GB2053949A - Anthraquinone dyes - Google Patents

Abstract

Dyestuffs which in the free acid form are of the formula: <IMAGE> wherein Y<1> and Y<2> are each independently H or SO <3H, X<1> and X2 are each independently H, halogen, SO3H or nitro, J and J<1> are each independently linear or branched C2-6 alkylene or C5 or C6 cycloalkylene with the N atoms attached to different carbon atoms, Q and Q<1> are the same or different cellulose reactive groups and R and R<1> are each independently H or optionally substituted C1-C4 alkyl groups. The dyes give colouration especially on cellulose having good strength and good wash-off properties.

Description

SPECIFICATION Anthraquinone dyes This invention relates to anthraquinone dyes in particular to cellulose reactive dyes of this type.

Many cellulose reactive dyes which incorporate an anthraquinone structural unit are known. For example UK Patent 1 386046 discloses dyes having cellulose reactive groups attached to a phenylamino group present as substituents on alkylamino groups in the 1,4- position of an anthraquinone nucleus. The present invention provides arthraquinone reactive dyes which are easily manufactured and usually associated with good strength and good wash-off properties, e.g. lack of staining on any uncoloured textiles present during a washing procedure.

According to the present invention there are provided dyestuffs which in the free acid form are of the formula:

wherein Y' and Y2 are each independently H or SO3H, X' and X2 are each independently H, Halogen, SO3H or nitro, J and J' are each independently linear or branched C26 alkylene or C5 or Ce cycloalkylene with the N atoms attached to different carbon atoms, Q and Q' are the same or different cellulose reactive groups and R and R' are each indepentently H or optionally substituted C1-C4 alkyl groups.

It is usually preferred that the dyestuffs of formula (1) are water-soluble and this may be achieved by having two or more water-solubilising groups present such as SO3H, C00H, PO3H2, or OS03H.

As examples of the optionally substituted C1-C4 alkyl groups represented by R and R', there may be mentioned methyl, ethyl, p-hydroxyethyl and cyanoethyl It is usually preferred that X', X2, y1, Y2, R and R1 are all H.

As examples of alkylene or cycloalkylene groups represented by J and J1 there may be mentioned: 1,2-propylene 1 6-hexamethylene 1,3 or 1,4-cyclohexylene and especially preferred are ethylene or 1 3-propylene.

It is usually preferred that J and J' are the same.

The cellulose reactive groups Q and Q' may be any groups capable of forming a covalent bond with a cellulose substrate. They may be any conventional cellulose reactive groups of this type such as those disclosed in patent specifications and other literature on reactive dyes, e.g. UK Patent Specification No. 1440948.

As examples of cellulose reactive groups there may be mentioned aliphatic sulphonyl groups which contain sulphate ester group in /3-position to the sulphur atom, e.g. p-sulphatoethylsulphonyl groups, a,-unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, a- chloroacrylic acid, a-bromoacrylic acid, propiolic acid, maleic acid and mono and dichloro maleic acids; also the acyl radicals of acids which contain a substituent which reacts with cellulose in the presence of an alkali, e.g. the radical of a halogenated aliphatic acid such as chloroacetic acid, p-chloro and p- bromopropionic acids and a,-dichlorn- and bibromopropionic acids or radicals of vinylsulphonyl- or chloroethylsulphonyl- oir p-sulphatoethylsulphonyl-endo-methylene cyclohexane carboxylic acids.Other examples of cellulose reactive groups are tetrafluorocyclobutyl carbonyl triflurocyclobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl, triflurocyc/obutenylethenyl carbonyl; activated halogenated 1,3dicyanobenzene radicals such as 2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6nitrophenyl, 2,4-dicyano-3,5,6-trifluorophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5difluorophenyl, 2,4,6-tricyano-3,5-dichlorophenyl and heterocyclic radicals which contain 1, 2 or 3 nitrogen atoms in the heterocyclic ring and at least one cellulose reactive substituent on a carbon atom of the ring.

It may be noted that many reactive groups may be defined as both heterocyclic or acyl groups since they consist of an acyl group carrying a heterocyclic substituent. For convenience in such cases where the heterocyclic ring carries the cellulose substituent these are usually referred to as heterocyclic reactive groups in this specification.

As examples of such heterocyclic radicals there may be mentioned for example: 2:3-dichloroquinoxaline-5- or -6-sulphonyl, 2:3-dichloroquinoxaline-5- or -6-carbonyl, 2 :4-dichloroquinazolin-6- or -7-sulphonyl, 2:4:6-trichloroquinazolin-7- or -8-sulphonyl, 2:4:7- or 2:4:8-trichloroquinazolin-6-sulphonyl, 2:4-dichloroquinazolin-6-carbonyl, 1:4-dichlorophthalazine-6-carbonyl, 4:5-dichloropyridazon-1 -yl-ethylcarbonyl, 2:4-dichloropyrimidine-5-carbonyl, 4-(4'-dichloropyridaz-6'-on- 1 -yl)benzoyl, 2-chlorobenzthiazole-6-carbonyl, 3,6-dichloropyrazin-4-carbonyl, 4-(4' :5'-dichloropyridaz-6'-on-1 '-yl)phenylsulphonyl; activated 4,6-dihalopyridin-2-yl and 2,6-dihalopyridin-4-yI groups such as 3,4,5,6-tetrafluoropyridin-2-yl, 2,3,5,6-tetrafluoropyridin-4-yl, 2,5,6-trifluoro-3-cyanopyridin-4-yl, 2,5, 6-trichloro-3-cyanopyridin-4-yl, 2,6-difluoro-3-cyano-5-chloropyridin-4-yl, 2,6-difluoro-3,5-dichlropyridin-4-yl and more particularly triazinyl or pyrimidinyl groups.

Examples of particular pyrimidinyl groups are pyrimidin-2-yl or -4-yl groups having a cellulose reactive atom or a group especially Cl, Br or F in at least one of the remaining 2-, 4- and 6-positions. The 5-position may carry various substituents such ad Cl or CN which are not normally cellulose reactive in themselves but may enhance the rectivity of substituents in other positions of the pyrimidine ring.As specific examples of such pyrimidinyl groups there may be mentioned:- 2,6-dichloropyrimidin-4-yl, 4,6-dicloropyrimidin-2-yl, 2,5,6-trich Ioropyrimidin-4-yl, 4,5,6-trichloropyrimidin-2-yl, 5-chloro-2-methylsulphonyl-6-methylpyrimidin-4-yl, 2,6-dichloro-5-cyanopyrimidin-4-yl, 4,6-dichloro-5-cyanopyrimidin-2-yl, 2,6-difluoro-5-chloropyrimidin-4-yl, 4,6-difluoro-5-chloropyrimidin-2-yl, 2,6-difluoro-5-cyanopyrimidin-4-yl, 4,6-difluoro-5-cyanopyrimidin-2-yl, Examples of particular triazinyl groups ar triazin-2-yl groups having cellulose reactive atoms or groups on one or both of the 4- and 6-positions.In this instance a wide range of cellulose reactive atoms or groups are available such as activated aryloxy or various groups linked through a sulphur atom but the preferred reactive atoms or groups are F, Br or especially CI; quaternary ammonium groups such as tri-lower alkyl ammonium, e.g. (CH3)3N- and pyridinium groups especially these derived from pyridine carboxylic acids in particular from nicotinic acid.

The triasinyl groups having only one reactive atom or group on the nucleus in the 4- or 6-position may have a substituent not reactive to cellulose in the remaining 4- or 6-position.

As examples of such non-reactive substituents there may be mentioned alkyl or aryl thio groups, alkoxy or aryloxy groups and optionally substituted amino groups.

Preferred forms of these groups include lower, i.e. C1 4alkoxy, e.g. methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy and lower alkoxy lower alkoxy, e.g. ,B-methoxy-ethoxy, p-ethoxyethoxy, phenoxy and sulphonphenoxy; amino; lower alkylamino, e.g. methylamino, ethylamino, butylamino, di(lower alkyl)amino, e.g. dimethylamino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types in which the alkyl groups are substituted, in particular by OH, CN or SO3H, e.g. p- hydroxyethylamino, di(P-hydroxyethyl)amino, p-cyanoethylamino, di(P-cyanoethyl)amino, P- sulphoethylamino, p-hydroxypropylamino, (p-hydroxybutyl)ethylamino and (P- hydroxyethyl)methylamino; cycloalkylamino, e.g. cyclohexylamino; cyclic amino, e.g. morpholino or piperazino; naphthylamino substituted by 1 , 2 or 3 SO3H groups and optionally substituted phenyl amino groups.

As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups of the formula:

where G = H, methyl, ethyl w-sulphomethyi, P-carboxy-, ,5-hydroxy or p-cyanoethyl and Z and X are each independently selected from H, COOH, SO3H, CH3,C2H5,OCH3, OC2Hs, Cl Br CN, NO NHCOCH3 and p-sulphatoethylsulphonyl.

As specific examples of such groups there may be mentioned anilino, o-,m- and p-sulphoanilino, o-, m- and p-carboxyanilino, 4- and 5-sulpho-2-carbozyanilino, 4- and 5-sulpho-o-tolylamino-, 2,4-, 2,5and 3,5-disulphoanilino, 2,4-dicarboxyanilino, 4- and 5-sulpho-2-methoxyanilino, N-methyl-o-, m- and p-sulphoanilino, N-w-sulphomethylani lino, N-(p-hydroxyethyl)-3-sulphoanilino.

If desired, the groups Q and/or Q1 may consist of a triazinyl residue having one or two hydrocarbylamino substituents which bear a phosphorus acid especially phosphonic acid group, e.g.

metaphosphonoanilino or y-phosphopropylamino. Such groups may be fixed to substrates such as cellulose under acid conditions using a fixing agent such as cyanamide or dicyandiamide as described in UK 1 311306. Such fixation may be contrasted with the usual fixation of most reactive dyes which involve acid-binding agents wich are frequently alkaline.

For reasons of ensuring adequate water solubility it is often preferred that the reactive groups 0 and Q1 are such as to contribute a solubilising effect e.g. they are p-sulphatoethylsulphonyl or monohalotriaz-2-yl having a substituent in the 4- or 6-position which carries a water solubilising group such as sulphoanilino.

It is usually preferred that Q and Q1 are the same.

Thus especially preferred dyes have JNRQ the same as J1NRlQl.

The present invention further provides a process for the manufacture of dyestuffs of formula (1 ) which comprises reacting a mixture of diamines of formula H2NJNHR and H2NJ1NHR, in either order with (a) - mole of a dihydroxyanthraquinone of the formula:

where X1, X2, Y1 andY2 have the meanings given above, or the leuco form of this dihydroxyanthraquinone followed by oxidation, and (b) 1 mole of a mixture of Qhal and Q1hal where hal is Cl, F or Br and 0 and Q1 have the meanings given above other than p-sulphatoethyl sulphonyl or of carbyl sulphate and Olhal where 0 is to be p- sulphatoethylsulphonyl.

Naturally in the case of preferred dyes when J and J1 are less the same and 0 and Q1 are the same, the above process is conducted using a single diamine H2NJNH2 and single reagent as specified in (b) viz. carbyl sulphate or Qhal.

Without limiting the invention to any mechanism of reaction it may be noted that it is believed that the reaction of diamine H2NJNHR or H2NJ1NHR1 usually takes place most readily, possibly exclusively, with the leuco form of the dihydroxy-anthraquinones (2). However, it is also believed that the reaction product of diamine and leuco compound rapidly becomes oxidised by any dihydroxyanthraquinone of formula (2) present, concurrently generating futher leuco form of the dihydroxyanthraquinone of formula (2). Thus the presence of a small proportion of leuco form in the dihydroxy-anthraquinone of formula (2) enables it all to be reacted with diamine. A convenient mode of conducting the reaction is to use dihydroxyanthraquinone of formula (2) in which about 30% is in the leuco form.The reaction is conveniently carried out in an aqueous or alcoholic medium or in the absence of added solvent at temperature of 20-1 2O0C especially 40-1 000C. Higher temperatures, e.g. 1 000C can lead in some instance to unwanted cyclisation products e.g. with ethylene diamine and temperatures of 40--600C are appropriate in such cases. At the end of the reaction any product in leuco form is oxidised to the required form, e.g. by blowing air through the reaction mass or by introducing a mild oxidising agent such as meta-nitrobenzene sulphonic acid. Further information on the reaction of diamines with 1,4dihydroxyanthraquinones is available, in J.Chem.Soc. C 1968, 1284.

The reaction of the diamines H2NJNHR or H2NJ'NHR1 or their reaction products with the dihydroxyanthraquinoine (2) with carbyl sulphate or Ohal or O'hal may conveniently be carried out in an aqueous medium at a temperature of 0--1000C appropriate to the reactivity of the Qhal or Qlhal being used and usually the pH is maintained in the range 4-8 especially 6-7 by the addition of acid-binding agents such as sodium bicarbonate, carbonate, or hydroxide.

It is usually preferred to conduct the reaction of the diamine H2NJNHR or H2NJ'NHR1 with the dihydroxy anthraquinone (2) before reaction with the reagents defined in (b) above. It is often desirable to have unsymmetrical diamines with amino groups of differing reactivity to minimise formation of unwanted reaction products of the diamine with two moles of the other reactant. Alternatively especially with symmetrical diamines the desired reaction may be facilitated by either using an excess of the diamine or by protecting one amino group e.g. by acetylation and removing the protecting group e.g.

by hydrolysis of acetyl groups, after reaction with the dihydroxyanthraquinone (2) and before reaction with the reagents defined in (b) above.

As examples of suitable diamines H2NJNHR and H2NJ1NHR1 for use in the above process there may be mentioned: ethylene diamine 1,2-propylene diamine hexamethylene diamine p-hydroxyethylethylene diamine 1 ,3-propylenediamine 2,3-butylenediamine 1,3for 1 ,4-cyclohexanediamine.

As examples of dihydroxyanthraquinones of formula (2) for use in the above process there may be mentioned Quinizarin ( 1 ,4-di hydroxyanthraquinone) Quinizarin-5-sulphonic acid Quinizarin-6-sulphonic acid 5,8-dichloroquinizarin 5-chloroquinizarin 5-nitroquinizarin.

Specific examples of compounds Ohal and Olhal will be apparent from the specific examples of Q and Q1 given above. It is normally preferred that hal is chlorine, e.g. Ohal is ss-chloropropionyl chloride, cyanuric chloride, methoxydichloro-s-triazine, 2,4,5,6-tetrachloropyrimidine etc., but in some instances hal may be more conveniently another halogen, e.g. fluorine, when this is the cellulose reactive substituent present in O, e.g. Ohal may be 2,4,6-trifluoro-5-chloropyrimidine to introduce the difluoro5-chloropyrimidinyl group.

The reactive dyes of formula (1 ) wherein one or both of the cellulose reactive groups 0 and Q1 are s-triazine nuclei substituted by a Cl, Br or F atom and an amino or substituted amino group can also be obtained by reacting a dye of formula (1) in which 0 and/or Q1 are dichloro, dibromo or difluoro-2-trizine groups with ammonia or an amine.

This process can conveniently be carried out by stirring the reactants in an aqueous medium, optionally in the presence of a water-woluble organic solvent, at a temperature of from 30-600C, and preferably maintaining the pH at from 5-8 by adding an acid binding agent to neutralize the hydrogen halide formed during the reaction. Suitable acid binding agents are alkali metal hydroxides, carbonates and bicarbonates, or an excess of ammonia or aliphatic amine where this is one of the reactants.

In the instances where one or both of 0 and Q1 are triazinyl groups having quaternary ammonium or pyridinium substituents as the cellulose reactive substituent these dyes may often be conveniently obtained by reacting the corresponding chloro-, bromo- or fluorotriazinyl dyestuffs with the appropriate tertiary amine or pyridine compound. Such a reaction is normally carried out in aqueous media at 300C to 1000C.

The dyestuffs prepared by the above processes may be isolated by any conventional means, e.g.

spray drying or precipitation and filtration.

The dyes are represented above in their free acid form and may be sometimes isolated as such.

However, it is usually found more convenient to isolate the dyes in the form of salts particularly alkali metal salts, especially sodium.

The dyestuffs of the present invention may be used for colouring a wide range of textile materials containing hydroxyl or amino groups, e.g. wool, silk, synthetic polyamides and natural or regenerated cellulose, for example cotton or viscous rayon materials, by conventional methods used for colouring such materials with water-soluble reactive dyes. e.g. in the case of cellulose they are preferably applied in conjunction with a treatment with an acid binding agent, e.g. caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, which may be applied to the cellulose textile materials before, during or after the application of the dyestuff.The method, technique and conditions used for applying the dyestuff to the textile material will be selected according to various factors, e.g. the nature of the fibre or fibres present and the physical form of the textile material, for example methods will vary depending on whether the fibre is loose or spun into thread which in turn may be in hanks or wound on bobbins or converted into cloth or garments by knitting or weaving. Any of the usual methods of dyeing or printing may be employed to apply the dye to the textile material and other dyestuffs and/or pigments may also be applied simultaneously or sequentially with the dyestuffs of the present invention using such combinations of conditions as are dictated by the properties of the dyestuffs and/or pigments.

Such mixed dyeings are particularly valuable if the textile containing OH or NH2 groups is blended with other textile fibres free from such groups, e.g. polyesters. the dyeing may be carried out in a batchwise manner using, for example, exhaustion techniques in a beck, winch, jet, paddle or jig device, in particular for hanks, woven or knitted fabrics or garments; or it may be applied by a "package" dyeing technique to fibres wound in cakes or on cones, bobbins or warp beams, especially when these supports are perforated, or to loose fibres in permeable containers such as cages, pressure and/or vacuum may be employed to facilitate penetration and circulation through the packages. Alternatively, continuous or semi-continuous dyeing methods may be employed, such as those employing padding techniques, e.g. by padding mangles whereby the textile material is impregnated with dye liquor and then passed through rollers to control the amount of liquor retained, followed by one or more of a variety of post treatments, e.g. drying, jig or winch development, baking, steaming, repadding in further solutions such as acid binding agents as mentioned above, storage in a moist condition at ambient or elevated temperatures, passing over heated rollers or passing through batchwise or continuous washing procedures. These post treatments may also incorporate finishing stages at which, for example, antistatic or crease resistance agents can be incorporated.Textiles in sheet form may also be coloured by textile printing methods such as printing with engraved or embossed rollers or through screens or by transfer techniques such as wet transfer printing. Details of these and other suitable printing methods are described in "The Principles and Practise of Textile Printing" by E. Knecht, J. B. Fothergill and G. Hurst, 4th Edition 1 952 published by Griffin or in "An Introduction to Textile Printing" by W. Clarke, 4th Edition 1 974 published by Newnes Butterworth.

The new dyes of the present invention form a valuable class of dyes and textiles coloured with these dyestuffs shown good resistance to washing and other wet treatments. The present dyes are associated with good dyeing and printing behaviour and show good levels of fixation to the substrates, good build-up and easy wash-off of unfixed dyestuff.

The invention is iliustrated by the following Examples in which all parts are by weight and proportions in wt/vol are kgs/litre.

EXAMPLE 1 To 6.7 parts of anilino-2,5-disulphonic acid in the form of 1 50 ml of aqueous solution at pH 7 at O5 0 is added 0.1 parts of calsolene oil and 6.0 parts of technical quality cyanuric chloride. The pH is maintained at 6.5 to 7.5 by addition of 1 M sodium hydroxide solution and the temperature at 0--50 until the uptake of alkali has practically ceased. (about 21 hours). The solution is filtered to remove excess cyanuric chloride and to it is added at O5 3.24 parts of 1 P-bis(P- aminoethylamino)anthraquinone (prepared as described in J.Chem.Soc. C 1 968, 1284) in 80 parts of ethyl alcohol.The pH is maintained at 7-8 by addition of sodium hydroxide solution as necessary and the temperature raised to 40" until the uptake of alkali has practically ceased (about 1 hour). The resulting dyestuff solution is adjusted to pH 7 and the dye is salted out with 60% potassium acetate solution at pH 7. The resulting solid is dissolved in the minimum quantity of cold water and the dye is reprecipitated by addition of ethanol, filtered off, washed with ethanol and dried. The resulting dye when applied to cotton in conjunction with an acid binding agent imparted bright blue shades with good fastness properties. Unfixed dyestuff was easily washed off the fabric after the application process.

EXAMPLE 2 The procedure of Example 1 is followed except that the 1,4-bis-B-aminoethyl anthraquinone is added to the solution of 2-(2,5-disulphoanilino)-4,6-dichlorotriazine as a solid, and the dyestuff is isolated after the reaction by conventional precipitation with sodium chloride. The resulting dyestuff had essentially the same dyeing, wash-off and fastness properties as did the dye of Example 1.

EXAMPLE 3 Leucoquinizarin (12.1 parts) is added to propylenediamine (125 parts) under nitrogen and the mixture stirred for 2 hours under nitrogen at 5055 . Air is then blown through the mixture or oxidise it, and the resulting suspension is poured into water (500 parts) containing sodium hydroxide (5 parts).

After stirring the solid is filtered off, giving 34 parts of essentially pure 1,4-bis-(3aminopropylamino)anthraquinone. The method of Example 2 is then followed, using 3.52 parts of the dyebase in place of the 3.24 parts of 1 ,4-bis-(P-aminoethylamino) anthraquinone. The resuming dyestuff imparted particularly bright blue shades with good fastness properties when applied to cotton by printing.

EXAMPLE 4 1 2 parts of the dyestuff of Example 2 are stirred in 200 part sof aqueous solution of pH 8 with 3 parts of nicotinic acid at 9095 for 6 hours. The resulting bis-quaternary dyestuff is isolated by precipitation with potassium acetate solution, stirred in aqueous solution at pH 7 and reprecipitated with ethanol. When applied by conventional printing methods for cellulose reactive dyes to cotton it gave bright blue shades of excellent fastness properties.

EXAMPLES 5-30 By following the method of Examples 1 or 2 using an equivalent amount of compound given in column II of Table 1 in place of the 6.7 parts of the aniline -2,5-disulphonic acid and a diamino anthraquinone prepared from the dihydroxyanthraquinone in column Ill and the diamine of column IV in place of the 1,4-bis(p-aminoethylamino) anthraquinone there are obtained blue dyestuffs which will colour cellulose fibres when applied with an acid binding agent, the dyed fabrics having good fastness to light and washing.

TABLE I

Example I II III 6 Phenol 2,4-disulphonic acid Qui nizarin (1,4-dihydroxy Ethylenediamine anthraquinone) 7 Phenol sulphonic acid (mixed isomers obtained by sulphonation) 8 Metanilic acid " " 9 Aniline 2,5-disulphonic acid " 1,3-propylenediamine 10 .. " 1 ,2-propylenediamine 11 Aniline 2,4-disulphonic acid ,, 1::1 mixture of ethylene diamine and 1,3-propylene diamine 12 Aniline 2,6-disulphonic acid " 1,4-cyclohexenediamine 13 Aniline 2,4-disulphonic acid ,, 1,6-hexanediamine 14 1:1 sulphanilicacid: " ethylenediamine aniline 2,5-disulphonic acid 15 Thiophenol-4-sulphonic acid 16 Aniline 2,5-disulphonic acid 5,8-dichloroquinizarin 17 Phenol 2,4-disulphonic acid " " 18 Metanilic acid 5,8-dichloroquinizarin N-ss-hydroxyethyl ethylenediamine 19 Aniline 2,4-disulphonic acid Quinizarin 5-sulphonic 1,3-propylenediamine acid 20 " Quinizarin 6-sulphonic Ethylenediamine acid 21 " Quinizarin 2,3-butanediamine 22 Phenol-4-sulphonic acid " ss-hydroxyethyl ethylenediamine 23 2-methylphenol-4- " " sulphonic acid 24 Orthanilic acid " 25 m-aminophenyl sulphonic acid 26 Aniline 2,5-disulphonic acid 27 2-hydroxynaphthalene- " " 3,6-disulphonic acid 28 Metanilic acid " 29 2-amino-5-sulphobenzoic acid ,, 30 " " Propylenediamine EXAMPLE 31 To 6.7 parts of aniline-2,5-disulphonic acid in 1 50 ml of aqueous solution of pH 7 is added at -3 to 0 4 4.5 parts of cyanuric fluoride over about 10 minutes, the pH being maintained at 4.3-4.8 by addition of dilute sodium carbonate solution. To the resulting solution is then added at 0-5 3.52 parts of 1 ,4-bis-(y-aminopropyl) anthraquinone. The pH is maintained at 6-7 and the temperature below 10 until uptake of alkali has virtually ceased. The resulting dye is isolated by salting out after addition of neutral phosphate buffer salts. When applied to cotton in conjunction with a suitable acid binding agent it imparts bright blue shades with good wash-off and fastness properties.

EXAMPLES 32-36 By following the method of Example 31, other bis(monofluorotriazine) dyes are prepared as indicated in Table 2, where the columns have the same significance as those in Table 1.

TABLE II

Example I II II 32 Aniline 2,4-disulphonic acid Quinizarin 1,3-propylenediamine 33 2-methyl an I ine-5-sulphonic acid ,, Nss-hydroxyethyl ethylene diamine 34 Orthanilic acid .. .. S, 35 Aniline 3,5-disulphonic acid 1, Ethylenediamine 36 2-aminonaphthalene-5,8 disulphonic acid EXAMPLE 37 The method of Example 1 is followed using an equivalent amount of cyanuric bromide in place of the cyanuric chloride.The resulting dyestuff when applied to cotton in the presence of a suitable acidbinding agent imparts bright blue shades with good fastness properties.

EXAMPLES 38-44 Quaternised dyestuffs are prepared essentially by the method of Example 4 by taking the dyestuff of the example number given in column II of Table 3, and treating it with an equivalent amount of the quaternising agent given in column Ill.

TABLE Ill

Il lii Example Dyestuff of Example Quatemising agent 38 8 Nicotinic acid 39 9 Pyridine 40 10 Nicotinic acid 41 11 Nicotinamide 42 25 Trimethylamine 43 8 1,4-diazabicyclo [2,2,2] octane 44 26 EXAMPLE 45 9.7 parts of the potassium salt of the dyestuff of Example 8 is stirred with 1 00 parts of water at pH 7-8 and 5 parts sodium sulphite at 6070 until the reaction is complete. The resulting dyestuff is salted out and dried.When applied to cotton in the presence of a suitable acid-binding agent it imparts blue shades with excellent fastness properties.

EXAMPLE 46 11 parts of the sodium salt of the dyestuff of Example 25 is stirred with water (1 50 cc) and 40% methylamine solution (5 parts) is added. The mixture is heated at 8090 for 2 hours and the resulting dyestuff is isolated by salting; the salt is removed by dialysis. The resulting dyestuff solution is padded onto cotton in the presence of dicyandiamide, the fabric being then dried and heated to fix the dyestuff.

The cotton is thereby coloured a bright blue shade.

EXAMPLES 47-50 The 1 ,4-bis(aminoalkylamino)anthraquinone used in the example given in column II is reacted with two molecular equivalents of the acylating agent given in column Ill, using methods conventionally used with this acylating agent. The resulting dyestuffs impart blue shades when applied to cotton in the presence of a suitable acid-binding agent.

TABLE IV

ll Ill Example bi s-(ami noalkyl)anthraquinone as in Acylating Agent 47 Example 2 Carbyl sulphate 48 Example 26 ..

49 Example 26 50 Example 2 5-chloro-4-(3,5- disulphoani lino) 2,6-difluoro pyrimidine

Claims (1)

1. CLAIM

   1. Dyestuffs which in the free acid form are of the formula:

   wherein Y' and Y2 are each independently H or SO3H, X1 and X2 are each independently H, halogen, SO3 or nitro, J and J1 are each independently linear or branched C26 alkylene or C5 or C8 cycloalkylene with the N atoms attached to different carbon atoms, Q and Ql are the same or different cellulose reactive groups and R and R1 are each independently H or optionally substituted C1-C4 alkyl groups.