The invention relates to triazine compounds, in particular to functionalised triazine compounds which can be used in the textiles industry.

Water is the application medium for wet chemical processing of textiles, with textile mills typically located in areas where the freshwater supply is sufficiently clean and plentiful throughout the year. However, it is becoming widely accepted that, within 10 years, two thirds of the world will suffer from a lack of freshwater (2007 World Water Day 22 March 2007 "Coping with water scarcity - challenge of the 21st century"). This will have a huge impact on the agricultural, manufacturing and energy sectors, and on the availability of water for domestic consumption. High population growth, scarcity of natural water resources and lack of investment in infrastructure will all contribute to this water shortage. As a result, freshwater can no longer be considered to be the abundant natural resource it once was, and the current levels of water usage across a wide range of industries cannot be sustained. This will inevitably impact the textile industry, where until now, a ready supply of freshwater for textile wet processing has been essential. Cotton in particular needs high levels of water at all stages of processing, from growing the plant, to the scouring, dyeing and general wet processing during textile production. Therefore the need to develop new technology that is less dependent upon water supply in the textile sector is evident.

Within the textiles industry there is a recognition that regenerated cellulosic fibres, such as viscose and lyocell, have a significant role in not only addressing this environmental challenge, but also in providing opportunities for the recycling of textile apparel. Lyocell technology in particular, developed by Courtaulds and Lenzing, offers a closed loop process in which cellulosic fibres are produced from wood pulp. This process is not only low in water consumption relative to other textile production processes, but also provides a product, lyocell, which satisfies the consumer demand for the "comfort" of cotton-type fibres. Specifically, following extraction from wood pulp (a renewable resource), cellulose is dissolved directly into the solvent N-methylmorpholine-N-oxide (NMMO). Advantageously, NMMO is biodegradable and non-toxic, and only a small amount is wasted in the process. As such, lyocell offers clear environmental benefits over traditional textiles.

Lyocell fibres (sold in the UK under the tradename Tencel ^® ) have a better wet and dry strength than viscose. However, the fibres have a higher degree of crystallinity and orientation, which results in fibrillation (i.e. formation of fibrils on the fibre and fabric surface). During wet processing, such as dyeing and laundering, such fibrils can pose a problem, as they can result in surface defects, such as pills and result in a dulling of the fabric colour. To combat these issues, cross-linked versions of lyocell have been fabricated, such as Lyocell Axis A-100 and Tencel LF, which are more resistant to fibrillation.

Whilst Lyocell Axis A-100 and Tencel LF offer an improvement to dyeing capabilities and more environmentally friendly wet processing procedures, there is a continuous need for a more environmentally friendly cellulosic dyeing processes and better dye fixation.

Another growing concern with conventional textiles (if not laundered regularly) and sanitary textile products, is the unpleasant odour generated from decomposition of urea (from sweat or urine) into ammonia and carbon dioxide, or from microbial growth. There is therefore a desire to generate textiles, which can inhibit this ammonia production and/or, which also have antimicrobial properties.

Another concern in the textile industry is the high degree of flammability associated with commonly used textiles. Specifically, cotton and other cellulosic fabrics have the worst flammability performance of any of the commodity textile fibres. The ignition temperature of cellulosic fibres is relatively low and it requires only 18% oxygen in the atmosphere to sustain a flame. Cotton is often treated with a phosphorus-based flame retardant, which operates in the solid phase and encourages the formation of an inert char on the fabric leading to a flame retardant effect. However, both of the commercial phosphorus based flame retardants (Pyrovatex CP and Proban) have technical deficiencies and could be improved. These existing systems are known to provide poor fabric handle, disadvantageously require the presence of carcinogenic formaldehyde in the formulation, and can lead to durability issues if laundering in hard water. Whilst flame retardant versions of viscose exist, such as viscose rayon containing pyrophosphate, there is still a need for development of a more environmentally friendly flame retardant lyocell fibre.

The invention is intended to overcome or ameliorate at least some aspects of the above problems.

Accordingly, in a first aspect of the invention there is provided a triazine compound of formula I or formula II:

II

Wherein X comprises a cellulosic material; Ri and R are independently selected from -ONR'R", -NR'R", or -Y; wherein R' and R" are independently selected from H, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof; or wherein the alkyl, alkoxy or alkenyl may be substituted with at least one acid selected from a carboxylic acid, phosphonic acid, and sulfonic acid, an amino acid moiety, a compound of formula I or formula II, and a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S; or wherein R' and R" comprise a saturated or unsaturated cyclic moiety comprising 4, 5 or 6 carbons, wherein one or more of the carbons in the cyclic moiety may be replaced by a heteroatom selected from N, O or S; and wherein Y is a sulphur containing moiety selected from cysteamine, cysteine, sulphide, sulphite, bisulphite, thiosulphate, -S=C=N , or -N=C=S, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof, or a phenolic moiety which may be substituted at one or more sites with -OH or (CH ) _x OH where x may be 1 - 5. The triazine compounds according to the first aspect of the invention provide a reactive cellulosic fibre, which can offer performance improvements in a wide range of sectors in the textile industry, including colouration, colour fastness, odour control (for instance through the provision of fibres with antimicrobial and/or antiviral properties) and flame reta rdancy.

Further, cellulosic fibres comprising the triazine compounds of the invention can be generated with minimal changes to current production processes. As such, textile fibres comprising the triazine compound of the invention can be prepared on a large scale, using existing production facilities, allowing rapid uptake of the technology.

In formulae I and II above, Ri and R2 may be the same or different; and each substituent thereof may be the same of different.

When Ri or R2 are selected from -NR'R", it is often the case that at least one of R' or R" are hydrogen or an alkyl group, often both R' and R" are hydrogen, such that Ri and/or R2 may be ammonia. When R' or R" is an alkyl group, it will often have 1 to 5 carbon atoms, often 1 to 3 carbon atoms. It may be the case that one or more carbons in the alkyl group will be replaced with O, N or S, often with O or N. Often Ri and/or R2 are ammonia, methanolamine or ethanolamine. The presence of the ammonia, methanolamine and ethanolamine functionalities in the triazine compounds of the invention, in particular, and other amines as can be formed through substitution of a carbon in a R' or R" alkyl group with nitrogen, have been demonstrated to provide fibres with excellent dye fixation properties.

When Ri and/or R2 are selected from -ONR'R", it is often the case that at least one of R' or R" is hydrogen or an alkyl group, often both R' and R" are hydrogen. When R' or R" is an alkyl group, it will often have 1 to 5 carbon atoms, often 1 to 3 carbon atoms. It may be the case that one or more carbons in the alkyl group will be replaced with O, N or S, often O or N. Often Ri or R2 are hydroxy la mine. The presence of hydroxylamine in the triazine compounds of the invention (and other -ONR'R" functionalities) is believed to provide for potent urease inhibition, offering odour control in fibres comprising the inventive compounds.

For the avoidance of doubt, the term "alkyl" is intended to take its usual meaning and covers linear, branched and cyclic saturated hydrocarbons having a carbon length in the range Ci to Cis- Often the alkyl group will be linear or branched, typically linear. Whilst the exact length of the alkyl group may vary, it is typically the case that the alkyl group has a carbon length in the range Ci to Cis, more typically Ci to C12, or Ci to C ₆ , and most typically Ci to C3. Typical alkyl groups are selected from, but not limited to: methyl, ethyl, propyl, isopropyl, butyl or tertiary butyl. Similarly, the term "alkoxy" is intended to carry its usual meaning i.e. this term is identical to "alkyl" described above with the exception that said alkyl group is covalently bonded to the triazine skeleton via an oxygen atom (as would be familiar to one skilled in the art).

For the avoidance of doubt, the term "alkenyl" is also intended to take its usual meaning and covers linear, branched and cyclic partially saturated hydrocarbons having a carbon length in the range C2 to Cis- The term "partially saturated" refers to the presence of at least one C=C bond within the structure. Often the alkenyl group will be linear or branched, typically linear. Whilst the exact length of the alkenyl group may vary, it is typically the case that the alkenyl group has a carbon length in the range C2 to Cis, more typically C2 to C12, and most typically C2 to C ₆ - Typical alkenyl groups are selected from, but not limited to: vinyl, propenyl, isopropenyl or butenyl. The alkenyl may comprise one or more than one C=C bond, these may be spaced by at least one C-C bond, or on rare occasions directly adjacent to one another to form a C=C=C moiety. Where a C=C=C moiety is provided, it will generally be the case that at least one of the terminal carbons will be replaced with O, N or S, often both terminal carbons, such that groups such as -N=C=0, -S=C=N-, or -N=C=S could be formed. However, often there will be just one C=C double bond, or two, such that a dialkenyl may be formed.

For the avoidance of doubt, the term "polyamine" is intended to cover organic compounds having two or more amino groups. The polyamine may be an alkyl or alkenylpolyamine, often however alkylpolyamines will be used.

In such structures, optionally, Ri and R2 are -NR'R", and at least one of R' and R" may be selected from alkyl, wherein in the alkyl at least one carbon atom may be replaced with N or with O. Where at least one carbon atom (for instance a -CH2- group) is replaced by N, often two or more carbon atoms will be replaced by N. Typical alkylpolyamines include ethyleneamines comprising 2 to 5 nitrogens, such as diethylenetriamine or triethylenetetramine; or polyethyleneimines which can be straight chain or branched chain or additionally dendritic. Often the polyethyleneimines will be branched, and often functionalised. In some cases polyethyleneimines such as Lupasol P (BASF) will be used. Polyethyleneimines will often be of molecular weight in the range 500 - 50,000, often 20,000 - 30,000. The polyethyleneimines and alkylpolyamines offer excellent dye uptake and fixation. Without being bound by theory this is believed to be as a result of the protonation of the amines promoting exhaustion of the anionic dyes on to the positively charged Lyocell fibre and where reactive dyes are applied improved nucleophilic addition or substitution reactions with reactive groups on the dyes, particularly where the dyes are sulfonated reactive dyes. Processes of this type have the potential to reduce the environmental impact of the dyeing process by reducing the levels of salt required to fix the dye, and hence reducing the salination of freshwater courses when the waste water is released from the dyeing process. Further, it has been found that chelation of polyamines can provide for triazine-containing fibres which have the ability to inhibit urease activity relative to untreated Lyocell. Without being bound by theory, it is believed that this inhibition is achieved by chelating the nickel core of the urease. The chelator may be, for instance, an acid chelator, for instance a carboxylic acid chelator, such as a di-carboxylic acid (e.g. maleic acid or glutamic acid), tri carboxylic acid (e.g. citric acid) or tetra -carboxylic acid (e.g. EDTA).

Where Ri and R2 are -NR'R", and an alkylpolyamine is formed, it may be the case that at least one -CH2- unit in the alkylpolyamine backbone will be replaced by O, such that, for instance, diamines of polyethylene glycol can be formed. These structures, when present in the triazine compounds of formulae I or II, can provide for fibres and textiles with excellent dye fixation and retention.

The term "amino acid" is intended to take its usual meaning, and relates organic compounds containing amine and carboxyl functional groups. The amino acid is often selected from cysteine, cysteamine, glycine, tyrosine, lysine, taurine, glutamic acid, arginine or combinations thereof. It may be the case that the amino acid moiety is a poly(amino acid) or amino acid polymer. As used herein, the term "poly(amino acid)" or "amino acid polymer" are used interchangeably, and relate to a polymer in which the monomer units are amino acids. Examples of amino acid polymers include, but are not limited to, functional proteins, polypeptides, peptides, and polymers derived from amino acids, such as poly(P-alanine) and poly(lysine). It may be the case that the amino acid moiety is poly(lysine). It has been found that these amino acid functionalities, when incorporated into the triazine compounds of the invention can provide fibres and fabrics which have the ability to control odour through urease inhibition. Of these, glycine and taurine have been found to be particularly effective. Moreover, poly(lysine) functionality, when incorporated into the triazine compounds of the invention, can provide fibres and fabric with excellent dye uptake, but which also have antimicrobial properties, such that the fibres kill and/or inhibit the growth of microorganisms including bacteria, fungi, algae, protozoa, viruses and sub-viral agents. The term "microorganism" (or "microbe") is intended to take its usual meaning, and relates to microscopic organisms that are unicellular, multicellular, or exist as a cell cluster. Without being bound by theory, it is believed that, due to the cationic nature of poly(lysine), it exhibits such antimicrobial behaviour by either damaging or disrupting the cell membranes of microbial cells, protein denaturation, inhibiting DNA replication, inhibiting synthesis of mRNA, or preventing protein synthesis from taking place.

It may be the case that the amino acids (often selected from cysteine, glycine, tyrosine, lysine, taurine and/or arginine), may be connected together in a sequence, forming protein residues, this can provide the urease inhibition of amino acids together with other biochemical and physiological benefits depending on the protein selected.

As used herein, a "cyclic moiety" is a cyclic hydrocarbon, in which the carbon chain forms a ring, typically the ring is 5- or 6-membered, often the atoms in the ring will be primarily if not entirely carbon atoms; however, these may be substituted with one or more heteroatoms such as N, O or S, often N or O. Often the cyclic moiety will be a 5- membered ring, often substituted with N, often at more than one carbon, such that a 5- membered ring with one or two nitrogens within the ring may be formed. The term "unsaturated" as pertaining to cyclic moieties, refers to the presence of at least one C=C bond within the structure, and aromatic refers, as is common, to conjugated ring structures. Typical cyclic and/or aromatic moieties include imidazole, pyrrole, pyrazole, oxazole, benzimidazole, pyridine, pyrimidine, phenol, aniline and furan. Often the cyclic/aromatic moiety will include pyrimidine, phenol, aniline, or imidazole. As a result, it may be that Ri and R ₂ are both -NR'R", and R' and R" may independently comprise a saturated or unsaturated cyclic moiety comprising 4, 5 or 6 carbons, wherein one or more of the carbons in the cyclic moiety may be replaced by a heteroatom selected from N, O or, on occasion, S. Often the cyclic moiety will be imidazole, although together with the other cyclic moieties listed here, it is believed that the use of imidazole will provide for a fabric with excellent dye uptake and exhaustion.

For the avoidance of doubt, the terms "phenol" or "phenolic moiety" are intended to take their usual meaning, and cover a compound consisting of a hydroxyl group bonded directly to a six-membered aromatic hydrocarbon group. Typically, the phenolic moiety is selected from phenol, di-hydroxy phenol or tri-hydroxy phenol, although often the moiety will be phenol (-C ₆ H ₄ OH). As such, Ri and R ₂ may independently be -Y, wherein Y is a phenolic moiety which may be substituted at one or more sites with -OH or - (CH ₂ ) _X OH where x may be 1 - 5. Typically x will be 5, such that a six-membered "phenol" ring is formed. The term "sulphur-containing moiety" is intended to cover any functional group which comprises sulphur. Typically the sulphur-containing moiety is selected from sulphates, sulphites, and sulfonic acids. The sulphur-containing moiety may be selected from cysteamine, cysteine, sulphide, inorganic sulphite, inorganic thiosulphate (such as sodium thiosulphate), bisulphite, or thiocyanate. Often, sulphite or thiosulphate are present, such that optionally, Ri and R2 are independently -Y, wherein Y may be selected from sulphite or thiosulphate. The sulphur containing triazine compounds, for instance those which comprise or can break down in situ to form sulfonic acid, are believed to be advantageous in reducing textile odour, as sulfonic acid acts to inhibit urease breakdown preventing the release of ammonia and the associated unpleasant smells. Examples of such functionalities include bisulphite, sulfonic acid, or thiosulphate. Bisulphite functionalities have been found to be particularly effective in odour control due to an unexpected selective binding to urease.

Optionally, Ri and R2 are -NR'R", and at least one of R' and R" may be selected from an alkyl, wherein the alkyl may be substituted with at least one acid selected from a carboxylic acid (such as ethanoic acid), phosphonic acid, and sulphonic acid. It is often the case that the at least one acid is phosphonic acid or carboxylic acid. It may be the case that the acid comprises more than one acid group, for instance the acid may be a chelator as described above with multiple acid groups, for instance it could be a diacid, such as maleic acid or glutamic acid, a tri-acid such as citric acid, or a tetra-acid such as EDTA. The presence of these chelators has been found to enhance the urease inhibition properties of the fibres and fabrics incorporating them. In particular, maleic acid and other diacids have been found to strongly chelate the nickel centre of the urease providing excellent inhibition of the urease activity.

Optionally, Ri and R2 are -NR'R", and at least one of R' and R" may be selected from an alkyl, alkenyl or alkoxy, wherein the alkyl, alkenyl or alkoxy may be substituted with at least one conjugate base of an acid selected from a carboxylic acid (i.e. a carboxylate), phosphonic acid (i.e. phosphonate), and sulphonic acid (i.e. sulphonate), or sulphuric acid (i.e. sulphate). It has been found that conjugate base functionalities, when incorporated into the triazine compounds of the invention, can provide fibres and fabrics which have antimicrobial and antiviral properties. The term "virus" is intended to take its usual meaning and includes any infectious agent that is only capable of growth and multiplication in living cells. Without being bound by theory, it is believed that conjugate bases are able to complex with active functionalities in microbial and viral enzymes. Typically, where the at least one acid is phosphonic acid, often, the phosphonic acid is (aminomethyl)phosphonic acid. It has been found that textiles comprising triazine compounds of formula I or formula II, where at least one of Ri and R2 is -NR'R", and at least one of R' and R" is selected from an alkyl, wherein the alkyl may be substituted with an acid as defined above, and particularly phosphonic acid functionalities and phosphonic acid containing functionalities, display excellent flame retardant properties. As such, this chemical structure provides for the possibility of generating enhanced flame retardant textiles.

Often, the sulphonic acid is aminoethanesulphonic acid (taurine). The use of taurine provides for a textile fibre with good anti-odour properties, as it can selectively bind to urease, inhibiting urease breakdown, thereby reducing or preventing the release of ammonia and the associated unpleasant smells.

Optionally, Ri and R2 are independently -NR'R", and at least one of R' and R" may be selected from an alkyl, wherein in the alkyl at least one carbon atom may be replaced with N, or wherein the alkyl is substituted with a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S. It has been found that cellulosic fibres comprising triazine compounds of formula I or formula II, as described here, can provide for extremely high - often as high as 100% - dye exhaustion, and subsequently similarly high levels of dye fixation. The term "dye exhaustion" is defined as the mass of the dye taken up by the material divided by the total initial mass of dye in the bath. As noted above, without being bound by theory, it is believed that the presence of the amine or other moieties which can be readily protonated, in the compounds of formulae I and II, results in their protonation under weakly acidic or neutral conditions - as are commonly found during the dye process. This provides for excellent dye fixation, improving uptake from around 40% of the applied dye to, in some instances, almost 100% dye fixation and retention. As a result there is less wastage of dyes. Further, the protonation removes the need for high levels of sodium chloride to be present in the process, reducing costs as this additive is not needed in such high amounts, if at all, and providing a more environmentally friendly process than typical cellulosic dyeing processes, as salination of freshwater courses is reduced upon release of the wastewater from the dyeing process.

Optionally, Ri and R2 are -NR'R", and at least one of R' and R" optionally selected from an alkyl, wherein the alkyl is substituted with a compound of formula I or formula II. In such examples, the substitution of the compound of formula I or formula II with a further compound of formula I or formula II provides for a strong retention of the desirable properties of, for instance, existing lyocell or viscose materials in terms of low fibrillation of the fibre, whilst providing for excellent dye retention, of up to 100% dye retention and fixation as described above. Typically the chains of compounds of formula I and/or II formed will be terminated with cellulosic material X, such that they are terminated with the cellulosic fibre forming component and in some senses encased therein. The chains may comprise 1 - 5 compounds of formulae I and II.

Alternatively, R', R" and Y may independently be an alkyl, wherein in the alkyl at least two adjacent carbon atoms are replaced with O, such that a peroxide functionality is formed. As such, it could be said that typically, the alkyl comprises a peroxide group. This can be advantageous as it has been found that by incorporating triazine compounds of formula I or formula II which have peroxide functionality into textile fibres, the textiles produced demonstrate antimicrobial behaviour. The inclusion of this functionality can therefore help to reduce textile odour.

It is often the case that the cellulosic material comprises lyocell cellulose fibres, although viscose fibres are also often used. Lyocell textiles are popular as they offer a consumer perception of comfort and softness, whilst providing the benefits of a natural cellulosic fibre. In addition, lyocell production involves a closed loop production of cellulosic fibres from wood pulp, which not only reduces water consumption relative to other fabric production techniques, providing a more environmentally friendly solution to the provision of textiles to the end user.

In a second aspect of the invention there is provided a triazine compound of formula III or formula IV for use in dye fixation, the reduction of textile odour, for instance through the inhibition of urease breakdown or the provision of antimicrobial properties to fibres including the compounds, and/or as a flame retardant.

IV

In a third aspect of the invention there is provided a process for the preparation of a compound of formula I or formula II comprising reacting a compound of formula III or formula IV

IV

With a compound selected from: HONR'R", HNR'R", or Y wherein R' and R" are independently selected from H, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof; or wherein the alkyl, alkoxy or alkenyl may be substituted with at least one acid selected from carboxylic acid, phosphonic acid, and sulphonic acid, an amino acid moiety, a compound of formula I or formula II, and a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S; or wherein R' and R" comprise a saturated or unsaturated cyclic moiety comprising 4, 5 or 6 carbons, wherein one or more of the carbons in the cyclic moiety may be replaced by a heteroatom selected from N, O or S; or wherein Y is a sulphur-containing moiety selected from cysteamine, cysteine, C1-C5 alkylthiols, inorganic sulphites and inorganic thiosulphates, R ³ -S=C=N-, or R ³ -N=C=S, R ³ -0-0-R ³ wherein R ³ is selected from H, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof, phenyl, or benzyl; or phenol which may be substituted at one or more sites with -OH or (CH ₂ ) _X OH where x may be 1 - 5; and wherein X is a cellulosic derivative.

In a fourth aspect of the invention, there is provided use of the triazine compound of the invention in dye fixation, the reduction of textile odour, for instance by the inhibition of urease breakdown or the provision of antimicrobial properties to fibres including the compounds, and/or to provide flame retardant properties.

In fifth, sixth and seventh aspects of the invention, there is provided a textile product, sanitary product or flame retardant textile comprising the triazine compound of the invention. As noted above, the textile product is generally a cellulosic product, often viscose or lyocell, most often lyocell. Such products benefiting from the enhanced dyeing, in particular dye uptake and fixation, which is offered by selecting the functionalisation of the triazine compounds as described above, in particular by providing amine functionalities.

The sanitary product may be a nappy, sanitary towel, incontinence pad or similar, such products benefiting from reduced odour production either because of antimicrobial properties imbued to the textile fibres by virtue of the functionalisation of the compound of formula I and/or II (for instance peroxide), or because the functionalisation imparts the fibres containing the claimed compounds with the ability to inhibit urease breakdown, such that sweat or urine in contact with the textile do not release ammonia, and so the unpleasant smell associated with urease breakdown is either eliminated or greatly reduced. The urease inhibition is particularly associated with glycine, taurine and thiosulphate, or chelator-functionalised polyamines, such as maleic acid polyethylene imine.

The flame retardant textile may be used in a wide variety of ways, including home and public space furnishings such as sofas, curtains, carpets, bedding, insulation to provide fire barriers etc. Such products benefit from improved flame retardancy when certain functionalities are present in the compounds of formulae I or II as described above. In particular aminomethylphosphonate. According to further aspects, there is provided an antimicrobial agent and antiviral agent comprising the triazine compound of the invention.

Unless otherwise stated, each of the integers described may be used in combination with any other integer as would be understood by the person skilled in the art. Further, although all aspects of the invention preferably "comprise" the features described in relation to that aspect, it is specifically envisaged that they may "consist" or "consist essentially" of those features outlined in the claims. In addition, all terms, unless specifically defined herein, are intended to be given their commonly understood meaning in the art.

Further, in the discussion of the invention, unless stated to the contrary, the disclosure of alternative values for the upper or lower limit of the permitted range of a parameter, is to be construed as an implied statement that each intermediate value of said parameter, lying between the smaller and greater of the alternatives, is itself also disclosed as a possible value for the parameter.

In addition, unless otherwise stated, all numerical values appearing in this application are to be understood as being modified by the term "about".

In order that the invention may be more readily understood, it will be described further with reference to the figures and to the specific examples hereinafter.

Figure 1 is a dyeing profile for 50g/L polyethylene imine (MW = 600) modified never dried Lyocell Axis A-100. A - 2, 4, 6, 8 and 10% o.m.f. Procion Navy HE-R, 2.5g modified tow, L.R. 10: 1, pH7. All dyeings were soaped-off; and

Figure 2. is a photograph of untreated Lyocell Axis A-100 (Figure 2a) and Lyocell Axis A- 100 treated with diethylene triamine (Figure 2b) after treatment with 2% Remazol Brilliant Red 3B (2% o.m.f.) at 90°C for a period of 30 minutes (zero salt addition and neutral pH conditions). EXAMPLES

Materials

Lyocell Axis A-100 (supplied by Lenzing) - Lyocell fibre cross-linked with 1,3,5- triacryloylhexahydro-s-triazine (TAHT)

TAHT (supplied by Lenzing) - 1,3,5-triacryloylhexahydro-s-triazine, a cross-linking agent Lupasol P ^® (supplied by BASF) - Polyethyleneimine

Remazol Brilliant Red 3B ^® (C.I. Reactive Red 23, supplied by DyStar) - sulphato- ethylsulphone reactive dye

Example 1: Preparation of Axis A100 Lyocell using 1,3,5-triacryloylhexahvdro-s-triazine (TAHT ^’ )

TAHT is a tri-functional cross-linker that is commonly used to generate Lyocell Axis A- 100. Lyocell Axis A-100 was produced by application of TAHT continuously to the Lyocell tow by a pad-steam process (J-Box) using an alkali mix of sodium hydroxide and tri sodium phosphate. If all three acryloyl residues in the TAHT undergo Michael addition with Cell-O , then the fully cross-linked cellulose has the structure X.

Example 2: Activation of Lyocell Axis A-100 by alkali catalysed b-elimination of cross- linked cellulose

Whilst the formation of fully cross-linked cellulose is common, there may be incomplete reaction with the fibre leading to residual "free" acryloyl residues as shown by compound A in scheme 1 below.

Following a subsequent alkali catalysed b-elimination, further acryloyl residues can be formed in situ (B, scheme 1).

B

Scheme 1. Alkali catalysed b-elimination of cross-linked cellulose

Example 3: Dyeing Results of Lvocell A-100 with amines to deliver salt-free, 100% fixation reactive dve coloration

Lyocell Axis A-100 possessing some free acryloyl residues (scheme 1) was reacted following after-treatment with amines to form structures C and D according to the following scheme;

Scheme 2. Reaction of activated, TAHT cross-linked cellulose with amines

It has been found that, through the use of multi-functional amines, the application of the amine will not interfere with the existing low fibrillation properties of the substrate fibre due to the supply of additional cross-links, as demonstrated in Scheme 3. In addition, without being bound by theory, it is believed that by dyeing under weakly acidic/neutral conditions, the amine moieties became protonated, eliminating the need for high levels of sodium chloride, and resulting in 100% dye exhaustion and fixation.

Scheme 3. Reaction of activated, TAHT cross-linked cellulose with polyamines, where — — indicates further cross-links

Example 4: Modification of Lyocell Axis A-100 with 50a/L polyethylene imine (Lupasol P ^® ) Lyocell Axis A-100 was modified with 50g/L polyethylene imine (MW = 600) at pH 11.5, 70°C for 30 seconds using a liquor ratio of 10: 1. The modified Lyocell A-100 tow was then dyed. The dyeing profile is shown in Figure 1.

Example 5: Dve exhaustion and fixation efficiency of modified Lyocell A-100 fibre

Table 1 below indicates the dye exhaustion and total fixation efficiency are close to 100% for the modified Lyocell A-100 fibre, and significantly better than the dyeing of Lyocell Axis A-100 using the "eco-unfriendly" conventional dyeing process ("untreated"). This indicates that the combination of high dye fixation coupled to zero salt addition and neutral pH conditions offers significant economic and environmental benefits over current commercial cellulosic dyeing processes.

Table 1. Procion Navy HE-R Dyeing performance indicators for 50g/L polyethylene imine (PI, Mol. Wt. = 600) modified never dried Lyocell Axis A-100 and standard Lyocell Axis

A-100.

Example 6: Initial dyeing study

Lyocell Axis A-100 knitted fabric was treated (40 minutes, 20°C, pH 11.5) with a 2.5% w/w solution of diethylene triamine, ethanolamine or imidazole. The treated fabric was washed in running water to remove unreacted amine and then dried.

Dyeing of the above fabrics with the sulphato-ethylsulphone reactive dye, Remazol Brilliant Red 3B ^® (2% o.m.f.) was carried out at pH 7 in the absence of salt, raising the temperature to 90°C and continuing for 30 minutes. Under these conditions the sulphato-ethylsulphone dye readily converts to the more reactive vinylsulphone dye.

The results with diethylene triamine showed significant improvements with full dyebath exhaustion achieved. The results obtained from the diethylene triamine after-treatment, dyeing with 2% Remazol Brilliant Red 3B (2% o.m.f.), are shown in Figure 2. As can be seen, the treated sample is significantly more vibrant in colour, clearly indicating better absorption of the dye than the untreated comparison. With ethanolamine and imidazole, good increases in colour vibrancy were observed. Example 7: Anti-Ammonia Odour Resistance in Urine Stained Lvocell Textiles

The ammonia odour often detected in poorly washed textiles, or in sanitary products such as incontinence pads, results from the decomposition of urea in the presence of the enzyme urease. To seek to reduce this odour, modifications were made Lyocell Axis A- 100 in order to embed a variety of functionalities that would interfere with the urease catalysed decomposition of urea.

(i) Fabrics evaluated: 1. Untreated cotton (control)

2. Lyocell Axis A-100 fabric

3. Lyocell Axis A-100 fabric was boiled for 1 hour in a 5% w/w sodium thiosulphate solution with pH adjusted to pH 5, the TAHT derivative electrophilic double bond adds to the nucleophilic sodium thiosulphate to form the Lyocell Axis A-100 Bunte salt modified fabric. As expected, the pH of the treatment solution rose from 5 to 8 as the Bunte salt formation reaction proceeded

4. Lyocell Axis A-100 fabric treated with glycine - Lyocell Axis A-100 fabric was left for 48 hours in a 5% w/w glycine solution adjusted to pH 9.5 with sodium bicarbonate. This ensured attachment of carboxymethyl amino residues to the Lyocell Axis A-100 modified fabric. The glycine reaction is shown below in scheme 4:

Scheme 4. Reaction of glycine with "activated" Lyocell Axis A-100 (ii) Urease inhibition study

To test the potential urease inhibitors attached to the Lyocell Axis A-100 modified lyocell, fabrics 1 to 4 were impregnated with 20% w/w urea solution and partially dried. One half of the fabric was then dusted with soil which naturally contains urease; all samples were separated and sealed in polyethylene bags. Within 1-2 days the soil within the sealed bags containing urea-treated cotton had generated an obvious odourous ammonia smell. The comparative results are shown in Table 2: Table 2. Urease inhibition studies of fabrics 1 to 4.

Example 8: Development of Wash-durable Flame Retardant (FR) Lyocell

A preliminary study assessing the reaction of the pre-activated Lyocell Axis A-100 fabric with sodium hexameta-phosphate (10% o.m.f., pH 3, 30-60 minutes and 70°C) prepared fabric 5.

The performance of the modified lyocell fabric 5 was determined using a Limiting Oxygen Index Tester, Vertical Strip Flammability testing and Kawabata Evaluation System for Fabrics (Fabric handle). The modified fabric showed evidence of reduced flammability.