Treatment of cellulosic fibres to reduce their fibrillation tendency

Abstract: A solvent-spun cellulose fibre having a reduced fibrillation tendency is provided by a process comprising treating the fibre with a chemical reagent having two to six functional groups reactive with cellulose. Preferably the fibre has the same colour before and after the treatment, which is suitably carried out with the chemical reagent dissolved in an aqueous solution before or after the solvent-spun fibre is first dried.

Description: This invention is concerned with the treatment of solvent-spun cellulose fibres to reduce their tendency to fibrillation. Proposals have been made to produce cellulose fibres by spinning a solution of cellulose in a suitable solvent. An example of such a process is described in GB-A-2043525, the contents of which are incorporated herein by way of reference. In such a solvent-spinning process, cellulose is dissolved in a solvent for the cellulose such as a tertiary amine N-oxide, for example N-methylmorpholine N-oxide. The resulting solution is then extruded through a suitable die to produce a series of filaments, which are washed in water to remove the solvent and subsequently dried. Such cellulose fibres are referred to herein as "solvent-spun" cellulose fibres and are to be contrasted with fibres produced by chemical regeneration of cellulose compounds, such as viscose fibres, cuprammonium fibres, polynosic fibres and the like. The present invention is particularly concerned with the treatment of such solvent-spun cellulose fibres so as to reduce the tendency of the fibres to fibrillate. Fibrillation is the breaking up in a longitudinal mode ofa fibre to form a hairy structure. A practical process to reduce fibrillation tendency needs not only to inhibit fibrillation but also to have a minimal effect on subsequent processability of the fibre and to have as little as possible effect on tenacity and extensibility of the fibre. Some processes which have been investigated by the applicants and which will reduce the fibrillation tendency have the unwanted side effects either of reducing the tenacity and the extensibility of the fibre or of embrittling the fibre so as to make it unprocessable. Cellulose fabrics have been treated with resins to give improved crease resistance. This type of treatment is described in an article entitled "Textile Resins" in Encyclopaedia of Polymer Science and Technology, Volume 16 (1989, Wiley-Interscience) at pages 682-710. The resins used are generally polyfunctional materials which react with and crosslink cellulose. Resin treatment may reduce breaking strength and tearing strength as well as abrasion resistance. Fabrics are usually dyed before crosslinking because the dye cannot penetrate the crosslinked fibre. The literature on the dyeing of fibres, including natural cellulosic fibres such as cotton and artificial cellulosic fibres such as cuprammonium and viscose rayon, is extensive. Representative examples of this literature include: Man-Made Fibres, R.W. Moncrieff, 6th Edition (Newnes-Butterworth, 1975), Chapter 49 (pages 804-951); an article entitled "Dyeing" in Encyclopaedia of Polymer Science and Engineering, Volume 5 (Wiley-Interscience, 1986), pages 214-277; and Textile Dyeing Operations, S.V. Kulkami et al. (Noyes Publications, 1986). Common types of dye for cellulose include direct dyes, azo dyes, fibre-reactive dyes, sulphur dyes and vat dyes. The choice of dye for any particular application is governed by various factors including but not limited to the desired colour, levelness of dyeing, effect on lustre, wash-fastness, light-fastness and cost. Reactive dyes are described in an article entitled "Dyes, Reactive" in Kirk-Othmer, Encyclopaedia of Chemical Technology, 3rd edition, Volume 8 (1979, Wiley-Interscience) at pages 374-392. Reactive dyes are coloured compounds that contain functional groups capable of forming covalent bonds with active sites in fibres such as hydroxyl groups in cellulose. These dyes contain a chromophore system attached directly or indirectly to a unit which carries one or more functional groups reactive with the material to be dyed. Reactive dyes for cellulosic materials are particularly described at pages 380-384 of the above-mentioned article. The reactive functional groups tend to hydrolyse in the dye bath, and reactive dyes containing several reactive groups have been used to provide higher fixation efficiency. GB-A-878655 describes a process in which a synthetic resin is incorporated in a regenerated cellulose fibre. Never-dried conventional viscose rayon fibre has a water imbibition of 120-150% and is squeezed to reduce the water imbibition to 100%. (Water imbibition is defined as the weight of water retained per unit weight of bone-dry fibre.) The squeezed fibre is then treated with a crosslinking agent, for example a formaldehyde resin precondensate, squeezed again to reduce the water imbibition to 100%, dried, and heated to cure the resin. The cured resin crosslinks the fibre, and the treated fibre has improved processability into yarn and cloth. GB-A-950073 describes a similar process. Such processes do, however, embrittle the fibre and reduce extensibility. FR-A-2273091 describes a method of manufacturing polynosic viscose rayon fibre with reduced fibrillation tendency. The fibre is treated in the primary gel state characteristic of polynosic viscose rayon manufacture with a crosslinking agent containing at least two acrylamido groups and an alkaline catalyst. This primary polynosic gel is a highly swollen gel having a water imbibition of 190-200%, which is only found in polynosic viscose rayon that has never been dried. EP-A-118983 describes a method of treating natural textile fibres, for example wool and cotton, and synthetic polyamide fibres to enhance their affinity for disperse or anionic dyestuffs. The fibres are treated with an aqueous solution or dispersion of an arylating agent. The arylating agent contains both a hydrophobic benzene or naphthalene ring and a reactive group such as a halotriazine group. EP-A-174794 describes a method of treating natural textile fibres, for example wool and cotton, and synthetic polyamide fibres with an arylating agent. This treatment provides cellulose fibres and fabrics with improved dye affinity and crease recovery. The arylating agent preferably contains at least one functional group which is a vinyl sulphone or a precursor thereof. GB-A-950,073 discloses a process in which regenerated cellulose fibre in the gel state (i.e., never-dried fibre) prepared by the viscose process is treated with a permanently soluble cross-linking agent of known type and of molecular weight not greater than 1000 and then pressed to reduce the liquid content of the treated fibre to a figure below the normal water imbibition of the fibre in the gel state. After curing, the treated fibres are said to exhibit good processability without fibre breakage, good handle, even dyeability and improved tensile properties in comparison with fibres treated by other impregnation processes. A paper entitled "Precipitation and crystallisation of Cellulose from Amine Oxide Solutions" by M Dubé & R H Blackwell in Proceedings of the Technical Association of the Pulp and Paper Industry, 1983 Dissolving and Specialty Pulps Conference, TAPPI Press (1983), pages 111-119, discloses cellulose fibres prepared by solvent-spinning a solution of cellulose in a tertiary amine oxide such as N-methylmorpholine N-oxide. The fibres can be treated with a textile resin of the glyoxal resin type. The resin acts as a cross-link between fibrillar elements in the fibres; and because the resin is cured when the sample is dried, the fibrils are cross-linked in the compacted state. Upon rewetting, swelling is restricted and no regular fibril separation takes place. This accords with the teaching of the article entitled "Textile Resins" discussed hereinabove, that resin-finishing reduces the accessibility of cellulose fibres to dyestuffs. The present invention addresses the need for a process which not only reduces the fibrillation tendency of solvent-spun cellulose fibres, but also produces no significant reduction in tenacity and extensibility and has no significant deleterious effect on processability. Maintaining a balance between all of the required properties of the solvent-spun fibre is extremely difficult because it is not sufficient to produce a fibre which will not fibrillate but which has a very low tenacity or a very low extensibility or a very poor processability. In some cases it would also be unsatisfactory to produce a fibre which would be unsuitable for subsequent dyeing. A process according to the present invention for treating a solvent-spun cellulose fibre to reduce its fibrillation tendency is characterised in that a substantially colourless chemical reagent having two to six functional groups reactive with cellulose is applied from an aqueous system to solvent-spun cellulose fibre which has previously been dried and is caused to react therein under alkaline conditions. When the chemical reagents are used in the absence of dyes, the untreated and treated fibre are of substantially the same colour, that is to say the treatment does not substantially affect the colour of the fibre. Fibrillation of cellulose fibres as herein described is believed to be due to mechanical abrasion of the fibres whilst being processed in a wet and swollen form. Solvent-spun fibres appear to be particularly sensitive to such abrasion and are consequently more susceptible to fibrillation than other types of cellulose fibres. Higher temperatures and longer times of wet processing tend to lead to greater degrees of fibrillation. Wet treatment processes such as dyeing processes inevitably subject fibres to mechanical abrasion. Reactive dyes generally demand the use of more severe dyeing conditions than other types of dyes, for example direct dyes, and therefore subject the fibres to correspondingly more severe mechanical abrasion. The chemical reagents utilised in the present invention differ from reactive dyes in that they do not contain a chromophore, and so are substantially colourless. Treatment with such reagents in the absence of dyes therefore does not substantially alter the colour of the solvent-spun cellulose fibre. Accordingly, the treated fibre is suitable for dyeing in any manner known for cellulose fibres, yarns or fabrics. The functional groups reactive with cellulose may be any of those known in the art. Numerous examples of such groups are given in the above-mentioned article entitled "Dyes, Reactive". Preferred examples of such functional groups are reactive halogen atoms attached to a polyazine ring, for example fluorine, chlorine or bromine atoms attached to a pyridazine, pyrimidine or sym-triazine ring. Other examples of such functional groups include vinyl sulphones and precursors thereof. Each functional group in the reagent may be the same or different. The chemical reagent preferably contains at least one ring with at least two, in particular two or three, reactive functional groups attached thereto. Examples of such rings are the polyhalogenated polyazine rings hereinbefore mentioned. Such reagents have been found to be more effective at reducing the fibrillation tendency than reagents in which the functional groups are more widely separated, for example reagents in which two monohalogenated rings are linked together by an aliphatic chain. One preferred type of reagent contains one ring having two reactive functional groups attached thereto. Other types of reagent, which may also be preferred, contain two or three rings linked by aliphatic groups and having two reactive functional groups attached to each ring. Preferred types of reagent include reagents containing a dichlorotriazinyl, trichloropyrimidinyl, chlorodifluoropyrimidinyl, dichloropyrimidinyl, dichloropyridazinyl, dichloropyridazinonyl, dichloroquinoxalinyl or dichlorophthalazinyl group. Other preferred types of reagent include reagents having at least two vinyl sulphone, beta-sulphatoethyl sulphone or beta-chloroethyl sulphone groups attached to a polyazine ring. The chemical reagent is applied to the fibre in an aqueous system, more preferably in the form of an aqueous solution. The chemical reagent may contain one or more solubilising groups to enhance its solubility in water. A solubilising group may be an ionic species, for example a sulphonic acid group, or a nonionic species, for example an oligomeric poly(ethylene glycol) or poly(propylene glycol) chain. Nonionic species generally have less effect on the essential dyeing characteristics of the cellulose fibre than ionic species and may be preferred for this reason. The solubilising group may be attached to the chemical reagent by a labile bond, for example a bond which is susceptible to hydrolysis after the chemical reagent has reacted with the cellulose fibre. The known processes for the manufacture of solvent-spun cellulose fibres include the steps of: (i) dissolving cellulose in a solvent to form a solution, the solvent being miscible with water; (ii) extruding the solution through a die to form a fibre precursor; (iii) passing the fibre precursor through at least one water bath to remove the solvent and form the fibre; and (iv) drying the fibre. The wet fibre at the end of step (iii) is never-dried fibre, and typically has a water imbibition in the range 120-150%. The dried fibre after step (iv) typically has a water imbibition of around 60-80%. In the present invention, the fibre is treated with the chemical reagent after it has been dried, that is to say after step (iv). The fibre may be in the form of staple fibre or tow, depending on the configuration of the equipment. The method of treatment of the invention may be carried out using conventional techniques for reactive dyestuffs, in which the chemical reagent is used in the same or similar manner as a reactive dyestuff. The method may be carried out on tow or staple fibre, yarn or fabric. The method of treatment may be carried out on dried fibre after or more preferably before or simultaneously with dyeing. If the treatment is performed before or after dyeing, the fibre is preferably not dried between the treatment and dyeing processes. The method of treatment may be carried out using a dye bath which contains both a monofunctional reactive dyestuff and the substantially colourless chemical reagent. The method of treatment may be carried out using a bath containing more than one type of chemical reagent, for example one or more dyestuffs and one or more substantially colourless reagents. The functional groups in any such dyestuffs and reagents may be the same or different chemical species. The functional groups reactive with cellulose in reactive dyes as well as in the chemical reagents used in the present invention may react most rapidly with cellulose under alkaline conditions. Examples of such functional groups are the halogenated polyazine rings hereinbefore mentioned. Such chemical reagents may therefore be applied from weakly alkaline solution, for example from a solution made alkaline by the addition of sodium carbonate (soda ash), sodium bicarbonate or sodium hydroxide. Alternatively, the fibre may be made alkaline by treatment with mild aqueous alkali in a first stage before treatment in a second stage with the solution of the chemical reagent. The first stage of this two-stage technique is known in the dyeing trade as presharpening. It has the advantage that hydrolysis of the functional groups in the solution of the reagent is reduced, since hydrolysis of such groups is more rapid under alkaline conditions. The solution of the chemical reagent used in the second stage of the two-stage technique may or may not contain added alkali. If the two-stage technique is used then preferably substantially all the alkali is applied in the first stage. Fibre treated in this manner has generally and surprisingly been found to have a lower fibrillation tendency than in the case when alkali is applied in both of the stages. It has surprisingly also been found that the fibrillation tendency of the treated fibre may be less after a two-stage treatment in which substantially all the alkali is added in the first stage than after a single stage treatment, although the reason for this is not known. This two-stage technique is accordingly a preferred method of putting the invention into practice. The functional groups of the chemical reagent may react with cellulose at room temperature, but it is generally preferable to apply heat to induce a substantial degree of reaction. For example, the reagent may be applied using a hot solution, or the fibre wetted with the reagent may be heated or steamed, or the wetted fibre may be heated to dry it. Preferably, the wetted fibre is steamed because this method of heating has generally been found to yield fibre with the lowest fibrillation tendency. Low-pressure steam is preferably used, for example at a temperature of 100 to 110°C, and the steaming time is typically 4 seconds to 20 minutes, more narrowly 5 to 60 seconds or 10 to 30 seconds. In chemical reagents carrying more than one of a particular type of functional group, it is often found that the functional groups have different reactivities. This is true for example for the polyhalogenated polyazines hereinbefore mentioned. The first halogen atom reacts more rapidly with cellulose than a second or subsequent halogen atom. The method of the invention may be carried out under conditions such that only one such functional group reacts during the treatment stage, and the remaining functional group or groups is or are caused to react subsequently, for example by the application of heat during steaming or drying or by the application of alkali during subsequent fabric wet processing. The fibre may be rinsed with a mildly acidic aqueous solution, for example a weak solution of acetic acid, after reaction of the chemical reagent with the cellulose in order to neutralise any added alkali. The fibre may be treated with 0.1 to 10%, preferably 0.2 to 5%, further preferably 0.2 to 2%, by weight of the chemical reagent, although some of the reagent may be hydrolysed and so not react with the fibre. In the preferred form of the invention the chemical reagent may be reacted with the cellulose fibre so that less than 20%, and preferably less than 10% and further preferably 5% or less, of the dye sites on the cellulose fibre are occupied, so as to permit subsequent colouration of the fibre with coloured dyes which may or may not be reactive dyes. Cellulose fibres, particularly in the form of fabrics made from such fibres, may be treated with a cellulase enzyme to remove surface fibrils. The cellulase enzyme may be in the form of an aqueous solution, and the concentration may be in the range 0.5% to 5%, preferably 0.5% to 3%, by weight. The pH of the solution may be in the range 4 to 6. There may be a nonionic detergent in the solution. The fabric may be treated at a temperature in the range 20°C to 70°C, preferably 40°C to 65°C, further preferably 50°C to 60°C, for a period in the range 15 minutes to 4 hours. This cellulase treatment may be utilised to remove fibrils from solvent-spun fibres, yarns and fabrics which have been treated with a chemical reagent according to the method of the invention. Solvent-spun cellulose fibre is commercially available from Courtaulds Fibres Limited. The invention is illustrated by the following Examples. Fibre was assessed for degree of fibrillation using the method described below as Test Method 1 and assessed for fibrillation tendency using the techniques described below as Test Methods 2-4. Test Method 1 (Assessment of Fibrillation) There is no universally accepted standard for assessment of fibrillation, and the following method was used to assess Fibrillation Index. A series of samples of fibre having nil and increasing amounts of fibrillation was identified. A standard length of fibre from each sample was then measured and the number of fibrils (fine hairy spurs extending from the main body of the fibre) along the standard length was counted. The length of each fibril was measured, and an arbitrary number, being the product of the number of fibrils multiplied by the average length of each fibril, was determined for each fibre. The fibre exhibiting the highest value of this product was identified as being the most fibrillated fibre and was assigned an arbitrary Fibrillation Index of 10. The wholly unfibrillated fibre was assigned a Fibrillation Index of zero, and the remaining fibres were evenly ranged from 0 to 10 based on the microscopically measured arbitrary numbers. The measured fibres were then used to form a standard graded scale. To determine the Fibrillation Index for any other sample of fibre, five or ten fibres were visually compared under the microscope with the standard graded fibres. The visually determined numbers for each fibre were then averaged to give a Fibrillation Index for the sample under test. It will be appreciated that visual determination and averaging is many times quicker than measurement, and it has been found that skilled fibre technologists are consistent in their rating of fibres. Test Method 2 (Scour, Bleach, Dye) (i) Scour 1 g fibre was placed in a stainless steel cylinder approximately 25 cm long by 4 cm diameter and having a capacity of approximately 250 ml. 50 ml of a conventional scouring solution containing 2 g/l Detergyl (an anionic detergent) (Detergyl is a Trade Mark of ICI plc) and 2 g/l sodium carbonate was added, a screw cap fitted, and the capped cylinder tumbled end-over-end at 60 tumbles per minute for 60 minutes at 95°C. The scoured fibre was then rinsed with hot and cold water. (ii) Bleach 50 ml of a bleaching solution containing 15 ml/l 35% hydrogen peroxide, 1 g/l sodium hydroxide, 2 g/l Prestogen PC as a peroxide stabiliser (Prestogen is a Trade Mark of BASF AG) and 0.5 ml/l Irgalon PA as a sequestrant (Irgalon is a Trade Mark of Ciba Geigy AG) was added to the fibre and a screw cap fitted to the cylinder. The cylinder was then tumbled as before for 90 minutes at 95°C. The bleached fibre was then rinsed with hot and cold water. (iii) Dye 50 ml of a dyeing solution containing 8%, on weight of fibre, Procion Navy HER 150 (Procion is a Trade Mark of ICI plc) and 55 g/l Glauber's salt was added, the cylinder capped, and tumbled as before for 10 minutes at 40°C. The temperature was raised to 80°C and sufficient sodium carbonate added to give a concentration of 20 g/l. The cylinder was then capped once more and tumbled for 60 minutes. The fibre was rinsed with water. 50 ml of a solution containing 2 ml/l Sandopur SR (an anionic detergent) (Sandopur is a Trade Mark of Sandoz Ltd) was then added and the cylinder capped. The cylinder was then tumbled as before for 20 minutes at 100°C. The dyed fibre was then rinsed and dried. It was then assessed for fibrillation using Test Method 1. Test Method 3 (Ball Bearing) 1 g fibre was placed in a 200 ml metal dye pot together with 100 ml of a solution containing 0.8 g/l Procion Navy HER 150 (Procion is a Trade Mark of ICI plc), 55 g/l Glauber's salt and a 2.5 cm diameter ball bearing. The purpose of the ball bearing was to increase the abrasion imparted to the fibre. The pot was then capped and tumbled end-over-end at 60 tumbles per minute for 10 minutes at 40°C. The temperature was raised to 80°C and sufficient sodium carbonate added to give a concentration of 20 g/l. The pot was then capped once more and tumbled for 3 hours. The ball bearing was then removed and the fibre rinsed with water. 50 ml of a solution containing 2 ml/l Sandopur SR (an anionic detergent) (Sandopur is a Trade Mark of Sandoz Ltd) was then added and the cylinder capped. The cylinder was then tumbled as before for 20 minutes at 100°C. The dyed fibre was then rinsed and dried. It was then assessed for fibrillation using Test Method 1. Test Method 3 provides more severe fibrillating conditions than Test Method 2. Test Method 4 (Blender) 0.5 g fibre cut into 5-6 mm lengths and dispersed in 500 ml water at ambient temperature was placed in a household blender (liquidiser) and the blender run for 2 minutes at about 12000 rpm. The fibre was then collected, dried and assessed for fibrillation using Test Method 1. Test Method 4 provides more severe fibrillating conditions than either Test Method 2 or Test Method 3. The following Examples illustrate the preferred form of the invention. Example 1 Sandospace R (Sandospace is a Trade Mark) is a colourless chlorotriazine compound available from Sandoz AG in the form of a paste and used to provide dye-resist effects on natural and synthetic polyamide fibres. A solution was made up containing 50 g/l Sandospace R paste, 20 g/l sodium carbonate, 25 g/l Glauber's salt and 10 g/l Matexil PAL (a mild oxidising agent-nitrobenzene sulphonic acid-used as a textile auxiliary to prevent dye reduction) (Matexil is a Trade Mark of ICI plc). A hank of dried solvent-spun cellulose fibre weighing 50 g was immersed in the solution, removed and squeezed to remove excess treatment liquor. The wetted hank weighed 90 g, corresponding to a liquor uptake of 80%. The wetted hank was placed in a steamer at 102°C for 8 minutes, after which it was neutralised by washing with cold 0.1% by volume aqueous acetic acid and dried. The treated fibre exhibited a Fibrillation Index of 0.6 as measured by Test Method 2. Example 2 Previously-dried solvent-spun cellulose fibre was padded with solutions containing Sandospace R and other components, steamed at 102°C, rinsed with 0.1% by volume aqueous acetic acid and dried. The treated fibre was assessed for fibrillation tendency by Test Methods 2-4. Experimental conditions and results are shown in Table 1, in which Matexil is Matexil PAL: Ref. Sandospace R g/l Other Components Fibrillation Index Scour-bleach-dye Ball bearing Blender 2A 50 Na 2 CO 3 20 g/l; Matexil 10 g/l 0.0 0.94 3.0 2B 50 Na 2 CO 3 20 g/l 0.0 2.6 3.2 2C 50 Na 3 PO 4 10 g/l; Matexil 10 g/l 0.0 1.38 2.4 2D 50 Na 3 PO 4 10 g/l 0.7 1.8 2.3 2E 50 NaHCO 3 5 g/l; Matexil 10 g/l 0.1 0.6 2.2 2F 50 NaHCO 3 5 g/l 0.0 0.6 3.8 2G 50 Na 2 CO 3 20 g/l; Na 2 SO 4 25 g/l; Matexil 10 g/l 0.6 0.1 2.1 2H 50 Na 2 CO 3 20 g/l; Na 2 SO 4 25 g/l 0.2 1.2 0.6 2I 80 Na 2 CO 3 20 g/l; Matexil 10 g/l 0.0 1.34 3.2 2J 80 Na 3 PO 4 10 g/l; Matexil 10 g/l 0.0 0.6 3.9 2K 80 Na 2 CO 3 5 g/l; Matexil 10 g/l 0.0 0.2 3.3 2L 80 Na 2 CO 3 20 g/l; Na 2 SO 4 25 g/l 0.3 2.8 2.8 The following Examples illustrate the production of a chemical reagent for use in the invention. Example 3 Cyanuric chloride was reacted with an equimolar quantity of poly(ethylene glycol) monomethyl ether having molecular weight 550 to prepare a colourless chemical reagent having two functional groups reactive with cellulose. Example 4 Poly(ethylene glycol) monomethyl ether (molecular weight 2000) (100 g, 0.05 mol) was dissolved in tetrahydrofuran (400 ml). Cyanuric chloride (0.05 mol) and tertiary amine (0.05 mol) (pyridine or triethylamine) were added to the solution which was maintained at 30°C for 2 hours. Amine hydrochloride was removed by filtration and solvent removed by evaporation to yield a chemical reagent which was denoted SCIII. This is believed to have the chemical constitution: (where n corresponds to the degree of polymerisation of the poly(ethylene glycol) monomethyl ether starting material), and therefore to have two functional groups reactive with cellulose. The reagent was soluble in water due to the presence of the poly(ethylene glycol) chain. Example 5 Cyanuric chloride was reacted with various substances to give chemical reagents having four functional groups reactive with cellulose. The reference codes of the chemical reagents and the names of the substances reacted with cyanuric chloride are listed below: SCV Jeffamine ED2001 (Texaco Inc.) - H 2 N(C 2 H 5 O) n NH 2 SCVI Poly(ethylene glycol), mol. wt. 5000 SCVII Poly(ethylene glycol), mol. wt. 2000 The reactions were carried out according to the general procedure of Example 4, except that 2 moles of cyanuric chloride and 2 moles of tertiary amine were reacted with each mole of substance. The preparation of SCV was carried out at 0°C. These reagents are believed to have the chemical constitution: where x represents NH or O and Q represents (C 2 H 4 O) n C 2 H 4 , n being an integer representative of the degree of polymerisation of the starting substance. These reagents each therefore contained two sym-triazine rings connected by an aliphatic chain, each of the rings carrying two functional groups reactive with cellulose. Each reagent contained a poly(ethylene glycol) chain and was soluble in water. Example 6 Cyanuric chloride was reacted with an equimolar quantity of N-methyltaurine to give a chemical reagent containing two functional groups reactive with cellulose and an ionic solubilising group, namely 2-dichlorotriazinylamino-2-methylethanesulphonic acid. To further improve the appearance and handle of a fabric treated according to the invention, it may be treated with cellulase enzymes, as illustrated below. The cellulase enzyme treatment may also be carried out on undyed solvent-spun fibre material treated according to the invention. Cellulase enzymes work by cleaving the beta-1,4-glycoside bond in the cellulose converting it to soluble glucose. As a result of this hydrolytic effect, the fabric becomes smooth due to loss of the surface fibre and the handle becomes softer. This hydrolytic effect will also result in a negative effect on fabric strength. On solvent-spun cellulose fabrics, cellulase enzymes have been found to be extremely effective at removing fibrillation that has occurred during the dyeing process. A number of cellulase enzymes were tested on a badly fibrillated solvent-spun cellulose woven fabric. The effectiveness of each enzyme was numerically assessed by carrying out a colour difference measurement before and after treatment. The higher the total colour difference (DE) the more effective the treatment due to removal of the apparently white surface fibrils. The system is most applicable on a batchwise system as the mechanical agitation of a winch or jet machine is beneficial at removing loose fibres. Standard process: x% by weight cellulase 0.75 g/l Rucogen SAS (nonionic detergent) pH set as required 60 mins 55-60°C Enzyme pH Max Conc DE Manufacturer Cytolase 123 4.8 1.5% 1.4 Genencor Rucolase CEL 4.8 1.0% 1.3 Rudolf Celluclast 4.8 1.0% 1.0 Novo All the above enzymes are-acid activated. The maximum concentrations quoted are maximum percentages by weight of enzyme that have been found to be able to be used without resulting in a strength loss of greater than 10%. Strength losses of up to 30% can occur with high enzyme concentration and extended treatment times, but this may make the fabric unacceptably weak for many applications. Two neutral activated systems were also evaluated. These have the advantage that strength losses are very low (less than 5%) even at high concentrations of cellulase enzymes but the effectiveness at removing fibrillation is reduced. Enzyme Conc(wt) DE Manufacturer Deltazyme 3% 0.9 Rexodan Denimax 3% 0.85 Novo The following characteristics of the process have been determined by these trials:- i) Acid-activated enzymes display much higher activity than their neutral counterparts. ii) Concentrations and times should be carefully controlled to prevent excessive strength losses. iii) Every fabric will be affected to a lesser or greater degree; preliminary trials should be carried out to define the degree of fibre loss that will yield a smoother, softer product and still maintain adequate strength. iv) Inclusion of a nonionic detergent assists action. Enzyme treatment is preferably carried out as a discrete step, which makes the control of pH, time and temperature easier to achieve.

Claims: A process for treating a solvent-spun cellulose fibre to reduce its fibrillation tendency, characterised in that a substantially colourless chemical reagent having two to six functional groups reactive with cellulose is applied from an aqueous system to solvent-spun cellulose fibre which has previously been dried and is caused to react therewith under alkaline conditions. A process according to claim 1, further characterised in that the chemical reagent contains at least one ring having at least two functional groups reactive with cellulose attached thereto. A process according to claim 2, further characterised in that the chemical reagent contains one ring having two or three functional groups reactive with cellulose attached thereto. A process according to either of claims 2 and 3, further characterised in that the or each ring is a polyazine ring. A process according to claim 4, further characterised in that the or each ring is selected from pyridazine, pyrimidine and sym-triazine rings. A process according to either of claims 4 and 5, further characterised in that at least one of the functional groups reactive with cellulose is a fluorine, chlorine or bromine atom attached directly to the ring. A process according to claim 6, further characterised in that the chemical reagent contains a dichlorotriazinyl, tri- chloropyrimidinyl, chlorodifluoropyrimidinyl, dichloropyrimidinyl, dichloropyridazinyl, dichloropyridazinonyl, dichloroquinoxalinyl or dichlorophthalazinyl group. A process according to any of claims 2 to 5, further characterised in that at least one of the functional groups reactive with cellulose is a vinyl sulphone group or precursor thereof. A process according to any preceding claim, further characterised in that the chemical reagent contains a solubilising group to enhance its solubility in water. A process according to claim 9, further characterised in that the solubilising group is a sulphonic acid group or an oligomeric poly(ethylene glycol) or poly(propylene glycol) chain. A process according to any preceding claim, further characterised in that from 0.1 to 10% by weight of the chemical reagent is applied to the fibre. A process according to claim 11, further characterised in that from 0.2 to 5% by weight of the chemical reagent is applied to the fibre. A process according to claim 12, further characterised in that from 0.2 to 2% by weight of the chemical reagent is applied to the fibre. A process according to any preceding claim, further characterised in that the chemical reagent is applied to the fibre in the form of an aqueous solution. A process according to claim 14, further characterised in that the aqueous solution of the chemical reagent is applied to the fibre under mildly alkaline conditions. A process according to claim 14, further characterised in that a mildly alkaline aqueous solution is applied to the fibre before treatment with the solution of the chemical reagent. A process according to claim 16, further characterised in that the solution of the chemical reagent contains no added alkali. A process according to any of claims 14 to 17, further characterised in that the fibre to which the chemical reagent has been applied is heated to induce a substantial degree of reaction between the cellulose and the functional groups reactive with cellulose. A process according to claim 18, further characterised in that the fibre is heated using steam. A process according to claim 19, further characterised in that the fibre is heated using steam at a temperature of 100 to 110°C for 4 seconds to 20 minutes. A process according to any of claims 14 to 20, further characterised in that the aqueous solution of the chemical reagent is applied to the fibre simultaneously with a conventional dyestuff for cellulose. A process according to any of claims 14 to 20, further characterised in that the solution of the chemical reagent is applied to the fibre, and the fibre without having been dried is then dyed with a conventional dyestuff for cellulose. A process according to any of claims 1 to 20, further characterised in that the untreated and treated fibre are of substantially the same colour. A process according to any preceding claim, further characterised in that the treated fibre is subsequently treated with an aqueous solution of a cellulase enzyme.

Inventors: TAYLOR JAMES MARTIN, TAYLOR, JAMES MARTIN
Applicants: COURTAULDS PLC
Application year: 1992
Main classification: D01F11
IPC codes: D06M13, D06M16, D06M101, D06P1, D01F11, D06P3, C08B15, D06L3, D01F2, D06M11, D06P5