GB1576063A - Monoazo disperse dyes - Google Patents

Description

(54) MONOAZO DISPERSE DYES (71) We, YORKSHIRE CHEMI CALS LIMITED, a British Company of Black Bull Street, Leeds, LS10 lHP, West Yorkshire, 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: The present invention relates to monoazo dyes and to processes for their preparation and use.

Blue monoazo disperse dyes are known which are based on N - (hydroxyalkyl) - 1naphthylamine and N,N - (dihydroxyalkyl)1 - naphthylamine type coupling component.

These dyes possess good build up properties and are particularly economical to manu fracture but suffer from the disadvantage that under normal dyeing conditions they are very susceptible to reduction and are stable only over a small pH range. It has now been found that chemical modification of a hydroxyl group in such compounds increases the stability of the dyes to reduction in the dyebath and renders them less pH sensitive without impairing their good build up properties.

According to the present invention therefore, water-insoluble monoazo dyes are provided having the general formula:

wherein R represents a nitro group, and R' represents a chlorine or bromine atom or a cyano group, or R and R' both represent a cyano group, R2 represents a straight or branched chain alkylene group, R3 represents a straight or branched chain alkyl, a phenyl group, or a phenyl group substituted by a methoxy group or a halo gen atom, When R3 represents a straight or branched chain alkyl group, R2 is unsubstituted but when R3 represents a phenyl group or a substituted phenyl group, R2 may be substituted by a hydroxyl group.

The preferred dyes are those in which the alkyl and alkylene groups contain one to four carbon atoms.

The invention also includes a process for the preparation of dyes of general formula I which comprises coupling one mole of the diazo component of an amine of general formula:

with one mole of a secondary amine of general formula:

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

Specific examples of amines of general formula II are: 2 - bromo - 4,6 - dinitroaniline 2 - chloro - 4,6 - dinitroaniline 2,6 - dicyano - 4 - nitroaniline 2 - cyano - 4,6 - dinitroaniline Specific examples of secondary amines of general formula III are: N - (2 - methoxyethyl) - 1 - naphthylamine N - (2 - ethoxyethyl) - 1 - naphthylamine N - (2 - n - propoxyethyl) - 1 - naphthyl amine N - (2 - n - butoxyethyl) - 1 - naphthyl- amine N - (3 - methoxypropyl) - 1 - naphthyl- amine N - (3 - ethoxypropyl) - 1 - naphthylamine N - (3 - isopropoxypropyl) - 1 - naphthyl amine N - (3 - n - butoxypropyl) - 1 - naphthyl amine N - 3 - (2 - ethyffiexoxy) - propyl - 1 naphthylamine N - (1 - methyl - 2 - methoxyethyl) - 1 naphthylamine N - (1 - methyl - 3 - methoxypropyl) 1 - naphthylamine N - (1,1 - dimethyl - 3 - ethoxypropyl) 1 - naphthylamine N - (2 - methyl - 3 - methoxypropyl) - 1 naphthylamine N - (2 - phenoxyethyl)~- 1 - naphthylamine N - (2 - hydroxy - 3 - phenoxypropyl) 1 - naphthylamine N - [2 - hydroxy - 3 - (4 - methoxy)phen oxypropyl] 1 - naphthylamine N - [2 - hydroxy - 3 - (3 - chloro)phen oxypropyl] 1 - naphthylamine The coupling components of formula III may be prepared by known methods, for example the condensation of the appropriate halogenated alkoxyalkane with 1-naphthylamine in the presence of an acid binding agent, the condensation of the appropriate aryloxyepoxyalkane with 1-naphthylamine or the condensation of 1-naphthol with an excess of the appropriate alkoxy-alkylamine in the presence of sodium sulphite or bisulphite solution (the Bucherer reaction).

The invention further includes a process for the dyeing or printing of hydrophobic fibres, in which the dye is an azo dye of general formula I.

Specific examples of hydrophobic fibres are cellulose acetate fibres such as secondary cellulose acetate and cellulose triacetate, polymide fibres, polyester fibres such as " TERYLENE " (' TERYLENE" is a Registered Trade Mark) and polyacrylonitrile fibres such as "COURTELLE" (" COURTELLE " is a Registered Trade Mark).

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

Dyapol SL. Dyeing may be carried out on polyester fibres from, for example, an aqueous bath at 95100 C. containing a carrier, eg.

an emulsion of 2-phenylphenol such as that sold as "Optinol B", or in pressurised vessels at 125140 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 15-25 Ib per square inch or by heating the fabric at 160-2200 C for 30---90 seconds.

The dyes may also be applied by dyeing or printing on to secondary cellulose acetate, cellulose 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). In addition the dyes may also be applied by transfer printing whereby a paper or foil is printed with the dye contained in a printing ink composition. The printed paper or foil is then heated in contact with a cellulose acetate, e.g. a secondary cellulose acetate or cellulose triacetate, polyamide, polyacrylonitrile or polyester fabric, advantageously under reduced presure. The colourations so obtained are blue and have good fastness to light, washing, sublimation, rubbing and dry cleaning.

Alternatively, the dyes may be dispersed in an organic solvent, for example, chloroethylene, tetrachloroethylene or carbontetrachloride, and colouration carried out from such a dispersion to the same fibres and under condition of time and temperature similar to those used for aqueous application. The colourations so obtained are equivalent in hue and fastnes properties to those obtained by aqueous methods of application.

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 nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 300 C by external cooling. The temperature is then raised to 700 C before cooling to 0 C. 21.8 parts of 2 - chloro - 4,6 - dinitroalinine are then added during one hour at 0 C, and the mixture stirred for 2 hours at this temperature.

Then it is carefully run into a stirred mixture of 21.5 parts of N - (3 - methoxypropyl)1 - naphthylamine, 20 parts of 100% sulpuric acid and 500 parts of iced water at 0 C.

The mixture is stirred for 4 hours at 0 C when the precipitated dye of formula:

is filtered off, washed acid free and dried.

One part of the dyestuff so obtained 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 , 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 1300 C 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.

Preparation 1.

The N- (3 -hydroxypropyl ) - 1 -naphthylamine used in Example 1 may be prepared as follows: An autoclave fitted with stirrer is charged with 288 parts of water, 58 parts of sodium metabisulphite, 144 parts of a-naphthol and 135 parts of 3-methoxypropylamine. The auto crave is sealed and then heated at 1300 C with stirring for 24 hours before cooling. The mixture is added slowly to a solution of 180 parts of sodium hydroxide in 1600 parts of water and the resulting mixture stirred until the product is crystalline. It is filtered off, washed and dried.

Example 2.

If the 215 parts of N - (3 - methoxy propyl) - 1 - naphthylamine used in example 1 are replaced by 201 parts of N - (2- methoxyethyl) - 1 - naphthylamine, the dye obtained has the formula:

One part of the dyestuff so obtained 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 ,. This is then added to a mixture of 5 parts of a galactomannan thickening agent, such as that sold as "Indalca PA3 (Indalca is a registered Trade Mark), 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 20 lb.

per square inch. After this time the fabric is removed, washed and dried. The blue print so obtained has very good fastness to light, washing and sublimation.

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

Shade on Example R R' R2 R3 Polyester No. R R1 R2 R3 Fibres 3 NO2 Cl (cur2)2 CH2CH3 Blue 4 NO2 Br (cur2)2 (CH2)2CH3 Blue 5 NO2 Br (CR,)2 (CH2)3CH3 Blue 6 NO2 Br (CII,), CH3 Blue 7 NO2 Cl (CR,), CH2CH3 Blue 8 NO2 Cl (cur2)3 (CH2),CH, Blue 9 NO2 Br (cur2)3 (CR2),CH3 Blue 10 NO2 Cl (cur2), CH2CH(C2Hs)CH2CH2CH2cH3 Blue 11 NO, Cl CH(CH3)CH2 CH3 Blue 12 NO2 Cl CH(CH3)CH2CH2 CH3 Blue 13 NO2 Cl CH(CH3)2CH2CH2 CM Blue 14 NO2 Cl CH2CH(CH3)CH2 CH3 Blue 15 NO, Cl (CH,), Blue 16 CN CN (CH,)3 CH3 Greenish-blue 17 CN CN (CII,), C,Hs Greenish-blue 18 NO, CN (CH2), CH3 Greenish-blue 19 ' NO, CN (CR,), CH3 Greenish-blue 20 NO, Cl CH,CH(OH)CH, Blue 21 NO, Cl CH,CH(OH)CH, e SOCH3 Blue 22 NO, Br CH,CH(OH)CH, < ( Blue

Claims (20)

WHAT WE CLAIM IS:

1. A water-insoluble monoazo dye having the general formula:

wherein R represents a nitro group, and R1 represents a chlorine or bromine atom or a cyano group, or R and R1 both represent a cyano group, R2 represents a straight or branched chain alkylene group, R3 represents a straight or branched chain alkyl group, or a phenyl group optionally substituted by a methoxy group or a halo gen atom, with the proviso that when R9 represents a straight or branched chain alkyl group, R2 is unsubstituted but when R9 represents a phenyl or substituted phenyl group, R2 may be sub stituted by a hydroxyl group.

2. A water-insoluble monoazo dye as claimed in claim 1 in which the alkyl and alkylene groups contain one to four carbon atoms.

3. A water-insoluble monoazo dye as claimed in claim 1 or 2, in which R and Rt have the meanings given in claim 1, R2 repre sents an unsubstituted straight or branched chain alkylene group and R3 represents an unsubstituted straight or branched chain alkyl group or an unsubstituted phenyl group.

4. A water-insoluble monoazo dye substanially as hereinbefore described in any one of Examples 1 to 19.

5. A water-insoluble monoazo dye substantially as hereinbefore described in any one of Examples 20 to 22.

6. A process for the preparation of a dye of general formula I as defined in claim 1, which comprises coupling one mole of the diazo component of an amine of general formula:

with one mole of a secondary amine of general formula:

wherein R, R', R2 and R3 are as defined in claim 1.

7. A process as claimed in claim 6, in which the alkyl and alkylene groups contain 1 to 4 carbon atoms.

8. A process as claimed in claim 6 or 7, in which R, R1, R2 and R3 have the meanings given in claim 3.

9. A process for the preparation of a waterinsoluble monoazo dye substantially as hereinbefore described in any one of Examples 1 to 19.

10. A process for the preparation of a waterinsoluble monoazo dye substantially as hereinbefore described in any one of Examples 20 to 22.

11. A process for the dyeing or printing of hydrophobic fibres, in which the dye is an azo dye of general formula I as defined in claim 1 or 2.

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

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

14. A process as claimed in any one of claims 11 to 13, in which polyester fibres are dyed from an aqueous bath at 95--100"C. containing a carrier, or in pressurised vessels at 125140 C.

15. A process as claimed in any one of claims 11 to 13, in which the dye dispersion is thickened with a thickener and applied to polyester fabrics by padding or printing with roller or through a screen, the fabric is dried and the dye is fixed.

16. A process as claimed in claim 11 or 12 in which a paper or foil is printed with the dye contained in a printing ink composition, and the printed paper or foil is then heated in contact with a cellulose acetate, polyamide, polyacrylonitrile or polyester fabric.

17. A process as claimed in claim 11 or 12, in which the dye is disposed in an organic solvent.

18. A process as claimed in any one of claims 11 to 17 in which the dye of general formula I is as defined in claim 3.

19. A process for the colouration of hydrophobic fibres substantially as hereinbefore described in any one of Examples 1 to 19.

20. A process for the colouration of hydrophobic fibres substantially as hereinbefore described in any one of Examples 20 to 22.