GB2291655A - Oil and water repellent dyestuffs - Google Patents

Description

2291655 1 OIL AND WATER REPELLENT DYESTUFFS.

The present invention relates to oil and water repellent dyestuffs, to dyeing methods for use with such dyestuffs, and to fabrics dyed thereby.

Treatment of fabrics to render them water repellent is commonplace, while treatments to render them oil repellent are necessary when providing protective clothing for the chemical industry and the military. The military have a particular need for clothing that is water repellent, chemical agent proofed and camouflaged.

Current low-cost air-permeable nuclear biological and chemical (NBC) protective clothing ensembles, such as the UK Mark IV suit, offer the wearer lower physiological burden than corresponding impermeable or semipermeable systems. Excellent liquid control characteristics (ie. the ability to preve nt bulk liquid ingress into the anti-gas underlayers) can be conferred to air-permeable fabrics by employing a fluoropolymer finish. In addition to displaying low surface energy characteristics,'it is essential that any liquid repellent finish intended for military use must possess excellent chemical and mechanical abrasion resistance.

Many classes of hydrophobic textile finishes have been used commercially, the most common being fluorochemicals, silicones, wax emulsions and methylol stearamides. In order to improve durability, proprietary fluoropolymer treatments for imparting oil and water repellency to textiles usually employ resin systems. Such finishes can suffer catastrophic failure however, particularly on exposure to organic solvents.

Thus there is a continued need for treatments which can produce cloths with durable oil and water repellent properties. It would be particularly advantageous if these could also simulataneously impart 2 required camouflage colour characteristics.

The present invention provides a novel approach to production of durable oil and water repellent fabrics suitable for clothing use. This approach is characterised in that it uses dyestuffs which impart both colour and waterproofing properties to fabric in a single treatment, and preferably simultaneously impart oil repellency. These dyestuffs are particularly characterised in that they comprise a long chain hydrocarbon group or a perhaloalkyl group, preferably a perfluorogroup, together with a colour forming group in the same molecule.

The use of monomeric fluorocarbon repellents is not new, the first oil repellents being fluorocarbon analogues of known metallised carboxylic acid complexes (see eg US 2662835; Philips et al (1957) Text. Res. J 22, 369; Tripp et al (1957) Text. Res. J. 27- 340; Segal et al (1958) -2a 233). Attempts to covalently bond perfluorinated groups to cellulose to improve durability have been made by reacting perfluorinated acid chlorides with cotton in DMF in the presence of tertiary amine. However the resultant finishes, although displaying excellent oil repellency, were destroyed by hydrolysis in alkaline detergents (see Benerito et al (1960) 3Q 393). The application of fibre reactive dye chemistry to waterproofing has also been explored (see A J Hall, Textile Finishing. 3rd Edition. Heywood Books, London P344 (1966), GB 818492, GB 818778, US 2670265).

In copending UK patent application 9414570.3 the present inventor has demonstrated that dichlorotriazines bearing long chain hydrocarbon ballasts confer durable water repellency to cotton and has extended this to include novel halocarbon, eg. fluorocarbon containing dyes which display excellent durable oil repellency.

Dyestuffs with perfluorinated ballasts have been reported (see GB 840725 and EP 0323060) and have been proposed as-colourants for 0 3 fluoropolymers, such as Teflon, and perfluorinated solvents; although reference to their surfactant properties has been superficial. The solid surface tension of nylon-6 dyed with a series of azoic dyes has been measured however (see Shiraiwa (1982) Journal of the Japan Research Association for Textile End-Uses, 23 480) and the film forming properties of certain hydrocarbon ballasted azo dyes at liquid/liquid and liquid/air interfaces has also been described (Giles et al (1952) J. Chem. Soc. 918 and Giles (1981) Rev. Prog.

Coloration 11 89. Metal containing liquid crystals based upon long chain alkylated azobenzenes are also known (Hudson et al (1993) Chem. Rev. 93 86122).

No documents are known to the applicant that disclose use of long chain hydrocarbons and/or perfluorinated dyestuffs for the simultaneous colouring, water proofing and/or oil proofing of fabrics.

Thus, in a first aspect, the present invention provides a water resistant fabric characterised in that it includes a colour imparting chemical moiety that incorporates a colour forming group and one or more groups selected from long chain alkyl groups of 7 carbons, or more, and perhaloalkyl groups. preferably perfluoroalkyl groups. Where the dyestuff incorporates a long chain alkyl group this is preferably of 10 carbons or more, most preferably being about 10 carbons.

Preferably the fabric is both water resistant and oil resistant and is characterised in that it comprises a dyestuff that incorporates a perfluoroalkyl group. Preferably the perfluoroalkyl group is of 7 carbons or more, conveniently being C8F,7, but no particular limit is placed upon this.

The long chain alkyl group or perfluoroalkyl group is preferably distal to the part of the dye molecule that is affixed to the fabric where reactive dyes are used, but otherwise no particular limit is placed upon its position.

4 The linking of the long chain alkyl group or perhaloalkyl group to the colour forming group may be direct, but is conveniently provided through a linking group, eg. a cyanuric group. Alternatively the colour forming group and proofing group or groups may be attached to the fabric through use of a coupler such as a naphthol compound.

The fabric may be any fabric that benefits from a water or oil repellency treatment and the dye is selected for its suitability for dyeing that fabric. Thus where a synthetic dye is being used conventional vat dyeing conditions might be discarded in favour of a reactive dye. Cotton however, which benefits greatly from water proofing and oil proofing, may be conveniently vat dyed.

Further provided by the present invention are dyestuffs per se that are capable of dyeing fabrics while simultaneously imparting water resistance to them, and preferably also oil resistance. Specific examples are set out below.

Still further provided is a method for water proofing and preferably oil proofing a fabric comprising treating it with a dyestuff of the invention. Such method is characterised by the dyestuff used rather than any particular protocol.

The fabrics, dyestuffs and methods of the invention will now be described by way of illustration only by reference to the following non-limiting Examples; further embodiments falling within the scope of the invention will occur to those skilled in the art in the light of these.

TI e -'1-11ted d' EXAMPLE- 1: Production of C10H21 SUbSt A compound incorporating dye and hydrophobic groups was provided by reaction following the scheme I below:

C H r, H C H 21 10 21 10 21 [a -: C, + 19 '1 1 NH 2 N 2 N=N SCHEME 1 QH Sulphuric acid was added dropwise to an ice bath cold solution of 1.00g pdecylaniline (4.29mmol) in dilute acetic acid (10m1 acetic acid: 5m1 water) and sodium nitrite solution (0.309 in 10m1 water: 4.29mmol) was added and the temperature maintained at 80C. The resulting suspension was added dropwise to a stirred ice cold solution of sodium phenolate (0.4og: 4.29mmol phenol and 6.0Og: 150mmol sodium hydroxide in 20m1 water) and the mixture acidified to pH5 with sulphuric acid. The subsequent precipitate was collected at the pump, washed with copious amounts of water and dried under vacuum at 50T. Crude product was chromatographed on silica using 4:1 hexane/ethyl acetate with yield 0.759, 52%. The dye and hydrophobic group containing compound was then reacted with 2,4,6- trichlorotriazine (cyanuric chloride) according to the following reaction scheme II.

SCHEME II 10H Cl N Cl C H 21 1 10 21 + OH 1 ro, O N N Q Cl =N OH N N-O 5 N Cl N:::l- Cl 6 A solution of sodium carbonate (0.22g anhydrous: 2.08mmol) in 10m1 water was added dropwise to a stirred solution of the product from Scheme I (0. 709:2.07mmol) in a water/acetone mixture (10m1:20m1) and the resultant mixture cooled in an ice bath. To this cold solution was added a solution of cyanuric chloride in 10m1 acetone and the light yellow mixture was allowed to stir for 10 minutes. The resulting suspension was poured into rapidly stirred water and the solid collected at the pump. washed with copious amounts of water and dried under vacuum at 500C. Yield was 0.82g, 82%.

EXAMPLE 2: Dyeing of cotton interlock with dye of Example 1. Cloth used in the experiments described below consisted of 100% two-fold cotton yarns for both warp and weft with a continuous filament polyester yarn ripstop. The cotton yarns were woven to give a 2 x 2 "S" twill with two continuous filament yarns verey two 32 cotton yarns in the warp and four continuous filament yarns every 12 cotton yarns in the weft. The cloth was disruptively patterned.

For chloroform treatment treated cloth samples (10cm x 10cm) were placed into a conical flask containing 200ml chloroform and then gently agitated at 25'C for five minutes using a Stuart Scientific Orbital shaker. The sample was then removed, allowed to dry in a fume hood, ironed (cotton hot, no steam) and the repellency ratings measured and recorded. The conical flask was refilled with 200ml fresh chloroform and the operation repeated on the extracted cloth sample a total of three times.

Dyeing: Cotton interlock was immersed in 7.5% sodium carbonate solution, dried and then further immersed for 15 minutes in a 2.4 wt/voll' solution of the dye of Example 1 in chloroform. After drying the impregnated cloth was steamed for 30 minutes, washed with detergent and air dried. The resulting pale yellow cloth retained water repellency after three five minute extractions with chloroform. Boil washing in detergent destroyed the finish by hydrolysis of dye.

11 p 7 EXAMPLE: Preparation of naphthol based perfluoro azo-dyes 4-aminophenyl- (1',1',2',2'-perfluoro-n-decyl)ether, empiracle formula C8 F 17 CH 2 CH 20-C6H4 -NH 2. was weighed into a 150cm 3 beaker, 0.6CM3 Of 15% aqueous hydrochloric acid added followed by approx. 10CM3 Of methylated spirits. On warming a pink/orange solution was produced to which 2 to 39 of ice was added followed by a solution of sodium nitrite (0.059, 725Pmol) in water (ca. 1CM3). The resultant solution was left to stand for 10 minutes at 0 to 5T, then sufficient solid sodium acetate was stirred into this solution to make the pH neutral to Congo red paper.

Coupling agents:

OH H Y Naphthol AS X=Y-H Naphthol AS BI X=Br, Y=OCH 3 1 / Nt XWC H 0 Four cloth samples, 2 impregnated with coupling component naphthol ASBI, 2 impregnated with coupling component naphthol AS, were immersed in the solution produced above. The originally pale yellow/off-white cotton cloth samples turned pink-purple. On drying and washing the 3M water repellency test was attempted. Both samples showed excellent water repellency and repelled organic liquid mixtures up to 50% v/v water/isopropanol; water forming a small angle between cloth and droplets. 50% water/isopropanol gives a greater angle. Both fabrics had a 3M oil repellency of 06 (n-decane) and water repellency of 30:70 water/isopropanol; oil repellency was lost after chloroform wash.

EXAMPLE 4: Improved method of dveing with Perfluoro-azo dyes, Diazonium solution was prepared by dissolving 0.25 (0.3956mmol) of the amine:

C2 H5 1 H 2 N--G-CH 2 N SO 2 CBFI:

8 with heating in 3m1 acetic acid and 0.25m1 sulphuric acid was added dropwise to the resulting solution. The precipitated bisulphate salt separates out on cooling. Sulphuric acid (0.25m1) was added to 0.028g (0. 4mmol) NaNO 2 and warmed to provide a solution. cooled, acetic acid (lml) added and this mixture added to the bisulphate solution and precipitate with stirring (glass rod) such that the bisulphate dissolves to give a pale yellow solution. This mixture is allowed to stand with occasional stirring for 5 minutes.

EXAMPLE 5: Cloth dyeing with dye of Example 4. Cotton cloth (AG) approx Y' x Y' was soaked for 40 minutes in a solution of ASBI coupler (0.2g/2m1 ethanol/0.5M1 2M NaOH/15m1 H 2 0) then pad mangled to remove excess liquor before drying at 800C for 3 to 4 minutes.

The diazonium solution was neutralised with NaOH solution (4g anhydrous NaOH in 10m1 water) and the cloth immersed immediately in this and agitated for 15 minutes. The cloth was then removed and washed thoroughly with tap water. then distilled water and finally dried and ironed. The resultant material passes the 3M test to 02 (65:35 Kaydol/n-hexadecane) and W5 (50:50 water:isopropanol) The cloth was then soaped in 10g/200m1 Persil (RTM) solution and brought to the boil. After 1 minute the cloth was removed, rinsed, dried and ironed. This treated reduced the oil repellency to 01 (100% Kaydol white mineral oil) while water repellency remained W5. Both repellencies were lost after chloroform wash.

EXAMPLE 6: Azoic dyes bearing various groups. Further dyes were prepared by the method of Example 3 as follows: The naphtholic coupler (Naphthol AS or Naphthol ASBI) (0.2g) was mixed with ethanol (2ml) and stirred to give an even suspension. Sodium hydroxide solution (0.5ml, 2M) was added and the resulting solution diluted with water (15ml). Cotton cloth samples (ca. 100CM2) b 0 9 were then immersed in this solution for 15 minutes. washed under running water, washed with detergent, rinsed then dried. The naphthol-impregnated cloth samples so-formed were used in the following stage.

The respective alkylated or perhaloalkylated aniline derivative (0. 05mmol) was weighed into a 150m1 beaker and hydrochloric acid added (0. 6mi of 15% wt./vol.) followed by methylated spirits (10m1). On warming the amine dissolves to give an orange solution. Ice (2-39) was added followed by a solution of sodium nitrite (0.059, 0.73mmol) in water (lml) with stirring. The resulting solution was left to stand for 10 minutes at 0-5'C with occasional stirring, then sufficient sodium acetate was added to make the solution neutral to Congo Red paper. Into this solution was immersed a naphthol -impregnated cloth sample as described above and coupling allowed to proceed over 45 minutes with occasional stirring. The resulting dyed cloth sample (orange to dark red in colour) was then removed, washed under running water, washed with detergent, rinsed then dried.

Water repellency values were determined by the ability to resist wicking of various mixtures of isopropanol/water. 30:70 isopropanol/water resistance is set as a repellency value 7; 20:80 at 8 etc. Oil repellency values Were determined similarly but using hydrocarbons as is known in the art.

A 0 N=N 1 OH )OOZ Y H i C - N-6 11 0 TABLE 1.

Compound A X Y Repellency Oil Water(aq/IM) 6a n-dodecyl H H + 6b n-dodecyl Br 0Me - + 6c O(CH 2)2 C8F, 7 H H 6 7 (30:70) 6d O(CH 2)2 C8F 17 Br 0Me 6 7 6e CH2 N(Et)SO 2 c 8 F 17 H H 5 8 (20:80) 6f CH 2 N(Et)SO 2 c 8 F 17 Br 0Me 5 9 (10:90) aq/IPA represents the highest water/isopropanol mix that the material was repellent to. + is repellent but the velaue not established. The dyes could be removed by washing cloth samples with organic solvents such as chloroform or acetone.

EXAMPLE 7: reactive azoic dye. 7-amino-4-hydroxy-2-naphthalenesulphonic acid monohydrate (5.09. 19mmol) was condensed with cyanuric chloride (3. 59, 19mmol) in acetone/water under basic conditions (sodium bicarbonate/sodium carbonate). Cotton interlock cloth was immersed in the resulting mixture and the temperature raised to 50-600C. After 20 minutes the cloth was removed, washed under running water, then in detergent, rinsed and dried.

4-(1H, 1H, 2H, 2H-perflurooctyloxy)-aniline (0.279, 0.5mmol) was dissolved with warming in a mixture of hydrochloric acid (0.6m1 of 15% wt. /vol.) and methylated spirits (10m1). Ice (2-39) was added, followed by a solution of sodium nitrite (0.059, 0.73mmol) in water (lml) with stirring and the resulting solution left to stand for 1 hour at 0-5'C. Into this solution was immersed a sample of the above cloth moistened with 10% sodium carbonate solution. The cloth immediately turned pink, indicating that coupling was occuring.

1 11 After 20 minutes the cloth was removed, reimmersed in 10% sodium carbonate solution. pad mangled to remove excess liquor and then reapplied to the diazonium bath. This process was repeated a total of three times, the cloth then washed under running water followed by methylated spirits, methanol, acetone and acetonitrile and then dried. The resultant cloth displayed oil and water repellency ratings of 5 (dodecane) and 5 (50:50 IPA/water) respectively. The cloth sample was subjected to three five minute boil washes in 2% wt./vol. alkaline detergent giving the results shown in Table 2.

TABLE 2.

No. of Boil Washes Oil (0), and Water (W) Repellency Rating 1 05 W3 2 02 W2 3 01 EXAMPLE 8: Dichlorotriazinyl fibre-reactive water repellent dyes.

cl N l-NH-ON=N-GOCH 2 CH 2 c 6 F 17 cl Preparation of 4-amino-4'-hydroazobenzene: finely-divided sodium bicarbonate (0.67g, 8mmol) was added in small portions to a stirred solution of sodium sulphide nonahydrate (2.0g, 8.3mmol) in water (15m1). When the sodium bicarbonate had completely dissolved methanol (15m1) was added and the solution cooled to precipitate sodium carbonate which was removed by filtration, washed with methanol, and the combined filtrate and washings (sodium hydrogen sulphide 12 solution) used immediately for the next step.

4-hydroxy-4'-nitro azobenzene (1.00g, 4.1mmol) prepared by coupling sodium phenolate with diazotised p-nitroaniline, was dissolved in methanol (40mi) with stirring followed by addition of the sodium hydrogen suplhide solution as prepared above. The mixture was heated under reflux for 2 hours, allowed to cool to room temperature and the mixture then concentrated to low bulk under reduced pressure. The pH was adjusted to 6 using 2M acetic acid (CARE: H 2 S evolved) and the mixture extracted twice with ethyl acetate (2 x 20m1. The combined organic layers were dried over anhydrous sodium sulphate, filtered and the ethyl acetate removed under reduced pressure to yield 0.86g (98%) of crude product. Recrystallisation from methanol/water (1:1, 30m1) gave 0.54g (74%) of clean product.

PreDaration of IH.1H.2H.2H-perfluoromethanesulphonate: A solution of 1H, 1H,2H,2H-perfluorooctanol (22.89g, 62mmol) in pyridine (5.159, 65mmol) was added slowly with efficient stirring to an ice cold solution of triflic anhydride (18.259. 65mmol) in dichloromethane (70m1) and the resulting mixture allowed to stir for 0.5 hours. The solid pyridinium salt was then removed by filtration and the dichloromethane filtrate extracted twice with water (2 x 50m1). Drying of the organic layer over anhydrous sodium sulphate and removal of the dichloromethane under reduced pressure afforded 309 of crude product. Vacuum distillation (380C at 0.05bar) gave 26.8g (90%) of clean product.

Prenaration of 4-(lH.lH.2H.2H-Derfluorooctyloxy)-4'-aminoazobenzene: 4amino-4'-hydroxyazobenzene (0-759, 3-5mmol) was added portionwise to a stirred solution of sodium ethoxide in ethanol (0.08g. 3-5mmol sodium in 30ml ethanol), followed by dropwise addition of 1H,lH,2H,2Hperfluorooctyl trifluoromethanesulphonate (1-74g, 3-5mmol). After 1 hour the resulting precipitate was collected by 13 filtration, washed with 2M sodium hydroxide followed by water and finally a little chilled ethanol. Weight of clean product on drying was 0.8g (40%). Note the moderate yield of desired product is thought to be due to a competing elimination reaction and up to 15% product can be further isolated from the filtrate upon addition of 1.0g of triflate.

Preparation of Dye 8: [C6F 13 (CH2) 20C6HN=N-C6H, -NH-s (C 3 N 3C12)]. A solution of 4-(1H,1H,2H,2H-perfluorooctyloxy)-4'-aminobenzene (0.839. 1. 5mmol) in chloroform (50M1) was added dropwise to a rapidly stirred twophase mixture containing solutions of cyanuric chloride (0.28g, 1.5mmol) in chloroform (20m1) and sodium bicarbonate (0.139, 1.5mmol) in water (20m1) held at O'C. The resulting mixture was stirred for 45 minutes, the organic layer then separated and dried with anhydrous sodium sulphate. and the chloroform finally removed under reduced pressure to afford 0.90g (90%) of clean Dye 8.

Dyeing of cotton interlock with Dye 8: Cotton interlock cloth was immersed in a 7.5% aqueous solution of sodium carbonate, pad mangled to remove excess liquor and then dried at 1OTC for 30 minutes. The impregnated cloth was then immersed in a 50mM solution of Dye 8 in acetone for 15 minutes, pad-mangled to remove excess liquor and then allowed to air dry at room terature. The cloth was steamed for 15 minutes, washed in warm detergent, rinsed thoroughly with water and then boiled in acetone until no more dye could be removed. The resulting yellow cloth displayed a water repellency rating of 3 (30:70 IPA/water) but no oil repellency.

EXAMPLE 9: Dichlorotriazinvl fibre reactive dye -alkylated.

cl N 0 11 N NH N=N OCH 2 CH 2 C 6 F 17 00 N cl 14 Dye 9: [Cl,H21-C6H4-N=N-C6H,-0-s(C 3 N 3C12)3 was prepared by adding concentrated sulphuric accid (0.1m1) dropwise with stirring to a cold (ice bath) solution of p-decylaniline (1.009g, 4.3mmol) in acetic acid/water (10m1:5m1). To the resulting suspension was added a solution of sodium nitrite (0.39, 4.3mmol) in water (10m1) at such a rate as to maintain the temperature below 80C. This mixture was then added dropwise to a stirred ice cold solution of phenol (0.4og, 4.3mmol) and sodium hydroxide (6.0g, 150mmol) in water (20m1), the pH adjusted to 5 with sulphuric acid and the resulting precipitate collected by filtration, washed with copious amounts of water and dried. Chromatography on silica using 4;1 hexane/ethyl acetate afforded 0.759 (52%) of clean reactive dye base.

A solution of anhydrous sodium carbonate (0.22g. 2.1mmol) in water (10m1) was added dropwise to a stirred solution of the above dye base (0.709, 2. 1mmol) in acetone/water (20m1:1Oml repsectively) and the resulting mixture cooled in an ice bath. Cyanuric chloride (0.38g, 2Ammol) in acetone (10m1) was added to the cold solution produced and the light yellow mixture allowed to stir for 10 minutes. The suspension was then poured into rapidly stirred water (100m1) and the solid collected by filtration, washed with water and dried to give 0.82g (82%) of clean Dye 9.

Dyeing of cotton interlock with Dye 9: Cotton interlock cloth was immersed in a 7.5% aqueous solution of sodium carbonate, pad mangled to remove excess liquor and then dried at 1OWC for 30 minutes. The impregnated cloth was then immersed in a 50mM solution of Dye 9 in chloroform for 15 minutes, pad mangled to remove excess liquor then allowed to air dry at room temperature. The cloth was then steamed for 30 minutes, washed in warm detergent, rinsed thoroughly with water and dried. The resulting yellow cloth displayed a water repellency rating of 1 (10:90 isopropyl alcohol/water) and was unaffected by repeated washings in chloroform.

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Claims (21)

CLAIMS.

1. A fabric is characterised in that it has been dyed using a dyestuff which imparts both colour and waterproofing properties to fabric in a single treatment.

2. A fabric as claimed in claim 1 characterised in that the dyestuff simultaneously imparts also oil repellency.

3. A fabric as claimed in claim 1 or claim 2 characterised in that the dyestuff comprises a long chain hydrocarbon group or a perhaloalkyl group together with a colour forming group in the same molecule.

4. A fabric characterised in that it includes colour imparting chemical moiety that incorporates a colour forming group and one or more groups selected from long chain alkyl groups of 7 carbons or more and perhaloalkyl groups.

5. A fabric as claimed in claim 4 wherein the colour imparting chemical moiety incorporates a long chain alkyl group of 10 carbons or more.

6. A fabric as claimed in claim 4 or 5 characterised in that it comprises a colour imparting moiety that it incorporates a perhaloalkyl group which is a perfluoroalkyl group.

7. A fabric as claimed in claim 6 wherein the perfluoroalkyl group is of 7 carbons or more.

8. A fabric as claimed in claim 6 or 7 wherein the linking of the long chain alkyl group or perfluoroalkyl group to the colour forming group through a linking group.

16

9. A fabric as claimed in claim 8 wherein the linking group is a triazine group.

10. A fabric as claimed in any one of claims 1 to 9 wherein the colour forming group and proofing group or groups are be attached to the fabric through use of a coupler.

11. A fabric as claimed in claim 10 wherein the coupler is a naphthol coupler.

12. A dyestuff comprising comprises a long chain hydrocarbon group or a perhaloalkyl group together with a colour forming group in the same molecule.

13. A dyestuff as claimed in claim 12 comprising a colour forming group and one or more groups selected from long chain alkyl groups of 7 carbons or more and perfluoroalkyl groups.

14. A dyestuff as claimed in claim 12 wherein the a long chain alkyl group is of 10 carbons or more.

15. A dyestuff as claimed in claim 12 wherein the perfluoralkyl group is of 7 carbons or more.

16. A dyestuff as claimed in any one of claims 12 to 15 wherein the linking of the long chain alkyl group or perfluoroalkyl group to the colour forming group through a linking group.

17. A dyestuff as claimed in claim 16 wherein the linking group is a triazine group.

18. A dyestuff as claimed in any one of claims 12 to 15 characterised in that it is a diazonium compound.

JC 17

19. A dyestuff as claimed in claim 17 or 18 characterised in that it is a reactive azoic dye.

20. A method of dyeing a fabric comprising treating it with a dye as claimed in any one of claims 12 to 18.

21. A method, dyestuff or fabric substantially as described in any one of the Examples and claimed in claims 1 to 20 herein.

21. A method. dyestuff or fabric substantially as described in any one of the Examples and claimed in claims 1 to 20 herein.

Amendments to the claims have been filed as follows 1. A fabric is characterised in that it has been dyed using a dyestuff which imparts both colour and waterproofing properties to fabric in a single treatment.

2. A fabric as claimed in claim 1 characterised in that the dyestuff simultaneously imparts also oil repellency.

3. A fabric as claimed in claim 1 or claim 2 characterised in that the dyestuff comprises a long chain hydrocarbon group or a perhaloalkyl group together with a colour forming group in the same molecule.

4. A fabric characterised in that it includes colour imparting chemical moiety that incorporates a colour forming group and one or more groups selected from long chain alkyl groups of 7 carbons or more and perhaloalkyl groups.

5. A fabric as claimed in claim 4 wherein the colour imparting chemical moiety incorporates a long chain alkyl group of 10 carbons or more.

6. A fabric as claimed in claim 4 or 5 characterised in that it comprises a colour imparting moiety that it incorporates a perhaloalkyl group which is a perfluoroalkyl group.

7. A fabric as claimed in claim 6 wherein the perfluoroalkyl group is of 7 carbons or more.

8. A fabric as claimed in claim 6 or 7 wherein the linking of the long chain alkyl group or perfluoroalkyl group to the colour forming group through a linking group.

i f A 1 -9 9. A fabric as claimed in claim 8 wherein the linking group is a triazine group.

10. A fabric as claimed in any one of claims 1 to 9 wherein the colour forming group and proofing group or groups are be attached to the fabric through use of a coupler.

11. A fabric as claimed in claim 10 wherein the coupler is a naphthol coupler.

12. A dyestuff comprising a long chain hydrocarbon group or a perhaloalkyl group together with a colour forming group in the same molecule.

13. A dyestuff as claimed in claim 12 comprising a colour forming group and one or more groups selected from long chain alkyl groups of 7 carbons or more and perfluoroalkyl groups.

14. A dyestuff as claimed in claim 12 wherein the a long chain alkyl group is of 10 carbons or more.

15. A dyestuff as claimed in claim 12 wherein the perfluoroalkyl group is of 7 carbons or more.

16. A dyestuff as claimed in any one of claims 12 to 15 wherein the linking of the long chain alkyl group or perfluoroalkyl group to the colour forming group through a linking group.

17. A dyestuff as claimed in claim 16 wherein the linking group is a triazine group.

18. A dyestuff as claimed in any one of claims 12 to 15 characterised in that it is a diazonium compound.

:;I (D 19. A dyestuff as claimed in claim 17 or 18 characterised in that it is a reactive azoic dye.

20. A method of dyeing a fabric comprising treating it with a dye as claimed in any one of claims 12 to 18.