aqueous dispersion of the dye indicated as Dye A in the following Table and 6.0 parts of a 5% aqueous dispersion of the dye indicated as Dye B in the following Table. Dyes A and B are of the general formula

1} UYB A UYE 1) II 1 3 P 3 Exampio R R I 9 Na, NHCOCH3 C3Ht CaH5 h'Oa CH3 nC,H7 1H, 4 NO2 NHCOC2H5 C::3H6 C2H5 NO2 CH3 nC3Ii7 n3H7 3 3 C2H5 C3116 H C2H5 No2 H 25 5 NO2 NHCoCH C H NO,, H C H C H 6 NO2 NIICuC c::' O C2H5 NO2 H nc3H7 "C3)17 7 NO2 NIICOCH3 C3H6 0 C2H5 NO2 H CHz 0 C2H5 8 NO2 NHCOCH3 C3H6 O c2H5 NO2 CH3 C2H5 C2'L5 9 CN NHCOCH3 C3H6 C2H5 CN CH3 CH2 nC4H9 10 N02 NHCOCH3 C2H5 C2H5 N 2 CH3 C2H5 C2H5 11 NO2 NHCUC2H5 C2H5 C2H5 NO2 CH3 C H C21i5 12 CN NHCOCH3 nC H nC H CN CH3 C3H6 C2H5 13 CN NHCOCH3 nC H nC H CN CH3 CH2 0 C2H5 14 CN NHCOCH3 CH CH CN CH C II C H 3 2 25 3 25 25 15 NO2 NHCOCH3 C2 CH2, OCOCH NO2 CH3 C2H4OCOCH C2H 3 5 C2H4 3 3 5 16 NO2 NHCOCH3 C3H6 C2H5 Z 5 NO2 CH3 nCiHg C2H40COOCzH5 17 NO2 NHCOCH3 C2H CN C2H5 NO2 CH3 C2H5 C2HI,CN 18 NO NHCOCH3 C2H OCOOC H nC H NO CH C H C H 2 3 4 2 5 4 9 2 3 2 5 2 5 Each mixture dyes polyester blue of high tinctorial strength.

Example 19 12 parts of a 5% aqueous dispersion of the dye of formula I in which R=NO2, R'=NHCOCH3,

R3=C2H5,6 parts of a 5% aqueous dispersion of the dye of formula I in which R=NO2, R'=CH3, R2=R3=C2Hs and 2 parts of a 5% aqueous dispersion of the dye of formula I in which R=NO2, R'=H, R2=R3=C2Hs are mixed together. The mixture when applied to polyester by the method described in Example 1 gives blue shades of high tinctorial strength.

Example 20 26.2 parts of 2-bromo-4,6-dinitroaniline are diazotised and coupled to a mixture of 14.8 g N-l'- phenylpropyl-N-ethyl-3-acetylaminoaniline and 10.3 g N,N-diethyl-3-methylaniline by the procedure described in the Preparations above. The dye mixture is further reacted with 1.14 g cuprous cyanide as described in the Preparations above.

The resultant dye mixture when applied to polyester fibres in the form of an aqueous dispersion by the method described in Example 1 yields blue shades of very good build up and high tinctorial strength.

Claims

Claims (filed 25 Aug 1982)

1. A mixture of two or more monoazo dyes of the formula:

wherein R represents a cyano or a nitro group, R' represents a hydrogen atom or an alkyl or alkanoylamino group, R2 represents a substituted or unsubstituted alkyl or aralkyl group, R3 represents a substituted or unsubstituted alkyl group; provided that the mixture contains at least one component in which R1 is an alkanoylamino group and one component in which R' represents an alkyl group or a hydrogen atom.

2. A mixture as claimed in claim 1, in which each alkyl substituent present contains from 1 to 4 carbon atoms and is unsubstituted.

3. A mixture as claimed in claim 1 or 2, which comprises two dyes of formula I in one of which R is NO2, Or is NHCO alkyl, R2 is C3H6 phenyl, R3 is alkyl and in the other of which R is NO2, R1, R2 and R3 are independently alkyl, the alkyl groups containing 1-4 carbon atoms.

4. A mixture as claimed in claim 1, 2 or 3, which comprises only two components, these components being present in the mixture in a ratio of from 95:5 to 5:95 parts by weight.

5. A mixture as claimed in claim 4, in which the two compounds are present in a ratio of from 20:80 to 80:20 parts by weight.

6. A mixture of dyes as claimed in claim 1 , substantially as hereinbefore described in any one of the foregoing Examples.

7. A process for the manufacture of a mixture of disperse dyes as claimed in claim 1, which comprises reacting a mixture of at least two dyes of formula:

wherein R1, R2 and R3 have the meanings given in claim 1, R4 represents a chlorine, bromine or iodine atom and R5 represents a chlorine, bromine or iodine atom or a cyano or nitro group, in known manner with cuprous cyanide, a cyano cuprate complex or another metal cyanide in the presence of a copper compound in an organic solvent or an aqueous medium.

8. A process for the manufacture of a mixture of dyes as claimed in claim 1, which comprises mixing together the individually prepared component dyestuffs of the mixture.

9. A process as claimed in claim 7 or 8, in which the mixture is as claimed in any one of claims 2 to 6.

1 0. A process for the manufacture of a mixture of dyes as claimed in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.

11. A process for the dyeing and printing of hydrophobic fibres which comprises using a mixture of dyes as claimed in any one of claims 1 to 6.

12. A process as claimed in claim 11, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyacrylonitrile fibres, or polyester fibres.

13. A process as claimed in claim 11 or 12, in which the dyes are dispersed by grinding with water and a dispersing agent.

14. A process as claimed in claim 11, 12 or 13, in which dyeing is carried out on cellulose triacetate fibres from an aqueous bath at 95-1 000C containing a carrier.

15. A process as claimed in claim 11, 12 or 13, in which dyeing is carried out on polyester fibres from an aqueous bath at 95-1 O00C containing a carrier, or in a pressurised vessel at 125-1 400 C.

16. A process as claimed in claim 11, 12 or 13, in which dispersion of the dyes 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.

17. A process for the dyeing and printing of hydrophobic fibres substantially as hereinbefore described in any one of the foregoing Examples.

18. Hydrophobic fibres whenever coloured by a process as claimed in any one of claims 11 to 1 7.