GB2216539A - Anionic triaminotriazinyl disazo dyes - Google Patents

Description

r 1-169381= Apionic disazo dyes The present invention relates to anionic

disazo dyes of formula 6 5 t 3 ?H v 1 '. 0 0 D-N=N-;'I \\,N=N-1,1_ \ 11 9 R 4 M03S/ \NHI kN/ wherein D is a radical of formula 1 or (S03W (S03W n (a) (b) X is -COOM or -S03M. R' and R2 are each independently of the other hydrogen, halogen, Cl-C4alkyl or Cl-C4alkoxy, m is 0, 1 or 2, n is 0 or 1, and m + n are 1 or 2, with the proviso that two sulfo groups present in the same ring may not be in ortho-position to each other, R3 is hydrogen, Cl-C4alkyl or Cl-C4alkoxy, R' is hydrogen or Cl-C4alkyl, with the proviso that the two substituents p3 and R are in para-position to each other if they have a meaning different from hydrogen, q R' ishydrogen, Cl-C4alkyl or R6, R6 is B-O-R7, wherein B is straight-chain or branched C2-C6alkylene and R7 is Cl-C4alkyl or Cl-C4alkoxy-Cl-C4alkyl, or RS and R6, together with the linking nitrogen atom, are a pyrrolidino, piperidino, morpholino, or piperazino radical which is unsubstituted or substituted by Cl-C4alkyl or Cl-C4hydroxyalkyl or Cl-C4alkoxy C2-C4-alkyl or Cl-C4-aminoalkyl at the nitrogen atom which is not attached to the triazine ring, - - R' and R9 are each independently of the other hydrogen, Cl-C6alkyl, a radical R6 or a radical -CHRIO--CHR10-0--CHR11--CHR" 0) R wherein R10 and R11 are each indpendently of the other hydrogen, methyl or ethyl, with the proviso that one radical R10 and one radical R11 must be hydrogen, or R8 and Rg, together with the linking nitrogen atom, are a pyrrolidino, piperidino, morpholino or piperazino radical which is unsubstituted or substituted by Cl-C4alkyl, Cl-C4hydroxyalkyl, Cl-C4alkoXY-C2-C4alkyl or Cl-C4aminoalkyl at the nitrogen atom which is not attached to the triazine ring, p is 0 or a whole number not greater than 3, and M is hydrogen or the equivalent of a colourless cation.

X in the radical of formula (a) is preferably the sulfo group.

R1 and R2 as halogen in compounds of formula (1) are, for example, chloro or bromo, preferably chloro. R1 and R2 as alkyl are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl. R' and R2 as alkoxy are, for example, methoxy, ethoxy or butoxy.

R1 is preferably hydrogen, chloro, methyl, methoxy or ethoxy, in particular hydrogen, methyl or methoxy and, most preferably, hydrogen or methyl.

R2 is preferably hydrogen, chloro or methyl, in particular hydrogen or methyl and, most preferably, hydrogen.

If R' and R2 are hydrogen, the substituent X may be in ortho-, meta- or para-position to the azo group.

3 If the radical of formula (a) contains a further substituent in addition to the substituent X, then X and R' or R2 are preferably in meta-position to each other, and are preferably in positions 2 and 4 to the azo group. The substituent X is also preferably in 3-, 5- or 4-position to the azo group and R1 or R2 is in ortho- or para-position to the substituent X, i. e. X and R1 or R2 are preferably in 2,5- or 3,4-position to the azo group.

If the radical of formula (a) contains two further substituents in addition to the substituent X, then X is preferably in position 4 or 5 and the two substituents R' and R2 are in positions 2,5 and 2,4 respectively to the azo group.

If D is a radical of formula (b), then two sulfo groups present in the same ring cannot be in ortho-position to each other. A sulfo group present in the radical of formula (b) is, for example, in positions 5, 6, 7 or 8, preferably in positions 5 or 6. If the radical of formula (b) is substituted by two sulfo groups, these are, for example, in positions 3,6, 3,7, 4,8, 5,7 or 6,8, preferably in positions 3,6, 4,8 or 6.8.

D is preferably a radical of formula (a).

Alkyl or alkoxy groups R3 andlor R are, for example, the groups cited for R1 and R2. Preferably R3 and C are each independently of the other hydrogen, methyl, methoxy or ethoxy and, most preferably, are each hydrogen.

The preferred meaning of R' is hydrogen.

In the radical -B-O-R? as It, B is straight-chain or branched C2C6alkylene, for example ethylene, propylene, trimethylene, ethylethylene, 1-methyl-1,3-trimethylene or pentamethylene. Preferably B is ethylene, propylene or trimethylene. R7 is, for example, methyl, ethyl, n- or isopropyl, n-, sec- or tert-butyl, methoxymethyl, ethoxyethyl or methoxypropyl. The preferred meaning of R' is methyl or ethyl.

4 -NRSR" can also form a pyrrolidino, piperidino, morpholino or piperazino radical. This radical may be substituted by Cl-C4alkyl or ClC4hydroxyalkyl at the nitrogen atom which is not attached to the triazine ring. The preferred substituent is hydroxyethyl.

Particularly preferred meanings of R6 are methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, or -WRI is a morpholino radical.

R8 is preferably hydrogen, methyl, ethyl, hydroxyethyl or methoxyethyl, or -NR8R9 is a morpholino radical.

R9 is preferably hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, hydroxyethoxye thyl or methoxyethoxyethyl.

M is hydrogen or the equivalent of a colourless cation, for example lithium, sodium, potassium, ammonium or the protonated form of a C4CIZtrialkylamine, C4-C12diamine or C2-C12alkanolamine.

M as a protonated C4-C12trialkylamine may be, for example, protonated Nethyldimethylamine, N,N-diethylmethylamine, tri-n-propylamine, trinbutylamine, triisobutylamine and, in particular, triethylamine or triisopropylamine. Mixtures of different protonated amines are also suitable.

M as a protonated C4-C12diamine is, for example, an ethylenediamine or 1, 3-diaminopropane in which one or both N-atoms are additionally substituted by one or two Cl-C4alkyl radicals, preferably by methyl or ethyl groups. M is in this case preferably a N,N-dialkylet'iiylenediamine or N,N-dialkyl-1,3-diaminopropane, for example N-ethylethylenediamine, N, N-dimethylethylenediamine, N,N'-dimethylethylenediamine, Njdiethylethylenediamine, 3-dimethylamino-l-propylamine or 3-diethylaminolpropylamine.

M as a protonated C2-CI2alkanolamine may be, for example, the protonated form of a monoalkanolamine, dialkanolamine, monoalkanolmonoalkylamine, monoalkanoldialkylamine, dialkanolalkylamine.or trialkanolamine, or a mixture of different protonated alkanolamines. Examples are protonated 2aminoethanol, bis(2-hydroxyethyl)amine, N-(2-hydroxyethyl)dimethylamine, N-(2-hydroxyethyl)diethylamine, N,N-bis(2-hydroxyethyl)methylamine, N,Nbis(2-hydroxyethyl)ethylamine or tris(2-hydroxyethyl)amine, 2-(2aminoethoxy)ethanol or diethylaminopropylamine.

The preferred meaning of M is Na 0, Li (D or protonated C4-C6alkanolamine, and tris(2-hydroxyethyl)amine, bis(2-hydroxyethyl)amine or a mixture of these two amines are the preferred C4-C6-alkanolamines.

A particularly preferred embodiment of the invention comprises the disazo dyes of formula 1 3 ?H. R Y6 v A/ (2) /x; "c \NH/ \\NI MO 3 14 MO 3 S1 wherein R1 and R2 are each independently of the other hydrogen, halogen, Cl- C4alkyl or Cl-C4alkoxy, - R 3 is hydrogen, Cl-C4alkyl or Cl-C4alkoxy, R' is hydrogen or Cl-C4alkyl, with the proviso that the two substituents R3 and R' are in para-position to each other if they have a meaning different from hydrogen, R, is hydrogen, R is methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, or -NRSR6 is a morpholipo radical, R8 is hydrogen, methyl, ethyl, hydroxyethyl or methoxyethyl, R9 is hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, hydroxyethoxyethyl or methoxyethoxyethyl, or -NR8R9 is a morpholino radical, and M is hydrogen or the equivalent of a colourless cation.

6 Among these compounds, those compounds are especially preferred in which R' is hydrogen, methyl or methoxy, R2 is hydrogen or methyl, R3 and R are each independently of the other hydrogen, methyl, methoxy or ethoxy, R5 is hydrogen, R6 is methoxyethyl or methoxypropyl, R8 is hydrogen, methyl, ethyl, methoxyethyl or hydroxyethyl, R' is hydrogen, hydroxy (D E) ethyl, hydroxypropyl, methoxyethyl or methoxypropyl, M is Na ' Li or protonated C4-Csalkanolamine.

The azo dyes of formula (1) are prepared in a manner known per se, for example by reacting a cyanuric halide with a compound of formula ?H M03S/ a compound of formula HY R6 and a compound of formula HY/R "'Rg with either the compound of formula (3) or one of the reaction_ products containing the compound of formula (3) being reacted with a diazotised amine of formula 3 D-N=N-11 \\---NH2 (6), in which formulae ( 3) to (6) above the substituents M, RS, R6, R8, R9, D, R 3 and R are as defined for formula (1).

The order in which the amines of formulae (3), (4) and (5) are reacted with the cyanuric halide is in principle optional; but each individual amine must be added in an amount sufficient to ensure that, stepwise, 4 1 always only one halogen atom of the cyanuric halide is replaced. The hydrohalic acid set free from the cyanuric halide in this reaction must in all cases be neutralised. Neutralisation can be effected, for example, by using an excess of amine component or by addition of a base or of salts which can be hydrolysed under alkaline conditions.

The individual reaction steps are freely interchangeable and can be carried out by conventional methods. Thus, for example, the reaction of the cyanuric halide with a compound of formula (3) is carried out, as first step, under weakly acid reaction conditions, preferably at pH 5-6 and in a preferred temperature range from 0 to 2CC. The subsequent reaction with a compound of formula (4) is carried out in a preferred temperature range from 20' to WC and in the pH range from about 6 to 8. The replacement of the third halogen atom by reaction with a compound of formula (5) is preferably carried out in a temperature range from about 600 to 1OCC and in a pH range from about 8 to 10.

The coupling reaction is also carried out in a manner known per se, for example in the temperature range from 0' to 75% preferably from 0' to 3Sc'C, and in the.pH range from 5 to 9.

It is preferred to react cyanuric chloride first with an amine of formula (3), then with an amine of formula (4) and, finally, with an amine of formula (5), and then to couple the resultant product with a diazotised amine of formula (6), all these reactions being carried out without isolation of the intermediates.

The compounds of formulae (3) to (6) are known or can be obtained in known manner.

The resultant compounds of formula (1) can be isolated in a manner known per se, e.g. by salting them out.

The novel compounds of formula (1) are preferably used as dyes for dyeing and printing textile materials, paper, leather, and for the preparation of inks.

8 If the azo dyes of the present invention are used for dyeing and printing textile materials, then suitable materials are in particular those made of cotton. The novel dyes have good affinity for these textile materials, a good degree of exhaustion and good build-up. They give red dyeings of good fastness properties, in particular good wetfastness and lightfastness properties.

The preferred utility of the novel dyes of formula (1) is for dyeing and printing paper of all kinds, especially bleached and sized lignin-free paper.

The dyes of formula (1) exhaust very well on to these substrates, and the wastewater - even when dyeing in deep shades (up to greater than 1/1 standard depth dyeirig) - remains almost colourless, which is an outstanding technical and environmental advantage. The good degree of exhaustion is also advantageous for a good reproducibility of shade. The dyeings are wetfast, i.e. they exhibit no tendency to bleeding when dyed paper in the wet state is brought into contact with moist white paper. This property is particularly desirable for tissues, of which it can be expected that the dyed paper in the wet state (e.g. impregnated with water, alcohol, surfactant solution and the like) will come into contact with other substrates such as textiles, paper and the like, which have to be protected against soiling.

The red dyeings are brilliant in shade and have very good fastness properties, especially lightfastness.

Further, the dyes of formula (1) are used for dyeing leather materials by a-very wide range of application methods such as spraying, brushing and immersing, and for the preparation of inks of all kinds, such as for ballpoint pens and printing inks.

The invention is illustrated by the following non-limitative Examples, in which parts and percentages are by weight.

Example 1: 19.8 parts of cyanuric chloride and 24.4 parts of I-acid are suspended in 100 parts of ice and 100 parts of water, while keeping the pH between 2 and 3 with 2N sodium hydroxide solution. After no more starting material can be detected by thin-layer chromatography, 11.6 parts of 3-methoxypropylamine are added at room temperature and the pH is kept at 6-7 with 2N sodium hydroxide solution. When the reaction is complete, 9 parts of ethanolamine are added dropwise at 8CC while keeping the pH between 9-10 with 2N sodium hydroxide solution. The reaction mixture is stirred for 6 hours at this temperature, cooled to. 00-50C, and then coupling is effected with 27 parts of diazotised 4-amino-1,1'azobenzene-4'-sulfonic acid, while keeping the pH between 6-7 with 2N sodium hydroxide solution. The dye of formula ?H VH-CH2CH20H --- 6---. - 0 0 H03S-''.-N=N-.11 \\.-N=N-., // \ / k - H03S/ \J/ \NHI NI \NH-CH2-CH2-CH2-OCH3 is then salted out with NaCl. It dyes paper in bluish red shades. The tinctorial properties such as lightfastness, fastness to bleeding and affinity for paper, are excellent.

The dye is also very suitable for dyeing cotton, preferably by the exhaust process at 900C or 13CC (under HT conditions). The bluish-red dyeings obtained have good light- and wetfastness properties.

Example 2: 19.8 parts of cyanuric chloride and 24.4 parts of I-acid are suspended in 100 parts of ice and 100 parts of water, while keeping the pH between 2 and 3 with 2N aqueous sodium hydroxide. After no more starting material can be detected by thin-layer chromatgraphy, coupling is carried out at C-5'C with 27 parts of diazotised 4amino-1,1'azobenzene-C-sulfonic acid, while keeping the pH at 6-7 with 2N aqueous sodium hydroxide solution. Then 11.6 parts of 3-methoxypropylamine are added at 3C-40'C and the pH is kept at 7-8 by addition of 2N aqueous sodium hydroxide solution. When the reaction is complete, 9 parts of diethanolamine are added. The reaction mixture is then stirred for 4 hours at 8CC while keeping the pH at 9-10 with 2N sodium hydroxide solution. The dye solution is then dialysed and concentrated to a volume of 400 parts. The stable dye solution so obtained dyes paper in bluish red shades. The tinctorial properties are identical to those in Example 1. -

Examples 3-42: The following Table lists further disazo dyes which can be prepared in accordance with the procedure described in Example 1. The meanings of R,, R2 and R3 are also indicated in the Table. The dyeings obtained on paper are red to bluish-red.

YH 2 D-N=N- lk.-N=N-O /. k./. \. /1 0 0 _\1 ---R3 H03S y N / Ex D R2 R 3 3 H03s-.// CHzCH2CH2OCH3 CH2CH2OCH3 4 H03S- CHZCH2CH20CH3 -XCH2CH2CH2OCH3 -X 0-0 H03 S-., CH2CH2CH2OCH3 -X-H-CH20H =. -X H3 6 H035-// -X CH2CH2CH2OCH3 -XCH2CH20-CH2CH20H 7 H03 S- CH2CH2CHzOCH3 _xl \ o 8 H03S- CH2CH2CH2OCH3 -XCzHs 9 H03S- -X CH2CH2OCH 3 -XCH2CH2OCH3 CH2CH2CH2OCH3 -XCH2CH2CH2OCH3 H03S/.- 11 H035 -X CH2CH2OCH3 -XCH2CH20H 12 H03S- CH2CH2OCH3 H2CHzOH -X CH2CH20H 13 H03S -X CH2CH2OCH3 -XCH2CH2-0-CH2CH20H 14 H03S-// \\--- CHzCH2OCH3 -N-1 \ 0 12 Ex. D R2 R3 H03 S-// CH2CH2OCH3 -NH2 16 H035'/ -N \ -CH2CH20H CH2CH20H 17 H03 S-/ -NI \O-C? \CHzCH20H 18 R03s-., -MI 19 H03S- // \\--- -MI \ o -XC2Hs CH3 H03S- CHZCH20CH3 -XCH2CH20H \.=. / -X /CH 3 21 H03S- I-CH2CH2CH2OCH3 -XCHzCH20H CH3 CH2CH20H 22 H03SCH2CH2CH2OCH3 -Xl T \CH2CH20H /CH3 23 H035- CH2CH2CH2OCH3 CH2CH20-CH2CH20H \ = / T /CH 3 24 k--- --CH2CH2CH20CH3 -XCH2CH20H H03' S CH3 CH2CH20H I-CH2CH2CH2OCH3 CH2CHzOH H03S S03H 26 CH3- CH2CH2CH2OCH3 -XCH2CH20H Ex. D R2 R3 S03H 27 CH3 // - \\--- CH2CH2CH2OCH3 -N CH2CH20H CH2CH20H H03S 28 CH3 CH2CH2CH20CH3 -CH2CH20H H03S H2CH20H 29 CH3 CH2CH2CH2OCH3 \CH2CH20H H03S CH3 CH2CH2CH2OCH3 -N-CH-CH20H \. / -X A &3 S03H 31 CH2CH2CH2OCH3 -XCH2CH20H 32 CH2CH2OCH3 -XCH2CH20H H03S 33 CH2CH2CH2OCH3 -XCH2CH20H H035 34.:/ CH2CH2CH2OCH3 -Xl CH2CH20H -X \ CHZCH20H H035 CH3 H03S- CH2CH2CH2OCH3 -CH2Cil2OH CH3 CH3 CH2CH20H 36 H03SCH2CH2CH2OCH3 -Xl CH2CH20H CH3 CH3 37 CH3- CH2CH2CH2OCH3 CH2CH20H CH2CH20H H03S - 14 Ex. R1 R3 R2 CH2CH20H 38 HOOC- CH2CH2CHZOCH3 - \CH2CH20H 39 CH2CH2CH2OCH3 -14/ CH2CH20H \CH2CH20H HOOC/ 0-0 CH2CH2CH2OCH3 -XCH2CH20-CH2CH20-CH3 HOOC/ HOOC\ 41 CH2CH2CH20CH3 -XCH2CH20H HOOC/ HOOC 42 -X CH2CH2CH2OCH3 -NH2 HOOC/ Example 43: 200 parts of the dye of Example 1 are homogenised in the form of the free dye acid of low salt content by stirring in 500 parts of water and dissolved at 400C by addition of 58 parts of diethanolamine and 100 parts of urea. The solution is clarified by filtration by adding a filter aid. The filtrate is allowed to cool to room temperature and made up to 1000 parts with water, to give a stable dye solution.

Instead of using diethanolamine it is also possible to use monoethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, polyglycolamine, ammonia, tetramethylammonium hydroxide, lithium hydroxide or lithium carbonate.

A dye solution of similar stability and concentration can also be obtained by dialysis of the sodium salt of the dye of formula I.

Example 44: 70 parts of chemically bleached softwood sulfite pulp and 30 parts of chemically bleached birchwood sulfite pulp are beaten in 2000 parts of water in a hollander. To this pulp is added 0.2 part of the dye formulation described in Example 43. After mixing for 20 minutes, paper is prepared from this pulp. The absorbent paper so obtained is dyed red. The wastewater is almost colourless.

Example 45: 0.5 part of the dye powder of Example 1 is dissolved in 100 parts of hot water and the solution is cooled to room temperature. This solution is added to 100 parts of chemically bleached sulfite pulp which has been beaten in 2000 parts of water in a hollander. After mixing thoroughly for 15 minutes, sizing is effected in conventional manner with rosin size and aluminium sulfate. Paper prepared from this pulp is dyed in a red shade of good wetfastness properties.

16

Claims (22)

What is claimed is:

1. A disazo dye of formula YH D-N-N-. 9 R /X.=./ M035/ \NH"' wherein D is a radicai of formula 1 or (S03W m (S03W n (a) (b) X is -COOM or -503M. R1 and R2 are each independently of the other hydrogen, halogen, Cl-C4alkyl or Cl-C4alkoxy, m is 0, 1 or 2, n is 0 or 1, and m + n are 1 or 2, with the proviso that two sulfo groups present in the same ring may not be in ortho-position to each other, R3 is hydrogen, Cl-C4alkyl or Cl-C4alkoxy, R4 is hydrogen or Cl-C4alkyl, with the proviso that the two substituents R3 and R are in para-position to each other if they have a meaning different from hydrogen, R is hydrogen, Cl-C4alkyl or R6, R6 is BO-R7, wherein B is straight-chain or branched C2-C6alkylene and R7 is Cl-C4alkyl or Cl-C4alkoxy-Cl-C4alkyl, or R5 and R6, together with the linking nitrogen atom, are a pyrrolidino, piperidino, morpholino, or piperazino radical which is unsubstituted or substituted by Cl- C4alkyl or ClC4hydroxyalkyl or Cl-C4alkoxyC2-C4-alkyl or Cl-C4-aminoalkyl at the nitrogen atom which is not attached to the triazine ring, R8 and R9 are each independently of the other hydrogen, Cl-C6alkyl, a radical R6 or a radical -CHR10-CH R10-04CHR11-CHR11 0) p R4, wherein R10 and W' are each indpendently of the other hydrogen, methyl or-ethyl, with the proviso that one radical R10 and one radical W' must be hydrogen, or R8 and Rg, together with the linking nitrogen atom, are a pyrrolidino, piperidino, morpholino or piperazino radical which is unsubstituted or substituted by Cl-C4alkyl, Cl-C4hydroxyalkyl, Cl-C4alkoXY-C2-C4alkyl or Cl-C4aminoalkyl at the nitrogen atom which is not attached to the triazine ring, p is 0 or a whole number not greater than 3, and M is hydrogen or the equivalent of a colourless cation.

2. A dye according to claim 1, wherein D is a radical of formula (a).

3. A dye according to claim 2, wherein R' is hydrogen, chloro, methyl, methoxy or ethoxy.

4. A dye according to claim 3, wherein R' is hydrogen, methyl or methoxy.

c

5. A dye according to any one of cla ims 1 to 4, wherein R2 is hydrogen, chloro or methyl.

6. A dye according to any one of claims 1 to 5, wherein X is sulfo.

7. A dye according to any one of claims 1 to 6, wherein R3 and R4 are each independently of the other hydrogen, methyl, methoxy or ethoxy and are preferably hydrogen.

8. A dye according to any one of claims 1 to 7, wherein RS is hydrogen.

- 18

9. A dye according to any one of claims 1 to 8, wherein R6 is a radical - B-O-R7, wherein B is ethylene, propylene, trimethylene, ethylethylene, 1- methyl-1,3-trimethylene or pentamethylene, and R? is methyl, ethyl, nor isopropyl, n-, sec- or tert-butyl, methoxymethyl, ethoxyethyl or methoxypropyl.

10. A dye according to claim 9, wherein B is ethylene, propylene or trimethylene, and R7 is methyl or ethyl.

11. A dye according to any one of claims 1 to 8, wherein R6 is methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, or -NRSR6 is a morpholino radical.

12. A dye according to any one of claims 1 to 11, wherein R' is hydrogen, methyl, ethyl, hydroxyethyl or methoxyethyl, or -NR8W is a morpholino radical.

13. A dye according to any one of claims 1 to 12, wherein R9 is hydrogen. methyl, ethyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, hydroxyethoxyethyl or methoxyethoxyethyl.

9) (D

14. A dye according to any one of claims 1 to 13, wherein M is Na ' Li or protonated C4-C6alkanolamine.

15. A dye according to claim 1, of formula 6 5 1 3 ?H. v (2) /X / \. 0 / y',) 9 M035 2 M035/ \NH/ wherein R' and p2 are each independently of the other hydrogen, halogen, Cl-C4- alkyl or Cl-C4alkoxy, R3 is hydrogen, Cl-C4alkyl or Cl-C4alkoxy, R is hydrogen or Cl-C4alkyl, with the proviso that the two substituents R3 and R' are in para-position to each other if they have a meaning different from hydrogen, RS is hydrogen, R6 is methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, or -NIt5R6 is a morpholino radical, R' is hydrogen, methyl, ethyl, hydroxyethyl or methoxyethyl, R' is hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, metoxyethyl, methoxypropyl, hydroxyethoxyethyl or methoxyethoxyethyl, or -NRSR9 is a morpholino radical, and M is hydrogen or the equivalent of a colourless cation.

16. A dye according to claim 15, wherein R1 is hydrogen, methyl or methoxy, R2 is hydrogen or methyl, R3 and R4 are each independently of the other hydrogen, methyl, methoxy or ethoxy, RS is hydrogen, R6 is methoxyethyl or methoxypropyl, W is hydrogen, methyl, ethyl, methoxyethyl or hydroxyethyl, R9 is hydrogen, hydroxyethyl, hydroxypropyl, methoxyethyl or methoxypropyl, M is Na 0, Li G) or protonated C4- C6alkanolamine.

17. A process fo r the preparation of an azo dye of formula (1) as claimed in claim 1, which comprises reacting a cyanuric halide with a compound of formula TH (3), \NHz MO 3 S1 a compound of formula H \\R6 (4), and a compound of formula 8 H \R9 (5), with either the compound of formula (3) or one of the reaction products containing the compound of formula (3) being reacted with a diazotised amine of formula 3 D-N=N-. '.-NH2 in which formulae (3) to (6) above the substituents M, R, Rs, D, R 3 and R4 are as defined for formula (1).

18. A process according to claim 17,-which comprises reacting cyanuric chloride first with an amine of formula (3), then with an amine of formula (4) and, finally, with an amine of formula (5) and subsequently coupling the resultant product with a diazotised amine of formula (6), and carrying out said reactions without isolation of the intermediates.

19. A process for dyeing and printing textile materials, paper, leather and for the preparation of inks, which comprises the use of a compound of formula (1) as claimed in claim 1.

20. A process according to claim 19 for dyeing or printing paper of all kinds.

21. Paper dyed with a dye of formula (1) as claimed in claim 1.

22. A dye according to claim 1 substantially as hereinbefore described with reference to any one of Examples 1 to 42.

Published 1989 atThe Patent Office, State HouBe.68!71 High H'olbornLondonWClR4TP. Further copies maybe obtainedfrom The Patent Oface. Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent, Oo33- 1/87