EP3807459A1

EP3807459A1 - Method for the conditioning of textiles and conditioned textiles produced thereby

Info

Publication number: EP3807459A1
Application number: EP19731776.1A
Authority: EP
Inventors: Marieta TZELILI; Richard Gar Chang YU; Aidan Lavery
Original assignee: Xeros Ltd
Current assignee: Xeros Ltd
Priority date: 2018-06-12
Filing date: 2019-06-07
Publication date: 2021-04-21
Also published as: CN112368442B; WO2019239110A1; CN112368442A; GB201809610D0; MX2020013605A

Abstract

A method for conditioning a textile comprising agitating the textile with a plurality of non-porous solid thermoplastic particles with a size in the range of from 0.1mm to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface.

Description

METHOD FOR THE CONDITIONING OF TEXTILES AND CONDITIONED TEXTILES

PRODUCED THEREBY

Field of the Invention

[0001] The present invention is concerned with a method for the conditioning of textiles and to textiles produced by this method. The method is particularly suited to desizing textiles and giving new textiles a faded appearance.

Background to the Invention

[0002] Many traditional methods of conditioning textiles, such as denim stone washing, require the use of pumice stones or abrasive particles, in conjunction with one or more enzymes, to modify the surface of the textile. Though these methods offer reasonably conditioned textiles, they do suffer from drawbacks. Examples of such drawbacks include that: the current techniques are expensive; the current techniques can lead to damage of the textile; the current techniques are wasteful, because the enzymes used in the process are seldom recoverable; and the current techniques have an adverse environmental impact since they generate large volumes of waste water and require higher temperatures to be effective. There is also a need for improving the degree to which the current techniques reduce the colour intensity of the textile.

[0003] Several attempts have been made to overcome the problems listed above, for example, Japanese patent publication JP-H-04-241165 used abrasive rubber balls containing MgO as an abrasive agent in place of pumice. The rubber balls exert a rubbing or abrasive action on the denim. PCT patent application W02009153345 describes the use of rough porous granules for the abrasion of denim, wherein the granules were made porous by the inclusion of a foaming agent prior to extrusion. The porosity and abrasiveness of the granules were reported as pivotal to the effectiveness of the process disclosed in W02009153345.

[0004] In the present invention the applicant has found that, by using non-porous solid thermoplastic particles of a defined shape, it is possible to overcome the problems mentioned above. The applicant has also found that these particles are of benefit not just in denim stone washing but in a number of textile conditioning applications where they are able to enhance the effectiveness, recoverability and reuse of the conditioning enzyme.

Brief Description of the Drawings

[0005] Figure 1 shows a scanning electron microscope image of the surface of a non-porous solid thermoplastic particle comprising polypropylene (38wt%) and barium sulfate filler (62wt%) having a density of 1.63 g/cm³ and size of 7mm prepared by hot melt extrusion. [0006] Figure 2 shows a scanning electron microscope image of the surface of a porous solid polypropylene particle, Accurel™ MP100 from 3M.

[0007] Figure 3 shows a scanning electron microscope image of the surface of a second porous solid polypropylene particle, Accurel™ XP100-84 from 3M.

[0008] Figure 4 shows a scanning electron microscope image of the surface of a sample of pumice stone.

[0009] Figure 5 shows a comparison of the surfaces of the particles from Figures 1 to 4 opposite a qualitative roughness scale.

[0010] Figure 6 shows optical micrographs to demonstrate the curvilinear shape of the 4mm and 7mm non-porous solid thermoplastic particles.

Summary of the Invention

[0011] According to a first aspect of the present invention there is provided a method for conditioning a textile comprising agitating the textile with a plurality of non-porous solid thermoplastic particles with a size in the range of from 0.1 mm to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface.

[0012] Preferably, the method is not and does not comprise cleaning. Preferably, the method is not and does not comprise laundering. Accordingly, it is preferred that conditioning preferably does not include cleaning and/or laundering.

[0013] Preferably, prior to conditioning in the method of the present invention the textile is clean. By clean it is meant that the textile is free or substantially free from dirt, sweat and stains. Preferably, prior to the method according to the first aspect of the present invention the textile has been cleaned. Clean may also refer to the textile during the manufacturing process or having been manufactured but prior to use or wear by the intended user of the textile.

[0014] In the present application the term conditioning preferably means an enzyme-mediated change to the textile properties, in particular to the surface properties, of the textile. This can encompass a number of conditioning methods according to the first aspect of the present invention such as:

i. Desizing, preferably using an amylase to remove starch size;

Preferably, conditioning is or comprises desizing and the enzyme is or comprises an amylase.

ii. Bioscouring, preferably where pectate lyase and/or polygalacturonase are used to remove pectin impurities from cotton; Preferably, the conditioning is or comprises bioscouring and the enzyme is or comprises a pectate lyase and/or polygalacturonase.

iii. Fabric biofinishing, preferably where cellulase is used, more preferably prior to dyeing, to reduce pilling and create a higher quality surface by removing the fibrils that make the textile surface rough;

Preferably, the conditioning is or comprises biofinishing and the enzyme is or comprises a cellulase.

and more preferably;

iv. Fading, preferably using an enzyme to give the textile an aged or less colourful appearance such as cotton (preferably denim) finishing where the enzyme is preferably a cellulase, a laccase, a peroxidase, a polygalacturonase, a pectin lyase, or a catalase or a mixture thereof.

Preferably, the conditioning comprises fading and the enzyme is or comprises a cellulase, a laccase, a peroxidase, a polygalacturonase, a pectin lyase, or a catalase or a mixture thereof.

[0015] Preferably, the textile is or comprises a natural, synthetic or semi-synthetic fibre, or a mixture thereof.

[0016] Preferably, the textile is or comprises a cellulosic material, polyester, or a mixture thereof, silk, wool or chiffon.

[0017] Preferably, the textile is or comprises a cellulosic material which is more preferably a cellulosic fibre. Examples of suitable cellulosic materials include hemp, linen, flax, jute, ramie, sisal and especially cotton.

[0018] It is especially preferred that the textile is or comprises cotton and more preferably denim.

[0019] Depending on which conditioning method will be used the textile may be either coloured or uncoloured. If the textile is coloured then it may be coloured with a pigment or a dye or a combination thereof. Preferably the textile is coloured by a dye. When the textile is coloured by a dye (i.e. dyed) it may be dyed by any of the dyes known to be suitable in the art. If the textile is dyed it is preferred that the dye is an indigoid or sulfur dye, more preferably if the textile is dyed then it is dyed with indigo. The indigo used to dye the textile may be either natural or synthetic. Preferably the textile can a shade which is blue, purple or black.

[0020] In order of increasing preference the textile is preferably agitated in an amount of at least 1 Kg, at least 5Kg, at least 10 Kg, at least 15Kg, at least 20Kg, at least 25Kg or at least 50 Kg. The amount of textile agitated is preferably no more than 10,000Kg and especially no more than 1 ,000Kg. Preferably, these amounts of textile refer to the amount which is loaded into a suitable apparatus for performing the method according to the first aspect of the present invention to form a single conditioning load along with the plurality of non-porous solid thermoplastic particles, the liquid medium and the enzyme.

Non-porous solid thermoplastic particles

[0021] In the method of the present invention the non-porous solid thermoplastic particles preferably are or comprise a polymeric material preferably selected from the group consisting of a poly(haloalkylene), a polyester, a polyamide, a polyalkylene, a polyurethane, a polystyrene, and a copolymer or mixture thereof.

[0022] Preferably, the non-porous solid thermoplastic particles are or comprise a polymeric material preferably selected from the group consisting of a poly(haloalkylene), a polyester, a polyalkylene, a polyurethane, a polystyrene, and a copolymer or mixture thereof.

[0023] Preferably, the non-porous solid thermoplastic particles are or comprise a polyalkylene and/or a poly(haloalkylene) such as a polytetrafluoroethylene (PTFE), and preferably the non- porous solid thermoplastic particles are or comprise a polyalkylene or a poly(haloalkylene) such as a polytetrafluoroethylene (PTFE). More preferably the non-porous solid thermoplastic particles are or comprise a poly C^ alkylene, especially a polypropylene and more especially a high density polypropylene. Non-porous solid thermoplastic particles which are or comprise polyalkylenes are especially reusable, cleanable and can be readily used in multi-step variations of the present invention especially when desizing and/or a second conditioning step are to be performed either in sequence or simultaneously.

[0024] Preferably, the non-porous solid thermoplastic particles comprise at least 20wt%, more preferably at least 30wt% and especially at least 40wt% of said polymeric material.

[0025] Preferably, the non-porous solid thermoplastic particles comprise at least 20wt% of a polyalkylene or a poly(haloalkylene), more preferably at least 30wt% of a polyalkylene or a poly(haloalkylene) and especially at least 40wt% of a polyalkylene or a poly(haloalkylene).

[0026] It is particularly preferred that the non-porous solid thermoplastic particles comprise at least 40wt% polypropylene, especially high density polypropylene.

[0027] Preferably, the non-porous solid thermoplastic particles are hydrophobic. Preferably, the non-porous solid thermoplastic particles are or comprise a polymeric material which is hydrophobic. Preferred polymeric materials which are hydrophobic comprise few or, more preferably, no hydrophilic groups within their structure. Examples of hydrophilic groups which are preferably absent include ionic groups such as carboxylic acid, sulphonic acid, phosphonic acid and boronic acid as well as hydrophilic non-ionic groups such as -OFI, -SH, - NH2, -NH-, - (OCH2CH2)- and the like. Preferably, the polymeric material comprises only carbon and hydrogen atoms. Examples of which include polyalkylenes, especially polypropylene.

[0028] By“hydrophobic”, it is preferably meant that the polymeric material and/or non-porous solid thermoplastic particles have a large contact angle with water.

[0029] In order of increasing preference, the polymeric material and/or non-porous solid thermoplastic particles preferably have a contact angle of at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95 or at least 100° with pure water. Preferably, the solid particles and/or polymeric material have a contact angle of no more than 120, more preferably no more than 115° with pure water. Pure water is preferably distilled water. Preferably, the measurement is recorded at a temperature of 20°C or 25°C. Preferably, the relative humidity for measuring the contact angle is 65% RH. The contact angle is suitably measured as per international standard ISO 15989:2004. The contact angle can also be, and preferably is, measured using a contact angle telescope-goniometer (for instance using equipment available from Rame-Hart), in which the method comprises direct measurement of the tangent angle at the three-phase contact point on a sessile droplet profile. A static contact angle method is preferred. A planar sample of the polymeric material of the solid particle is preferably used for the measurement. The droplet is preferably backlit.

[0030] The polymeric material and/or non-porous solid thermoplastic particles preferably have a contact angle with water in the range of from 50° to 110°, more preferably in the range of from 60° to 105°.

[0031] By non-porous it is preferably meant that the non-porous solid thermoplastic particles have a water absorption less than 3.0wt%, more preferably less than 2.0wt%, even more preferably less than 1.0wt%, especially less than 0.5wt%, more especially less than 0.1wt% and most especially less than 0.05wt%, relative to the weight of the dry non-porous solid thermoplastic particles. The water absorption was measured in accordance with the method, ASTM D570. In this method the particles are dried at 50°C to 60°C in an oven for 24 hours and then placed in a desiccator to cool. Immediately upon cooling the particles are weighed. The particles are then immersed in water for 24 hours, preferably at a temperature of 25°C. After this contact period, any water merely on the outside of the non-porous solid thermoplastic particles is removed, suitably by dabbing the non-porous solid thermoplastic particles on a filter paper. After dabbing, the wet weight (Ww) of the non-porous solid thermoplastic particles is recorded. The dry weight (Wd) of the non-porous solid thermoplastic particles is established, preferably after vacuum drying of the particles. The weight% of water absorption is then given by 100x (Ww - Wd) / Wd.

[0032] Another way to determine the porosity of the non-porous solid thermoplastic particles is to immerse them in a suitable oil, such as a vegetable oil, containing an oil-soluble dye such as Sudan 111. If the particles are porous the dye will enter the pores and remain there after separation from the oil and rinsing in water. The relative degree of porosity can be estimated by an increase in colour or weight of the porous particles relative to the non-porous particles.

[0033] The non-porous solid thermoplastic particles are preferably inert. By“inert” it is preferably meant that the non-porous solid thermoplastic particles have few or no functional groups which are capable of reacting or being oxidized. Thus, preferably the non-porous solid thermoplastic particles preferably have no hydroxy, acid or amine groups.

[0034] In increasing preference, the non-porous solid thermoplastic particles preferably have a size of no more than 40mm, no more than 30mm, no more than 25mm, no more than 20mm, no more than 15mm or no more than 10mm.

[0035] In increasing preference, the non-porous solid thermoplastic particles preferably have a size of at least 0.5mm, at least 1 mm, at least 2mm, at least 3mm or at least 4mm.

[0036] It is especially preferred that the non-porous solid thermoplastic particles have a size in the range of from 1 to 20mm.

[0037] The surface area of a non-porous solid thermoplastic particle is preferably from 10mm² to 400mm², more preferably from 40 to 200mm² and especially from 50 to 190mm².

[0038] The size is preferably a mean average size, more preferably an arithmetic mean average size. The arithmetic mean is preferably taken from at least 100, at least 1000 or at least 10,000 non-porous solid thermoplastic particles.

[0039] The size is preferably the longest linear dimension of the non-porous solid thermoplastic particle. The method of measuring the particle size is preferably performed by using callipers or a particle size measurement using image analysis, especially dynamic image analysis. A preferred apparatus for dynamic image analysis is a Camsizer as provided by Retsch.

[0040] In order of increasing preference, the non-porous solid thermoplastic particles preferably have a density of at least 0.5g/cm³, at least 0.75g/cm³, at least 0.9g/cm³, at least 1.0 g/cm³, at least 1.1 g/cm³, at least 1.2 g/cm³, at least 1.25 g/cm³, at least 1.30 g/cm³, at least 1.35 g/cm³, at least 1.40 g/cm³, at least 1.45 g/cm³, at least 1.50 g/cm³, at least 1.55 g/cm³, at least 1.60 g/cm³, at least 1.65 g/cm³, at least 1.70 g/cm³, at least 1.75 g/cm³, at least 1.80 g/cm³, at least 1.85 g/cm³ or at least 1.90 g/cm³.

[0041] In order of increasing preference, the non-porous solid thermoplastic particles preferably have a density of no more than 10.0 g/cm³, no more than 8.0 g/cm³, no more than 6.0 g/cm³, no more than 4.0 g/cm³, no more than 3.0 g/cm³, no more than 2.5 g/cm³, no more than 2.2 g/cm³ and especially no more than 2.0 g/cm³. [0042] The density of the non-porous solid thermoplastic particles is preferably in the range of from 0.5 to 4.0 g/cm³, more preferably in the range of from 1.0 g/cm³ to 3.0 g/cm³ and especially in the range of from 1.1 to 3.0 g/cm³.

[0043] Especially, where the cleanability of the non-porous solid thermoplastic particles is desired to be particularly easy then lower densities are preferred. Thus, densities of no more than 1.8, 1.6, 1.5 and 1.4 g/cm³ are also of value in the present invention.

[0044] Cleanability, as used herein preferably means the ability to remove from the non-porous solid thermoplastic particles any fragments and components derived from the textile after the non-porous solid thermoplastic particles have been used in the method of the present invention. This is especially desirable where the non-porous solid thermoplastic particles are re-used in one or more subsequent methods according to the first aspect of the present invention.

[0045] Preferably, the non-porous solid thermoplastic particles are more dense than the liquid medium, more preferably more dense than water and especially more dense than water comprising the relevant amounts of any optional additives.

[0046] Preferably, the non-porous solid thermoplastic particles comprise a filler.

[0047] Preferably the non-porous solid thermoplastic particles comprise a polymeric material, as described and preferred above and a filler, which is preferably an inorganic salt. The presence of a filler can have several advantages such as increasing the colour reduction in a denim finishing process and improving the ease of separating and recovering the non-porous solid thermoplastic particles from the textile after agitation.

[0048] Preferably, the non-porous solid thermoplastic particles comprise a polymeric material and a filler in a weight ratio in the range of from 90:10 to 20:80 and more preferably in the range of from 70:30 to 30:70 (polymeric materiakfiller). Where good cleanability is desired, the non- porous solid thermoplastic particles suitably comprise a polymeric material and filler in a weight ratio of no less than 50:50, more preferably no less than 70:30 and especially no less than 90:10 of polymeric materiakfiller.

[0049] The non-porous solid thermoplastic particles can comprise at least 5wt%, at least 10wt%, at least 20wt%, at least 30wt%, at least 35wt%, at least 40wt%, at least 45wt% or at least 50wt% of filler, which is preferably an inorganic filler. Optionally, the non-porous solid thermoplastic particles comprise at least 20wt% filler, particularly where faster and/or more efficient separation of the non-porous solid thermoplastic particles from the textile is desired.

The remainder of the non-porous solid thermoplastic particles required to make 100wt% is preferably said polymeric material.

[0050] The non-porous solid thermoplastic particles can comprise no more than 90wt%, no more than 80wt%, and no more than 70wt% of filler, which is preferably an inorganic filler. The remainder of the non-porous solid thermoplastic particles required to make 100wt% is preferably said polymeric material.

[0051] Preferably the non-porous solid thermoplastic particles comprise a filler in the range of from 20wt% to 80wt%.

[0052] Optionally, the non-porous solid thermoplastic particles can comprise a polymeric component and up to 30wt% of a filler. Optionally, the non-porous solid thermoplastic particles comprise a polymeric component and no filler (and in particular no inorganic filler).

[0053] The non-porous solid thermoplastic particles can have any shape which comprises a curvilinear surface. Preferred particles are ellipsoidal or spherical including any shape therebetween. Other suitable particle shapes include egg shaped, potato shaped, a cylinder with hemispherical ends, discs, and biconcave or monoconcave discs. Preferably at least 60%, at least 70wt%, at least 80wt%, at least 90wt% or at least 95wt% of the surface of the non- porous solid thermoplastic particles is a curvilinear surface. Preferably all of the surface of the non-porous solid thermoplastic particles is curvilinear.

[0054] Preferably, the non-porous solid thermoplastic particles have a shape which is ellipsoidal or spherical as these shapes tend to be gentler to the textile surface and they tend to separate well from the textile after performing the methods described herein. Such particle shapes have also been shown by the present inventors to permit more effective and/or better re-usability of the enzyme utilized in the method of the present invention.

[0055] Preferably, the non-porous solid thermoplastic particles have an aspect ratio of no more than 1.5, more preferably no more than 1.4, especially no more than 1.3 and most especially no more than 1.2. The aspect ratio is the ratio of the longest linear dimension to the shortest linear dimension for each particle. Preferably, the aspect ratio is a mean, especially an arithmetic mean. Preferably the average is of at least 100, more preferably at least 1000 and especially at least 10,000 non-porous solid thermoplastic particles.

[0056] It should be understood that the abrasive particles traditionally used in textile

conditioning have abrasive edges, or vertices. It can be geometrically appreciated that starshaped particles do not comprise a curvilinear surface. Thus, star-shaped particles are not suitable for or intended for use in the first aspect of the present invention. Preferably, the non- porous solid thermoplastic particles are not crown-shaped.

[0057] Preferably the non-porous solid thermoplastic particles have a smooth surface. By smooth it is meant that they have minimal abrasive surface features which could damage the textile. Preferably, the particle surface is substantially free from edges and/or vertices. This is illustrated in Figures 1 to 5 where SEM images show the difference in surface roughness of the non-porous solid thermoplastic particles as compared to the prior art particles. [0058] Preferably the non-porous solid thermoplastic particles do not in any way become permanently attached, affixed, integrated or associated with the textile in the method of the first aspect of the present invention. Thus, the non-porous solid thermoplastic particles may be readily separated from the textile at the end of the method according to the first aspect of the present invention and so are preferably not substantively consumed by the process.

[0059] Preferably, the non-porous solid thermoplastic particles are separated from the textile after agitation.

[0060] It will be appreciated that the non-porous solid thermoplastic particles are of such a size that does not permit them to enter inside the textile structure.

[0061] Preferably the amount of non-porous solid thermoplastic particles used in the method of the first aspect of the present invention is from 1 to 3000kg, preferably from 1 to 2000kg, more preferably from 10kg to 100kg, even more preferably from 10kg to 50kg. Preferably, the weight ratio of the non-porous solid thermoplastic particles to dry textile is in the range of from 10: 1 to 0.1 : 1 and more preferably is in the range of from 5: 1 to 0.5: 1.

[0062] Preferably, the non-porous solid thermoplastic particles are re-usable, especially re usable in further methods according to the first aspect of the present invention. Re-usable non- porous solid thermoplastic particles are not soluble or dissolvable (i.e. they are insoluble) in the liquid medium, more especially in aqueous liquid media and most especially in pure water. Preferably, no more than 0.5% by weight, more preferably no more than 0.2% by weight, and especially no more than 0.1 % of the non-porous solid thermoplastic particles dissolves in water at 25°C over a period of 24 hours when 1 0g of non-porous solid thermoplastic particles are mixed with 99. Og of pure water.

Liquid Medium

[0063] Preferably, the liquid medium is aqueous. To put this another way, the liquid medium preferably is or comprises water. Where water is used in conjunction with other liquids, these other liquids may be organic liquids such as alcohols, esters, ethers, amides and the like.

[0064] In order of increasing preference, the liquid medium comprises at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt% or at least 99wt% of water. Preferably the liquid medium consists of water.

[0065] Preferably, the liquid medium is or comprises softened water, especially water containing less than 100mg of calcium per litre, more preferably less than 50mg of calcium per litre, especially less than 20mg of calcium per litre and most especially less than 10mg of calcium per litre.

[0066] Preferably, the liquid medium is or comprises water which contains less than 100mg of dissolved salts per litre, more preferably less than 50mg of dissolved salts per litre, especially less than 20mg of dissolved salt per litre, more especially less than 10mg of dissolved salt per litre.

[0067] In order of increasing preference, the pH of the liquid medium is at least 1.0, at least 2.0, at least 3.0 or at least 4.0.

[0068] In order of increasing preference, the pH of the liquid medium is no more than 13.0, no more than 12.0, no more than 11.0, no more than 10.0, no more than 9.0, no more than 8.0, no more than 7.0 or no more than 6.5.

[0069] When the conditioning method comprises fading a dyed denim then preferably the pH is in the range of from 3.0 to 11.0, more preferably in the range of from 4.0 to 8.0, especially in the range of from pH 4.0 to 6.5.

[0070] In order of increasing preference, the liquid medium has a temperature of at least 0°C, at least 2°C, at least 5°C, at least 10°C, at least 15°C or at least 20°C.

[0071] In order of increasing preference, the liquid medium has a temperature of no more than 100°C, no more than 90°C, no more than 80°C, no more than 70°C, no more than 60°C, no more than 50°C or no more than 40°C.

[0072] Preferably, the liquid medium has a temperature in the range of from 5 to 70°C and more preferably in the range of from 5°C to 40°C.

[0073] The pH of the liquid medium can be adjusted to suit the chemistry of any additional components.

[0074] The above mentioned preferred pH values and temperatures are those whilst the textile is being agitated with said particles and said enzyme in said liquid medium.

[0075] It will be appreciated that the preferred pH and temperature depends on what conditioning method and enzyme are to be used.

[0076] Preferably, the weight ratio of liquid medium to dry textile is at least 1 : 1 , more preferably at least 2: 1 and especially at least 4: 1. Preferably, the weight ratio of liquid medium to dry textile is no more than 100: 1 , more preferably no more than 70:1 , especially no more than 50:1 , more especially no more than 40:1 , and yet more especially no more than 20: 1. The lower levels of water used in the present invention differentiate the method of the present invention from the prior art.

Enzyme

[0077] The enzyme to be used in the method of the present invention depends on what the desired conditioning step is and the conditions under which the method will be carried out (pH, temperature etc.). Thus, if the conditioning step is or comprises the desizing of a textile then the enzyme is or comprises an amylase. [0078] If the conditioning step is or comprises the fading of a textile, preferably to give it an aged appearance, then the enzyme is or comprises any of the following: a cellulase, a laccase, a polygalacturonase, a pectin lyase, a peroxidase (preferably in the presence of hydrogen peroxide) or a catalase (preferably in the presence of hydrogen peroxide). Of course, the preferred enzyme will match the materials of the textile. Preferably, the textile is or comprises cotton and the enzyme is or comprises a cellulase.

[0079] If the conditioning step is or comprises changing the appearance of textiles such as wool or silk then the enzyme is preferably a protease.

[0080] Optionally, the conditioning method of the present invention may comprise a cleaning step comprising one or more lipase(s) in order to remove oily stains picked up during a textile processing step. Such a cleaning step may be conducted prior to, during or after the

conditioning step. Such a cleaning step is suitably conducted by agitating the textile with said particles and said lipase(s) in said liquid medium.

[0081] Preferably the enzyme is or comprises one or more of; a protease, a cellulase, a laccase, a peroxidase, an amylase, a polygalacturonase, a pectin lyase or a catalase.

[0082] A notable and surprising advantage of the present invention is that the enzyme can be re-used, preferably in further methods for conditioning according to the first aspect of the present invention. Preferably, at least some (preferably at least 10%, more preferably at least 25%, even more preferably at least 50%) of the enzyme is re-used, preferably in at least one further method according to the first aspect of the present invention. A preferred method for re using at least some of the enzyme is to recover at least some of the liquid medium and at least some of the enzyme after the method according to the first aspect of the present invention and then to use this recovered liquid medium/enzyme in a subsequent method according to the first aspect of the present invention.

[0083] A first preferred embodiment of the first aspect of the present invention provides a method which is or comprises fading a dyed textile, preferably dyed cotton, more preferably dyed denim (a process also known as stonewashing). The textile is preferably dyed with an indigoid dye, preferably indigo dye, or sulfur dye. So here the conditioning is in the form of fading the colour of the textile.

[0084] Preferably, the conditioning is or comprises fading a dyed textile and the enzyme is or comprises a cellulase, a laccase, a peroxidase, a polygalacturonase, a pectin lyase, a catalase or a mixture thereof. [0085] Preferably, the conditioning method is or comprises fading, the textile is or comprises cotton and the enzyme is or comprises a cellulase. Preferably, this method is or comprises fading a dyed denim and the enzyme is or comprises a cellulase.

[0086] In the first preferred embodiment the enzyme may be any enzyme able to bring about fading of the textile but preferably the enzyme comprises, and preferably consists of, a cellulase.

[0087] Any suitable cellulase may be used and the choice of enzyme will depend on the nature of the denim and the agitation conditions. Suitable cellulases include cellulase LT, especially cellulase LT 19500 L commercially available from Novozymes, Ecostone® LT from AB

Enzymes, IndiAge® Super L from DuPont, Beizym cellulases from CHT Group, Denimax® CORE S from Novozymes.

[0088] A second preferred embodiment of the first aspect of the present invention provides a method of desizing a textile. So here the conditioning is in the form of desizing. Preferably, the conditioning is or comprises desizing and the enzyme is or comprises an amylase.

[0089] Preferably, the conditioning of the textile is or comprises desizing. In the case of desizing the enzyme is or preferably comprises an amylase.

[0090] Thus, the present invention provides a method which comprises conditioning a textile by desizing with a plurality of non-porous solid thermoplastic particles and amylase.

[0091] Typically, in desizing, the coloured textile initially has starch size on its surface. The desizing step removes the starch size.

[0092] Preferably, desizing is performed at a temperature of at least 0°C, more preferably at least 5°C, even more preferably at least 10°C, especially at least 15°C and most especially at least 20°C.

[0093] Preferably, desizing is performed at a temperature of no more than 60°C, more preferably no more than 50°C and especially no more than 40°C.

[0094] Preferably, desizing is performed at a temperature of from 5 to 60°C, more preferably from 20 to 40°C.

[0095] Preferably, desizing is performed in a liquid medium having a pH of from 4.0 to 8.0, more preferably from 6.0 to 7.0.

[0096] Any suitable commercial enzyme may be used, depending on the agitation conditions and the textile, for example, Beisol T 2090, from CHT Group, include Aquazym® R L from Novozymes, PrimaGreen® ALL from DuPont, or Stainzyme® Plus L from Novozymes. Desizinq and Further Conditioning

[0097] A third preferred embodiment of the first aspect of the present invention provides a method of desizing a textile combined with a further conditioning step of the textile, preferably wherein said further conditioning step is fading a textile.

[0098] Preferably, the method according to the third preferred embodiment of the present invention comprises:

(i) a conditioning which is or comprises desizing and wherein the enzyme is or comprises an amylase; and

(ii) a conditioning which is other than desizing and a second enzyme which is not an amylase; wherein steps (i) and (ii) may be performed simultaneously or in order.

[0099] Preferably, the non-porous solid thermoplastic particles used in step (ii) are the same as the non-porous solid thermoplastic particles of step (i). When steps (i) and (ii) are performed in order then preferably, the non-porous solid thermoplastic particles used in step (ii) are the same non-porous solid thermoplastic particles used in step (i) and optionally recovered therefrom. In other words, it is preferred that the same batch of non-porous solid thermoplastic particles used for step (i) are used in step (ii).

[00100] Surprisingly, it was found that a significant advantage to the method described herein is that the same non-porous solid thermoplastic particles can be used in both steps (i) and (ii) without necessarily cleaning the particles, or if the particles are cleaned then this can be readily effected. This advantage is more pronounced when the non-porous solid thermoplastic particles are inert or hydrophobic, and most especially wherein the non-porous solid

thermoplastic particles are or comprise a polyalkylene. This allows the method to be performed with little or no cleaning of the non-porous solid thermoplastic particles between steps (i) and (ii), which means that the overall method is more efficient, quicker and more economic.

[00101] In step (i) of the third preferred embodiment of the first aspect of the invention the conditions are as preferred for desizing in the second preferred embodiment of the invention.

[00102] Step (ii) of the third preferred embodiment of the first aspect of the invention is preferably a method of fading as in the first preferred embodiment of the present invention.

[00103] It is particularly preferred that step (ii) of the third preferred embodiment is preferably a method which is or comprises fading and preferably wherein the enzyme is or comprises a cellulase.

Re-use of the non-porous solid thermoplastic particles

[00104] The non-porous solid thermoplastic particles are preferably separated from the textile after the method. [00105] Preferably, after separation the non-porous solid thermoplastic particles are re-used, more preferably they are re-used in further methods according to the first aspect of the present invention.

[00106] In order of increasing preference, the non-porous solid thermoplastic particles are re used at least 1 time, at least 3 times, at least 5 times, at least 10 times, at least 50 times, at least 100 times, at least 250 times, at least 500 times, at least 1 ,000 times or at least 2,000 times.

[00107] Accordingly, a preferred method comprises:

a method for conditioning a textile comprising agitating the textile with a plurality of non-porous solid thermoplastic particles with a size in the range of from 0.1 to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface;

separating the non-porous solid thermoplastic particles from the textile;

optionally cleaning the separated particles with a liquid comprising water; and

re-using the separated particles in one or more further methods for conditioning a textile comprising agitating the textile with a plurality of non-porous solid thermoplastic particles with a size in the range of from 0.1 to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface.

Agitating

[00108] Agitation in the method according to the first aspect of the present invention can be performed by stirring, rotating, shaking, vibrating and/or sonicating the textile, non-porous solid thermoplastic particles, liquid medium and enzyme. Agitation is preferably performed by rotating, especially by rotating a treatment chamber in which is contained the coloured textile, the non-porous solid thermoplastic particles, liquid medium and enzyme.

Apparatus

[00109] Preferably, the agitation is performed in a treatment chamber.

[00110] Preferably, the treatment chamber is a cylinder, more preferably a rotatable cylinder.

[00111] Preferably, the agitation is performed by rotating a cylindrical treatment chamber such that the centrifugal G force experienced at the inner walls of the chamber is from 0.05 to 2G, more preferably from 0.05 to 1 G and especially from 0.1 to 0.9G.

[00112] Apparatus suitable for performing the method according to the first aspect of the present invention preferably includes those described in PCT patent publications:

WO2011/098815, WO2014/147389, WO2015/049544, WO2016/193703 and the co-pending application PCT/GB2017/053815. [00113] Preferably, the agitation is performed within an apparatus comprising a treatment chamber (especially a rotatable cylinder) and optionally a particle storage tank or particle storage compartment.

[00114] Preferably, the apparatus for performing the method is capable of automatically separating the non-porous solid thermoplastic particles from the textile after the agitation. This can be achieved by holes in the treatment chamber which are larger than the non-porous solid thermoplastic particles but smaller than the textile or can be achieved by transferring the particles into a storage compartment which is preferably located on an outer wall of the treatment chamber.

[00115] Optionally, agitation is performed by means of an apparatus which comprises one or more nozzles which are configured so as to direct a jet of liquid medium which can impinge upon the textile.

[00116] Optionally, the apparatus may comprise a pump. The pump is preferably configured so as to be able to transfer liquid medium and non-porous solid thermoplastic particles from the particle storage tank to the treatment chamber. Preferably, the pump is activated during at least some, more preferably at least 10% of the time, so that non-porous solid thermoplastic particles and liquid medium are recirculated over the textile.

[00117] In one embodiment the enzyme is premixed with the non-porous solid thermoplastic particles. Premixing is preferably performed in the absence of the textile. Premixing is preferably performed in a liquid medium, preferably the liquid medium of the first aspect of the invention.

Regeneration of the particles

[00118] The particles can be cleaned after each method for conditioning a textile or they may be cleaned less frequently. A surprising advantage of the present invention is that the particles are easily cleaned and/or require less frequent cleaning. Thus, it is preferred that the particles are cleaned less frequently than every 2, more preferably less frequently than every 3 and especially less frequently than every 5 conditioning methods. The particles can be cleaned with (fresh or clean) liquid medium. Optionally, the liquid medium used to clean the particles comprises a surfactant. The particles are preferably cleaned at a temperature of from 5 to 40°C

Textiles resulting from the method

[00119] According to a second aspect of the present invention there is provided a conditioned textile obtained or obtainable by the method according to the first aspect of the present invention. [00120] It was surprisingly found that textiles prepared by the method according to the first aspect of the present invention have, compared to textiles prepared by prior art methods (i.e. methods which do not comprise agitating the textile with a plurality of non-porous solid thermoplastic particles with a size in the range of from 0.1 to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface), good softness and/or a better reduction in colour intensity whilst maintaining the mechanical strength of the textile. It will be appreciated that many denim bleaching processes can obtain good colour reduction but often at the undesirable expense of mechanical properties.

[00121] The invention is further illustrated by reference to the following examples. The examples are not intended to limit the scope of the invention as described above.

[00122] In the present invention any items expressed in the singular are also intended to encompass the plural unless stated to the contrary. Thus, words such as“a” and“an” mean one or more. So by example an enzyme means one or more enzymes and a textile means one or more textiles.

[00123] EXAMPLES

[00124] Materials

[00125] Solid Particles

[00126] Non-porous solid thermoplastic particles comprising polypropylene (PP) (38wt%) and barium sulfate filler (62wt%) having a density of 1.63 g/cm³ and a size of either 4mm or 7mm were prepared by hot melt extrusion.

[00127] Porous solid polypropylene particles 1 were semi-cylinder particles (Accurel™ MP100) obtained from 3M which had a size of 3mm.

[00128] Porous solid polypropylene particles 2 were 3mm porous PP pellets (Accurel™ XP100- 84) from 3M.

[00129] Nuts and magnets - (big nut (M10 M-SR-A4-80), small nut (M6-M-SR-A4-80), big star magnet (diameter 17mm, item no.3-CO-411117, Cowie, Schweiz via Bie & Berntsen) and small star magnets (diameter 14mm, item no.3-CO-411117, Cowie, Schweiz via Bie & Berntsen)).

[00130] Ethylene propylene diene monomer (EPDM) rubber balls containing 20% by weight MgO (EPDM rubber balls obtained from The Precision Plastic Ball Company Ltd, MgO mesh 100 (147 pm) obtained from Fischer Scientific) were made by coating the EPDM rubber balls with white silicon sealant and then rolling in MgO to cover the surface of the balls.

[00131] Denim

[00132] The denim sample used in the Examples was Swissatest (E-277) swatch available from Swissatest Testmaterialien AG. [00133] Enzymes

[00134] (i) Desizing enzyme: Amylase, Beisol™ T 2090, which was obtained from CHT Group.

[00135] (ii) Cellulase: Cellusoft® LT 19500 L which was obtained from Novozymes.

[00136] (iii) Cellulase: Ecostone® LT300 which was obtained from AB Enzymes.

[00137] Other Chemicals

[00138] Marloquest® G82: a polyester copolymer which was obtained from Sasol Limited

[00139] Palonon™ CAF: a non-ionic surfactant which was obtained from CHT Group.

[00140] Lutensol™ AT80: dispersant which was obtained from BASF

[00141] Determination of the porosity - 1 : Oil - Dye method

[00142] Sudan III dye in vegetable oil was used to provide a porosity measurement of the 4mm and 7mm non-porous solid thermoplastic particles via weight and colorimetric analysis. The weight (KERN PCB precision balance) and colour (Konica Minolta CM-3600A spectrometer) of 4.32g of 7mm non-porous solid thermoplastic particles were recorded before they were mixed with 0.0075g Sudan III diluted in 50g vegetable oil in a 125 mL sample pot (straight sample containers, with screw cap obtained from VWR). This was repeated with 4.03g of 4mm non- porous solid thermoplastic particles. The subsequent sample pots were placed on to a sample roller (IKA Roller 10 digital) and incubated for 24 hr at 20°C. After the 24 hr, the non-porous solid thermoplastic particles were removed from their solutions using a strainer and bench-dried for 24 hr. The non-porous solid thermoplastic particles were then rinsed with cold water and left to dry for a further 24 hr. The weight of the non-porous solid thermoplastic particles was recorded before and after the rinsing and drying process and all particles were subsequently measured for any colour change. The porosity of the porous solid polypropylene particles 1 was determined as above except that porous solid polypropylene particles 1 (4g) were used in place of the non-porous solid thermoplastic particles.

[00143] Determination of the porosity - 2: Water absorption method

[00144] The water absorption of the 4mm and 7mm non-porous solid thermoplastic particles was compared to that of the porous solid polypropylene particles 1 and 2 using the ASTM method D570. In this method the specimens were dried at 50°C to 60°C in an oven for 24 hours and then placed in a desiccator to cool. Immediately upon cooling the specimens are weighed. The material was then immersed in water for 24 hours. The samples were then removed, patted dry with a lint free cloth, and weighed. [00145] Porosity Results

[00146] Table 1 : Oil - Dve method

[00147] Table 2: Water absorption method

[00148] Clearly from the above results the particles for use in the present invention display a very low porosity.

[00149] Example 1

[00150] Two raw denim swatches (E-277, Swissatest) were cut to 11.5 cm long and 8 cm wide. The denim was rolled forming a tube with a length of 9.5 cm and a weight of about 3g thus equating to a total fabric weight of 6g. The tubes were placed in a 1 L rotary tumbler (KT-6808 MIN-TUMBLER) with the blue side facing outwards. To the tumbler, 200ml_ of pre-heated softened water (~40°C, pH 7, Ca <5 ppm) and 0.6g (10% on weight of dry fabric (o.w.f.)) of cellulase enzyme was added. 60g of the 7mm non-porous solid thermoplastic particles were then added into the tumbler. The tumbler was sealed and placed onto the accompanying tumbling mechanism which was set to 1 on the speed setting (-120 rpm) with multi-directional tumbling. 1 Hour later, the tumbler was stopped, and the denim swatches were removed and rinsed with hot water at about 50°C. The fading level of each of the denim samples was determined by measuring the reflectance value with pre-calibrated Konica Minolta CM-3600A spectrometer. Two readings were taken for each sample. The fading level was evaluated with the index CIE Lab colour space L* (lightness) unit and delta E (DE) which the Konica Minolta calculates from the L*, a* and b* data.

[00151] Comparative Example 1

[00152] Comparative Example 1 was performed exactly as described in Example 1 except that no solid particles were used.

[00153] Comparative Example 2

[00154] Comparative Example 2 was performed exactly as described in Example 1 except that the 7mm non-porous solid thermoplastic particles were replaced with the porous solid polypropylene particles 1.

[00155] Comparative Example 3

[00156] Comparative Example 3 was performed exactly as described in Example 1 except that the 7mm non-porous solid thermoplastic particles were replaced with 60g nuts and magnets.

[00157] Example 2

[00158] Two raw denim swatches (E-277, Swissatest) were cut to 11cm long and 5.5cm wide. The denim was rolled forming a tube with a length of 10cm and a weight of about 1 45g thus equating to a total fabric weight of 3.9g. The tubes were placed in a 1 L rotary tumbler (KT-6808 MIN-TUMBLER) with the blue side facing outwards. To the tumbler, 200mL of pre-heated softened water (~40°C, pH 7, pCa < 5ppm) and 0.195g (5% o.w.f.) of cellulase enzyme was added. 39g non-porous solid thermoplastic particles (7mm in size) were then added into the tumbler. The tumbler was sealed and placed onto the accompanying tumbling mechanism. The accompanying mechanism was set to 1 on the speed setting (~120rpm) with multi-directional tumbling. 1 hour (hr) later, the tumbler was stopped, and the denim swatches were removed and rinsed with hot water (~50°C). The fading level of each of the denim samples was determined by measuring the reflectance value with pre-calibrated Konica Minolta CM-3600A spectrometer. Two readings were taken for each sample. The fading level was evaluated with the index CIE Lab colour space L* (lightness) unit and DE. [00159] Comparative Example 4

[00160] Comparative Example 4 was performed exactly as described in Example 2 except that no solid particles were used.

[00161] Comparative Example 5

[00162] Comparative Example 5 was performed exactly as described in Example 2 except that the 7mm non-porous solid thermoplastic particles were replaced with 39g EPDM rubber balls containing 20% by weight MgO.

[00163] Example 3

[00164] Reuse of Cellulase

[00165] Two raw denim swatches (E-277, Swissatest) were cut to 11 5cm long and 8cm wide. The denim was rolled forming a tube with a length of 11 cm and a weight of about 3g thus equating to a total fabric weight of 6g. The tubes were placed in a 1 L rotary tumbler (KT-6808 MIN-TUMBLER) with the blue side facing outwards. To the tumbler, 250ml_ of pre-heated softened water (~40°C, pH = 7, pCa <5ppm) and 0.6g (10% o.w.f.) of cellulase enzyme was added, 60g of the 7mm non-porous solid thermoplastic particles were then added into the tumbler. The tumbler was sealed and placed onto the accompanying tumbling mechanism. The accompanying mechanism was set to 1 on the speed setting (~120rpm) with multi-directional tumbling. 1 hour (hr) later, the tumbler was stopped, and the denim swatches were removed and rinsed with hot water (~50°C). The fading level of each of the denim samples was determined by measuring the reflectance value with pre-calibrated Konica Minolta CM-3600A spectrometer. Two readings were taken for each sample. The fading level was evaluated with the index CIE Lab colour space L* (lightness) unit. The liquor was then separated from the particles and reintroduced into the tumbler with virgin swatches and particles. The tumbler was re-sealed and the 1 hr process was repeated. This was repeated one further time to simulate 3 sequential treatments in total.

[00166] Comparative Example 6

[00167] Comparative Example 6 was performed exactly as described in Example 3 except that no solid particles were used.

[00168] Comparative Example 7

[00169] Comparative Example 7 was performed exactly as described in Example 3 except that the 7mm non-porous solid polypropylene particles were replaced with 60g porous solid polypropylene particles 1. [00170] Example 4

[00171] In Example 4, Cellusoft™ LT 19500 L was used to measure enzyme efficiency in conjunction with 7mm non-porous solid thermoplastic particles with a simultaneous amylase- mediated desizing step. The apparatus used in this Example was similar to that described in WO 2011/098815. The apparatus comprised a treatment chamber in the form of a rotatable cylinder and a particle storage tank. The apparatus also comprised a pump to transfer the non- porous solid thermoplastic particles from the particle storage tank to the treatment chamber and an electric motor to rotate the treatment chamber. In the example 10kg of denim swatches were loaded into the rotatable cylinder. Softened water, 40L, (pCa < 5 ppm) was added to the apparatus. The composition comprising textile, particles and liquid medium was heated to and maintained at a temperature of 40°C. The composition was agitated by rotating the rotatable cylinder for a period of 5 minutes and in addition to the rotation, the liquor was recycled into the rotatable cylinder by means of a pump and a spray nozzle. The water was buffered to a pH between 6.3 and 6.6 using 14mM sodium citrate and citric acid, 10g of cellulase (0.1% o.w.f.), 50g amylase (5% o.w.f.), 42g Lutensol™ AT80 and 75.6g Marloquest™ G82 were mixed with 40kg of the non-porous solid thermoplastic particles in the existing 40L of softened water. The composition comprising textile, particles, enzymes and liquid medium was agitated by rotating the rotatable cylinder for a period of 30 minutes. The liquid medium was drained. A rinse step was performed using two lots of 50L water, one hot (40°C) followed by a cold (20°C). The liquid medium was drained after each rinse. A wash-off step was performed using 50g Palonon™ CAF mixed with 50L of softened water in the rotatable cylinder, the composition was agitated by rotating the rotatable cylinder for a period of 7 minutes. The liquid medium was drained after the wash-off step. A second rinse step was performed using two lots of 50L water, one hot (40°C) followed by a cold (20°C). The liquid medium was drained after each rinse. After rinsing the composition, the liquid medium was extracted by means of a high spin speed extraction.

Following the extraction, a 5 minutes separation cycle was performed to remove the non-porous solid thermoplastic particles from the denim swatches. In the separation cycle the non-porous solid thermoplastic particles return to the particle storage unit housed in the rotatable cylinder. The treated denim swatches were then dried in a conventional clothes drier at temperature ranges of from 50°C to 80°C. The fading level of each of the denim samples was determined by measuring the reflectance value with pre-calibrated Konica Minolta CM-3600A spectrometer. Four readings were taken for each sample. The fading level was evaluated with the index CIE Lab colour space L* (lightness) unit. The above method was repeated with 0%, 0.3%, 0.6%,

1 % cellulase (o.w.f.). [00172] Example 5

[00173] Scanning electron microscope (SEM) images of the surface of the 7mm non-porous solid thermoplastic particle comprising polypropylene (38wt%) and barium sulfate filler (62wt%); porous solid polypropylene particle 1 , Accurel™ MP100 from 3M; porous solid polypropylene particle, Accurel XP100-84 from 3M; and a pumice stone were taken using a Hitachi S-3000N, with accelerating voltage of 20 kV and a working distance of 25mm. Before imaging, the samples were coated with gold using low-vacuum sputter coater.

[00174] Example 6

[00175] Three denim swatches dyed with sulphur black 1 dye were cut to 8 cm wide and 11.5 cm long with the black dyed side facing outwards on a tube length of 4.5 cm. The total weight of the 3 swatches was 1 1.5g.

[00176] The swatches were placed in a 2L rotary tumbler (KT-2000 MIN-TUMBLER) with all of the swatches facing with the black side outwards.

[00177] Applying detergent:

150 ml of soft water (~40 °C, pH 7.5) and 0.58g of Palonon™ CAF (5% o.w.f.) was added. 115.5g of 7mm non-porous solid thermoplastic particles comprising polypropylene were added to the tumbler. The tumbler was sealed, the tumbling started at a rotation speed setting of 1 (approximately 79 rpm) with multi-directional tumbling (25 seconds clockwise then a stop for 5 seconds followed by 25 seconds anti-clockwise rotation then a stop for 5 seconds). The tumbling was continued for 5 mins, then the tumbler was stopped and the liquor removed.

[00178] Abrasion of the Denim:

1.15g of cellulase enzyme Cellulsoft™ LT 19500 L was added with 150ml of soft water (~40 °C, pH 7.5) then the tumbler was sealed and the bi-rotation of the tumbler recommenced at a rotation speed of 1 (approximately 79rpm) for 60 minutes. The tumbler was stopped and the liquor was removed.

[00179] Rinsing

150 ml of fresh soft water (~50 °C) was added to the tumbler. 5 minutes later the tumbler was stopped and the liquor, containing the loose lint and insoluble black colourant, were removed. The swatches were dried for 20 mins. After drying the swatches were rinsed in a beaker with 1 L of soft water (~55 °C, pH 7.5) for approximately 5 mins. This was repeated one more time to ensure all the surface debris (lint, fibres and loose colorant) was removed. After this the swatches were dried for 20 mins. The fading level of the denim samples was determined by measuring the reflectance value with a pre-calibrated Konica Minolta CM-3600A spectrometer. The fading level was evaluated using the index CIE Lab colour space L* (lightness).

[00180] Comparative Example 8

The same experiment was performed exactly as described in Example 6 above however, no solid polypropylene particles were added in this case.

[00181] Example 7

[00182] A composition comprising indigo dyed denim jeans (manufactured by Thaimid);

softened water, 30 L, (pCa < 5 ppm) and 7 mm non-porous solid thermoplastic particles comprising polypropylene (7 mm average diameter, density 1.65 g/cc, 60:40 BaS04 filler: PP polymer) was added to a 500 L conditioning apparatus (XDrum 500L). The XDrum 500L is a conditioning machine with apparatus to dispense and retain 7 mm non-porous solid

thermoplastic particles during the conditioning cycle. The composition was heated to and maintained at a temperature of 40°C. The water was buffered to a pH between 5.5 and 7 using 14 mM sodium citrate and citric acid, 30 g of ECOSTONE LT300 (supplied by AB Enzymes) (% o.w.f.), 35g amylase (% o.w.f.), 60 g Marloquest™ G82 and 30 g Palonon™ CAF were all mixed with 30 kg of the non-porous solid thermoplastic particles in the existing 30 L of softened water. The composition was agitated by rotating the rotatable cylinder for a period of 30 minutes. The liquid medium was drained. A rinse step was performed using 30 L water (40 °C) for 2 minutes. The liquid was drained after the rinse. A wash-off step was performed using 50 g Palonon™

CAF mixed with 50 L of softened water (20 °C) in the rotatable cylinder, the composition was agitated by rotating the rotatable cylinder for a period of 2 minutes. The liquid was drained after the wash-off step.

[00183] The denim samples were dried at a temperature ranging of from 50 °C to 80 °C. The fading level of the denim samples was determined by measuring the reflectance value (L*) with pre-calibrated Konica Minolta CM-3600A spectrometer. Four readings were taken for each sample and compared to readings taken of the raw denim before abrasion by the above method. The fading level was evaluated using the index CIE Lab colour space L* (lightness) unit.

[00184] Results

[00185] The results of the experiments carried out in the above Examples and Comparative Examples are shown in the following Tables. [00186] Table 3 - Results of Example 1

[00187] The higher the value for L* and DE the greater the degree of fade and the more successful the stonewashing process. Table 3 clearly shows that the method of the present invention is superior to a stonewashing process using cellulase alone or with abrasive and porous particles.

[00188] Table 4 - Results of Example 2

[00189] Table 4 clearly shows that the method of the present invention is superior to a stonewashing process using cellulase alone or with rubber balls.

[00190] Table 5 - Results of Example 3

[00191] Table 5 clearly shows that the method of the present invention allows cellulase to be re-used in a number of wash cycles. The raw denim sample of this swatch displays an L* of 25 and so there was effectively no cellulase left in the third wash of Comparative Example 7. [00192] Table 6 - Results of Example 4

[00193] Example 4 shows that the removal of size and a cellulase-mediated fading can be carried out simultaneously on a large scale.

SEM Results - Example 5

[00194] Figures 1 to 4 show the SEM images obtained from the surface of the 7mm non-porous solid thermoplastic particle; porous solid polypropylene particle 1 , Accurel™ MP100 from 3M; porous solid polypropylene particle 2, Accurel™ XP100-84 from 3M; and a pumice stone respectively. The surface of the 7mm non-porous solid thermoplastic particle as required in the present invention is clearly smoother, i.e. has less irregular features than the porous solid polypropylene particles and the pumice stone. Figure 5 shows a comparison of the surfaces of the different particles ranked opposite a relative roughness scale of 1 to 5. The figure shows that the particles are ranked as follows, in order of increasing roughness: 7mm non-porous solid thermoplastic particle < porous solid polypropylene particle 1 (Accurel™ MP100 from 3M) < porous solid polypropylene particle 2 (Accurel™ XP100-84 from 3M) < pumice stone.

[00195] Table 7 Results of Example 6

[00196] This provides a direct comparison of the fading results for sulphur black 1 dye on Denim with and without the solid polypropylene particles present. The higher L* value for Example 6 again demonstrates the effectiveness of the present invention.

[00197] Table 8 Results of Example 7

[00198] The higher L* value for Example 7 again demonstrates the effectiveness of the present invention.

Claims

1. A method for conditioning a textile comprising agitating the textile with a plurality of non- porous solid thermoplastic particles with a size in the range of from 0.1 mm to 100mm, a liquid medium, and an enzyme; wherein the particles comprise a curvilinear surface.

2. A method according to any one of the preceding claims wherein the textile is or

comprises a cellulosic material.

3. A method according to any one of the preceding claims wherein the textile is or

comprises cotton.

4. A method according to anyone one of the preceding claims wherein the textile is dyed with an indigoid dye.

5. A method according to any one of the preceding claims wherein the enzyme is or

comprises one or more of; a protease, a cellulase, a laccase, a peroxidase, an amylase, a polygalacturonase, a pectin lyase or a catalase.

6. A method according to any one of the preceding claims wherein the conditioning is or comprises desizing and the enzyme is or comprises an amylase.

7. A method according to claim 6 which comprises:

i) a conditioning which is or comprises desizing and wherein the enzyme is or comprises an amylase; and

ii) a conditioning which is other than desizing and a second enzyme which is not an amylase;

wherein steps (i) and (ii) may be performed simultaneously or in order.

8. A method according to any one of preceding claims 1 to 6 wherein the conditioning is or comprises fading a dyed textile and the enzyme is or comprises a cellulase, a laccase, a peroxidase, a polygalacturonase, a pectin lyase, a catalase or a mixture thereof, or a method according to claim 7 wherein conditioning step (ii) is or comprises fading a dyed textile and the enzyme is or comprises a cellulase, a laccase, a peroxidase, a polygalacturonase, a pectin lyase, a catalase or a mixture thereof.

9. A method according to claim 8 wherein the textile is or comprises cotton and the enzyme is or comprises a cellulase.

10. A method according to any one of the preceding claims wherein at least some of the enzyme is re-used.

11. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles have a surface which is substantially free from edges and/or vertices.

12. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles comprise a polymeric material which is hydrophobic.

13. A method according to claim 12 wherein the non-porous thermoplastic particles

comprise a polymeric material having a contact angle with water in the range of from 50° to 110°.

14. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles have a water absorption of less than 3wt%.

15. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles are or comprise a polymeric material selected from the group consisting of a poly(haloalkylene), a polyester, a polyalkylene, a polyurethane, a polystyrene, and a copolymer or a mixture thereof.

16. A method according to claim 15 wherein the non-porous solid thermoplastic particles are or comprise a polypropylene.

17. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles comprise a filler.

18. A method according to claim 17 wherein the filler is an inorganic salt.

19. A method according to either claim 17 or 18 wherein the non-porous solid thermoplastic particles comprise a filler in the range of from 20wt% to 80wt%.

20. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles comprise at least 40wt% of polypropylene.

21. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles have a size in the range of from 1 mm to 20mm.

22. A method according to any one of the preceding claims wherein the non-porous solid thermoplastic particles are separated from the textile after agitation.

23. A method according to claim 22 where after separation the non-porous solid

thermoplastic particles are re-used.

24. A method according to any preceding claim wherein prior to conditioning the textile is clean.

25. A conditioned textile product obtained or obtainable by a method according to any one of the preceding claims.