WO1995012585A1

WO1995012585A1 - Textile treatment

Info

Publication number: WO1995012585A1
Application number: PCT/GB1994/002403
Authority: WO
Inventors: David Malcolm Lewis; Peter Broadbent
Original assignee: University Of Leeds
Priority date: 1993-11-04
Filing date: 1994-11-02
Publication date: 1995-05-11
Also published as: AU8064394A

Abstract

A compound of formula (I), wherein H/C represents a nitrogen-containing heterocycle, the side chains of which are attached through carbon atoms in the heterocycle; Ar represents a substituted or unsubstituted benzene naphthalene or straight chain of cyclic alkyl residue; Q is a tertiary amine or an azide; B is hydrogen, alkyl or alkoxy; and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl, alkylaryl, or a substituted arylamino-s-triazine or pyrimidine or a quaternized arylamine-s-s-triazine or pyrimidine or a vinyl sulphone or a blocked vinyl sulphone or group containing a vinyl sulphone or blocked vinyl sulphone; where each D is not necessarily the same; and X is an anion. The agent increases the affinity of cellulosic, keratinous and polyamide textiles for disperse dye stuffs.

Description

TEXTILE TREATMENT

This invention relates to a method of treating textiles and in particular relates to a method for treating cellulosic, keratinous and polyamide textiles to increase their affinity for disperse dyes, and novel compounds therefor.

Keratinous fibres such as wool, natural polyamides such as silk and natural cellulosic fibres such as cotton do not normally exhibit any marked affinity for disperse dyestuffs. Again attempts to dye these fibres with disperse dyes result in poor colour yields, dull shades and poor wet and light fastness. Disperse dyestuffs are used largely with synthetic fibres such as polyesters and are therefore commonly available. Furthermore, disperse dyes are often sublimable and form the basis of the well known "transfer printing" process in which papers are printed with a design using disperse dye and these papers may then be subsequently used to colour the textile fabric merely by placing the paper and the fabric together and heating in a press for a short period of time, typically half a minute at 180-220°C (French Patent No. 1,223,330).

Synthetic polyamide fibres ("nylon") have apparent adequate affinity for disperse dyes but the wash fastness of dyeings and prints of these dyes on this substrate is inadequate.

The invention seeks to provide a method of increasing the affinity of these fibres for disperse dyes and to allow deeply coloured, high wet-fast dyeings and prints to be produced. The invention also seeks to provide novel compounds useful in this method.

In accordance with the present invention there is provided a compound of the formula:

wherein : H/C represents a nitrogen-containing heterocycle, the side chains of which are attached through carbon atoms in the heterocycle; Ar represents a substituted or unsubstituted benzene naphthalene or straight chain of cyclic alkyl residue; Q is a tertiary amine or an azide; B is hydrogen, alkyl or alkoxy; and D is hydrogen, halogen, cyano, substituted amino, alkyl, alkoxy, aryl, alkylaryl, or a substituted arylamino-s-triazine or pyrimidine or a quatermized arylamine-s-s-triazine or pyrimidine or a vinyl sulphone or a blocked vinyl sulphone or group containing a vinyl sulphone or blocked vinyl sulphone; where each D is not necessarily the same; and X is an anion.

Ar may be substituted by alkyl or alkoxy groups or by chlorine atoms.

Each B may be, independently, hydrogen, or an alkyl group containing 1 to 6 carbon atoms, which may be substituted by hydroxy or alkoxy groups containing 1 to 4 carbon atoms or may be joined to form with the unit HN-Ar-NH a cyclic heteroaliphatic ring system. Preferably the latter may be:

Wherein two of the Y's represents nitrogen atoms and the other nitrogen or carbon atom carrying a hydrogen atom or a chlorine atom or a cyano group.

The fibre reactive arylating agents of general formula I may be prepared by condensation of a halogenoheterocyclic compound of general formula IA.

wherein Hal represents a chlorine, bromine or fluorine atom and Y is as hereinbefore defined with an amine of general formula IB and then with a further amine of general formula IB:-

D-Ar-NHB

(IB)

and reacting the product with a tertiary amine of general formula Q as hereinbefore defined.

The fibre reactive arylating agents of general formula (I) where the bracketed portion has the value 2, may be prepared by reacting, in any order a halogenoheterocyclic compound of general formula (IA) with an amine of general formula IB and one of the amino groups of a diamine of general formula ID.

B-NH-Ar-NH-B

(ID) and reacting a halogenoheterocyclic compound of general formula IA with an amine of general formula IB and the other amino group of the diamine of general formula IA and finally reacting the product with a tertiary amine Q.

As examples of halogenoheterocyclic compounds there may be mentioned cyanuric chloride, cyanuric bromide, cyanuric fluoride, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4,6-trifluoropyrimidine and 5-cyano-2,4,6-trichloro-pyrimidine.

As examples of amines of general formula IB there may be mentioned aniline, p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4-dimethylaniline, 2,4,5-trimethylaniline, p-butylaniline, p-dodecylaniline, p-aminoacetanilide, N-methylaniline, N-butylaniline, p╌aminobenzonitrile, p-benzylaniline, 4-aminobiphenyl, α-naphthylamine, 2-ethoxy-1-aminonaphthalene.

As examples of diamines of general formula ID there may be mentioned o, m and p-phenylene diamine, 2-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diamonobenzene, 2-methoxy-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 4-chloro-1,3-diaminobenzene, N,N'-dimethyl-p-phenylene diamine, N,N'-di-(β-hydroxyethyl)-p-phenylene diamine, dianisidine, ethylene diamine, propylene diamine, butylenediamine, 1,6╌diaminohexane, 1,12-diaminododecane, N,N'-dimethylethylenediamine, N-β-hydroxyethylene diamine, piperazine.

As examples of tertiary amines represented by the symbol Q there may be mentioned trimethylamine, dimethylethylamine, N,N-dimethylhydrazine, 1,4-diazabicyclo{2,2,2}octane, pyridine, nicotinic acid, ethyl nicotinate, nicotinamide, N-methylpyrollidine, N-methylpiperidine, N-methylmorpholine, quinuclidine, N-methyl imidazole.

The invention further provides a method of treating natural (proteinaceous polyamide and cellulosic) textile fibres and synthetic polyamide fibres to enhance their affinity for disperse dyestuffs which comprises treating the fibres with an aqueous solution or aqueous dispersion of fibre reactive arylating agent of formula (I).

In the treatment, one or two of the quaternary ammonium groupings Q⁺ present in the arylating agent are displaced by nucleophilic centres present in the fibre causing the arylating agent to become covalently bound into the fibre. Such treatment involves reacting the fibre reactive arylating agent with the textile material under conditions of pH and temperature analogous to those used in the application of reactive dyes to textile materials. Such conditions are well known to those skilled in the art.

The treatment can be carried out prior to or simultaneously with dye application.

According to a further aspect of the invention there is provided a composition comprising: a disperse dye, a non-ionic dispersing agent, and an arylating agent as defined above.

The arylating agent may contain one or more benzene or naphthalene residues and is covalently bonded to the fibre by a suitable reactive group. Three such preferred compounds have the formulae:

A typical pyrimidine derivative would be

The amount of arylating agent employed is preferably between 2 and 20% on weight of fibre (o.w.f) and is conveniently in the range 6 to 15% o.w.f.

A particularly useful arylating agent has the structure of formula (II) above.

This compound is water soluble, cationic and extremely reactive to cotton, silk, wool and nylon under neutral to slightly acidic conditions; its substantivity for these fibres is also excellent. If co-applied with a disperse dye by the simple procedure of raising to the boil and boiling one hour, dyeings of excellent brilliance, colour yield (water-white dye bath exhaustion) and colour fastness are achieved. Alternatively co-application by padding processes may be carried out, fixation of the disperse dye and arylating agent occurring simultaneously on drying, or steaming or batching.

The preferred amino-triazinyl reactive arylating agents may be applied either by exhaustion from long liquors, or by padding. In the former case the arylating agent is dissolved or dispersed in water, optionally in the presence of a non-ionic surfactant and a buffer. The textile material may be immersed in the bath which is raised to the necessary treatment temperature and held at this temperature for a period of, for example, from 10 minutes to 2 hours. Where the arylating agent is applied by padding, the agent is dispersed or dissolved in water optionally together with a swelling agent for the textiles, for example urea and a thickener. The fabric or material may be padded, steamed or baked to fix the reagent and then rinsed to remove unfixed arylating agent; alternatively the fabric or material may be padded with the reactive agent, batched for periods up to 48 hours to allow reaction to occur and then rinsed to remove unfixed reagent. In a further aspect of the invention the agent may simply be applied by a pad→dry procedure and fixed during the sublimation transfer printing process (30 sees - 60 sees at 180-210°C). The arylating agent may conveniently be any suitable compound according to formula (I) which contains both one or more benzene rings and a reactive amino-quaternized s-triazine group. Such compounds are conveniently prepared by the reaction of water insoluble halo-s-triazines with selected tertiary amines; the reaction products become water soluble by virtue of the introduced quaternary ammonium residue. The following scheme describes this general reaction:

Wherein Ar, Q and D have the meanings ascribed hereinabove, and X is a halogen. In particular, D may be phenyl, phenyl amide, or 1-amino-3-halo-5-aryl s-triazine or 1-amino-3-quaternized amino-5-aryl-s-triazine.

Compound (II) to (VI) are cationic in character and thus have substantivity for wool, silk, nylon and cotton fibres from neutral to weakly alkaline baths, since these fibres are all negatively charged under these conditions. This has numerous advantages in that the nucleophilicity of the reactive sites in the fibres increases with increasing pH and it is thus easier to covalently bind the sorbed reactive agent than if the agent were sorbed under acidic conditions. However, they should not be employed with commercially available disperse dye compositions as these contain anionic dispersing agents which react adversely with the arylating agents. Instead it is preferred to take wet filter cake from the disperse dye manufacturer and mill it with non-ionic dispersing agents. Disperse dyes combined with the arylating agents can thus be viewed as a universal dyeing system, a concept which has wide implications, not least in the dyeing of blends of fibres.

Nucleophiles available for reaction depend on the fibre to be treated. In wool there are highly reactive thiol residues, slightly less reactive amino residues and much lower reactivity hydroxyl groups. Silk contains amino and hydroxy nucleophiles but the concentration of amino groups in silk is low compared with wool. Cotton contains relatively weak cellulosate nucleophiles; the C₆ primary hydroxyl group and the C₂ secondary hydroxyl group in the anhydro-glucose monomer units have been identified as being reactive to reactive dyes and are expected to be involved in covalent reactions with the preferred reactive arylating agents.

The reaction of the water soluble quaternized amino s-triazine with fibre nucleophiles may be summarized:

Where Ø is the nucleophilic residue.

The compounds of the invention are also useful in the tanning of leather, and the preparation of paper for printing. They may also be used in wood treatments to render the wood more hydrophobic and receptive to subsequent treatment e.g. with dyes, preservatives, etc. In addition they may be used for hair treatments e.g. prior to colouring with disperse dyes, and may give improved heat settability.

The invention will be illustrated further by the following non-limiting Examples.

EXAMPLE 1. PREPARATION OF FIBRE MODIFYING AGENTS

The chemicals used throughout the following preparations were of laboratory reagent grade, unless otherwise stated. A number of fibre reactive agents were prepared as follows:

PREPARATION OF PRECURSORS :

(i) 6- Anilino-2,4-dichloro-s-triazine (ANEX)

Cyanuric chloride (0.25 mole, 46.2g) was dissolved and sodium carbonate (0.5 mole, 53.0g) suspended in acetone (400 ml) at 0-5°C. Aniline (0.25 mole, 22.8 ml) was dissolved in acetone (100 ml) and added to the cyanuric chloride/sodium carbonate suspension dropwise, whilst keeping the temperature below 5°C. When no positive test for free aromatic amine was obtained (aniline was diazotised and coupled to β-naphthol), the reaction was stopped and any solid present was removed by filtration. The acetone present was removed on a rotary evaporator to leave the required product, a white solid which was stored at 0°C.

* (Throughout these Examples the symbol ⊳ is used as shorthand to represent the s-triazine heterocyclic ring system.)

(ii) 4.6-Dianilino-2-chloro-s-triazine (AAEX)

ANEX (0.25 mole, 60.3g) and sodium carbonate (0.5 mole, 53.0g) were dissolved/suspended in acetone (400 ml) and the solution was heated to 35-40°C; at this point aniline (0.25 mole, 22.8 ml), dissolved in acetone (100 ml), was gradually added. The reaction was stopped when no positive test for free aromatic amine was obtained. Any solid present was removed by filtration and the acetone was removed to yield a white solid.

Both ANEX and AAEX have been mentioned in an earlier patent publication (D M Lewis and Wool Development International - EP 0 118 983 A - 1984) for arylating fibres to improve disperse dye substantivity. However, the present compounds, which use these as precursors only, have been found to give superior performance, particularly on cellulosic fibres.

Using these precursors the following novel compounds were prepared: I 6-Aniline-4-chloro-2-diazabicyclo-2,2,2-octane ammonium- chloride-s-triazine (AC3)

Diazabicyclo-2,2,2-octane (DABCO) (0.5 mole, 56.0g) was dissolved in acetone (100 ml) and added dropwise to a solution of ANEX (0.1 mole, 24.1g) in acetone (200 ml) at 15-20°C. A white precipitate was obtained, which was collected, washed with acetone and dried in a vacuum desiccator. The dry solid was stored at 0°C.

II 4,6Dianililino-2-diazabicvclo-2,2,2-octane ammonium Chloride- s-triazine (AC)

DABCO (0.5 mole, 56.0g) was dissolved in acetone (100ml) and gradually added to a solution of AAEX (0.1 mole, 29.8g) in acetone (300ml) at 60°C. A white precipitate was formed which was collected, washed with acetone and dried. III Bis-1',4' -(2-diazabicyclo-2,2,2-octane ammonnium-chloride-4-anilino-s-triazine-6-yl)-diaminobenzene (AC2).

P-phenylene diamine (0.1 mole, 10.8g) was dissolved in acetone (200 ml) and added dropwise to an ice cold solution of cyanuric chloride (0.2 mole, 37.0g) and suspension of sodium carbonate (0.8 mole, 84.8g) in acetone (300 ml). When no free aromatic amine was detected, the temperature of the mixture was increased to 35-40°C and aniline (02. mole, 18.2 ml) in acetone (100 ml) was gradually added. When no positive test for free aromatic amine could be obtained, the solid present was removed by filtration and the acetone removed to yield a white solid.

The white solid obtained (0.1 mole, 51.7g) was dissolved in dimethylformamide (DMF) (200 ml) and was then added gradually to a solution of DABCO (0.5 mole, 56.0g) dissolved in DMF (400 ml) at 30°C. A white precipitate was produced, which was collected, washed with acetone and dried.

By replacing DABCO with the tertiary amine, N-methylmorpholine, the more reactive, water soluble, cationic arylating agent AC 24 was prepared: this compound has the following structure:

This compound was found to be especially useful having high neutral reactivity, good water solubility and good substantivity for cellulose.

If the following tertiary amines were employed instead of DABCO valuable water soluble, cationic arylating could be prepared according to the following table:

The compound prepared from trimethylamine was found to be highly water soluble and reactive to cellulose at neutral pH: however the fishy smell of trimethylamine may be a disadvantage.

EXAMPLE 2

The effectiveness of these products was evaluated by pre-treating cotton fabrics with various amounts of the particular arylating agent and assessing the colour yield and wet fastness of subsequent disperse dyeings. A number of pretreatment methods were employed including long liquor treatments, pad-batch and pad-bake; these methods are well known to those skilled in the art of textile dyeing and finishing and conditions were varied according to the known reactivity of the reactive arylating agent. All test dyeings were produced using a 2% o.w.f. shade of CI Disperse Blue 183 (Foron Blue SE-2R Sandoz) at pH 6.0, 1 hr at the boil. The colour yields were expressed in terms of the Kubelka Munk K/S function at 620 nm.

Untreated cotton gave an extremely low colour yield (K/S = 0.28) following the above dyeing procedure.

Both the precursors ANEX and AAEX were tried but found to be unsuitable arylating agents for cotton; the reaction with the fibre is inefficient and hence little improvement in disperse dyeability is obtained. The hydrophobic AAEX dispersions do not react readily with the fibre even under relatively severe conditions.

(i) AC3

In the case of the water soluble derivative, AC3, the following results were obtained:

AC3 PRE-TREATMENT K/S OF

APPLICATION pH DISPERSE DYEING

Long Liquor

15% AC3 o.w.f. 6.0 0.58

40°C, 1 hr

" " 7.0 0.62

" " 8.0 0.55

While this compound does not render cotton disperse dyeable, it is nevertheless useful in other applications. (ii) AC

In the case of AC, the following results were obtained:

AC PRE-TREATMENT K/S OF

APPLICATION pH DISPERSE DYEING

METHOD

Long Liquor

15% o.w.f. AC 6.0 0.75

100°C, 1 Hr

" " 6.5 0.86

" " 7.0 0.95

" " 7.5 1.04

" " 8.0 1.06

Pad→Dry→Bake

(200°C, 1 min) 6.0 3.0

4% o.w.f. AC

" " 7.0 4.1

" " 8.0 4.7

" " 9.0 3.9

Clearly, compared with the other compounds evaluated, AC shows more promise as a pretreatment agent to improve disperse dyeing; it is more effective when applied by a pad→dry→bake method but due to solubility problems only 4% o.w.f. could be applied. (iii) AC2

In the case of AC2 the following results were obtained:

AC2 PRE-TREATMENT K/S OF

APPLICATION pH DISPERSE DYEING

METHOD

Long Liquor

15% AC2 o.w.f. 6.0 4.05

100°C, 1 Hr

" " 6.5 4.41

" " 7.0 4.75

" " 7.5 5.21

" " 8.0 5.65

Long Liquor

15% AC2 o.w.f.

pH7. 80°C 30 mins 10.4

Then pH12 1 Hr. 100°C

Clearly this product shows great promise when applied to cotton at high pH. Colour yields in this case were excellent and the dyeings were fast to washing.

EXAMPLE 3

Cotton fabric was padded with a solution/dispersion * of 100 g/l AC2 (*the solubility of AC2 in water at 20°C reaches a maximum of 40 g/l) and sufficient sodium hydroxide to give pH12. The samples were padded to a wet pick-up of 80% and dried at 100°C and then fixed by thermosol treatment at 200°C for 60 sees.

The above pretreated cotton was sublimation transfer printed for 30 seconds at 200°C in a Kannegiesser press with a disperse dye transfer printing paper normally employed for printing polyester fabrics (dyes were C1 Disperse Red 60 and Disperse Yellow 3). For comparison a piece of untreated cotton as control was also transfer printed with the same paper. The prints obtained on the cotton pretreated with AC2 were observed to be very much stronger than the prints on untreated cotton. These prints were tested for wash fastness using the IS03 test and for light fastness. On the pretreated cotton a change in shade of 4-5 was recorded in the IS03 test whereas the corresponding change in shade on the printed untreated cotton was 1 - indicating very low wet fastness in this case. Light fastness on the printed pretreated cotton was assessed as 5 and on the printed untreated cotton as 3.

EXAMPLE 4

Cotton fabric was pretreated by a long liquor process using 15%o.w.f. AC2 at pH 12 at an aqueous liquor: goods ratio of 10:1. the bath was raised to the boil and maintained at the boil for 1 Hr; rinsing in cold water completed the process. When the dried fabric was transfer printed as in Example 3 above, very good quality prints were obtained on the pretreated cotton.

EXAMPLE 5

Wool fabric was treated with 15% o.w.f. AC2 at pH 8. The bath was raised to the boil and boiled 1 Hr; rinsing in cold water completed the process. The dried pretreated fabric was transfer printed as described in Example 3 - very good quality prints of high light and wet fastness were obtained.

An additional advantage of the invention is that fabrics from the treated fibres show improved easy-care properties.

EXAMPLE 6

Silk fabric was padded with a dispersion prepared with 150 g/l AC2 plus 10 g/l sodium bicarbonate (pH 8.5) at a wet pick-up of 80%. The fabric was then dried at 100°C and baked at 180°C for 2 minutes. The fabric was then washed off in water and dried. This fabric could be readily transfer printed using disperse dye papers as described in Example 3 hereinabove to obtain bright, wash-fast prints.

By way of comparison, the procedure was repeated on untreated silk: very weakly coloured prints were obtained which were very fugitive to washing.

EXAMPLE 7

Cotton fabric was pretreated by a long liquor process using 15% o.w.f. of the N-methylmorpholine derivative (AC24); the bath was set at pH 7.5 and the temperature slowly raised to 130°C and maintained at this temperature for 40 minutes. Following cooling the fabric was removed, thoroughly rinsed in cold water and dried.

This pretreated fabric was found to exhibit enhanced appearance retention after washing and also excellent substantivity for disperse dyes. When transfer printed as described in example 4, excellent print colour yields were obtained and these prints were fast to washing at 60°C in the presence of laundry detergents.

EXAMPLE 8

The procedure of example 7 was followed except that the fabric employed was a 50/50 cotton/polyester blend fabric. On dry transfer printing (200°C 30 sees) with disperse dye papers, solid prints were obtained, which exhibited excellent wet fastness properties. If the untreated cotton/polyester blend fabrics were transfer printed in this manner then an unlevel print would result since only the polyester portion would take up disperse dye. EXAMPLE 9

A 100% wool fabric was treated at pH 6 in a bath containing 15% o.w.f. AC24. The bath was raised to the boil and maintained at the boil for 1 hour. Thorough rinsing in cold water completed the process.

The treated wool fabric exhibited easy care properties; better appearance retention after washing and excellent shrink resistance; these were in marked contrast to the poor performance of the untreated fabric.

In addition the treated wool fabric could be dyed to full depths with the disperse dyes whereas untreated wool fabrics were only lightly stained by such dyes. When transfer printed with disperse dye papers (200°C 30 sees) excellent colour yields were obtained.

EXAMPLE 10

The procedure of example 9 was followed except that the wool fabric was replaced by silk.

The treated silk showed improved easy-care properties over untreated controls, especially in terms of smooth drying performance after laundering.

When the treated silk was transfer printed with disperse dyes (200°C 30 sees) excellent colour yields were recorded and the prints were fast to washing. This was in marked contrast to the untreated silk fabric.

The treated silk fabric was dyed at pH 6 at 100°C for 1 hour with 4% o.w.f. of the navy blue disperse dye, C.I. Disperse Blue 79, and total exhaustion of the dyebath was noted; the dyeing was level and also fast to laundering. EXAMPLE 11

The procedure of example 9 was followed except that the wool fabric was replaced by a blend fabric containing 55% polyester and 45% wool.

The treated blend fabric could be dyed with disperse dyes at 130°C for half an hour to give solid shades of excellent colour yield and wet fastness. If the untreated blend fabric were to be dyed under these conditions the wool component would be left virtually undyed and a melange effect produced.

Similarly the treated blend fabric could be transfer printed (disperse dye printed papers - 200°C 30 sees) to give solid level prints with excellent wet fastness. Untreated wool/polyester blend fabrics when transfer printed in this manner gave unlevel prints since only the polyester portion of the blend was able to take up disperse dye.

EXAMPLE 12

C.I. Disperse Blue 79 was obtained as a filter cake and milled on a ball-mill using 20% (by weight) of the non-ionic dispersant, Symperonic PE/F85. These dispersions were found to be compatible with the cationic AC24 (commercially produced disperse dyes are usually dispersed with anionic dispersing agents which would clearly precipitate with AC24 - thus it is necessary, for a combined application of AC24 with disperse dye, to use either non-ionic or cationic dispersing systems).

When the above dispersion was applied to cotton fabric in the absence of AC24 little dyeing could be produced. However from baths set with 2% o.w.f. CI Disperse Blue 79, 20% o.w.f. AC24, pH 7.5, excellent dyeings could be achieved following treatment at 130°C for 30 minutes. These dyeings were level, well penetrated and fast to washing - dyebath exhaustion was almost complete which is a further advantage of such a procedure. EXAMPLE 13

The procedure of example 12 was followed except that the disperse dye employed was CI Disperse Red 277. Again excellent dye uptake was obtained and the dyeings were level and fast.

EXAMPLE 14

The procedure of example 12 was followed except that the disperse dye employed was CI Disperse Yellow 119. Again excellent dye uptake was obtained and the dyeings were level and fast.

EXAMPLE 15

A cotton/polyester (50/50) blend fabric was dyed as described in example 12. A level, well penetrated wash fast dyeing was produced. If AC24 was omitted from the bath an unlevel (melange) effect was produced since the cotton remained undyed.

EXAMPLE 16

Wool fabric was dyed with a dispersion of CI Disperse Blue 79 (prepared as described in example 12). The dyebath was set at pH6 and 15% o.w.f. AC24 added; on raising to the boil and boiling 1 hour, a level, wash fast dyeing was achieved. If AC24 was omitted from the dyebath hardly any dye uptake was obtained.

EXAMPLE 17

Silk fabric was dyed as described in example 16. Again level, excellent dyeings of good wash fastness were achieved. If AC24 was omitted from the dyebath hardly any dye uptake was obtained.

EXAMPLE 18

As per example 16 except CI Disperse Blue 79 was replaced with CI Disperse Yellow 119. Level wash fast dyeings were obtained. EXAMPLE 19

As per example 17 except CI Disperse Blue 79 was replaced by CI Disperse Red 277. Level, wash fast dyeings were obtained.

Claims

CLAIMS 1. A compound of the fomula:

2. A compound according to claim 1 wherein Ar is substituted by alkyl or alkoxy groups or by chlorine atoms.

3. A compound according to either of claims 1 or 2 wherein each B is independently, hydrogen, or an alkyl group containing 1 to 6 carbon atoms, which may be substituted by hydroxy or alkoxy groups containing 1 to 4 carbon atoms or may be joined to form with the unit HN-Ar-NH a cyclic heteroaliphatic ring system.

4. A compound according to claim 3 in which the ring system is:

wherein two of the Y's represents nitrogen atoms and the other nitrogen or carbon atom carrying a hydrogen atom or a chlorine atom or cyano group.

5. A method of preparing a compound according to claim 1 which comprises condensation of a halogenoheterocyclic compound of general fomula IA:

wherein Hal represents a chlorine, bromine or fluorine atom and Y is as hereinbefore defined with an amine of general formula IB and then with a further amine of general formula IB:

D-Ar-NHB

(IB) and reacting with the product with a tertiary amine of general formula Q as hereinbefore defined.

6. A method of preparing a compound according to claim 1 which comprises reacting, in any order, a halogenoheterocyclic compound of general formula (IA) with an amine of general formula IB and one of the amino groups of a diamine of general formula ID,

B-NH-Ar-NH-B

(ID) and reacting with a halogenoheterocyclic compound of general fomula IA with an amine of general formula IB and the other amino group of the diamine of general fomula IA and finally reacting the product with a tertiary amine Q.

7. A method according to either of claims 5 or 6 wherein the halogenoheterocyclic compound is cyanuric chloride, cyanuric bromide, cyanuric fluoride, trichloropyrimidine, tetrachloropyrimidine, 5-chloro-2,4,6-trifluoropyrimidine and 5-cyano-2,4,6-trichloro-pyrimidine.

8. A method as claimed in any of claims 5 to 7 in which amines of general formula IB are selected from anilin p-chloroaniline, 2,5-dichloroaniline, p-anisidine, p-phenetidine, p-toluidine, 2,4-dimethylaniline, 2,4,5-trimethylaniline, p-butylaniline, p-dodecylaniline, p-aminoacetanilide, N-methylaniline, N-butylaniline, p╌aminobenzonitrile, p-benzylaniline, 4-aminobiphenyl, α-naphthylamine, 2-ethoxy-1-aminonaphthalene.

9. A method as claimed in any of claims 5 to 7 in which diamines of general formula ID are selected from o, m and p-phenylene diamine, 2-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4- diamonobenzene, 2-methoxy-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 4-chloro-1,3-diaminobenzene, N,N'-dimethyl-p-phenylene diamine, N,N'-di-(β-hydroxyethyl)-p-phenylene diamine, dianisidine, ethylene diamine, propylene diamine, butylenediamine, 1,6╌diaminohexane, 1,12-diaminododecane, N,N'-dimethylethylenediamine, N-β-hydroxyethylene diamine, or piperazine.

10. A method as claimed in any of claims 5 to 9 in which the tertiary amines represented by the symbol Q are selected from trimethylamine, dimethylethylamine, N,N-dimethylhydrazine, 1,4-diazabicyclo{2,2,2}octane, pyridine, nicotinic acid, ethyl nicotinate, nicotinamide, N-methylpyrollidine, N-methylpiperidine, N-methylmorpholine, quinuclidine, or N-methyl imidazole

11. A method of treating natural (proteinaceous polyamide and cellulosic) textile fibres and synthetic polyamide fibres to enhance their affinity for disperse dyestuffs which comprises treating the fibres with an aqueous solution or aqueous dispersion of fibre reactive arylating agent of formula (I).

12. A method according to claim 11 wherein the treatment is carried out prior to or simultaneously with dye application.

13. A composition comprising: a disperse dye, a non-ionic dispersing agent, and an arylating agent of formula I.

14. An arylating agent according to claim 1 of the fomula: