GB2091752A - Monoazo disperse dyes - Google Patents

Abstract

There are disclosed dyes of the general formula: <IMAGE> wherein R represents an aryl group of formula: <IMAGE> or a heterocyclic group, R<1> represents a straight or branched chain alkylene group, R<2> represents a straight or branched chain alkyl group, R<3> and R<6> each independently represents H, Cl, Br, Alk, OAlk, CN, CF3, NO2SO2Alk or COOAlk, R<4> represents H, Cl, Br, NO2, COOR<7>, SO2R<7>, SO2OR<7>, SO2NR<8>R<9>, OCOOR<7>, OSO2R<7>, OSO2NR<8>R<9>, OCONR<8>R<9>, CN or CF3, R<7>, R<8> and R<9> each independently represents alkyl, aryl, or cycloalkyl, R<5> represents H, Cl, Br, Alk or OAlk, with the proviso that when R<3> represents H, Cl or Br, R<5> represents H and R<6> represents a group other than H, R<4> may not represent NO2, and the naphthalene nucleus may be further substituted. There are disclosed processes for their preparation and use. The dyes produce violet to greenish blue colourations on hydrophobic fibres.

Description

SPECIFICATION Monoazo disperse dyes Blue monoazo disperse dyes are known which are based on N - (hydroxy - alkyl) -1 - naphthylamine coupling components. These dyes possesses good build-up properties on hydrophobic fibres and are particularly economical to manufacture but suffer from the disadvantage that under normal dying conditions they are susceptible to reduction and are stable only over a small pH range. It has now been found that chemical modification of the OH group and substitution of the 1 - naphthylamine ring in 5 position with an OH group thereby enabling a less electronegatively substituted diazo compound to be used, 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 an aryl group of formula:

or a heterocyclic group, R' represents a straight or branched chain alkylene group, R2 represents a straight of branched chain alkyl group, R3 and R6 each independently represents H, Cl, Br, Alk, OAlk, CN, CF3, NO2, SO2Alk or COOAlk, R4 represents H, Cl, Br, NO2, COOR7, SO2R7, SO2OR7, SO2NR8R9, OCOOR7, OSO2R7, OSO2NR8R9, OCON R8R9, CN or CF3, R7, R8 and R9 each independently represents alkyl, aryl orcycloalkyl, R5 represents, H, Cl, Br, Alk, or OAlk, with the proviso that when R3 represents H, Cl, or Br, R6 represents H and R6 represents a group otherthan H, R4 may not represent NO2.

The naphthalene nucleus may be further substituted.

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: R-NH2 with one mole of a secondary amine of general formula

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

Specific examples of amines of general formula I are: 3-nitroaniline 4-nitroaniline 4-methoxycarbonylaniline 2-methyl4-methoxycarbonylaniline 2-chloro4-ethoxyca rbonylaniline 4-phenoxycarbonylaniline 2-chloro4-methylsulphonylaniline 2-nitro4-methylsulphonylaniiine 3-phenoxysulphonylaniline 2,5-dichloro4-dimethylsulphonamidoaniline 2,5-dibromo4-dimethylsulphonamidoaniline 2,6-dichloro4-dimethylsu Iphonamidoaniline 2,6-dibromo4-dimethylsulphonamidoaniline 4-ethoxycarbonyloxyaniline 3-phenylsulphonyloxyaniline 2-chloro4-dimethylsuIphonamidooxyaniline 4-dimethylca rbonamidooxyan iline 2-trifluoromethyl4-chloroaniline 2-trifluoromethyl4-cyanoaniline 2-nitro4-cyanoaniline 2-bromo4-cyanoaniline 2-methoxy4-cyanoaniline 2-methoxycarbonyl4-cyanoaniiine 2-chloro4-trifluoromethylaniline 2-cyano4-bromoaniline 2-methylsulphonyl4-chloroaniiine 2,6-dimethyl4-nitroaniline 2-methyl4-nitro-6-methoxyaniline 2,5-dimethyl-4-nitroaniline 2,5-dimethoxy4-nitroaniline 2-methoxy-5-methyl4-nitroaniline 2-methoxy4-nitro-5-chloroaniline 2-aminothiazole 2-amino-5-nitrothiazole 2-amino-6-nitrobenzthiazole 2-amino-6-methylsulphonylbenzthiazole 2-amino-6-thiocyanatobenzthiazole 3-amino-2,1 -isobenzthiazole 3-amino-5-nitro-2,1 -isobenzthiazole Specific examples of amines of general formula IV are: 1 -N-(2-methoxyethyl)-amino-5 hydroxynaphthalene 1 -N-(2-ethoxyethyl)-amino-5 hydroxynaphthalene 1 -N-(2-n-propoxyethyl)-amino-5 hydroxynaphthalene 1 -N-(2-n-butyroxyethyl)-amino-5 hydroxynaphthalene 1 -N-(3-methoxypropyl )-am ino-5- hydroxynaphthalene 1 -N-(3-ethoxypropyl)-amino-5 hydroxynaphthalene 1 -N-(3-isopropoxypropyl)-amino-5 hydroxynaphthalene 1-N-(3-n-butoxypropyl)-amino-5- hydroxynaphthalene 1 -N-(2-ethylhexoxy)propyl-amino-5- hydroxynaphthalene 1 -N-(1 -methyl-2-methoxyethyl)amino-5 hydroxynaphthalene 1 -N-(1 -methyl-3-methoxypropyl)amino-5- hydroxynaphthalene 1 -N-(1,1 -dimethyl-3-ethoxypropyl)amino-5- hydroxynaphthalene 1 -N-(2-methyl-3-methoxypropyl)amino-5- hydroxynaphthalene The coupling components offormula IV may be prepared for example by the condensation of the appropriate halogenated alkoxyalkane with 1 amino - 5 - hydroxynaphthalene in the presence of an acid binding agent or preferably by the condensation of 1,5 - dihydroxynaphthalene with an excess of the appropriate alkoxyalkylamine in the presence of sodium sulphite or bisulphite solution (the Bucherer reaction).

The invention further includes a process for the dyeing and printing of hydrophobic fibres, in which the dye is an azo dye of general formula 1.

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 2phenylphenol such as that sold as "Optinol B", or in pressurised vessels at 125-140"C. Alternatively the dye dispersion may be thickened with sodium alginate orotherthickeners commonly used in textile printing and applied to polyester fabrics in the usual way by padding or printing with a roller or thorough 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 60-220 C for 3090 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, cellulosetriacetate, 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, Bardford, England). The colourations so obtained are violet to greenish 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 carbon tetrachloride, and colouration carried out from such a dispersion to the same fibres and under conditions of time and temperature similar two those used for aqueous application. The colourations so obtained are equivalent in hue and fastness 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 I.

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 70at: before cooling to 25"C.

26.9 parts of 2,5 - dichloro - 4 - dimethylsulphonamidoaniline are then added portionwise and the mixture stirred for two hours at this temperature.

Meanwhile 23.1 parts of 1 - N - (3 - methoxypropyl)amino - hydroxynaphthalene are dissolved in 30 parts of glacial acetic acid and the solution added dropwise to a mixture of 25 parts of concentrated hydrochloric acid and 500 parts of iced water. The diazo solution is added slowly and the mixture stirred for four 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,zbm, 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.

The 1 - N - (3 methoxypropyl)amino - 5 - hydroxynaphthalene used in Example 1 may be prepared as follows: 5.8 parts of sodium metabisulphite are charged into 135 parts of water followed by 17.7 parts of3 methoxypropylamine and 21.5 parts of 1,5 - dihydroxynaphthalene. The mixture is refluxed for 24 hours, cooled and made strongly alkaline with sodium hydroxide solution. The bis -1,5 - di - N - (3 methoxypropyl) - aminonaphthalene is removed by filtration and the pH of the filtrate made strongly acidic by the dropwise addition of concentrated hydrochloric acid. The 1,5 - dihydroxynaphthalene which precipitates is filtered off and the pH of the filtrate is adjusted to 7 with sodium hydroxide solution. The suspension is stirred for several hours when the product is filtered off, washed and dried.

Example 2.

20.6 parts of 2 - chloro - 4 - methylsulphonylaniline are added to a solution of 40 parts of 36.5% hydrochloric acid in 130 parts of water and the mixture is stirred for two hours. The temperature is then adjusted to 7"C by the addition of ice and 69.0 parts of a 10% solution of sodium nitrite is added. After stirring for two hours at 7"C, any excess nitrous acid is destroyed by the addition of sulphamic acid after cooling to 0 C and the diazo solution is filtered.

Meanwhile 23.1 parts of 1 - N - (3 - methoxypropyl)amino - 5 - hydroxynaphthalene are dissolved in 30 parts of glacial acetic acid and the solution added dropwise to a mixture of 25 parts of concentrated hydrochloric acid and 500 parts of iced water.

The diazo solution is added slowly and the mixture stirred for four 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 m. 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.

In the following table data is given referring to other monoazo dyes of the present invention 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 Polyester No. RNH2 R' R2 Fibres 3 4-methoxycarbonylaniline (CH2)2 CH2CH3 violet 4 3-nitroaniline (CH2)2 (CH2)2CH3 violet 5 4-nitroaniline (CH2)2 CH3 violet 6 2-methyl-4-methoxycarbonylaniline (CH2)2 CH3 bluish violet 7 2chloro4ethoxycarbonylaniline (cH2)3 CH3 blue 8 4-phenoxycarbonylaniline (CH2)3 CH3 violet 9 2-chloro-4-methylsulphonylaniline (CH2)2 CH(CH3) blue 10 2-chloro-4-methylsulphonylaniline CH(CH3)CH2 CH3 blue 11 2-nitro-4-methylsulphonylaniline (cH2)3 CH3 bluish green 12 3-phenoxysulphonylaniline (CH2)3 CH2CH3 violet 13 2.5-dichloro4-dimethylsulphonamidoanilin (CH2)3 CH2CH3 blue 14 2,5-dibromo-4-dimethylsulphonamidoaniline (CH2k CH2CH3 blue 15 2,6-dichloro-4-dimethylsulphonamidoaniline (CH2)3 CH2CH3 bluish violet 16 2,6-dibromo-4-dimethylsulphonamidoaniline (CH2)3 CH2CH3 bluish violet 17 4-ethoxycarbonylaniline (CH2)2 CH(CH3)2 violet 18 3-phenylsuiphonyloxyaniline (CH2)3 CH3 violet 19 4-dimethylsulphonamidooxyaniline (CH2)3 CH3 violet 20 4dimethylcarbonamidooxyaniline (CH2)2 CH3 violet 21 2-trifluoromethyl-4-chioroaniline CH(CH3)2CH2CH2 C2H5 blue 22 2-trifluoromethyl-4-cyanoaniline CH(CH3)2CH2CH2 C2H3 bluish green 23 2-nitro-4-cyanoaniline (CH2)3 CH3 bluish green 24 2-bromo-4-cyanoaniline CH2CH(CH3)CH2 CH3 blue 25 2-methoxy-4-cyanoaniline (CH,)3 CH3 blue 26 2-chloro-4-trifluoromethylaniline (CH2)3 CH(CH3)2 blue 27 2-cyano-4-bromoaniline (CH2)3 CH3 blue 28 2-methylsulphonyl4-chloroaniline (CH2k CH2 blue 29 2-nitro4-chloroaniline (CH2)3 CH3 blue 30 2,6-dimethyl4-nitroaniline (CH2)3 CH3 blue 31 2-methyl-4-nitro-6-methoxyaniline (CH2)3 CH2CH(C2H5)CH2CH2CH2CH3 blue 32 2,5-dimethyl-4-nitroaniline (CH2)3 CH3 blue 33 2,5-dimethoxy-4-nitroaniline (CH2)2 (CH2)3CH3 blue 34 2,5-dichloro-4-nitroaniline (CH2)3 CH3 greenish blue 35 2,5-dibromo-4-nitroaniline (CH2)3 CH(CH3)2 greenish blue 36 2-methoxy-4-nitro-5-methylaniline (CH2)3 CH(CH3)2 blue 37 2-methoxy-4-nitro-5-chloroaniline (CH2)3 CH3 blue 38 2-aminothiazole (CH2)3 CH(CH3)2 blue 39 2-amino-5-nitrothiazole (CH2)3 CH3 greenish blue 40 2-amino-6-nitrobenzthiazole (CH2)2 CH3 blue 41 2-amino-6-methylsulphonylbenzthiazole (CH2)2 (CH2)3CH3 blue 42 2-amino-6-thiocyanatobenzthiazole (CH2k CH3 blue 43 3-amino-2,1 -isobenzthiazole CH2CH(CH3)CH2 CH3 blue 44 3-amino-5-nitro-2,1-isobenzthiazole (CH2k CH3 greenish blue

Claims (13)

1. CLAIMS 1. A water insoluble monoazo dye having +'--a general formula:

   wherein R represents an aryl group of formula:

   or a heterocylic group, R' represents a straight or branched chain alkylene group, R2 represents a straight of branched chain alkyl group, R3 and R3 each independently represents H, Cl, Br, Alk, OAlk, CN, CF3, NO2, SO2Alk or COOAlk, R4 represents H, Cl, Br, NO2, COOR7, SO2R7, SO2OR7, SO2NR8R9, OCOOR7, OSO2R7, OSO2NRR9, OCONR8R, CN or CF3, R7, RI and Re each independently represents alkyl, aryl, orcycloalkyl, R5 represents H, Cl, Br, Alk or OAlk, with the proviso that when R3 represents H, Cl, or Br, R5 represents H and RS represents a group otherthan H, R4 may not represent NO2, and the naphthalene nucleus may be further substituted.
2. 2. A dye as claimed in claim 1, in which the alkyl and alkylene groups contain one to four carbon atoms.
3. 3. A dye as claimed in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.
4. 4. Aprocessforthe preparation of a dye of general formula I which comprises coupling one mole of the diazo component of an amine of general formula: R-NH2 with one mole of a secondary amine of general for mula

   wherein R, R', and R2 have the meanings given in claim 1.
5. 5. A process as claimed in claim 4, in which the alkyl and alkylene groups contain 1 to 4 carbon atoms.
6. 6. A process for the preparation of a dye as defined in claim 1, substantially as hereinbefore described in any one of the foregoing Examples.
7. 7. A process for the dyeing and printing of hydrophobic fibres, in which the dye is an azo dye of general formula las claimed in any one of claims 1 to 3.
8. 8. A process as claimed in claim 7, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyacrylonitrile fibres or polyester fibres.
9. 9. A process as claimed in claim 7 or 8, in which the dye is dispersed by grinding with water and a dispersing agent.
10. 10. A process as claimed in any one of claims 7 to 9, in which dyeing is carried out on polyester fibres from an aqueous bath at 95-1 00 C containing a carrier, or in a pressurised vessel at 125-140 C.
11. 11. A process as claimed in any one of claims 7 to 9, in which a dispersion of the dye is thickened with a thickener and applied to polyester fabrics in the usual way by padding or printing with a roller or through a screen, the fabric is dried and the dye is fixed.
12. 12. A process as claimed in claim 7 or 8, in which the dye is dispersed in an organic solvent and colouration carried out from such a dispersion.
13. 13. A process for the dyeing or printing of hydrophobic fibres, substantially as hereinbefore -described in any one of the foregoing Examples.