GB2526044A - Methods relating to wool treatment - Google Patents

Abstract

A composition comprising a compound of formula E-L-Q+ is applied to the material, preferably polyamide fibres or wool, wherein: E is an electrophile, preferably with chloro (Cl), bromo (Br), sulphate (SO4) or sulphonate (SO3) leaving group, or methacrylate; L is a linking moiety, preferably alkylene, optionally substituted by a hydroxy group; and Q+ is a quaternary ammonium (N+(R)3) residue. The exemplified composition comprises 3-chloro-2-hydroxy-propyl trimethyl ammonium chloride and triethanolamine (to adjust the pH of the liquor to 10.5) and it was applied for 5-10 minutes at 50-70°C. The treated material is then dyed with an anionic dye.

Description

Methods Relating to Wool Treatment The present invention relates to an improved method of treating a material, in particular a material containing wool. In preferred embodiments the present invention relates to a pre-treatment method which may be used in advance of other treatments, for example dyeing of wool or applying a flame retardant composition to wool.

One common current method of dyeing wool involves a first step of treating the wool with a reactive dye at a pH of 4.5 and a temperature of 100°C for up tol hour (depending on the desired depth of shade), followed by a second step of after-treatment with ammonia at 80°C for 20 to 25 minutes. The wool is then rinsed with water at 40°C. To dye 270 kilograms of wool, for example, a total of over 10 tonnes of water is needed, and the total treatment time involved is usually approximately 3 hours. This has a number of disadvantages.

Environmentally, the use of large volumes of water is unfavourable and this must also be disposed of which is expensive. In addition, the water must be heated using considerable amounts of energy, which is again detrimental both environmentally and in terms of cost.

Further, the long processing time limits the number of batches of material which can be dyed in a given period.

It is an aim of the present invention to provide a wool processing method which overcomes at least one disadvantage of the prior art, whether mentioned herein or otherwise.

In particular it is an aim of the present invention to provide a wool treatment method which uses less water and/or less energy and/or takes less time.

According to a first aspect of the present invention there is provided a method of treating a material, the method comprising applying to the material a composition comprising a compound of formula E-L-Q wherein E is an electrophile, L is a linking moiety and Q is a quaternary ammonium residue.

Preferably the material treated in the method of the present invention comprises polyamide fibres, including natural polyamide fibres, for example wool, silk, alpaca, angora, leather and the like; and synthetic polyamide fibres, for example Nylon 6, Nylon 6, 6, and the like. Materials comprising blends or mixtures of polyamide fibres and other types of fibres are within the scope of the invention.

Preferably the material treated by the present invention comprises wool. It may be pure wool or it may be a mixture or blend comprising wool and one or more other materials. In embodiments in which the material is a mixture or blend, it preferably comprises at least 20 wt% wool, preferably at least 30 wt% for example at least 40 wt%, more preferably at least 50 wt%. Such blends or mixtures may suitably comprise one or more further materials selected from nylon, viscose, acrylics and polyester.

The material may comprise wool in any suitable form, for example as wool yarn, wool top, wool fabric, or loose wool and may include cashmere and non-sheep origin animal fibres. The material may alternatively be in the form or a garment or other finished article containing wool or a woven fabric containing wool or non-sheep origin fibres.

In some embodiments the material may be a fabric, including a knitted or woven fabric or a non-woven material.

E may be any suitable electrophile. For example E may be an alkene, in particular an alkene activated to Michael addition. Thus in some embodiments E may be a group of formula CHR1=CR2CO, CHR1=CR2SO2 or CHR1=CR2NO2 wherein each of R1 and R2 may be independently selected from hydrogen and an optionally substituted alkyl, alkenyl, alkynyl or aryl group. Preferably each of R1 and R2 is independently selected from hydrogen and an optionally substituted alkyl group. Most preferably each of R1 and R2 is independently selected from hydrogen and a C1 to C4 alkyl group, for example methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.

Preferably the group E comprises a carbon atom having an induced positive charge such that it is activated to nucleophilic addition. Thus E may be a group of formula C6-X6 wherein Xis a leaving group. X may be selected from any suitable leaving group, for example halides (suitably bromide or chloride), sulphate, sulphite, thiosulphate or sulfonates (for example tosylate, mesylate or triflate). Most preferably X is selected from halide or sulfate. In especially preferred embodiments E is selected from C-Cl, C-Br and C-0303.

L is a linking group which is used to join the quaternary ammonium residue to the electrophile. L may be a bond. Preferably however L is an organic moiety comprising at least one carbon atom. L may be an optionally substituted alkylene, alkenylene, alkynylene, or arylene residue. Any such residue may be optionally substituted with one or more groups, along the chain or within it. Along the chain group L may be substituted with one or more substituents selected from halo, amino, nitro, acetoxy, mercapto, hydroxyl, sulfo or alkoxy.

Within the chain the group L may include a hetero atom, for example 0, $ or N to form an ether, thioether or amine linkage or it may include a carbonyl moiety to form, for example, a ketone, ether or amide.

In preferred embodiments L is an optionally substituted alkylene residue, preferably comprising from ito 10, more preferably ito 6, preferably ito 4 and most preferably 2 or 3 carbon atoms. Such an alkylene group may be optionally substituted with one or more groups selected from amino, hydroxy, sulfo, nitro, halo, acetoxy, alkoxy and mercapto.

Most preferably L is an alkyl group having Ito 4 carbon atoms which may be optionally substituted with one or more hydroxy groups.

may be selected from any quatemary ammonium residue. Q may include one or more alkyl, alkenyl, alkynyl or aryl groups incorporating a quaternary nitrogen. For example Q may be a group selected from the moities shown in figure 1 in which Alk is a Cl to C4 alkyl group, most preferably Me: Al k 1 + Me N N PVPh Q Figure 1 It will be appreciated that the nitrogen bearing the positive charge in the structures shown in figure 1 is also bound to linking group L. Preferably Q is a group of formula NR3 wherein each R may be independently selected from hydrogen and an optionally substituted alkyl, alkenyl, alkynyl oraryl moiety, each of which may be optionally substituted with one or more group selected from nitro, halo (especially chloro or bromo), hydroxy, alkoxy, sulfo, sulfoxy, mercapto and amino.

Preferably each R is independently selected from hydrogen and an optionally substituted alkyl or alkenyl group. More preferably each R is independently selected from hydrogen and an alkyl or alkenyl group which is not substituted. Preferably each R is independently selected from hydrogen and an alkyl or alkenyl group having 1 to 24, for example 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms. Most preferably each R is independently from an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms.

Most preferably each R is independently selected from methyl, ethyl, propyl, isopropyl, butyl tert-butyl, sec-butyl and isobutyl.

The person skilled in the art will appreciate that the compound of formula E-L-Q will be present in the composition used in the method of the present invention as a salt. It may be present as any suitable salt and thus the counterion may be a monovalent, divalent or polyvalent. It may be an organic or inorganic counterion. Preferred counterions include halide (especially chloride or bromide), sulphate, phosphate, acetate. Most preferred are bromide and especially chloride.

In some preferred embodiments the method of the present invention comprises applying to the material a composition having the formula shown in figure 2: Figure 2 wherein Y is selected from halide, sulfonate or sulphate, n is from 0 to 6, m is from 1 to 6, p is from 0 to 6, each R3 is independently selected from hydrogen, hydroxyl and C to 04 alkyl, and each R4 is independently selected from a C to 020 alkyl or alkenyl group.

PreferablyY is chloride, bromide or sulphate, especially chloride.

Preferably n is from 0 to 3, preferably 0 to 2. Most preferably n is 1.

Preferably m is from ito 4 preferably ito 3. Most preferably m is 1.

Preferably p is from 0 to 3, preferably 0 to 2. Most preferably p is i.

Preferably the or each R3 is independently selected from hydrogen, hydroxy and methyl.

Most preferably the or each R3 is hydroxy.

Preferably each R4 is independently selected from C to 020 alkyl, preferably C to 015 alkyl, preferably C to C12 alkyl, more preferably Cl to C alkyl and most preferably C1 to C4 a I kyl.

In especially preferred embodiments the or each R4 is independently selected from methyl, ethyl, propyl, butyl and isomers thereof More preferably each R4 is methyl or ethyl, most preferably each is methyl.

In an especially preferred embodiment the method of the present invention comprises applying to the material a composition comprising 3-chloro-2-hydroxy-propyl trimethyl ammonium chloride, the compound having the structure shown in figure 3:

OH I + -

ClA,,NMe3 Cl Figure 3 This compound is available from Dow Chemicals under the trade mark Qua! 1 881CR2000, from Quab Chemicals under the trade mark Quab 188, and from Sasol underthe trade name Servon XRK. It may suitably be supplied as an aqueous solution containing 60- 65% of the active ingredient. The bromide salt is also a preferred compound for use in the present invention.

In some other preferred embodiments, the method comprises treating the material with a composition comprising a compound having one of the structures shown in figure 4: ci 3 MeaN)* -NMe3 (a) (b) (c) cit( (d) (e) Figure 4 Without wishing to be bound by theory, it is believed that the compound shown in figure 3 and figures 4 (a) and (b) form the epoxide in situ and that this is the reactive species. These epoxide compounds are themselves commercially available and could be used directly in the method of the first aspect of the present invention. However the compounds shown in figures 3, 4(a) and 4(b) are preferred.

In the method of the present invention the composition may be applied to the material by any suitable means, such as will be well known to those skilled in the art.

The method of application of the composition will depend on the type of material being treated. For example, wool top may typically be treated in a bump machine; fabric may suitably treated in a jet machine or winch machine; garments or other finished articles are preferably treated using a paddle machine; and for yarn a package machine is preferred.

The liquor ratio used may suitably depend on the chosen treatment method. For example when using a bump machine a suitable liquor ratio is 7.5-10:1; for a jet machine a liquor ratio of 5-10:1 is preferable; in a winch machine a liquor ratio of 20-50:1 is typical and on a package machine a liquor ratio of about 10:1 is preferred. The liquor ratio is the weight ratio of the composition to material being treated. Selection and variation of an appropriate liquor ratio is well within the competence of the person skilled in the art.

The concentration of the compound of E-L-Q may suitably vary according to the method and liquor ratio used. The concentration is in each case selected to provide a desired treatment level of the compound on the material.

The treatment level is measured to give a desired % "on mass of fibre" (or %omt). This is the percentage by mass of the compound of formula E-L-Q which is fixed onto the material during the treatment process and is calculated by measuring the dry mass of material at the start and end of the process. For example, if 1 OOg of dry wool is treated and after processing (dyeing, rinsing, drying etc) has a new dry mass of 103g, then a treatment level of 3%omf been achieved.

A treatment level of the compound of formula E-L-Q of at least 0.1% omf is preferred, preferably at least 0.5% omf, more preferably at least 0.8% omf and most preferably at least 1% omf A suitable treatment level of the compound of formula E-L-Q may be up to 20% omf, preferably up to 15% omf, more preferably up to 10% omf, preferably up to 7% and most preferably up to 4% omf.

Selection of an appropriate concentration to provide the desired %omf depending on the mass of material to be treated and the liquor ratio used is common-place to the person skilled in the art.

Preferably in the method of the present invention the material is treated with the composition comprising the compound E-L-Q at a temperature of at least 30°C, preferably at least 40°C, more preferably at least 50°C, most preferably at least 55°C.

Suitably the material is treated with the composition comprising the compound of formula E-L-Q at a temperature of up to 100°C, preferably up to 90°C, more preferably up to 80°C, suitably up to 70°C, for example up to 65°C.

An especially preferred treatment temperature is approximately 60°C.

Suitably the material is treated with the composition at a temperature of from 50 to 70°C for a period of at least 1 minute, preferably at least 2 minutes, more preferably at least 3 minutes.

The material may suitably be treated at a temperature of between 50 and 70°C for a period of up to 1 hour, preferably up to 45 minutes, more preferably up to 30 minutes, for example up to 25 minutes. Advantageously, a treatment time of less than 20 minutes may be used, preferably less than 15 minutes.

In preferred embodiments the material is treated at a temperature of between 50 and 70°C, for example about 60°C for a period of approximately 5 to 10 minutes.

The material may be treated with a composition which is already at an elevated temperature. However in some preferred embodiments the material is treated with a composition at ambient temperature or a cold composition which is then heated to the desired temperature for the required period.

Preferably the composition used in the method of the first aspect of the present invention is an aqueous composition.

Preferably the composition used in the method of the first aspect of the present invention has a pH of at least 7, preferably at least 8, more preferably at least 9, for example at least 9.5, preferably at least 10. It may have a pH of up to 14, for example up to 13, preferably up to 12, suitably up to pH 11. Preferably the composition used in the first aspect of the present invention has a pH of approximately 10.5.

The composition may further comprise a base. Any suitable base may be used, for example alkali metal hydroxides. Preferred bases are tertiary amines, especially triethanolamine.

Preferably the method of the first aspect of the present invention is a pre-treatment method. Without wishing to be bound by theory, it is believed that when the method of the present invention is used to treat wool, the compound of formula E-L-Q initially forms an electrostatic interaction with carboxylate residues on the surface of the wool. Following such interactions, it is possible for nucleophilic species in the wool to react with the electrophilic moiety E. Thus it is believed that the compound of formula E-L-Q becomes bound to the surface of the wool, providing the surface with a positive charge.

B

The method of the first aspect of the present invention is preferably a pre-treatment step which is followed by a step of treating the material with a composition comprising an anionic treatment agent.

The method of the first aspect may be used as a pre-treatment for any subsequent anionic treatment. Preferably it is used as a pre-treatment step prior to treatment with a composition comprising an anionic treatment agent selected from one or more of a flame retardant agent, a shrink resistant agent, a shine agent, a softener, an oleophobic agent, a hydrophobic agent, a hydrophilic agent, a stain guard, a stain repellent, a fragrance, a UV absorber, a moth-proofing agent, an antibacterial agent and a dye.

Suitable flame retardant agents include durable flame retardants, for example those described in the applicant's copending applications PCT/GB2008/050776, and GB0900624.8; and those sold under the trade mark Zirpro which contain potassium hexafluorozirconate and potassium hexafluorotitanate salts; as well as non durable flame retardants, for example phosphate and polyphosphate based flame retardant compositions. Suitable flame retardants also include those sold under the trade marks ITOFLAM LJ77, ITOFLAM LJ580 and ITOFLAM LJ68, available from U Specialities (UK). An advantage of some embodiments of the pre-treatment method of the first aspect of the present invention is that it may improve the durability of traditionally non-durable flame retardants.

In one preferred embodiment, the pre-treatment method of the first aspect may be followed by treatment with a flame retardant composition comprising urea and an acid or salt thereof, wherein the acid is selected from phosphorous acid, phosphoric acid, sulfamic acid and mixtures thereof. In some embodiments a base is also present.

Suitable shrink resistant agents include anionic polymers for example polymers of acrylic acid; polystyrene sulfonate and derivatives thereof; polyether blocked isocyanates (carbamoyl sulfonates), for example as sold by Bayer under the trade mark Synthappret BAP; and a Bunte salt terminated polyether sold under the trade mark Securlana by Cognis.

Suitable stain repellents include fluorocarbon based products for example those sold under the trade marks ASAHI GUARD AG1100 and ITOGUARD LJ1100, available from U Specialities (Chesterfield, UK); and CETAPROOF WR LT 64, available from Avocet Dye & Chemical Co. Ltd (Brighouse, UK).

Suitable fluorescent brightening agents include products sold under the trade marks ITOWI-IITE BHB and ITOWHITE GBP available from U Specialities (UK); and CETACLEAR B available from Avocet Dye & Chemical Co. Ltd (UK) Suitable softeners include products sold under the trade marks ITOLUSTER PNA284 and ITOSILICONE LJ100E, available from U Specialities (UK).

Suitable stiffeners include products sold under the trade marks KASESOL ESY and KASESOL 05, available from U Specialities (UK).

Suitable UV protecting agents include benzophenol based products, for example those sold under the trade marks ITOSORB LJ643 and ITOSORB AF2OPS, available from U Specialities (UK).

Suitable odour eaters I deodorisers include products sold under the trade marks ITODEODORISER UN, ITOFIX LJMF, ITODEODORISER LJESA and ITODEODORISER LJ3S, available from U Specialities (UK).

Suitable moisturising I antiallergenic products include products sold under the trade marks NEOAGE GL, and NEOAGE UR, ITOFINISH VITAMIN E, AROMA GRANULE TEA TREE, available from U Specialities (UK).

Suitable fragrances include products such as AROMA GRANULE APPLE, AROMA GRANULE FOREST, AROMA GRANULE LAVENDER, AROMA GRANULE LEMON, AROMA GRANULE LIME, AROMA GRANULE ORANGE, AROMA GRANULE PEPPERMINT, AROMA GRANULE STRAWBERRY, AROMA GRANULE VANILLA, AROMA GRANULE EUCALYPTUS, all of which are available from U Specialities (UK).

Suitable Anti-Bacterials include products sold under the trade marks ITOMICROBIAL MCM and ITOMITE CBL, available from U Specialities (UK).

In an especially preferred embodiment the pre-treatment method of the present invention is followed by a dyeing step.

According to a second aspect of the present invention there is provided a method of treating a material, the method comprising the steps of: (a) treating the material with a composition comprising a compound of formula E-L-Q and (b) treating the material with a composition comprising a dye compound.

Preferably step (a) comprises the treatment method of the first aspect and preferred features of step (a) are as defined in relation thereto.

Preferably step (b) comprises treating the material with an anionic dye.

Preferably step (a) is carried out before step (b).

Suitable anionic dyes for use in step (b) include reactive dyes, direct dyes, acid levelling dyes, premetallised anionic dyes (including 2:1 premetallised acid dyes and 1:1 premetallised acid dyes), acid milling dyes, food dyes, natural dyes, leather dyes, pigment dyes, sulphur dyes, solvent dyes, vat dyes, ingrain dyes, mordant dyes, fluorescent brightening agents and disperse dyes.

Preferred dyes for use in step (b) are reactive dyes, acid levelling dyes, acid milling dyes, premetallised dyes, mordant dyes and fluorescent brightening agents.

The skilled person would be familiar with the above-mentioned classes of dye and would understand the types of compounds which fall within each class.

The Colour Index International is a standard classification system for dyes and pigments which contains historic, proprietary, generic names and generic numbers that have been applied to colours. It was first published in 1924 and has been updated and reprinted since.

The 2 (1956), 3 (1971) and 41h (2002) editions are jointly published and maintained by the Society of Dyers and Colourists (SDC) (UK) and American Association of Textile Chemists and Colourists (AATCC).

There are four volumes of the Colour Index International which classify the colorants by constitution and by application.

Volumes 1 to 3 classify the colorants according to application type resulting in 19 different classes with each colorant being given a Cl generic name (e.g. Cl Acid Orange 7 etc).

The information provided for each colorant includes chemical type (azo, anthraquinone etc), Cl constitution number, dyeing and printing behaviour and fastness properties.

Volume 4 of the Colour Index classifies colorants according to their constitution (i.e. their chromophoric system). When these colorants are divided by their chromophoric system, then 27 classes are established. As detailed above, dyes useful in the present invention may be selected from some of the 19 classes of colorants and 27 chromophoric classes.

Acid dyes are typically water soluble anionic dyes that contain one or more sulphonic acid groups, usually as the sodium salt, carboxylic acid groups or hydroxyl groups (less common). The structure on which the dyes are based depends on the colour. Acid dyes can be based on a number of chromophores, which tend to dictate the colour of the dye. For example, blue acid dyes are often based on an anthraquinone moiety, although some may be azo based, formazan or phthalocyanine based. Red, orange and yellow acid dyes tend to be based upon azo moieties, for example Cl Acid Orange 7: CI Acid Orange 7 Acid dyes are traditionally used for dyeing wool and polyamide fibres under acidic to neutral conditions. There are three main types of acid dyes: i) Acid levelling dyes, which have the highest level dyeing properties. They can be used in combination with other levelling dyes in order to give trichromatic shades.

They are relatively small molecules which exhibit high migration before fixation.

ii) Acid milling dyes, which tend to have more side chains and sulfonyl groups, and are larger in size than levelling dyes. Acid milling dyes in general are not combinable to form trichromatic shades, and tend to be used on their own.

iii) Metal complex acid dyes, which combine transition metals such as copper, zinc and chromium with dye precursors to produce a metal complex acid dye.

Methods of dyeing with mordant dyes involve pre-treating a textile with a solution of a metal salt. Mordant dyes are thus typically water soluble anionic dyes that contain OH, NH2 and COOH groups which are capable of forming a stable coordination complex with a metal ion on the inside of the fibre. An example is Cl Mordant Black 13: 303N a CT Mordant Black 13 0 HNflSOSNa Fluorescent brightening agents have the ability to absorb incident light in the UV region and to re-emit some of this absorbed light at higher wavelengths, normally in the blue region of the visible spectrum. An example is Cl Fluorescent Brightener 46: Na035 Hc CI Fluorescent Brightener 46 The term "reactive dyes" is used to define a particular class of dyes and would be readily understood by the person skilled in the art of colour science. A reactive dye typically contains an electrophilic group that can be activated and allowed to directly react with a nucleophile in the substrate, forming a covalent bond. Reactive dye compounds may typically include a vinyl sulfone, an acrylamido or a halogenated triazine moiety, but the skilled person would be aware of dyes of other structures falling within this class.

In step (b), the composition may be applied to the material by any suitable means, such as those used in step (a) and described in relation to the first aspect.

In a preferred method dyeing is effected by an exhaustion method. Such a method is known to those skilled in the art and involves contacting the material with a composition comprising the dye compound for a sufficient period such that substantially all of the dye compound leaves (is exhausted from) the solution and is fixed on to the material The composition used in step (b) of the second aspect of the present invention preferably has a pH of less than 12, preferably less than 11, more preferably less than 10, most preferably less than 9.

It suitably has a pH of at least 5, preferably at least 6, suitably at least 6.5, more preferably at least 7.

Preferably the composition used in step (b) is an aqueous composition.

In some embodiments of the second aspect of the present invention, the composition of step (a) may be removed from the material prior to step (b). For example it may be drained or rinsed from the material.

However in preferred embodiments, at the end of step (a) the pH of the treatment composition is adjusted and step (b) simply comprises adding a dye to the same mixture, that is the aqueous composition comprising the compound of formula E-L-Q.

Suitably in such embodiments, the pH is lowered at the end of step (a) by the addition of an acid, preferably an aqueous acid. Any suitable acid may be used. Preferred are organic acids, especially acetic acid and/or formic acid.

Suitably at the end of step (a) the pH is lowered from approximately 10 to 11 to approximately 7 to9.

When a dye is added to a composition comprising a compound of formula E-L-Q in which the material is immersed, the dye may be added neat. Preferably however the dye is added in a solvent, which is preferably water.

In step (b) of the second aspect of the present invention the material is treated with a composition comprising a dye for period of at least two minutes, preferably at least 5 minutes, more preferably at least 10 minutes, suitably at least 15 minutes, at least 20 minutes or at least minutes.

The material may be treated for a period of up to 6 hours, for example up to 2 hours, up to 90 minutes or up to 75 minutes. In some preferred embodiments a treatment time of less than 60 minutes may be used, preferably less than 50 minutes, for example less than 40 minutes or less than 35 minutes.

In step (b), the material is suitably treated with a composition comprising a dye at an elevated temperature, suitably at a temperature of greater than 60°C, preferably greater than 80°C, more preferably greater than 90°C, greater than 95°C or greater than 98°C. In some especially preferred embodiments the material is treated at a temperature of approximately 100°C.

It has been found in some cases that the treatment time needed to achieve effective dyeing of the material may depend on the treatment temperature. For example dyeing may be achieved after approximately 30 minutes at about 100°C, approximately 45 minutes at about 95°C or approximately 60 minutes at about 90°C.

In preferred embodiments the liquor ratios used in step (b) will be substantially the same as those used in step (a). As detailed above, the skilled person would be easily able to select an appropriate liquor ratio depending on the method used.

The concentration of dye used in the composition may depend on the desired shade and depth of colour required. The concentration of dye used in the composition will be selected to give a desired treatment level (in %omO and as mentioned above calculation of the appropriate concentration is simple for the person skilled in the art. Suitably the dye concentration is at least 0.1% omf, preferably at least 0.25% omf, more preferably at least 0.5% omf, most preferably at least 0.75% omf. The dye concentration may be up to 15% omf, suitably up to 10% omf, for example up to 6% omf or up to 6% omf. A dye treatment level of 1% omf or 2% omf is typical but levels of up to 5-8% omf are commonly used to achieve a deeper shade.

In some embodiments, step (b) may be followed by a step of rinsing the material with an acidic composition to help fix the dye. Suitable compositions include a solution of formic acid.

In such a solution, the formic acid may suitably be present at a concentration of from 1 to 100 gdm3, preferably 5 to 50 gdm3, more preferably 7 to 20 gdm3, for example about 10 gdm3.

The present inventors have found that using the method of the second aspect of the present invention to dye wool provides a significant improvement compared to process of the prior art. For example it is possible to dye 270kg of wool in a total treatment time of 80 minutes compared with 3 hours using methods of the prior art. In addition only one or two baths of water are needed instead of three. This provides a significant reduction in the amount of energy used to heat the water and there are associated cost and environmental benefits. A particular advantage of the invention is that the shorter processing time allows a larger number of batches of wool to be treated during a given period. Thus the process of the present invention is much more efficient than that of the prior art in terms of costs, energy and time. It is also less detrimental to the environment.

The invention will now be further described with reference to the following non-limiting

examples:

Example I

40g of wool top pie-treated with Hercosett (RTM) to provide shnnk-resistance was treated according to the method of the first aspect of the present invention was in a laboratory machine using a liquor ratio of 10:1 (400g liquor: 40g wool top) according to the following procedure: * Hercoseft treated wool top was placed into a dyepot and then the following chemicals were added: c 1.6g of 3-chlcro-2-hydroxy-propyltrimethylammoniumchloride (60% soln) [equivalent to 4% omf] o 4m1 triethanolamine to adjust pH of liquor to pHi 0.5 o O.2g of non ionic wetting agent * The machine was then heated to 60°C at a rate of 3°C/mm, and then held at 60°C for minutes.

* The wool was then removed from the dyepot and the residual liquor squeezed back into the pot.

Examples 2-5

The wool treated according to example 1 was then dyed a number of different shades using the following method: * The pH of the residual liquor was adjusted by adding acetic acid (10% w/w soln) to pH7.

* The following dyestuffs were then added to the liquor: Example 2 Example 3 Example 4 Example 5 Mass %omf Mass %omf Mass %omf Mass %omf (g) (g) (g) (g) Lanasol Black CE 2g 5% 3g 7.5% ---- Lanasol Red CE 0.2g 0.5% 0.08g 0.2% O.4g 1% -- Lariasol Yellow CE 0.2g 0.5% 0.04g 0.1% O.4g 1% -- Lanasol Blue CE ----O.4g 1% --Reolan Navy R ------1.12g 2.8% Intrafast Red CFE ------0.32g 0.8% * The wool was then placed back into the dyepot.

* The machine was then heated to 100°C at a rate of 2°C/mm, and then held at 100°C for 25 minutes.

* The wool is then removed from the dyepot and the residual liquor squeezed back into the pot.

* The pH of the liquor was then adjusted by adding sodium hydroxide (10% w/w soln) to pH9.

* The wool was then placed back into the dyepot.

* The machine was then held at 100°C for a further 10 minutes.

* The wool was then removed from the dyepot, and rinsed with water until no colour could be seen to be removed.

* The wool was then given a rinse with formic acid (lOg/I) for 5 minutes at room temperature.

* The dyed wool was then assessed by using a standard wash fastness test as described in BS EN ISO 105-C06 1997, and standard wet a& dry rub fastness tests as described in BS EN ISO 105-X12 2002.

o In each case, the dyed wool achieved a wash fastness level 5 on the grey scale for change in colou( and level 5 on the Grey scale for staining (both scales of 1-5, with 5 being highest standard).

o In each case, the wool also achieved a pass on both the wet & dry rub fastness tests.

Example 6

20Kg of Hercosett (RTM)-treated wool top was dyed in a bump machine using a liquor ratio of 7.5:1 (150L liquor: 20Kg wool top) to achieve a black shade, according to the following method: * Hercosett treated wool top was placed into a bump machine and then the following chemicals were added: o 800g of 3-chloro-2-hydroxy-propyltrimethylammoniumchloride (60% soln) [equivalent to 4%omt] o 1.SLtriethanolamine to adjust pH of liquor to pHlO.5 * The machine was then heated to 60°C at a rate of 3°C/mm, and then held at 60°C for minutes.

* The pH of the liquor was then adjusted by adding acetic acid (10% w/w soin) to pH7.

* The following dyestuffs were then added to the liquor: o 1kg Lanasol Black CE (5%omf shade) o 100g Lanasol Red CE (0.5%omf shade) o 1 DOg Lanasol Yellow CE (0.5%omf shade) * The machine was then heated to 100°C at a rate of 2°C/mm, and then held at 100°C for 25 minutes.

* The pH of the liquor was then adjusted by adding sodium hydroxide (10% w/w soln) to pH9.

* The machine was held at 100°C for a further 10 minutes.

* The bath was then dropped and rinsed with formic acid (log/I) for 5 minutes at room temperature.

* The wool was then spin dried and then dried in a radio frequency oven.

* The dyed wool was then assessed by using a standard wash fastness test as described in BS EN ISO 105-C06 1997, and standard wet a& dry rub fastness tests as described in BS EN ISO 105-X12 2002.

o The dyed wool achieved a wash fastness level 5 on the grey scale for change in colour and level Son the Grey scale for staining (both scales of 1-5, with S being highest standard).

o The wool also achieved a pass on both the wet & dry rub fastness tests.

Claims (19)

1. Claims 1. A method of treating a material, the method comprising applying to the material a composition comprising a compound of formula E-L-Q wherein E is an electrophile, L is a linking moiety and Q is a quaternary ammonium residue.
2. 2. A method according to claim 1 wherein the material treated comprises polyamide fibres.
3. 3. A method according to claim 1 or claim 2 wherein the material treated comprises wool.
4. 4. A method according to any preceding claim wherein E is a group of formula C6-X6 wherein X is a leaving group.
5. 5. A method according to claim 4 wherein X is selected from halide or sulfate.
6. 6. A method according to any preceding claim wherein E is selected from C-Cl, C-Br and I'-C-oso3-.
7. 7. A method according to any preceding claim wherein L is an optionally substituted alkylene, alkenylene, alkynylene, or arylene residue. a)

   O
8. 8. A method according to claim 7 wherein L is an alkyl group having 1 to 4 carbon atoms which may be optionally substituted with one or more hydroxy groups.
9. 9. A method according to any preceding claim wherein Q is a group of formula NR3 wherein each R may be independently selected from hydrogen and an optionally substituted alkyl, alkenyl, alkynyl or aryl moiety, each of which may be optionally substituted with one or more group selected from nitro, halo (especially chloro or bromo), hydroxy, alkoxy, sulfo, sulfoxy, mercapto and amino.
10. 10. A method according to claim 9 wherein each R is independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl and isobutyl.
11. 11. A method according to any preceding claim which comprises applying to the material a composition having the formula shown in figure 2: Figure 2 wherein Y is selected from halide, sulfonate or sulphate, n is from 0 to 6, m is from 1 to 6, p is from 0 to 6, each R3 is independently selected from hydrogen, hydroxyl and C to 04 alkyl, and each R4 is independently selected from a C to 020 alkyl or alkenyl group.
12. 12. A method according to any preceding claim which comprises applying to the material a composition comprising 3-chloro-2-hydroxy-propyl trimethyl ammonium chloride.
13. 13. A method according to any of claims I to 11 comprising treating the material with a composition comprising a compound having one of the following structures: ci 3 Me3N)* -OSO 0 (a) (b) (c) O ciJ3c (d) (e)
14. 14. A method according to any preceding claim in which the material is treated at a temperature of between 50 and 7000, for a period of approximately 5 to 10 minutes.
15. 15. A method according to any preceding claim wherein the composition applied to the material has a pH of at least 7.
16. 16. A method of treating a material, the method comprising the steps of: (a) treating the material with a composition comprising a compound of formula E-L-Q; and (b) treating the material with a composition comprising a dye compound.
17. 17. A method according to claim 16 wherein step (b) comprises treating the material with an anionic dye.
18. 18. A method according to claim 16 or claim 17 wherein step (a) is carried out before step (b).
19. 19. A method according to any of claims 16 to 18 wherein at the end of step (a) the pH is lowered from approximately 10 to 11 to approximately 7 to 9. IC) r a)