WO2007017668A1

WO2007017668A1 - Improvements in and relating to wool treatment

Info

Publication number: WO2007017668A1
Application number: PCT/GB2006/002955
Authority: WO
Inventors: David Malcolm Lewis; Jamie Anthony Hawkes
Original assignee: Perachem Limited
Priority date: 2005-08-10
Filing date: 2006-08-09
Publication date: 2007-02-15
Also published as: US20080282478A1; US20150252521A1; EP1913194B1; EP1913194A1; NZ565001A; RU2008108977A; AU2006277767B2; AU2006277767A1

Abstract

A method of treating a wool material, the method comprising the steps of: (a) contacting the wool material with a cationic surfactant; and (b) contacting the wool material with a nucleophile.

Description

IMPROVEMENTS IN AND RELATING TO WOOL TREATMENT

Field of the Invention

This invention relates to methods of treating a wool material, methods of shrink-proofing a wool material, and methods of pre-treating a wool material to render it more suitable for use in subsequent treatments .

Background to the Invention

In textile shrink-proofing applications, especially wool shrink-proofing applications, chlorination followed by polymer treatment is widely used. Wool materials (which may also be called herein wool textiles or simply wool) include loose wool, wool tops, wool yarns and wool fabrics . Also included are cashmere and other fibres derived from all animal sources, as well as garments or woven fabrics containing animal fibres. In particular, Hercosett (RTM) , a cationic cross-linkable polymer (supplied by Hercules, USA), is particularly effective after chlorination treatment in shrink-proofing wool . Hypochlorite is generated when dissolving dichlorodicyanuric acid or chlorine gas in water, or using hypochlorite itself, and the hypochlorite then oxidises the disulphide bonds present in wool to form sulphonic acid groups. Thus, the hydrophobic nature of the wool surface is disrupted, and hydrophilic sulphonic acid groups are presented in the wool. Cationic polymers can then be evenly spread over and absorbed into the wool ' s surface due to the presence of the hydrophilic sulphonic acid groups. Hercosett (RTM), a cationic polyamide epichlorhydrin resin, is particularly effective at covering chlorinated wool, and prevents the wool from shrinking after subsequent wetting, and also repeated laundering of the treated goods .

A consequence of known chlorination treatment is the generation of organic-chlorine containing compounds which are collectively known as adsorbable organic halides (AOX) .

In many countries, legislation limits the discharge of AOX compounds, which has implications for many industries. As a result, much research has been carried out to develop textile shrink-resistant processes based on non-AOX rapid oxidation of textiles . This is particularly pertinent in the wool industry.

Potassium peroxomonosulphate (PMS) , hydrogen peroxide and some peracids have been evaluated as possible alternatives, but with only limited commercial success.

A key difference in terms of polymer compatibility between chlorinated wool surfaces and PMS/hydrogen peroxide treated wool surfaces is the surface energy of the fibre surface (or wetability) after treatment. Surface energy has an influence on the spreading properties of cationic cross-linkable polymers such as Hercosett (RTM, and the wool/polymer interfacial adhesion. Recent research has shown that the difference is associated with the removal of fatty acids from the wool, especially 18-methyl eicosanoic acid, which is thought to be chemically bound to the surface of a wool fibre by a thio-ester linkage. In other words, chlorination is known to remove such fatty acids, but PMS and hydrogen peroxide treatments do not, or with very low efficiency. A further consequence of known chlorination treatment is the generation of wool which is yellow in colour and poor to handle. These properties limit end-uses for which the wool can be suitably employed.

It would therefore be advantageous to provide a method of improving the shrink-resistance of wool and other animal fibre based textile materials which does not utilise chlorine or chlorine-containing compounds, or generate adsorbable organic halides (AOX) . It would furthermore be advantageous to provide wool shrink-resistance treatments which are equally effective as chlorination, and which do not produce AOX chemicals, and which can be utilised under mild conditions .

It would furthermore be advantageous to provide wool pre- treatment processes, which can be followed up with a subsequent treatment step; for example a shrink resist treatment using a cationic cross-linkable polymer, for example Hercosett (RTM) , or an improved dyeing treatment; and which processes do not utilise chlorine-containing chemicals .

It would also be advantageous to provide a wool treatment process which produces wool material having excellent dyeing and printing properties, reduced yellow colour following treatment, improved comfort in wear properties such as water sorbancy etc, and which could be further treated if desired to incorporate shrink resistance in a straight-forward and cost-effective manner.

It is therefore an aim of preferred embodiments of the present invention to overcome or mitigate at least one problem in the prior art, whether expressly disclosed herein or not. Summary of the Invention

According to a first aspect of the invention, there is provided a method of treating a wool material, the method comprising the steps of:

(a) contacting the wool material with a cationic surfactant; and

(b) contacting the wool material with a nucleophile.

Steps (a) and (b) may be performed sequentially in either order or they may be combined in a single step.

Suitable cationic surfactants include quaternary ammonium compounds and salts thereof. Suitable quaternary ammonium compounds and salts thereof include alkyl ammonium halides such as alkyltrimethylammonium halides. Suitable alkyl trimethylammonium halides include bromide, chloride and fluoride salts of linear or branched C₁-C₂₆ trimethylammonium compounds . Particularly preferred as alkyl ammonium halides are N-hexadecyltrimethylammonium bromide (CTAB) or the chloride (CTAC) .

Other suitable quaternary ammonium salts include alkyl arylammonium halides, N-alkylpyridinium halides, N- alkylimidazolinium salts, N-alkylmorpholinium salts, N- alkylisothiouronium salts or mixtures thereof.

Suitable nucleophiles for use in step (b) include hydrogen peroxide and other sources of the perhydroxy anion, alkali metal or ammonium hydroxides or any suitable source of hydroxyl anions, sulphite anions, hydrosulphide anions, hydroxylamine, alkanolamines, thioglycolates, thioureas, thiocyanates, alcoholates, amines, thiols, phenols, or any mixture thereof .

Suitable sources of hydroxyl anions include alkali metal and ammonium hydroxides. Suitable sources of sulphite anions include alkali metal and ammonium sulphites . Suitable alkanolamines include ethanolamine, triethanolamine and propanolamine .

A preferred class of nucleophiles for use in step (b) are non-reducing nucleophiles. These include oxidising nucleophiles and neutral nucleophiles (i.e. nucleophiles that are non-oxidising and non-reducing) but most preferably the nucleophile of step (b) is an oxidising nucleophile.

By "non-reducing nucleophile" and "non-oxidising nucleophile" , we mean nucleophiles which are not reducing agents or oxidising agents respectively as would be clearly understood by a practitioner skilled in the art of wool treatment .

It has been found that the use of non-reducing nucleophiles, as opposed to reducing nucleophiles, enables the production of bulky wool which is a desirable feature. The use of reducing nucleophiles may damage the fibre and can lead to hardness in the wool through a setting effect. In addition the use of reducing nucleophiles may produce lank wool when wet which is more difficult to process and dry efficiently. The applicant has found that treatment with a cationic surfactant and a non-reducing nucleophile enables treatment times of 5 seconds or less .

Suitable oxidising nucleophiles useful in step (b) include oxidising species derived from hydrogen peroxide and other sources of the perhydroxy anion (including per-acids and polyper-acids) and the superoxide anion. Suitable neutral nucleophiles include alkali metal and ammonium hydroxides or any suitable source of the hydroxyl anions, hydroxylamine, alkanolamines , alcoholates, amines, phenols, or any mixture thereof and thiocyanates . The use of such non-reducing nucleophiles can lead to an increased number of anionic sites on the wool surface following treatment, and avoid the generation of sulphur and its derivates from the wool surface, which could otherwise create a yellow hue and foul odour.

Suitably step (a) comprises contacting the wool with a solution or dispersion of cationic surfactant in a suitable solvent. Preferably the solvent is an aqueous solvent and most preferably water, and preferably step (a) comprises contacting the wool with an aqueous solution of the cationic surfactant. Suitably the cationic surfactant is present in the solvent in a concentration of at least 50 mg/1, more preferably at least 1 g/1 and most preferably at least 2 g/1.

Suitably the wool is contacted with the solution of cationic surfactant at a temperature of at least 20° C, more preferably at least 3O⁰C, most preferably at least 40 "C, and especially at least 50⁰C.

Suitably step (b) comprises contacting the wool with a solution or dispersion of a suitable nucleophile in a suitable solvent. Preferably the solvent is an aqueous solvent and is most preferably water. Suitably the aqueous solution or dispersion is adjusted to an alkaline pH, preferably a pH at least 8, and more preferably a pH of at least 9. In preferred embodiments, the pH of the solution or dispersion of nucleophile is at least pH 10. The pH may be adjusted by the addition of a suitable buffer, such as a phosphate buffer, preferably derived from trisodium phosphate .

Suitably the wool is contacted with the solution of nucleophile at a temperature of at least 20°C, more preferably at least 3O⁰C, most preferably at least 40°C, and especially at least 50 °C.

A suitable temperature range for contacting the wool with the nucleophile is substantially 20⁰C to substantially 70 °C. A preferred temperature range is between 40° C and 60°C.

Suitably the nucleophile is present in the solvent in a concentration of at least 100 itιg/1, more preferably at least 1 g/1, and especially between 1 g/1 and 20 g/1, most preferably between 2 g/1 and 10 g/1.

Steps (a) and (b) may be sequential or simultaneous. Thus step (a) may be carried out first, followed by step (b) , or steps (a) and (b) may be carried out simultaneously, or step (b) may be carried out first followed by step (a) . When steps (a) and (b) are carried out simultaneously, preferably the cationic surfactant and nucleophile are contacted with the wool material in a single solution or dispersion. When steps (a) and (b) are carried out simultaneously by contacting the wool material with a cationic surfactant and nucleophile in a single solution or dispersion, preferably the pH of the solution is at least 8, more preferably at least 9, yet more preferably at least 10, and most preferably at least 11. Preferably the solution containing the cationic surfactant and nucleophile is contacted with the wool material at a temperature of at least 20^° C, more preferably at least 3O⁰C, most preferably at least 40 "C, and especially at least 60° C. A suitable temperature range for contacting the wool material with the solution of nucleophile and cationic surfactant is substantially 20° C to substantially 70 °C, and more preferably between substantially 40 °C and substantially 6O⁰C.

The preferred embodiments of this invention are capable of achieving treatment times consistent with the industrial requirements in both continuous processing of wool tops and batch treatment of woollen garments. In commercial scale continuous processing of wool tops, the total treatment time for steps (a) and (b) is suitably less than 60 seconds. Preferably it is less than 50 seconds, preferably less than 40 seconds, more preferably less than

30 seconds and most preferably less than 20 seconds. For continuous wool top processing it is desirable to have treatment times of about 10 seconds. For batch processing of for example woollen garments, substantially longer treatment times are typical, suitably 15 to 30 minutes, for example 20 minutes.

Optionally the method further comprises a step (c) of contacting the wool material with an acid having a pH of no more than substantially 6.

Steps (a)-(c) may be performed sequentially or in series, or may be performed in any suitable order. For example, step (c) may be performed before step (a) or between steps

(a) or (b) . In addition, steps (a) and (b) or steps (b) and (c) may be combined in a single step. In some preferred embodiments, step (c) is performed first, followed by a single combined step of steps (a) and (b) together .

There may be a step between steps (b) and (c) of contacting the wool material with an aqueous medium, preferably water.

Suitably, contacting the wool material with an aqueous solution comprises rinsing the wool material with an aqueous medium. Rinsing of the wool material with an aqueous medium may comprise immersing the wool material in an aqueous medium, preferably water. Alternatives include spraying, misting or jetting the aqueous medium onto the wool material, for example.

Preferably contacting the wool with an aqueous medium between steps (b) and (c) comprises contacting the wool material with an aqueous medium at a temperature of at least 20° C, more preferably at least 30° C, preferably no more than 70° C and more preferably no more than 60° C.

Preferably the acid contacted with the wool material in step (c) has a pH of substantially no more than 5 and more preferably substantially no more than 4.

Preferably step (c) comprises contacting the wool material with an acid selected from acetic acid, formic acid, or a mixture thereof. Other suitable organic acids include malic acid, maleic acid, succinic acid, citric acid and malonic acid, or mixtures thereof. Inorganic acids may also be used, and may be selected from sulphuric acid, boric acid, cyanic acid and any mixtures thereof, for example. Hydrochloric acid is not preferred as in any subsequent oxidation step utilised in the process, chlorine may be generated. Preferably the acid contacted with the wool material in step (c) is present in solution, and is preferably in an aqueous solution. Suitably the acid is present in solution at a concentration of at least 1 g/1, more preferably at least 2 g/1. Suitably the acid present in the solution is at a concentration of no more than 20 g/1 and preferably no more than 10 g/1.

Step (c) preferably comprises contacting the wool material with the acid at ambient temperature, and preferably between 10°C and 30°C.

Preferably the wool is contacted with the solution, aqueous medium or dispersion in steps (a)-(c) and the optional step of contacting the wool with an aqueous medium, by immersing the wool in each solution, aqueous medium or dispersion in steps (a)-(c) . Alternatively, the wool may be contacted with the solution, aqueous medium or dispersion in each of steps (a)-(c) and the optional step by spraying, misting, or jetting the solution, aqueous medium or dispersion onto the wool in each of steps (a)- (c) . Each of steps (a)-(c) and the optional step may comprise independently immersing, misting, spraying or jetting the wool, for example. In preferred embodiments, the wool is immersed in the solution, aqueous medium or dispersion used in each of steps (a)-(c), and the optional step of contacting the wool material in an aqueous medium between steps (b) and (c) .

Preferably the wool is contacted with the solution, aqueous medium or dispersion in each of steps (a)-(c), and the optional step of contacting the wool material in an aqueous medium between steps (b) and (c) , for a period of at least 1 second for each step. Preferably the wool is immersed in the solution, aqueous medium or dispersion in each of steps (a)-(c), and the optional step of contacting the wool material in an aqueous medium between steps (b) and (c) , and immersed for a period of at least 1 second for each step. More preferably, the wool is contacted with the solution, aqueous medium or dispersion in each of steps (a) -(c), and the optional step of contacting the wool material in an aqueous medium between steps (b) and (c) , for a period of preferably no more than 120 seconds, more preferably no more than 60 seconds, most preferably no more than 30 seconds, and especially no more than 15 seconds for each step. A suitable range is 5-20 seconds for each step.

There may be steps in between each of steps (a)-(b) and (b)-(c), and between the optional step of contacting the wool in an aqueous medium and step (c) , of removing excess liquid from the wool effected by contact of the wool with the solution, aqueous medium or dispersion utilised in the previous step of the method. Removal of excess liquid may be effected by squeezing, padding or pressing the wool with a suitable implement. For example, the wool may be passed between two counter-rotating rollers or pads .

Without being bound by any theory, it is believed that lipids on the wool surface are released as free lipid carboxylate in cationic micelles, after steps (a) and (b) , and acidification of the wool material in step (c) protonates the negatively charged carboxylates bound to the wool surface and allows the electro-statically bonded micelle complex to float free into solution. Thus the method of treatment of the invention produces wool which is easily wettable and has therefore improved dyeing and printing properties, and improved comfort in wear properties, such as increased water sorbancy.

Preferably the method comprises steps (a)-(c) sequentially in order, or steps (a) and (b) simultaneously, followed by step (c) sequentially. When the method comprises the optional step of contacting the wool material with an aqueous medium between steps (b) and (c) , this is preferably done in sequence between steps (b) and (c) .

Suitably steps (a) , (b) and (c) may be performed in any order suitable for pre-treating wool for subsequent treatment with a further agent.

The method of the first aspect of the present invention may further comprise a step (d) of contacting the wool material with an agent or agent (s) capable of promoting additional anionic character to the surface of the wool material .

The agent (s) used in step (d) is preferably capable of generating sulphonate or substituted sulphonate residues on the surface of the wool fibres . An example of substituted sulphonate is thio-sulphonate such as cysteine-S-sulphonate, which is a typical example of a Bunte salt.

In cases where the agent (s) or a composition containing the agent (s) in step (d) capable of promoting additional anionic character to the wool surface is acidic, steps (c) and (d) may be combined. It is also possible to perform step (d) prior to step (a) , between steps (a) and (b) or between steps (b) and (c) .

Suitably the agent(s) used in step (d) , capable of promoting additional anionic character to the surface of the wool material, comprises an oxidising agent. Preferred oxidising agents for use in step (d) include hydrogen peroxide, KHSO₅, permonosulphuric acid, Caro's salt (KHSO₄. KHSO₅), KHSO₅. KHSO₄. K₂HSO₄ (supplied under the brand name OXONE by Aldrich, UK) and per-acids including percarbamic acid, performic acid, peracetic acid, perbenzoic acid, pernonanoic acid, magnesium diperoxyphthalate, a permanganate, or any mixture thereof, for example. Suitable per-acids include those of formula R-CO-OOH, where R is preferably Ci to C12 linear or branched alkyl or aryl . Preferred aryl groups include phenyl. The per-acids may be generated in situ by the reaction of alkaline hydrogen peroxide with electrophiles, such as TAED or sodium nonanoyloxybenzenesulphonate. In addition to the above, it may be advantageous to use a water-soluble poly-peracid generated for example by the reaction of hydrogen peroxide with poly-acrylic acid and/or its co-polymers, polymethacrylic acid and/or its co-polymers, poly-itaconic acid and/or its co-polymers and so forth; it may be particularly advantageous to generate the peracids or other peroxy compounds by the in situ reaction of alkaline hydrogen peroxide solutions or with acrylic acid/ethyl-acrylate co-polymers. It is important to ensure water solubility in the above co-polymer systems by providing an acrylic acid content of at least 5-49%, more preferably 50-79%, and most preferably 80-99%.

An especially preferred oxidising agent for use in step (d) is potassium peroxomonosulphate .

Suitably step (d) comprises contacting the wool material with an oxidising agent at a temperature of at least 20° C, or preferably at least 30 "C. Preferably the oxidising agent is contacted with the wool material in step (d) at a temperature of no more than 70 "C, preferably no more than 60 °C. Preferably the oxidising agent is contacted with the wool material in step (d) in solution or in dispersion, and preferably in aqueous solution or an aqueous dispersion. Preferably the concentration of oxidising agent in the solution is at least 1 g/1, more preferably at least 2 g/1. Preferably the oxidising agent is present in solution at a concentration of no more than 40 g/1, or preferably no more than 20 g/1. A suitable concentration range of oxidising agents in solution is between 2 g/1 and 20 g/1.

Preferably step (d) further comprises contacting the wool material with a nucleophile. The nucleophile, when present, may aid the promotion of additional anionic character to the surface of the wool material .

Step (d) may comprise contacting the wool material with a single agent which functions as an oxidising agent and a nucleophile or it may comprise contacting the material with a series of agents .

When step (d) comprises contacting the wool material with a nucleophile, this is preferably carried out after step (a) , preferably after step (b) , preferably after step (c) when present, and preferably after contacting the wool material with a separate oxidising agent in step (d) .

The nucleophile used in step (d) may be a reducing nucleophile. Suitable reducing nucleophiles include sulphites, for example alkali metal and ammonium sulphites. A preferred nucleophile is sodium sulphite.

Other nucleophiles suitable for use in step (d) include hydrogen peroxide and derivatives of hydrogen peroxide, perhydroxy anion, alkali metal hydroxide, ammonium hydroxide, amine nucleophiles, nucleophiles containing acid functionality and the hydroxyl anion.

Nucleophiles are able to react with the disulphide and disulphide oxide residues on the wool material in order to produce further hydrophilic anionic residues on the wool fibre surfaces . These hydrophilic anionic residues include sulphonate, substituted sulphonate and carboxylate residues. These hydrophilic anionic residues enable substantial surface reaction with the subsequent cationic wool shrink resist polymer treatment.

When step (d) further comprises contacting the wool material with a nucleophile, this is preferably carried out at a temperature of at least 20° C, more preferably at least 30 °C. Preferably step (d) comprises contacting the wool material with the nucleophile at a temperature of no more than 70° C, preferably no more than 6O⁰C. Preferably the nucleophile is contacted with the wool material in solution, more preferably aqueous solution. Suitably the nucleophile is present in solution at a concentration of at least 1 g/1, more preferably at least 2.5 g/1, and most preferably at least 5 g/1. Preferably the nucleophile is present in solution at a concentration of no more than 50 g/1, preferably no more than 40 g/1. A suitable concentration range of the nucleophile in solution is between substantially 10 g/1 and substantially 40 g/1.

Preferably the method comprises a further step of contacting the wool material with an aqueous medium after contacting the wool material with the nucleophile. Suitably the aqueous medium and conditions for contacting with the wool material are as described for the optional step between steps (b) and (c) .

Preferably the wool is contacted with a solution or dispersion in each of the steps of the method, and the optional steps of contacting the wool material in an aqueous medium for a period of at least 1 second. Preferably the wool material is immersed in the solution or dispersion in each of the steps of the method, and the optional steps of contacting the wool material in an aqueous medium between steps (b) and (c) , and immersed for a period of at least 1 second. More preferably, the wool material is contacted with the solution or dispersion in each of the steps of the method, and the optional steps of contacting the wool material in an aqueous medium between steps (b) and (c) , for a period of no more than 120 seconds, more preferably no more than 60 seconds, most preferably no more than 30 seconds, and especially no more than 15 seconds for each step. A suitable range is 5-20 seconds for each step.

Preferably steps (a) and (b) are sequential or simultaneous, and steps (c) and (d) are sequential or simultaneous. After any step, there may be one or more additional steps of removing excess liquid from the wool material effected by contact of the wool with the solution or dispersion utilised in the previous step of the method. Removal of excess liquid may be effected by squeezing, padding or pressing the wool with a suitable implement. For example, the wool may be passed between two counter- rotating rollers or pads .

However, all the steps may be performed in any suitable order, and not necessarily sequentially or in series. For example, step (d) may be performed prior to step (a) , between steps (a) and (b) , or between steps (b) and (c) . Steps may be combined, for example, step (c) after (d) and the step of contacting the wool material with a nucleophile may be combined in a simultaneous step.

The method may further comprise an additional step (e) , of contacting the wool material with an alkali and/or applying a mechanical force. Step (e) may be carried out at any time after steps (a) and (b) but in preferred embodiments it is carried out following steps (a) and (b) .

Suitable alkalis for use in step (e) include alkali metal carbonates, for example sodium carbonate.

Optionally, the alkalis can be used in combination with surfactants . Suitable surfactants include non-ionic surfactants such as ethoxylated fatty alcohols . Suitable ethoxylated fatty alcohols include Listril NGS, supplied by Stephenson Speciality Chemicals, Bradford UK

Application of a mechanical force may suitably include methods known to those skilled in the art and could include spraying, use of paddles or application of a suction drum bowl.

Subjecting the material to, for example, a scour with sodium carbonate, will help remove from the surface of the wool the hydrated soluble protein material that has been formed during the delipidisation process of steps (a) and (b) . Typically such a scouring process should be carried out for batch treatments between 5 and 30 minutes, for example 10 minutes. For continuous treatment of wool tops or loose wool stock the scouring process should be carried out for between 5 and 30 seconds. The scouring process may suitably be carried out at a temperature of between 20 and 80 ²C, preferably between 50 and 60²C. The optimum temperature is often determined by the cloud point of the surfactant and is determined by an operator skilled in the art.

The method of the first aspect of the present invention may comprise a batch process or a continuous process .

The surprisingly high levels of delipidisation achieved by the method of the first aspect provides a wool material of considerable commercial usefulness . Disruption or removal of the lipid barrier makes the wool more receptive to many forms of subsequent processing, particularly processes involving aqueous chemicals.

The method of the first aspect of the present invention may be used to provide a material having a more completely and more evenly treated wool surface. When compared with existing commercial processes, the method enables more effective subsequent processing at lower temperatures and shorter treatment times and lower concentrations of reagents can be used having practical, cost and environmental benefits.

The method of the first aspect of the invention may be used as a method of pre-treatment of a wool material to prepare the wool for a subsequent treatment step. The subsequent treatment step may, for example, comprise dyeing or printing the material.

According to a second aspect of the invention, there is provided a method of treatment of a wool material comprising the steps of:

(i) performing a pre-treatment method comprising treating a wool material according to the method of the first aspect of the invention; and

(ii) contacting the wool with one or more agents capable of forming an interaction with the treated wool.

The agent (s) used in step (ii) may form a physical interaction with the wool or it may undergo a chemical reaction with the wool. For example, in some embodiments, an agent is a polymer capable of reacting with hydrophilic functional groups on the treated wool .

An agent used in step (ii) of the second aspect of the invention may be a cationic polymer.

In preferred embodiments, the method of the second aspect comprises a method of shrink-resistance treatment of a wool material and step (ii) may comprise contacting the wool with a polyamide polymer, preferably a polyamide- epichlorohydrin polymer. Suitable polyamide- epichlorohydrin polymers include the Hercosett (RTM) range of polymers supplied by Hercules, US. Particularly preferred is Hercosett (RTM) 125.

Further suitable cationic polymers include Basolan F

(RTM) , supplied by BASF, Germany; SoIfix E and Tinofix Eco

(both RTM), supplied by Ciba, UK, Indosol E-50, supplied by Clariant, UK, and Listrilan SR, supplied by Stephenson

Speciality Chemicals, UK.

Preferably the wool is contacted with a solution or dispersion of the polymer in a suitable solvent during step (ii) of the second aspect of the invention.

Preferably the solvent is an aqueous solvent, more preferably water, and preferably step (ii) comprises contacting the wool with an aqueous solution of the polymer .

Suitably the polymer is present in the aqueous solution at a concentration of at least lg/1, preferably at least 2g/l, more preferably at least 4g/l and most preferably at least 5g/l. A suitable range is 4-10g/l.The polymers may be supplied in diluted form and the ranges quoted are based on 100% material.

In alternative embodiments, the agent (s) contacted with the wool material in step (ii) of the second aspect of the invention may for example comprise a dye, a printing ink, a flame retardant or may comprise an agent capable of modifying the physical properties of the wool.

Examples of dyes suitable for use in step (ii) of the second aspect of the invention include reactive dyes, such as the Lanasol (RTM) range supplied by Ciba, premetallised dyes, milling dyes and chrome dyes. In addition to more effective and economic treatment, advantages in dye levelness, colour build up in heavy shades are observed.

Prints on fabrics made from the wool material in step (ii) of the second aspect of the invention show brilliant shade and unprinted areas remain white after steaming. This is a significant advantage over for example wool treated in a chlorine process which yellows on steaming.

Examples of agents capable of modifying the physical properties of the wool suitable for use in step (ii) of the second aspect of the invention include softening agents, surface energy modifying agents, flame retardant agents, curing agents, flattening agents, anti-creasing agents and agents promoting a permanent crease. Preferably step (ii) of the second aspect of the invention comprises immersing the wool in a solution or dispersion of the agent (s). Alternatively, step (ii) of the second aspect of the invention may comprise spraying, misting or jetting a solution of the agent (s) onto the wool, for example.

After any of the steps of the methods of the first and/or second aspects of the invention, there may be a further step of contacting the wool material with an aqueous medium. Such a step may suitably be carried out as described in relation to the optional step between steps

(b) and (c) of contacting the material with an aqueous medium.

The method of the second aspect of the present invention may comprise a batch process or a continuous process .

It is believed that the wool surface comprises fatty acids, including 18-methyleicosanoic acid, which are thought to be chemically bound to the cysteine residues of the wool fibre by a thio-ester linkage.

Chemically, the thio-ester bond is not strong, but the hydrophobic chain of the fatty acid is thought to protect the thio-ester bond by keeping hydroxyl ions and hydrogen peroxide anions out. Therefore a cationic surfactant in step (a) of the first aspect of the invention is used to help the nucleophile in step (b) of the first aspect of the invention to fuse into the hydrophobic shell covering the wool .

The liberated fatty acid should then preferably be removed from the wool surface as it is not water-soluble. It is believed that the optional oxidising agent and optional reducing agent of the first aspect of the invention provide sulphonic acid and -S-SO₃ ^" groups respectively, on the wool surface which are anionic and enable surface reaction with the agent in step (ii) of the second aspect of the invention.

According to a third aspect of the present invention, there is provided a wool material treated using the method of the first or second aspects of the invention.

The wool material may be a wool material, wool yarn, a wool top, a wool fabric, loose wool and the like, for example, and includes cashmere and non-sheep origin animal fibres . The wool material may also be a garment containing wool or a woven fabric containing wool or non-sheep origin fibres .

Examples

The various aspects of the invention will now be described by way of the following examples.

Example 1

A series of baths, such as those supplied by Fleissner

(UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths

1-6. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5 and Baths 5 and 6, padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients: Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, sodium hydroxide the concentration of which was 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 40⁰C.

Bath 3 - Acetic acid 3g/l in water. The temperature of Bath 3 was set at room temperature (~18°C) .

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. The temperature of Bath 4 was set at 40⁰C.

Bath 5 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 5 was set at 40⁰C.

Bath 6 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. The temperature of Bath 6 was set at 40⁰C.

Thus, the six baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse and acidification process (Baths 2 and 3), an oxidative sulphitolysis process (Baths 4 and 5) , and a reactive polymeric resin application (Bath 6) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by Bulmer and Lumb Ltd, UK) was run through the six baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process.

Wetting-out times

The wetting time is a good indication of the outcome of the shrinkage propensity of the treated wool and is proportional to the delipidisation efficiency. A long wetting time (>60 seconds) indicates a high shrinkage propensity in subsequent laundering, whereas a wetting time of less than 20 seconds indicates that the substrate has the correct hydrophilicity to be compatible with the

Hercosett SR process.

Samples of the wool top were taken after Bath 2 and Bath 3 and were dried so that the wetting out times (in water) could be assessed. The wetting out test comprised of a piece of wool top taken from the indicated point in the process, which is placed onto the surface of water (500ml at 20⁰C) . The time taken for the wool sample to sink to the bottom of the beaker is recorded.

The wetting out time for the sample taken after Bath 2 'wets-out' in >60 seconds, whereas the sample taken from Bath 3 'wets-out' in ~2 seconds. It is thought that this difference is due to the incomplete removal of the lipid from the wool web until acidification in Bath 3. The freed lipid carboxylate created after delipidisation in Bath 1 is thought to be bound to the fibre surface in a cationic micelle. Acidification protonates the negative carboxylates in the wool surface and allows the electrostatically bonded, cationic micelle complex to float free and disperse into the solution.

Staining Test By staining the treated wool with the anionic reactive dye, CI Reactive Blue 19 one can assess the evenness of the treatment and the amount of resin taken up during processing. The intensity of the blue stain is directly related to the amount of Hercosett resin that has been applied to the wool top. This test indicates the similarity between standard chlorine Hercosett wool and that treated with this process .

A sample of the wool top taken after Bath 6, where the process is complete was stained using a solution of CI Reactive Blue 19. The solution comprised CI Reactive Blue 19 at Ig/1, Sandozin NIN at Ig/1 (a non-ionic surfactant) and acetic acid at 3g/l. The temperature of this solution was ~20°C. The sample of wool was immersed in the dye solution (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

The results of this example show that the treated wool top after Bath 3 shows very significant lipid removal, and the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 2

The method used to set up the sequence of baths in Example 1 was repeated, as was the method for the ^vwetting-out ' test and the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients: Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l. The temperature of this bath was set at 50⁰C and the pH was pHl2.

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by Bulmer and Lumb Ltd, UK) was run through the five baths sequentially at a speed of 10 metres per minute.

Wetting-out times

The wetting out time for the sample taken after Bath 2 ^vwetted-out' in >60 seconds, whereas the sample taken from Bath 3 ^λwetted-out' in 14 seconds.

Staining Test The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

The results of this example show that the treated wool top after Bath 3 shows total lipid removal, and the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Example 3

The method used to set up the sequence of bowls in Example 1 was repeated, as was the method for the 'wetting-out' test and the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. The temperature of Bath 4 was set at 40⁰C. Bath 5 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 5 was set at 40⁰C.

Wetting-out times

The wetting out time for the sample taken after Bath 2 ^λwetted-out' in 18 seconds, whereas the sample taken from Bath 3 'wetted-out' in 6.1 seconds.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

Example 4

The method used to set up the sequence of bowls in Example 1 was repeated, as was the method for the ^λwetting-out ' test and the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriaπimonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was lOg/1. The temperature of this bath was set at 50⁰C and the pH was pHl2.

Wetting-out times The wetting out time for the sample taken after Bath 2 'wetted-out' in 20 seconds, whereas the sample taken from Bath 3 'wets-out' in 8.6 seconds.

Staining Test

The results of this example show that the treated wool top after Bath 3 shows total lipid removal, and the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 5

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l and Sodium Sulphite 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 40⁰C. Bath 3 - Acetic acid 3g/l in water. The temperature of Bath 3 was set at room temperature (~18°C) .

Bath 5 - Sodium Sulphite in water, the concentration of which was 35g/l. The temperature of Bath 5 was set at 40⁰C.

Wetting-out times

The wetting out time for the sample taken after Bath 2 "wetted-ouf in >60 seconds, whereas the sample taken from Bath 3 ^λwetted-out' in ~2 seconds.

Staining Test

Example 6

The method used to set up the sequence of bowls in Example 1 was repeated, as was the method for the "wetting-out ' test and the staining test. Only the contents and settings of the bowl were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l and Sodium Sulphite 5g/l. The temperature of this bath was set at 50⁰C and the pH was pHl2.

Wetting-out times

The wetting out time for the sample taken after Bath 2 ^λwetted-out ' in >60 seconds, whereas the sample taken from Bath 3 ^λwetted-out' in 19 seconds.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool.

Example 7

The method used to set up the sequence of bowls in Example 1 was repeated, as was the method for the ^Λwetting-out ' test and the staining test. Only the contents and settings of the bowl were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium Phosphate 1Og/I₇ and Hydrogen Peroxide

20g/l (30% aq. soln) . A sequestrant was also added (Dequest 2066. Monsanto TMDlE). The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Acetic acid 5g/l in water. The temperature of Bath 3 was set at room temperature (~18°C) .

Wetting-out times

The wetting out time for the sample taken after Bath 2 'wetted-out' in >60 seconds, whereas the sample taken from Bath 3 ^xwetted-out' in ~4 seconds.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool .

Example 8

A series of baths, such as those supplied by Fleissner (UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths

1-6. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4,

Baths 4 and 5 and Baths 5 and 6, padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, sodium hydroxide (as a nucleophile) the concentration of which was 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. The temperature of Bath 4 was set at 40⁰C. Bath 5 - Sodium Sulphite in water, the concentration of which was 35g/l. The temperature of Bath 5 was set at 40⁰C.

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by Bulmer and Lumb Ltd, UK) was run through the six baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process .

Example 9

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the ^vwetting-out ' test and the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l. The temperature of this bath was set at 50⁰C and the pH was pHl2.

Wetting-out times

The wetting out time for the sample taken after Bath 2 ^xwetted-out' in >60 seconds, whereas the sample taken from Bath 3 ^vwetted-out' in 14 seconds.

Staining Test

Example 10

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the ^λwetting-out ' test and the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l. Sodium sulphite (as a nucleophile) was then added, at a concentration of 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Wetting-out times

The wetting out time for the sample taken after Bath 2 ^xwetted-out' in 5 seconds, whereas the sample taken from Bath 3 ^λwetted-out' in -1.5 seconds.

Staining Test

Example 11

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, Sodium Hydroxide the concentration of which was 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 2 - Acetic acid 3g/l in water. The temperature of Bath 2 was set at room temperature (~18°C) .

Bath 3 - Warm water was used as a rinse. The temperature of Bath 3 was set at 40⁰C.

Wetting-out times The wetting out time for the sample taken after Bath 2 ^vwetted-out' in >60 seconds, whereas the sample taken from Bath 3 ^λwetted-out' in 6 seconds.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at -2O⁰C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

Example 12

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added hydrogen peroxide (as a nucleophile) 20g/l (30% soln) and an alkali, trisodium phosphate the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Staining Test

The results of this example show that the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Example 13 The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the staining test. Only the contents and settings of the bath were changed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecγltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added hydrogen peroxide 20g/l (30% soln) and an alkali, trisodium phosphate the concentration of which was lOg/1. To this solution was added a peroxide activator, N,N' ,N¹ ' ,N¹ ' ' -tetraacetylethylenediamine (TAED) , the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHll .5.

Bath 3 - Acetic acid 3g/l in water. The temperature of Bath 3 was set at room temperature (-18⁰C) .

Bath 6 - Hercosett (RTM)₇ 40g/l of 12.5% w/w Hercosett in water. The temperature of Bath 6 was set at 40⁰C.

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by Bulmer and Lumb Ltd, UK) was run through the five baths sequentially at a speed of 10 metres per minute. Staining Test

The results of this example show that the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 14

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added hydrogen peroxide 20g/l (30% soln) and an alkali, trisodium phosphate the concentration of which was lOg/1. To this solution was added a peroxide activator, sodium persulphate, the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Acetic acid 3g/l in water. The temperature of Bath 3 was set at room temperature (-18⁰C) . Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. The temperature of Bath 4 was set at 40⁰C.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool . The results of this example show that the treated wool top after Bath 6 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 15

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the staining test. Only the contents and settings of the bath were changed, and in particular no acid was used.

The baths were filled with the following ingredients : Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added hydrogen peroxide 20g/l (30% soln) and an alkali, trisodium phosphate the concentration of which was lOg/1. To this solution was added a peroxide activator, N, W ,N' ' ,N' ' ' -tetraacetylethylenediamine (TAED) , the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 3 was set at 40⁰C.

Bath 4 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. The temperature of Bath 4 was set at 40⁰C.

Staining Test

The results of this example show that the treated wool top after Bath 4 took up a similar amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process . Example 16

The baths were filled with the following ingredients :

Bath 1 - Permonosulphuric acid (Caro's salt) (as the acid) the concentration of which was 30g/l in water. The temperature of Bath 4 was set at 40⁰C.

Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 4O⁰C.

Bath 3 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added an alkali, sodium hydroxide the concentration of which was 5g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Bath 4 - Warm water was used as a rinse. The temperature of Bath 4 was set at 40⁰C.

Staining Test The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool.

The results of this example show that the treated wool top after Bath 6 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Example 17

The baths were filled with the following ingredients:

Bath 1 - Permonosulphuric acid (Caro's salt) the concentration of which was 30g/l in water. The temperature of Bath 4 was set at 40⁰C.

Bath 3 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added hydrogen peroxide 20g/l (30% soln) and an alkali, trisodium phosphate the concentration of which was lOg/1. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 4 - Warm water was used as a rinse. The temperature of Bath 4 was set at 40⁰C. Bath 5 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 5 was set at 40⁰C.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool.

The results of this example show that the treated wool top after Bath 6 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 18

The baths were filled with the following ingredients :

Bath 1 - Permonosulphuric acid (Caro's salt) the concentration of which was 35g/l in water. The temperature of Bath 1 was set at ~18°C. Bath 2 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was an alkali, trisodium phosphate the concentration of which was lOg/1. Sodium sulphite was then added at a concentration of 30g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Staining Test

The sample of wool was immersed in the CI Reactive Blue 19 dye solution at -2O⁰C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool.

The results of this example show that the treated wool top after Bath 4 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Example 19

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the staining test. Only the contents and settings of the bath were changed. The baths were filled with the following ingredients :

Bath 1 - Permonosulphuric acid (Caro's salt) the concentration of which was 35g/l in water. The temperature of Bath 1 was set at ~18°C.

Bath 2 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was an alkali, trisodium phosphate the concentration of which was lOg/1. Sodium sulphite was then added at a concentration of 53g/l. The temperature of this bath was set at 60⁰C and the pH was pHll .5.

Staining Test

The results of this example show that the treated wool top after Bath 4 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process . Example 20

The method used to set up the sequence of baths in Example 8 was repeated, as was the method for the staining test. Only the contents and settings of the bath were changed. In this example however, the initial treatment was done using a pad system rather than a bowl system.

The baths were filled with the following ingredients :

Pad - Permonosulphuric acid (Caro's salt) the concentration of which was 35g/l in water was placed into a pad. The wool was passed through the pad giving a 113% wet pick up which equates to 4% PMS on weight of wool. The temperature of the PMS was ~18°C.

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was an alkali, trisodium phosphate the concentration of which was lOg/1. Sodium sulphite was then added at a concentration of 30g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. The temperature of Bath 3 was set at 40⁰C.

The results of this example show that the treated wool top after Bath 3 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Example 21

The baths were filled with the following ingredients :

Pad - Permonosulphuric acid (Caro's salt) the concentration of which was 55g/l in water was placed into a pad. The wool was passed through the pad giving a 113% wet pick up which equates to 6% PMS on weight of wool. The temperature of the PMS was -18⁰C.

Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 40⁰C. Bath 3 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. The temperature of Bath 3 was set at 40⁰C.

A sample of wool top (scoured. Merino wool top, average diameter 21 micron, supplied by Bulmer and Lumb Ltd, UK) was run through the five baths sequentially at a speed of 10 metres per minute.

Staining Test

Example 22

The baths were filled with the following ingredients :

Pad - Permonosulphuric acid (Caro's salt) the concentration of which was 35g/l in water was placed into a pad. The wool was passed through the pad giving a 113% wet pick up which equates to 4% PMS on weight of wool . The temperature of the PMS was ~18°C. Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was an alkali, sodium hydroxide the concentration of which was 5g/l. Sodium sulphite was then added at a concentration of 30g/l. The temperature of this bath was set at 60⁰C and the pH was pHl2.

Staining Test

The results of this example show that the treated wool top after Bath 3 took up more Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Example 23

A series of baths, such as those supplied by Fleissner

1-3. Between Baths 1 and 2 and Baths 2 and 3, padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A seguestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Sulphuric acid lOg/1 in water. The temperature of Bath 3 was set at room temperature (-18⁰C) .

Thus, the three baths comprised, in sequence, a delipidisation process (Bath 1), a rinse (Bath 2) and an acidification process (Bath 3) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd. , UK) was run through the three baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process .

This example produces wool top which has been analysed for 18-methyleicosanoic acid (18-MEA) , which is the lipid associated with shrink resistance. Analysis of the lipids in wool top can be achieved by the digestion and extraction of the wool into a solvent which is then analysed by gas chromatography - mass spectrometry (GCMS) . The various lipids have been quantified and tabulated as shown below.

These results show that 97.2% of the 18-methyleicosanoic acid (18-MEA) present in untreated wool has been removed by the delipidisation process . Overall there has been an 80% reduction in the quantity of lipid on the wool top.

Example 24

A series of baths, such as those supplied by Fleissner

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 3 - Sulphuric acid lOg/1 in water. The temperature of Bath 3 was set at room temperature (~18°C) .

Thus, the three baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse (Bath 2) and an acidification process (Bath 3) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd., UK) was run through the three baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process. A sample of this wool was then taken and given a scour with sodium carbonate at 100⁰C for 10 minutes. This process will remove the hydrated soluble protein material that has been formed during the delipidisation process 5 from the surface of the wool.

With this protein layer removed, wool top is more susceptible to dye uptake. Simple dyeing experiments have shown at least 99.0% exhaustion of dye onto the delipidised wool top compared to 94-98% (depending on dye 0 used) on untreated and chlorine Hercosett treated wool top .

Dye Wool Sample % Exhaustion

Untreated Wool top 98.20%

Lanasol Red 6G Chlorine Hercosett Wool top 98.06% (CI Reactive Red 84] Delipidised Wool Top 64.00% Delipidised and scoured Wool Top 99.95% Untreated Wool top 97.72%

Lanasol Yellow 4G Chlorine Hercosett Wool top 98.52% (CI Reactive Yellow 39) Delipidised Wool Top 59.88% Delipidised and scoured Wool Top 99.97% Untreated Wool top 94.2%

Lanasol Blue 3R Chlorine Hercosett Wool top 94.55%

(CI Reactive Blue 19) Delipidised Wool Top 58.88%

Delipidised and scoured Wool Top 99.7%

Example 25 A series of baths, such as those supplied by Fleissner

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% ag. soln) . A seguestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 4 was set at room temperature (~18°C) .

Bath 6 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) , The temperature of Bath 6 was set at 40⁰C.

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd, UK) was run through the six baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process .

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

The results of this example show that the treated wool top after Bath 6 took up approximately the same amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of Bunte salt (1023cm^"1) , whereas conventional Chlorine Hercosett process shows a large amount of cysteic acid (1040cm^"1) .

Example 26

A series of baths, such as those supplied by Fleissner (UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths 1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5, Baths 5 and 6 and Baths 6 and 7, padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients :

Bath 3 - Sulphuric acid lOg/1 in water. The temperature of Bath 3 was set at room temperature (~18°C) . Bath 4 - Sulphuric acid lOg/1 in water. The temperature of Bath 4 was set at room temperature (~18°C) .

Bath 5 - Permonosulphuric acid (Caro's salt) the concentration of which was 5g/l in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 5 was set at room temperature (-18⁰C) .

Bath 6 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 6 was set at 40⁰C.

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) , The temperature of Bath 7 was set at 4O⁰C.

Thus, the seven baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse and acidification process (Baths 2 to 4) , an oxidative sulphitolysis process

(Baths 5 and 6), and a reactive polymeric resin application (Bath 7) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd, UK) was run through the seven baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process .

Staining Test The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

The results of this example show that the treated wool top after Bath 7 took up approximately the same amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

Example 27

A series of baths, such as those supplied by Fleissner

The baths were filled with the following ingredients : Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% ag. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was lOg/1 in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 4 was set at room temperature (~18°C) .

Bath 6 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) ,The temperature of Bath 6 was set at 40⁰C.

Thus, the six baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse and acidification process (Baths 2 and 3), an oxidative sulphitolysis process (Baths 4 and 5) , and a reactive polymeric resin application (Bath 6) . A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd, UK) was run through the six baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process .

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at -2O⁰C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool .

The results of this example show that the treated wool top after Bath 6 took up approximately the same amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin

Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top.

FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of Bunte salts (1023Cm^'1) , whereas conventional Chlorine

Hercosett process shows a large amount of cysteic acid at

(1040cm^"1) . Example 28

The baths were filled with the following ingredients:

Bath 4 - Sulphuric acid lOg/1 in water. The temperature of Bath 4 was set at room temperature (~18°C) .

Bath 5 - Permonosulphuric acid (Caro's salt) the concentration of which was lOg/1 in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 5 was set at room temperature (~18°C) . Bath 6 - Sodium Sulphite in water. The concentration of which was 35g/l. The temperature of Bath 6 was set at 40⁰C.

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) , The temperature of Bath 7 was set at 40⁰C.

(Baths 5 and 6), and a reactive polymeric resin application (Bath 7).

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at -2O⁰C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool.

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salts (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of Bunte salts (1023cm^"1) , whereas conventional Chlorine Hercosett process shows a large amount of cysteic acid at (1040cm^"1) .

Example 29

1-6. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4,

The baths were filled with the following ingredients:

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5. Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 40⁰C.

Bath 4 - Permonosulphuric acid (Caro's salt) the concentration of which was 20g/l in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 4 was set at room temperature (~18°C) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd, UK) was run through the six baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process . Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool.

Fourier Transform Infrared Spectroscopy

Example 30

A series of baths, such as those supplied by Fleissner (UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths 1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5 , Baths 5 and 6 and Baths 6 and 7 , padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients : Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pH11.5.

Bath 5 - Permonosulphuric acid (Caro's salt) the concentration of which was 20g/l in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 5 was set at room temperature (~18°C) .

Thus, the seven baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse and acidification process (Baths 2 to 4) , an oxidative sulphitolysis process (Baths 5 and 6) , and a reactive polymeric resin application (Bath 7) .

A sample of wool top (scoured Merino wool top, average diameter 21 micron, supplied by A.Dewavrin Ltd, UK) was run through the seven baths sequentially, with the wool running through the padding stations between adjacent bowls to remove excess liquid from the wool prior to immersion in the next bath. The speed at which the wool passed through the bowl system was 10 metres per minute, which is substantially the same speed used in a conventional Chlorine Hercosett process.

Staining Test

Fourier Transform Infrared Spectroscopy

Example 31

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of lg/1. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pH11.5.

Bath 5 - Permonosulphuric acid (Caro's salt) the concentration of which was lOg/1 in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 5 was set at room temperature (~18°C) .

(Baths 5 and 6), and a reactive polymeric resin application (Bath 7) .

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool . The results of this example show that the treated wool top after Bath 7 took up approximately the same amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

Example 32

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 0.5g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 4 - Sulphuric acid lOg/1 in water. The temperature of Bath 4 was set at room temperature (-18⁰C) .

(Baths 5 and 6) , and a reactive polymeric resin application (Bath 7).

Staining Test

Fourier Transform Infrared Spectroscopy

Example 33

A series of baths, such as those supplied by Fleissner

(UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths 1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5 , Baths 5 and 6 and Baths 6 and 7 , padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 40⁰C and the pH was pHll.5.

(Baths 5 and 6), and a reactive polymeric resin application (Bath 7) .

Staining Test

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top.

FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of Bunte salt (1023cm^"1) , whereas conventional Chlorine

Hercosett process shows a large amount of cysteic acid

(1040cm^"1) .

Example 34

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 20⁰C and the pH was pHll.5.

(Baths 5 and 6), and a reactive polymeric resin application (Bath 7).

The results of this example show that the treated wool top after Bath 7 took up approximately the same amount of Hercosett resin to wool treated with the conventional Chlorine-Hercosett process.

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top . FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of Bunte salt (1023cm^"1) , whereas conventional Chlorine Hercosett process shows a large amount of cysteic acid (1040cm^"1) .

Example 35

The baths were filled with the following ingredients : Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 6 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added Trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 6 was set at room temperature (-18⁰C) and pHll.5.

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) , The temperature of Bath 7 was set at room temperature (~18°C) .

Thus, the seven baths comprised, in sequence, a delipidisation process (Bath 1) , a rinse and acidification process (Baths 2 to 4) , an oxidation process (Baths 5 and 6) , and a reactive polymeric resin application (Bath 7) .

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool.

The results of this example show that the treated wool top after Bath 7 took up more Hercosett resin than wool treated with the conventional Chlorine-Hercosett process.

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process . Example 36

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriairanonium bromide (CTAB) at a concentration of 2g/l. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 5 - Permonosulphuric acid (Caro's salt) the concentration of which was lOg/1 in water. To this was added sodium sulphate lOOg/1. The temperature of Bath 5 was set at room temperature (~18°C) . Bath 6 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added Trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 6 was set at 60⁰C and pHll.5.

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) ,The temperature of Bath 7 was set at 40⁰C.

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool . The results of this example show that the treated wool top after Bath 7 took up more Hercosett resin than wool treated with the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process ..

Example 37

The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of lg/1. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5. Bath 2 - Warm water was used as a rinse. The temperature of Bath 2 was set at 40⁰C.

Bath 6 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added Trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 6 was set at room temperature (~18°C) and pHll.5.

Staining Test

The results of this example show that the treated wool top after Bath 7 took up more Hercosett resin than wool treated with the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process .

Example 38

A series of baths, such as those supplied by Fleissner

1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4,

Baths 4 and 5, Baths 5 and 6 and Baths 6 and 7, padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed. The baths were filled with the following ingredients :

Bath 1 - A cationic surfactant, N-hexadecyltriammonium bromide (CTAB) at a concentration of lg/1. To this was added Trisodium phosphate lOg/1, and Hydrogen peroxide 20g/l (35% aq. soln) . A sequestrant (Dequest 2066, Solutia) and an antifoam (PD2005/049B, Stephensons Specialty Chemicals, Bradford, UK) were also added at a concentration of 0.5g/l. The temperature of this bath was set at 60⁰C and the pH was pHll.5.

Bath 6 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added Trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 6 was set at 60⁰C and pHll.5.

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) , The temperature of Bath 7 was set at 40⁰C. Thus, the seven baths comprised, in sequence, a delipidisation process (Bath I)₇ a rinse and acidification process (Baths 2 to 4) , an oxidation process (Baths 5 and 6), and a reactive polymeric resin application (Bath 7).

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool .

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040Cm^'1) which is also present in the conventional Chlorine Hercosett process .

Example 39

The baths were filled with the following ingredients :

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) . The temperature of Bath 7 was set at 4O⁰C.

Staining Test

The sample of wool was immersed in CI Reactive Blue 19 dye solution at -2O⁰C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool .

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^") . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process .

Example 40

The baths were filled with the following ingredients :

Staining Test

Fourier Transform Infrared Spectroscopy

Example 41

A series of baths, such as those supplied by Fleissner

1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5 , Baths 5 and 6 and Baths 6 and 7 , padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients :

Bath 3 - Sodium Carbonate 5g/l in water. To this was added a non ionic surfactant (Listril NGS, Stephensons Specialty Chemicals, Bradford, UK) at a concentration of 2g/l. The temperature of Bath 3 was set at 60⁰C.

Bath 5 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 5 was set at room temperature (~18°C) and pHll.5.

Bath 6 - cold water was used as a rinse. The temperature of Bath 6 was set at room temperature (~18°C) . Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) . The temperature of Bath 7 was set at room temperature (~18°C) .

Thus, the seven baths comprised, in sequence, a delipidisation process (Bath 1), a rinse (Bath 2), a scour (Bath 3), an oxidation process (Baths 4 and 5), a rinse (Bath 6) and a reactive polymeric resin application (Bath 7) .

Staining Test

The sample of wool at the end of the process (after Bath 7) was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A very dark blue stain was obtained for this sample of wool.

Fourier Transform Infrared Spectroscopy Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such 5 as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^", . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process.

Dyeing test

0 Dyeing experiments using reactive dyes at 100⁰C for 60 minutes on wool taken after Bath 3 (sodium carbonate scour) show at' least 99.0% exhaustion of dye onto the delipidised wool top compared to 94-98% (depending on dye used) on untreated and chlorine Hercosett treated wool 5 top .

Dye Wool Sample % Exhaustion

Untreated Wool top 98.20%

Lanasol Red 6G

Chlorine Hercosett Wool top 98.06%

(CI Reactive Red 84)

Delipidised and scoured Wool Top 99.95%

, _, ... ._ Untreated Wool top 97.72%

Lanasol Yellow 4G

(CI Reactive Yellow 39) Chlorine Hercosett Wool top 98.52%

Delipidised and scoured Wool Top 99.97%

Untreated Wool top 94.2%

Lanasol Blue 3R

Chlorine Hercosett Wool top 94.55%

(CI Reactive Blue 19)

Delipidised and scoured Wool Top 99.96%

Example 42 A series of baths, such as those supplied by Fleissner (UK) in their backwashing system for wool scouring or post-dyeing were set up sequentially and designated baths 1-7. Between Baths 1 and 2, Baths 2 and 3, Baths 3 and 4, Baths 4 and 5 , Baths 5 and 6 and Baths 6 and 7 , padding stations were set up, which consisted of counter rolling padding rollers through which wool is passed.

The baths were filled with the following ingredients :

Bath 5 - Hydrogen peroxide the concentration of which was 20g/l (35% aq. soln) . To this was added trisodium phosphate lOg/1, and a sequestrant (Dequest 2066, Solutia) at a concentration of 0.5g/l. The temperature of Bath 5 was set at room temperature (~18°C) and pH11.5.

Bath 6 - cold water was used as a rinse. The temperature of Bath 6 was set at room temperature (~18°C) .

Bath 7 - Hercosett (RTM), 40g/l of 12.5% w/w Hercosett in water. To this was added sodium hydrogen carbonate 5g/l to adjust the pH to pH9 (industry standard conditions) . The temperature of Bath 7 was set at room temperature (~18°C) .

Thus, the seven baths comprised, in sequence, a delipidisation process (Bath 1), a rinse (Bath 2), a scour

(Bath 3), an oxidation process (Baths 4 and 5), a rinse

(Bath 6) and a reactive polymeric resin application (Bath

7) .

Staining Test

The sample of wool at the end of the process (after Bath 7) was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A dark blue stain was obtained for this sample of wool . The results of this example show that the treated wool top after Bath 7 has taken up an equal amount of Hercosett resin as the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

5 Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^", . FTIR 0 analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process .

Dyeing test

5 Dyeing experiments using reactive dyes at 100⁰C for 60 minutes on wool taken after Bath 3 (sodium carbonate scour) show at least 99.0% exhaustion of dye onto the delipidised wool top compared to 94-98% (depending on dye used) on untreated and chlorine Hercosett treated wool 0 top.

Dye Wool Sample % Exhaustion

Untreated Wool top 98.20%

Lanasol Red 6G

Chlorine Hercosett Wool top 98.06%

(CI Reactive Red 84)

Delipidised and scoured Wool Top 99.95%

Lanasol Yellow 4G ^Untreated Wool top 97.72%

(CI Reactive Yellow 39) Chlorine Hercosett Wool top 98.52%

Delipidised and scoured Wool Top 99.97% Untreated Wool top 94.2%

Lanasol Blue 3R

Chlorine Hercosett Wool top 94.55%

(CI Reactive Blue 19)

Delipidised and scoured Wool Top 99.96%

Example 43

The baths were filled with the following ingredients :

Bath 3 - Sodium Carbonate 5g/l in water. To this was added a non ionic surfactant (Listril NGS, Stephensons Specialty Chemicals, Bradford, UK) at a concentration of 2g/l. The temperature of Bath 3 was set at 6O⁰C.

Bath 6 - cold water was used as a rinse. The temperature of Bath 6 was set at room temperature (-18⁰C) .

Staining Test The sample of wool at the end of the process (after Bath 7) was immersed in CI Reactive Blue 19 dye solution at ~20°C (at a liquor ratio of 10:1) for 5 minutes, then rinsed with water to remove any surplus dye solution, and then dried. A moderate dark blue stain was obtained for this sample of wool.

The results of this example show that the treated wool top after Bath 7 has taken up an equal amount of Hercosett resin as the conventional Chlorine-Hercosett process .

Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) on a Perkin Elmer Spectrum One spectrometer using a golden gate ATR attachment has been used to analyse the treated wool top. FTIR is very sensitive to certain chemical residues such as cysteic acid (-SO₃ ^") and Bunte salt (-SSO₃ ^", . FTIR analysis of the treated wool top indicates a large amount of cysteic acid (1040cm^"1) which is also present in the conventional Chlorine Hercosett process .

Dyeing test

Dyeing experiments using reactive dyes at 100⁰C for 60 minutes on wool taken after Bath 3 (sodium carbonate scour) show at least 99.0% exhaustion of dye onto the delipidised wool top compared to 94-98% (depending on dye used) on untreated and chlorine Hercosett treated wool top. Dye Wool Sample % Exhaustion

Untreated Wool top 98.20%

Lanasol Red 6G Chlorine Hercosett Wool top 98.06% (CI Reactive Red 84) Delipidised and scoured Wool Top 99.95% _AΓΛ 97.72% Lanaso _Tl ,Y_rel_{n n}low 4G Untreated Wool top

(CI Reactive Yellow 39) Chlorine Hercosett Wool top 98.52%

Delipidised and scoured Wool Top 99.97% Untreated Wool top 94.2%

Lanasol Blue 3R Chlorine Hercosett Wool top 94.55% (CI Reactive Blue 19)

Delipidised and scoured Wool Top 99.96%

The applicant has therefore shown that an alternative method to known chlorination-based processes for wool shrink-resistance has been demonstrated which exhibits excellent wool shrink-resistance efficacy whilst utilising relatively mild chemicals compared to know chlorination- based processes. In particular, no harmful AOX halogenated compounds are produced in the present method, 0 and disposal of cationic and non-ionic surfactants will not constitute the same problems as when dealing with chlorinated or other halogenated compounds .

Claims

1. A method of treating a wool material, the method comprising the steps of:

(a) contacting the wool material with a cationic surfactant; and

(b) contacting the wool material with a nucleophile.

2. A method according to claim 1 wherein steps (a) and (b) are performed simultaneously.

3. A method according to claim 1 or claim 2 wherein the nucleophile in step (b) is non-reducing.

4. A method according to claim 3 wherein the nucleophile is selected from hydrogen peroxide and its derivatives, the perhydroxy anion, the superoxide anion, a per-acid, a polyper-acid, an alkali metal or ammonium hydroxide, the hydroxyl anion, hydroxylamine, an alkanolamine, an alcoholate, an amine, a phenol, thiocyanate or any mixture thereof .

5. A method according to any preceding claim wherein the total treatment time for steps (a) and (b) is less than 45 seconds .

6. A method according to any preceding claim wherein the wool material is contacted with the cationic surfactant of step (a) for between 1 and 120 seconds and with the nucleophile of step (b) for between 1 and 120 seconds.

7. A method according to any preceding claim which further comprises a step (c) of contacting the wool material with an acid having a pH of no more than substantially 6.

8. A method according to any preceding claim which further comprises a step (d) of contacting the wool material with an agent or agent (s) capable of promoting additional anionic character to the surface of the wool material.

9. A method according to claim 10 wherein the agent or agent (s) capable of promoting additional anionic character to the surface of the wool material comprises an oxidising agent .

10. A method according to claim 11 wherein the oxidising agent comprises potassium peroxomonosulphate .

11. A method according to claims 8 to 10 wherein step (d) further comprises contacting the wool material with a nucleophile.

12. A method according to claim 11 wherein the nucleophile comprises sodium sulphite or is selected from hydrogen peroxide and its derivatives, the perhydroxy anion, the superoxide anion, a per-acid, a polyper-acid, an alkali metal or ammonium hydroxide, the hydroxy1 anion, hydroxylamine, an alkanolamine, an alcoholate, an amine, a phenol, thiocyanate, cyanate or any mixture thereof.

13. A method according to any preceding claim which further comprises a step (e) , of contacting the wool material with an alkali and/or applying a mechanical force.

15. A method according to any preceding claim which comprises a continuous process .

16. A method of treatment of a wool material comprising the steps of: (i) performing a pre-treatment method comprising treating the wool material according to the method of any of claims 1 to 15; and

(ii) contacting the wool with one or more agents capable of forming an interaction with the treated wool .

17. A method according to claim 16 wherein the method comprises a method of shrink-resistance treatment of a wool material .

18. A method according to claim 16 or 17 wherein step (ii) comprises contacting the wool with a polyamide polymer.

19. A method according to claim 16 wherein the agent of step (ii) is selected from a dye, a printing ink, a softening agent, a curing agent, a flattening agent, a flame retardant an anti-creasing agent and an agent promoting a permanent crease.

20. A wool material treated according to the method of any of claims 1 to 19.

21. A wool material according to claim 18 wherein the wool material is selected from wool yarn, wool top, wool fabric, loose wool, cashmere, fibres from an animal other than a sheep, a garment or a woven fabric containing wool or fibres from an animal other than a sheep.