REACTIVE AZO DYES This invention relates to reactive azo dyes containing each of a triazine ring and at least one reactive vinyl sulphone group (or precursor thereof) and at least two azo groups. Such dyes are disclosed in, for example, EP-A- 0623655, EP-A-0685532 and EP-A-0764694 and typical dyes are as follows : (Example 46 of EP-A-0685532) (Example 81 of EP-A-0764694) Example 38 of EP-A-0623655).

However, none of the dyes disclosed in the abovementioned documents provide a particularly strong or bright yellow or reddish yellow shade with good migration properties, excellent build-up and good fastness properties.

Thus, the problem addressed by the invention is to provide such a dye capable of giving, particularly on cellulosic fabrics, a strong, bright yellow or reddish yellow shade with good migration properties, excellent build-up and which dyes are particularly easy and economical to produce.

We find surprisingly that it is possible to solve the abovementioned problems by the use of an azo dye containing, on the one hand, a monoazo dye component based on sulpho-J-acid or J-acid as coupling component and a markedly electron deficient aromatic amine as diazo component and, on the other hand, an azo dye component containing each of a phenylen group and an aromatic group or hetero aromatic group, each dye component being linked, via an amino linkage to a triazine group, the second dye component being so linked via the phenylen group.

Thus, according to one aspect the invention provides an azo dye of the formula (I) or an alkali metal salt thereof, wherein each of R'and R2 independently is hydrogen, optionally substituted C, 4 alkyl or optionally substituted phenyl ; A is in which formula (i), c is zero or 1; in which formula (ii), d is 1,2 or 3 and a group S03H is ortho to the azo group; and

in which formula (i) or (ii), Y is the group-CH = CH2 ;-CH2CH2U (wherein U is a leaving group); or-CH2CH=CH2 ; B is fluorine ; chlorine ; the group OR3 (in which R3 is hydrogen, C, 4 alkyl or phenyl) ; the group NR4R5 (in which each of R4 and R5 independently is hydrogen, C, 4 alkyl or phenyl ; or each of R4, R5 and N together form an optionally substituted aromatic heterocyclic ring); the group sNR6R7R8 (in which each of R6, R7 and R8 independently is C, 4 alkyl or phenyl or each of R6, R7 and R8 and N together form an optionally substituted aromatic heterocyclic ring); or the group SR9 (in which R9 is hydrogen, Cl. 4 alkyl or phenyl) ; C is an optionally substituted aromatic or heteroaromatic residue; D is Cq 4 alkyl, C, 4 alkoxy, C, 4 alkylthio, amino, acylamino or ureido; a is zero, 1 or 2; b is zero, 1 or 2 and when b is 2 each D is independent of the other; and n is zero or 1.

C, 4 alkyl residues may be straight-chained or branched and be for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec. butyl or tert.-butyl.

An alkali metal salt is preferably sodium, potassium or lithium, particularly preferably sodium.

Preferably, each of R'and R2 independently is hydrogen, methyl or phenyl.

Preferably, the substituent D is methyl, methoxy, acylamino or ureido and the substituent B is preferably chlorine or a 3-or 4-carboxypyridinium salt derived respectively from nicotinic and isonicotinic acid. n is preferably 1.

A heteroaromatic group standing for C is preferably a pyridonyl, pyrazolonyl, 2,6-diaminopyridinyl or 4-carboxy-2,6-dihydroxypyridinyl group. An aromatic group standing for C is preferably a hydroxynapthalene group or a group of the formula (iv)

wherein Ar'is an aromatic diazo component; g is zero, 1,2,3 or 4; h is zero, 1,2 or 3; and P, or each P independently, is C14 alkyl, nitro,-SO2NR3 (in which R3 is hydrogen, C, 4 alkyl or phenyl), carboxyl, cyano, S02Y' (in which Y'is vinyl, allyl or CH2CH2V, where V is a leaving grup) or-NHAr2 [in which Ar2 is an aromatic residue substituted by at least one group T, the group T, or each group T independently, being selected from cyano, carboxyl, sulphonic acid and S02Y2 (in which y2 is vinyl, allyl or CH2CH2W (where W is a leaving group)].

More preferably, at least one group P is a group SO2Y', where y1 is as defined above or a group NHAr2 substituted by a group T, which group T is the group S02 y2, in which y2 is as defined above.

Preferred values of Y, Y'and y2 independently are-CH = CH2 ; -CH2-CH=CH2 ;-CH2CH2C1,-CH2CH2Br ;-CH2CH2F ;-CH2CH20SO3M ; -CH2CH2SSO3M ;-CH2CH20COCH3,-CH2CH20PO3M2 ;-CH2CH20COC2H5 ; -CH2CH2OSO2NR9 (in which R9 is hydrogen, C, 4 alkyl or phenyl) ; and- CH2CH2OS02R'° (in which R° is hydrogen, Cl. 4 alkyl or phenyl), wherein M is hydrogen or an alklai metal salt like sodium, potassium or lithium.

Most preferably C is the group In the dye of the formula (1), the group A preferably has the formula wherein e is-S02CH2CH2OS03H or S02CH = CH2 and f, is absent; or e is- S03H and f is-SO2CH2CH20S03H or S02CH = CH2.

A preferred azo dye of the formula (I) has the formula (1') wherein each of R2, C, D a, b, e, f and n is as defined above.

More preferably in the azo dye of the formula (I'), at least one of the groups S03H or D is ortho to the azo group linking to the group C.

In one range of dyes of the formula (I') which is preferred, a is 1 or 2 and b is zero. More preferably, the group C is a heteroaromatic group, still more preferably a pyridonyl, pyrazolonyl, 2,6-diaminopyridinyl or 4-carboxy-2,6- dihydroxypyridinyl group, or is a hydroxynaphthalene group.

In another range of dyes of the formula (I') which is preferred a is zero or 1, b is 1 or 2 and D, or each D independently, is ureido, (C, 4 alkyl) carbonyl- amino, C, 4 alkoxy or C, 4 alkylthio.

For such dyes within this other range, a preferred group C has the formula (iv) given and defined above.

Typical azo dyes embodying the invention have the formula (12)

wherein n is zero or 1, preferably zero, and Z is selected from

Another typical azo dye embodying the invention has the formula (13) The azo dye of the formula (I) can have, within the meaning of Y and Y', respectively, structurally different fiber-reactive groups-SO2Y and-SOY', respectively. In particular, the fiber-reactive groups-S02Y and-S02Y', respectively, are partly-S02-CH=CH2 (vinylsulfonyl) and partly -S02-CH2CH2U,-SO2-CH2CH2V and-S02-CH2CH2W (ß-ethyl substituted residues), respectively, such as ß-chloroethylsulfonyl, ß-thiosulfatoethyl-

sulfonyl or ß-sulfatoethylsulfonyl. If the dye contains the respective dye component in the form of a vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the respective dye with S-ethyl substituted residues will be up to 30 mol-%, based on the respective dye chromophore.

Preference is given to the dyes in which the proportion of vinylsulfonyl dye to said 9-ethyl substituted dye is in terms of the molar ratio between 5: 95 and 30: 70.

An azo dye of the formula (I), given and defined above may be prepared by a process which comprises reacting a triazine dye of the formula (II) wherein each of R', n, A and B is as defined above and Hal is a halogen atom; with an azo dye of the formula (III) wherein each of a, b, R2, C and D is as defined above.

The process is preferably carried out in an aqueous solution at pH 4-6 and at a temperature of at least 30°C.

The triazine dye of the formula (II) may be prepared by diazotising an amine of the formula (IV) A-NH2 (IV) wherein A is as defined above and coupling the diazotised amine of the formula (IV) to a triazine compound of the formula (V)

wherein each of R', n and B is as defined above and Hal is a halogen atom, to obtain the triazine dye of the formula (II).

Typically, diazotisation of the amine is carried out in an acid medium at a pH of about 2-5, using, for example, acetic, propionic or hydrochloric acid in the presence of a nitrosating agent, such as nitrosyl sulphuric acid, an alkali metal nitrite (e. g sodium nitrite) or a C14 alkyl nitrite (e. g. methyl nitrite) at a temperature of from-10°C to 10°C.

The coupling reaction may be carried out by adding the diazotised amine of the formula (IV), to the triazine compound of the formula (V) in water at a temperature of from 0 to 10°C.

The triazine compound of the formula (V), given and defined above, may be prepared by reacting an aminonaphthalenesulphonic acid compound of the formula (VI) with a cyanuric halide of the formula (VII)

wherein each Hal is a halogen atom and B is as defined above, to form the triazine compound of the formula (V).

The reaction may be carried out by adding the aminonaphthalene sulphonic acid compound of the formula (VI) dropwise to a slurry of the cyanuric halide of the formula (Vil) in an ice/water/acetone mixture.

When in the azo dye of the formula (III) a is 1 or 2, b is zero and C is the residue of a heteroaromatic coupling component the azo dye of the formula (III) may be prepared by acylating a diamine of the formula (vil) where a is zero, 1 or 2 to form an amine of the formula (IX), where a is zero, 1 or 2 and Ac is an acyl group, diazotising the amino of the formula (IX) and coupling the diazotised amine to a coupling agent of the formula C-H where C is as defined above to form, after deacetylation, the azo dye of the formula (III).

When, in the azo dye of the formula (III), a is zero or 1, b is 1 or 2 and D, or each D independently, is ureido, (C14 alkyl) carbonyl amino, C14 alkoxy or Ca 4 alkylthio and the group C is a group (iv) wherein each of Ar', P, g, and h is as defined above, the azo dye of the formula (III) may be prepared by diazotising an amine of the formula (X)

wherein each of Ar', P, g and h is as defined above, and coupling the diazotised amine with a coupling agent of the formula (XI)

where D is as defined above, a is zero or 1 and b is 1 or 2.

In either of the above reactions, the diazotisation and coupling may be carried out in a manner analogous to that described in relation to the preparation of the triazine dye of the formula (II).

Dyes embodying the invention may be applied alone or in admixture with other dyestuffs.

Although in this specification, dye formulae have been shown in the form of their free acid, the invention also includes dyes and processes using dyes in the salt form, particularly their salts with alkali metals such as the potassium, sodium, lithium or mixed sodium/lithium salt.

The dyes may be used for dyeing, printing or ink-jet printing, for example of textile materials and paper.

The process for colouration is preferably performed at a pH of 7.1 to 13, more preferably 10 to 12. pH levels above 7 can be achieved by performing the process for colouration in the presence of an acid-binding agent. They can be applied at any temperature from room temperaure (e. g. 15°C) to 80°C, preferably from 40 to 60°C.

The substrate may be any of fibre material such as a textile material, leather, paper, hair or film, but is preferably a natural or artifiical textile material containing amino or hydroxyl groups, for example textile material such as wool, silk, polyamides and modified polyacrylonitrile fibres, and more preferably a cellulose, for example, that commercially available as Tencel. For this purpose the dyes can be applied to the textile materials at a pH above 7 by, for example, exhaust dyeing, padding or printing. Textile materials are coloured bright shades and possess good fastness to light and wet treatments such as washing.

The new dyes are particularly valuable for colouring cellulosic textile materials. For this purpose, the dyes are preferably applied to the cellulosic textile material at a pH above 7 in conjunction with a treatment with an acid-binding agent.

Preferred acid-binding agents include alkali metal carbonates, bicarbonates, hydroxides, metasilicates and mixtures thereof, for example sodium bicarbonate, sodium carbonate, sodium metasilicate, sodium hydroxide and

the corresponding potassium salts. The dyes benefit from excellent build-up and high fixation.

The new dyes can be applied to textile materials containing amine groups, such as wool and polyamide textile materials, from a neutral to mildly alkaline dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that it to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process.

The dyes may be in liquid or solid form, for example in granular or powdered form.

According to yet another aspect of the invention there is provided a process for colouring a fibre material containing a group reactive with a reactive dye or a fibre blend containing the fibre material, which method comprises applying thereto a dye of the formula (I), given and defined above, preferably at a pH above 7.

Preferred embodiments of the invention will now be described in more detail with reference to the following Examples, in which all parts are by weight unless otherwise stated.

Example 1 Preparation of the dye: The process may be represented by the following reaction scheme.

A solution of 2-amino-5-hydroxy-1,7-naphthalene disulphonic acid (50) (39. 0g, 0. 08mol) in water (500 mis) was added dropwise to a slurry of cyanuric chloride (51) (16. 2g, 0. 088M) in an ice/water/acetone mixture and allowed to stir for 1 hr to provide a solution of the dichlorotriazinyl complex (52).

Separately, 2N sodium nitrite solution was added dropwise to an ice cold slurry of 2-amino-5- (-sulphatoethylsulphone) benzenesulphonic acid (45. 2g, 0.093M) (4) and concentrated HCI (30 mis) in water (500 mis). After 1hr, excess nitrous acid was destroyed by the addition of sulphamic acid, leaving a

solution of the diazonium salt (53). The solution of the diazonium salt (53) was then added to the dichlorotriazine (53) solution and the mixture allowed to warm to room temperature while maintaining the pH at 6. After 4 hrs the resulting precipitate was filtered off and dried to give the reddish yellow dichlorotriazinyl dye (70g) (54). Analytical data were in full agreement with the expected structure.

2N sodium nitrite solution was added dropwise to an ice cold solution of 2 (2- sulpho-4-nitrophenylamino)-5-amino-1, 4-benzene disulphonic acid (6. 9g, 0. 01mol) and concentrated HCI (3mis) in water (1OOmls). After 1hr, excess nitrous acid was destroyed by the addition of sulphamic acid leaving a solution of the diazonium salt (55). The solution of the diazonium salt (55) was then added to a slurry of meta-ureidoaniline (56) (2.8g, 0. 01mol) in water (100 mis) and the mixture allowed to warm to room temperature over night maintained at pH 4. The product was precipitated by the addition of methylated spirits, filtered off and dried to give the monoazoamine dye (57) (9. 1 g). Analytical data were in full agreement with the expected structure.

An aqueous solution of dichlorotriazine dye (54) (5. 0g, 0.0045 mol) and monoazoamine dye (57) (5. 6g, 0.0045 mol) in water (100 mis) maintained at pH 5 was heated at 65°C for 2 hrs. The resulting solution was cooled and the product precipitated by the addition of methylated spirits. The precipitate was filtered off and dried to give the reactive dye (1) of Example 1 (6. 6g) max = 470nm 76306. Analytical data were in full agreement with the expected structure.

Example 2 Preparation of the dye : The process may be represented by the following reaction scheme.

A solution of 2-amino-5-hydroxy-1, 7-naphthalene disulphonic acid (50) (9. 72g, 0.02mol) in water 1100mis) was added dropwise to a slurry of cyanuric chloride (51) (4. 1 g, 0.022 mol) in an ice/water/acetone mixture and allowed to stir for 1 hr furnishing a solution of the dichlorotriazinyl complex (52).

A slurry of 6-amino-4-1-sulphatoethylsulphone)-1, 3-benzenedisulphonic acid (16. 5g, 0.037mol) and NaN0210. 041 mol) in water (150 mis) was added dropwise to ice/water (150g) and concentrated HCI. After 30 mins excess nitrous acid was destroyed with sulphamic acid, leaving a solution of

the diazonium salt (58). b of the diazonium salt (58) solution was added to the dichlorotriazine solution and the mixture allowed to warm to room temperature maintaining the pH at 6. After 1 hr the resulting precipitate was filtered off and shown to be the dichlorotriazinyl intermediate (59).

A solution of a monoazoamine dyebase (60) (0. 007 mol) and the dichlorotriazine (59) (0. 009 mol) in water (250 mis) was heated tQ 50°C and the pH maintained at 6 for 4 hrs. The product was precipitated by the addition of methylated spirits, filtered off and dried to give the reactive dye (2) of Example 2 (10. 6g) max = 464nm = 55500. Analytical data were in full agreement with the expected structure.

Example 3 Preparation of the dye: The process may be represented by the following reaction scheme.

2N NaNO2 (1 8mis, 0.036mol) was added dropwise to a solution of 2-amino-5- acetamido-benzene sulphonic acid (14g, 0.033mol) in water (250 mis) with concentrated HCI (8.5mis), cooled to OEC. The solution was stirred cold for 2 hrs before destroying excess nitrous acid by addition of sulphamic acid, to give a solution of a diazonium salt (62).

Half of the available diazonium salt solution (62) was added slowly to a stirred solution of citrazinic acid (63) (2. 55g, 0.016 mol) in water (100 mis) adjusted and maintained at pH7.

After 30 mins the coupling was complete and a monoazo-N-acetylamino dye base was precipitated by the addition of isopropyl alcohol. The N-acetyl

dyebase was then dissolved in 2N sodium hydroxide and heated at 60°C for 2 hrs before cooling and acidifying to pH2 with concentrated HCI to precipitate a dark solid. The solid was filtered off and dried to give the monoazoamino dyebase (64).

An aqueous solution of a dichlorotriazine dye (61) (3g, 0.003 mol, prepared as described in Example 1) and the monoazoamino dyebase (64) (1.2g, 0.003 mol) in water (100 mis) was adjusted to pH5 and heated at 60EC for 2 hrs.

The product was precipitated by addition of methylated spirits, filtered off and dried to give the reactive dye (35) of Example 3 as an orange powder (3.5g) max = 460nm = 62000. Analytical data were in full agreement with the expected structure.

Example 4 Preparation of the dye: The proceess may be represented by the following reaction scheme.

Reddish-yellow dichlorotriazinyl dye (54) was prepared as in Example 1.2N sodium nitrite solution was added dropwise to an ice cold solution of 2-amino- 5-1-sulphatoethylsulphone) benzene-sulphonic-acid 11 6. 75g, 0.025 mol) and concentrated HCI 16mis) in water (200 mis). After 1 hour, excess nitrous acid was destroyed by the addition of sulphamic acid leaving a solution of the diazonium salt (65). The solution of the diazonium salt (65) was then added to a slurry of meta-ureidoaniline (56) (6. 75g, 0.025 mol) in water (100 mis) and the mixture allowed to warm to room temperature over 2 hours maintained at pH 5. 5. The product was precipitated by the addition of methylated spirits,

filtered off and dried to give the monoazoamine dye (66) (14. 1 g). Analytical data were in full agreement with the expected structure.

An aqueous solution of the dichlorotriazinyl dye (54) (5. 0g, 0.0053 mol) and the monoazoamine dye (66) 15. 4g, 0.0053 mol) in water (200 mis) maintained at pH5 was heated at 50°C for 5 hours. The resulting solution was cooled and the product precipitated by the addition of methylated spirits. The precipitate was filtered off and dried to give the reactive dye (41) (6. 0g) max = 462nm = 50000. Analytical data were in full agreement with the expected structure.

Examples 5-45 In each of the following dyes, a triazine ring carries respective first and second yellow monoazo dye components, a first of which is derived from sulpho-J- acid as a coupling component. The second yellow monoazo dye components are also derived from a coupling component and a diazotized amine component.

The dyes of Examples 5-36 and 41-45 (dyes 3,5-12, 14-16, 18-19,21-34, 36-40 and 42-45) were prepared by the method of Example 1, so that the residue derived from the coupling component is linked to the triazine ring).

The dyes of Examples 36-40 (dyes 4,13,17,20 and 35) were prepared by the method of Example 3, so that the residue derived from the diazotised amine component is linked to the triazine ring.

Each of the dyes of Examples 5-45 (dyes 3-34,36-40 and 42-45) has the formula S03H OH N=N N HO3SOCH2CH202SI NH-N soh Soh Example Z Dye (max) NHCONH2S03H LL e N=N < S03H S03H 3 465 NHCONH2S03H SN=N 1 -han 6 SO3H (5) 477 NHCONH2S03H I \ N=N I \ \ -HO 7 SO, H jgj yg 7 SO3H 16) 476 jfyTfY NHCOCH3S03H Non has ocH3 so3H ( 472 NHCOCH3S03H I \ N=N I \ HN e e 9 SO3H (8) 472

The above reactive dyes embodying the invention contain a first monoazo component derived from sulpho-J-acid as coupling component and a strongly electron withdrawing diazo component giving a bright yellow shade, which may be matched and thereby enhanced by a second monoazo component, itself providing a bright yellow shade. Such dyes may thus be provided with an excellent strong and bright shade. They are found also to have excellent build-up and good migration properties and are relatively inexpensive, especially given the depth of shade achieved, and easy to prepare. They also exhibit beneficial fastness properties, especially excellent light and wash fastness.