This invention relates to reactive dyes, their preparation and use for the coloration of materials and to materials when coloured by the dyes.
According to the present invention there is provided a dye having at least two groups each of which independently is of the formula (1):
(Formula Removed)
wherein:
A is a halo triazinylamino reactive group;
L1 is an arylene group;
R1 and R2 are each independently H or alkyl;
Q is a group of the formula -CO- or -SO2-; and
B is an optionally substituted vinyl group or a group which is converted into an
optionally substituted vinyl group in the presence of aqueous alkali.
It is preferred that each group of formula (1) is attached to a carbon atom in an aromatic ring of the dye, for example a phenylene or naphthalene ring.
Preferred dyes according to the invention contain at least one, more preferably at least 3 and preferably less than 11 sulpho groups.
The halo triazinylamino reactive group is preferably a 2,4,6,-s-triazinylamino group carrying a CI or F atom, preferably a CI atom.
The arylene group L1 is preferably a mono- or dicyclic arylene group. The preferred arylene groups are optionally substituted phenylene and optionally substituted naphthylene. The optional substituents which may be present on L1 are preferably independently selected from halo, especially chloro; alkoxy, especially C1-6 alkoxy; alkyl, especially C1-6 alkyl; sulpho; carboxy; and hydroxy.
It is preferred that R1 and R2 are each independently H or C1-4 alkyl, more preferably H or methyl, especially H.
It is preferred that Q is a group of the formula -CO-.
B is preferably a group of the formula (2) or (3):
(Formula Removed)
2
wherein:
R3, R4 and R5 are each independently H, halo or alkyl; and
Y is -OSO3H, -SSO3H, halo or -OCOCH3.
When R3, R4 or R5 is halo it is preferably CI or Br. When R3, R4 or R5 alkyl it is preferably C1-6-alkyl, especially methyl and ethyl.
It is preferred that R3 is H, methyl, ethyl, CI or Br. More preferably R3 is H, methyl or CI. It is especially preferred that R3 is H.
Preferably R4 and R5 each independently is H or C1-4-alkyl, more preferably H or methyl. It is especially preferred that R4 and R5 are H.
Preferably Y is -OSO3H; -SSO3H; CI or Br, especially CI; or -OCOCH3; more preferably Y is -OSO3H or CI.
In light of the foregoing preferences, the group of Formula (1) is preferably of the Formula (4):

wherein:
W is halo;
(Formula Removed)M is one of the optional substituents described above for L1;
R6 is H or alkyl; and
R1, R2 and B are as hereinbefore defined.
W is preferably CI or F.
Preferably M is CI, methoxy, methyl, sulpho or carboxy, more preferably sulpho or methyl.
R6 is preferably H or C1-6-alkyl, more preferably H or methyl, especially H.
The dye according to the invention is preferably a water-soluble azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan dye. Thus preferred dyes of the present invention are of the formula D-(T)n wherein:
each T independently is a group of the Formula (1), preferably of Formula (4), as hereinbefore defined;
n is > 2; and
D is the residue of an azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan chromophore.
Examples of groups represented by D are given in the following pages in Formulae (5) to (12) wherein D is the portion of the illustrated molecules other than the groups represented by T.
Preferred azo dyes of the invention are monoazo and disazo dyes.
Preferred monoazo dyes are of the formula T-L2-N=N-L3-T wherein L2 and L3 are optionally substituted arylene, heteroarylene or stilbene groups and each T independently is as hereinbefore defined. It is preferred that each arylene group independently is a mono- or di-cyclic arylene group. Preferred arylene groups are optionally substituted phenylene and optionally substituted naphthylene. Preferred heteroarylene groups are pyridonylene and pyrazolonylene.
A first preferred monoazo dye is of the Formula (5) or salt thereof:
(Formula Removed)
wherein:
X is H or sulpho;
each T and L2 independently is as hereinbefore defined.
L2 is preferably optionally substituted phenylene or naphthylene, especially a phenylene or naphthylene group having at least one sulpho substituent. Further optional substituents which may be present on L2 include a halogen atom, especially chlorine; an alkyl group, especially C1-4-alkyl, more especially methyl; an acylamino group, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy group, especially C1-4-alkoxy, more especially methoxy. L2 preferably has from one to three of said substituents.
As examples of phenylene groups having at least one sulpho substituent there may be mentioned 2-sulphophenylene; 2-sulpho-4-nitro-1,3-phenylene; 2-sulpho-5-nitro-1,4-phenylene; 4-sulpho-2-methyl-1,3-phenylene; 5-sulpho-2-methyi-1,4'-phenylene; 2-sulpho-4-methyl-1,3-phenylene; 5-sulpho-2-methoxy-1,3-phenylene; 2-sulpho-4-methoxy-1,3-phenylene; 4-sulpho-2-chloro-1,3-phenylene; 5-sulpho-2-carboxy-1,3-phenylene; 2,4-disulpho-1,3-phenylene; 2,5-disulpho-1,3-phenylene; and 3,5-disulpho-1,4-phenylene.
As examples of naphthylene groups having at least one sulpho substituent there may be mentioned 1-sulpho-2,7-naphthylene; 1,5,7-trisulpho-2,8-naphthylene; 5,7-disulpho-2,8-naphthylene; 6-sulpho-3,7-naphthylene; 4-, 5-, 6-, or 7-sulpho-8,3-naphthylene; 7-sulpho-1-hydroxy-4-amino-5,8-naphthylene; 4,8-disulpho-1,6-naphthylene; 3,8-disulpho-4,7-naphthylene; 3,6-disulpho-1 -hydroxy-8-amino-2,7-naphthylene; 2,5,8-trisulpho-1,7-naphthylene; and 3,5,7-trisulpho-4,8-naphthylene.
4
In dyes of Formula (5), T is preferably at the 6-, 7- or 8-position, especially the 6-or 8- position. When T is at the 8-position, it is preferred that X is a sulpho group at the 5-or 6- position.
A second preferred monoazo dye is of the Formula (6) or a salt thereof.
(Formula Removed)
wherein:
each T and X independently is as hereinbefore defined.
A third preferred monoazo dye is of the Formula (7) or salt thereof:
(Formula Removed)
wherein:
Ph is an optionally substituted phenylene group, especially sulphophenylene;
R7 is CN, CH3 or carboxy; and
X and each T independently are as hereinbefore defined.
A preferred disazo dye is of Formula (8) or salt thereof:
T-L4-N=N-L5-N=N-L6-T (8) wherein:
L4, L5 and L6 are each independently optionally substituted phenylene or
naphthylene; and
each T independently is as hereinbefore defined.
It is preferred that L5 is optionally substituted naphthylene and L4 and L6 are optionally substituted phenylene. The optional substituents which may be present on L4, L5 or L6 are preferably independently selected from halo, especially chloro; alkoxy, especially C1-4-alkoxy; C1-4-alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino especially as acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups.
As examples of groups represented by L4, L5 and L6 there may be mentioned phenylene, ureidophenylene and the aforementioned phenylene and naphthylene groups which have at least one sulpho substituent.
A preferred anthraquinone dye is of the Formula (9):
(Formula Removed)
wherein the anthraquinone nucleus optionally contains a sulphonic acid group in the 5-, 6-or 7-, position; each V independently is a divalent organic linking group, preferably of the benzene series; and each T independently is as hereinbefore defined.
Each V independently is preferably a phenylene, diphenylene, 4,4'-divalent stilbene or azobenzene, optionally sulphonated. It is preferred that V contains one sulphonic acid group for each benzene ring present therein.
A preferred phthalocyanine dye is of the Formula (10):
wherein:
Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine;
each R1 is as hereinbefore defined;
(Formula Removed)
each G independently is a hydroxy or a substituted or unsubstituted amine group;
V1 is a divalent organic linking group, preferably a C1-4-alkylene or phenylene linking group;
b > 2; and a is 0, 1 or 2; provided that a + b is not greater than 4.
A preferred triphenodioxazine dye is of the Formula (11) or a salt thereof:
(Formula Removed)wherein :
each V2 independently is a divalent linking group, especially, C2-4-alkylene,
phenylene or sulphophenylene;
Z1 and Z2 are halo, C1-4alkyl, or C1-4-alkoxy; and
each X and T independently as hereinbefore defined.
Each V2 independently is preferably -C2H4- or -C3H6-, X is preferably SO3H, and
each Z1 and Z2 independently are preferably CI, methyl or ethyl, especially CI or methyl.
A preferred formazan dye is of the Formula (12) or a salt thereof:
(Formula Removed)
wherein :
X1 is H, SO3H or CI;
m and p each independently have a value of 0, 1 or 2; and
each T independently is as hereinbefore defined;
provided that the formazan group has at least one, and preferably at least two, sulpho groups.
It is preferred that m and p each have a value of 1.
Dyes according to the invention may be prepared by condensation of a dye having at least two dihalotriazinylamino groups with a compound of the Formula (13):
(Formula Removed)wherein:
R1, R2, L1, Q and B are as hereinbefore defined.
The condensation is preferably carried out at 0°-80°C, especially 0°-50°C, more especially at 0°-40°C. The condensation is preferably performed in the presence of an acid-binding agent. The function of the acid-binding agent is to neutralise the hydrogen-halo acid as it is formed during the condensation. Accordingly any acid-binding agent may be used provided that it is not present in such a concentration that it causes hydrolysis of the reactants or causes some other undesirable side-reaction. It is preferred to use an alkali metal hydroxide, carbonate or bicarbonate, preferably added at such a rate that the pH of the mixture stays within the range 6.0 to 7.0 during the condensation.
Dyes having at least two dihalotriazinylamino groups can be prepared by condensing a dye having at least two nucleophilic groups (e.g. amino groups) with a cyanuric halide.
The compounds of Formula (13) can be prepared by reaction of an amine of the formula (14) with a compound of the formula (15):
(Formula Removed)wherein:
R1, R2, L1, Q and B are as hereinbefore defined; and
U is halo.
The compound of formula (13) may also be prepared by reaction of the compound (15) with an amine containing a nitro compound of the formula (16):
(Formula Removed)
followed by reduction of the nitro group, preferably using a suitable reducing agent such as iron or sodium sulphide. The amine produced may then be condensed with a compound of formula R1U, wherein R1 and U are as hereinbefore defined to give the desired compound (13).
The dyes according to the present invention may also be prepared by condensation of a compound of formula (13) with a cyanuric halide. The resultant
dihalotriazinyl compound is then condensed with a dye having at least two nucleophilic groups.
Although dye formulae have been shown in the form of their free acid in this specification, the invention includes the dyes in their salt form, particularly their salts with alkali metals such as the sodium, lithium or mixed sodium/lithium salt.
The present invention also provides a process for the coloration of a substrate comprising applying thereto a dye according to the present invention, preferably in aqueous solution.
The reactive dyes of the present invention are suitable for colouring natural and artificial textile materials containing amino or hydroxyl groups, for example textile materials such as wool, silk, polyamides and modified polyacrylonitrile fibres, and more especially cotton, viscose rayon and other regenerated cellulosic materials. For this purpose the dyes can be applied to the textile materials by exhaust dyeing, or by padding or by printing using printing pastes containing the conventional thickening agents or oil-in-water emulsions, whereby the textile materials are coloured bright shades and possess good fastness to light and to wet treatments such as washing and also possess good wash off.
When applied under conventional reactive exhaust dyeing conditions the dyes give high fixation yields. Fixation yields of around 95% can be achieved even at relatively high dye on fibre concentrations, e.g. 5% by weight on weight. Such values are unusually high. As a consequence there is relatively little dye to remove during wash-off and the dyes are economical in use.
The new dyes are particularly valuable for colouring cellulosic textile materials. For this purpose the dyes are preferably applied to the cellulosic textile material in conjunction with a treatment with an acid-binding agent, for example, sodium bicarbonate, sodium carbonate, sodium metasilicate, trisodium phosphate or sodium hydroxide, which may be applied to the cellulose textile material before, during and after the application of the dye.
The new dyes can be applied to textile materials containing amine groups, such as wool and polyamide textile materials, from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is 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 invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight unless stated otherwise.
Example 1
Preparation of:
(Formula Removed)Stage (a)
Preparation of 4-amino-3,6-bis-(5-amino-2-sulphophenylazo)-5-hydroxy-naphthalene-2,7-disulphonic acid.
3-nitroaniline-6-sulphonic acid was diazotised by adding the 3-nitroaniline-6-sulphonic acid to an aqueous solution of concentrated HCI and 2N sodium nitrite solution at a temperature of 0-5°C. The diazonium salt was then coupled with an equimolar quantity of 4-amino-5-hydroxy-naphthalene-2,7-disulphonic acid under acidic conditions. The 4-amino-3-(5-nitro-2-sulphophenylazo)-5-hydroxy-naphthalene-2,7-disulphonic acid so formed was then coupled with an equimolar quantity of the diazotised 3-nitroaniline-6-sulphonic acid under alkaline conditions. The resulting dinitro disazo compound was then reduced to the triamino disazo compound by heating at 40°C for 1-2 hours with an aqueous solution of sodium sulphide. The pH of the reaction mixture was adjusted to pH 3 and the dis azo dye was collected by filtration and washed with brine solution. Stage (b)
Preparation of N -(3-amino-4-methylphenyl)acrylamide.
To a solution of 4-methyl-3-nitro-aniline (15.2g, 0.1 mol) in methylene chloride (300ml) was added acryloyl chloride (10g, 0.11 mol) and triethylamine (11.1g, 0.1 mol). The reaction mixture was then heated under reflux for 6 hours followed by filtration to remove triethylamine hydrochloride formed by the reaction. The reaction mixture was charged into water (500ml) and the organic layer was washed several times with water. The organic layer was then separated off and dried over magnesium sulphate. The methylene chloride was removed from the reaction mixture by distillation. Ethanol (250ml) and iron filings (10g) were then added to the reaction mixture, which was then heated under reflux for 4 hours. The reaction mixture was filtered and the product was isolated by evaporation to give a grey-green solid (7.3g).
Stage (c)
To a solution of 4-amino-3,6-bis-(5-amino-2-sulfo-phenyl-azo)-5-hydroxy-naphthalene-2,7-disulphonic acid (11g, 8mmol) in water (250ml) at 0°-5°C was added a solution of cyanuric chloride (3.2g, 17.4mmol) in acetone (50ml), with stirring whilst maintaining the pH between 5.0 and 6.0 by the addition of 2N sodium carbonate solution.
The mixture was stirred for three hours and N-(3-amino-4-methyl-phenyl)-acrylamide (4.1g, 17.5mmol) was added and the reaction was stirred for a further two hours at ambient temperature, whilst maintaining the pH between 6.0 and 7.0.
Sodium chloride (50g) was then added and the mixture was stirred for a further two hours. The dye was then collected by filtration, washed with sodium chloride solution (5%) and dried to give the final product (13.55g, 88% solid content) as a dark blue solid. It had a l max of 610nm (H20 at pH 7).
Dyeing
The title dye was applied to cotton under exhaust dyeing conditions using sodium carbonate as alkali, at 80°C. At 5% dye on fibre a fixation of 95% was achieved giving a strong greenish-navy shade. After washing off, the dyeing gave good wet fastness.
Example 2
Preparation of:
(Formula Removed)
Stage (9)
Preparation of:
(Formula Removed)
To a solution of 4-amino-4'-nitrostilbene-2,2'-disulphonic acid (4.1g, 9.2mmol) and 2N sodium nitrite (5mls, 10.1mmol) in water (100ml) was added a stirred mixture of
concentrated hydrochloric acid (2.3ml, 23.0mmol) and ice (200g). The reaction mixture was then stirred for 2 hours whilst maintaining the temperature below 5°C. Any excess nitrous acid was then destroyed by the addition of sulphamic acid. A solution of 3-aminoacetanilide (2.5g, 9.2mmol) in water (100ml) was added to the reaction mixture, the pH was adjusted to 6.0 and after stirring for 2 hours at 0-5°C, the precipitated solid was isolated by filtration.
The filter cake was dissolved in water (200ml) and the solution was added dropwise to a solution of sodium sulphide nonahydrate (5.9g, 24.8mmol) in water (100ml) whilst maintaining the temperature below 20°C. After stirring for 90 minutes at ambient temperature the pH of the reaction mixture was adjusted to 3.0 and the solid was collected by filtration and washed with saturated brine solution. Stage (b)
Preparation of:
(Formula Removed)
A solution of 2,4-diaminobenzene sulphonic acid (19g, 0.1 mol) in water (300ml) was adjusted to pH8 and cooled to 0-5°C. To the solution was added acryloyl chloride (11.14g, 0.12mol) over 30 minutes whilst maintaining the pH at 8. After stirring for 12 hours sodium chloride (60g) was added and the precipitated product was isolated by filtration to give a mixture of mono and bis acryloylated diaminobenzene sulphonic acid (37g). A solution of cyanuric chloride (3.7g, 20.2mmol) in acetone (50ml) was precipitated by pouring onto ice (100g). A solution of the mono and bis acryloylated diamino benzene sulphonic acid (8.1g) in water (100ml) was adjusted to pH 6 and charged to the cyanuric chloride solution whilst maintaining the temperature below 5°C. After stirring for 60 minutes the mixture was screened. Stage (c)
To a suspension of the product of stage (a) (10g, 9.2mmol) in water (500ml) was added dropwise the solution from stage (b) whilst maintaining the pH between 6.0 and 7.0. The reaction mixture was then stirred for 20 hours at 40°C, pH 5.0. Sodium chloride (32.5g) was then added to the reaction mixture and the product of the reaction was filtered off, washed with 50% brine solution and dried. The title dye obtained was an orange powder (17.8g, 76% solid content). It had a X max of 421 nm (H20 at pH 7).
Pyeing
The dye was applied to cotton under exhaust dyeing conditions using sodium carbonate as an alkali at 30°C, to give a bright reddish-yellow dyeing of very high fixation of 92 %. After washing the dyed cotton had good wet fastness.

We Claim:-
1. A dye having at least two groups each of which independently is of the formula (1) and salts thereof:
(Formula Removed)
wherein:
A is a halo triazinylamino reactive group;
L1 is an arylene group;
R1 and R2 are each independently H or alkyl;
Q is a group of the formula -CO- or -SO2-; and
B is an optionally substituted vinyl group or a group which is converted into an optionally substituted vinyl group in the presence of aqueous alkali.
2. A dye according to claim 1 wherein Q is a group of the formula -CO-.
3. A dye according to either of the previous claims wherein L1 is optionally substituted phenylene or optionally substituted naphthylene.
4. A dye having at least two groups each of which independently is of the formula (4) and salts thereof:
(Formula Removed)
wherein:
W is halo;
M is halo, alkoxy, alkyl, sulpho, carboxy, or hydroxy;
R6 is H or alkyl; and
R1, R2 and B are as defined in claim 1.
5. A dye according to any one of the previous claims wherein B is a group of the formula (2):
(Formula Removed)wherein:
R3, R4 and R5 are each independently H, halo or alkyl.
6. A dye according to any one of claims 1 to 4 wherein B is a group of the formula (3):
(Formula Removed)
wherein R3 and R4 are each independently H, halo or alkyl and Y is OSO3H, SSO3H, halo or -OCOCH3
7. A dye according to claim 1 which is of formula D-(T)n wherein each T independently is a group of formula (1) in claim 1; n > 2; and D is the residue of an azo, anthraquinone, phthalocyanine, triphendioxazine or formazan chromophore.
8. A process for the manufacture of a dye according to claim 1 comprising
condensation of a dye having at least two dihalotriazinylamino groups with a compound of the Formula (13):
(Formula Removed)
wherein:
R1, R2, L1, Q and B are as defined in claim 1.
9. A process for the colouration of a textile material comprising applying thereto a dye according to any one of claims 1 to 7.
10. A process according to claim 9 for colouring cellulosic textile materials wherein an aqueous solution of the dye is applied to the material which is also treated with an acid-binding agent before, during or after the application of the dye.
11. A textile material coloured by a dye according to any one of claims 1 to 7.
12. A textile material coloured by a process according to claim 9 or 10.
13. A dye substantially as herein described with reference to the foregoing examples.
14. A process for the manufacture of a dye substantially as hereinbefore described with reference to the foregoing examples.