Method of abrading and / or fading a textile substrate

Abstract

A method of abrading and / or fading a textile substrate is disclosed. The method comprises agitating a textile substrate with solid particles and a liquid, wherein at least some of the solid particles are a ceramic material, the solid particles of the ceramic material have a size of from 1 mm to 30 mm, the ceramic material is or comprises a sintered metal oxide, metalloid oxide or a mixture thereof, and the solid particles of the ceramic material have an apparent density of at least 1 g / cm3.

Description

METHOD OF ABRADING AND / OR FADING A TEXTILE SUBSTRATE

[0001] Field of the Invention

[0002] The present invention relates to a method of abrading and / or fading a textile substrate. In particular, the present invention provides a method to prepare abraded and / or faded textiles which have a worn-in, softened, flexible, vintage, less intense and / or bleached feel and / or appearance.

[0003] Background to the Invention

[0004] Many customers prefer new textiles that have a worn-in, softened, vintage, less intense and / or bleached feel and appearance. For cellulosic, especially cotton textile substrates and more especially for denim a particularly common technique for providing such feel and / or appearance is stone washing using pumice. The pumice material is a natural material and its use is inherently unsustainable. The pumice material wears down very quickly and is often used for around 3 treatment cycles. The pumice wears down to a fine sand which needs to be cleaned from the textile substrates and properly disposed of. Pumice is also highly irregular in shape and size, it often has sharp edges and faces which can produce irregular patterning on the final textile substrate as well as potentially causing damage such as cuts, tears, and rips etc. All that said, pumice has proven particularly effective at producing the desired appearance and feel.

[0005] PCT patent publication WO2019239111 discloses a method for reducing the color intensity of a coloured textile using a composition comprising 2,2,6,6,-tetramethylpiperidin-1-oxyl or a derivative thereof. No mention is made as to what the ceramics are or how they are made.

[0006] The present inventors have attempted to address, at least in part, one or more of the following technical problems: a. To provide a method which yields textile substrates with good characteristics in terms of appearance and / or feel but using solid particles which are more sustainable than pumice; b. To provide a method wherein the solid particles can be re-used many times, especially whilst reducing or preventing the production of fine particles or other broken particle fragments; c. To provide a method wherein the resulting textile substrate is less damaged; d. To provide a method wherein the surface characteristics of the resulting textile substrate are more uniform.e. To provide a method wherein the solid particles could be utilised in an apparatus designed to automatically and collect the solid particles; f. To provide a method which reliably provides textile substrates having the desired appearance and / or feel time after time. g. To provide a method where the solid particles are compatible with a wide range of ingredients often used in abrading and / or fading.

[0007] The present inventors found that solving any one of these technical problems was difficult but solving some of these problems in combination was especially difficult. As, an example solving technical problems a. and c. and optionally e. simultaneously proved difficult.

[0008] Summary of the Invention

[0009] According to a first aspect of the present invention there is provided a method of abrading and / or fading a textile substrate comprising agitating said textile substrate with solid particles and a liquid, wherein: at least some of the solid particles are a ceramic material; the solid particles of the ceramic material have a size of from 1 mm to 30 mm; the ceramic material is or comprises a sintered metal oxide, metalloid oxide or a mixture thereof; and the solid particles of the ceramic material have an apparent density of at least 1g / cm3.

[0010] Abrading and / or fading

[0011] By abrading we preferably mean a method in which the textile substrate has had mechanical action imparted to it. This mechanical action preferably results, at least partially, from the contact of the solid particles with the textile substrate during agitation.

[0012] The abrasion preferably produces a textile substrate with a worn-in, softened, flexible and / or vintage feel. Preferably, the textile substrate has a feel which differs after the method has been performed. So as examples the textile preferably feels softer, more flexible, aged or more comfortable after the method has been performed.

[0013] Abrading is distinguished from cleaning wherein stains are removed from the textile substrate because in cleaning the intention is not to abrade the textile substrate. Having a cleaning method which abrades the textile substrate would very soon wear out the textile after a number of cleaning cycles.

[0014] By fading we preferably mean a method in which the textile substrate has an initial colour which is reduced in intensity. For fading the textile substrate is preferably coloured, this is preferably achieved by the textile comprising one or more colorants. The colorants may be pigments or more preferably dyes. The colour may be anything perceptible to the human eyeincluding black, purple, blue, green, yellow, orange, red, brown, grey etc. Preferably, the fading acts on one or more colorants within the substrate which provide its colour. Thus, as an example the fading may act so as to reduce the colour intensity of a dye and / or a pigment within the textile substrate. In general fading preferably results in a colour which is closer to a white colour. Thus, black textile substrates often fade to grey and red textile substrates often fade to pink. Fading preferably means reducing the chroma of the coloured textile, preferably as indicated by the chroma c* value from the L*, a*, b* CIE 1976 colourspace of the coloured textile. Here c* = (a*2+ b*2)1 / 2.

[0015] Reducing colour can also optionally or additionally mean reducing the L* value.

[0016] Colour space measurements are preferably made by a spectrophotometer. A suitable apparatus is a Konica-Minolta CM-3600A spectrophotometer.

[0017] Fading is distinguished from cleaning wherein stains are removed from a textile substrate because in cleaning the intention is not to fade the textile substrate. Having a cleaning method which fades the textile substrate would very soon result in little or no colour in the textile after a number of cleaning cycles.

[0018] Often it is desirable to simultaneously abrade and fade the textile substrate.

[0019] Textile substrate

[0020] The textile substrate preferably is natural, synthetic, semi-synthetic or a mixture thereof. Preferred natural textiles substrates include wool, silk and cotton. Preferred synthetic textiles include those comprising polyamide, polyester, polyurethane, polyacrylic, polyacrylonitrile and mixtures thereof. Preferred semi-synthetics include derivates of cellulosic materials such as viscose and rayon.

[0021] Preferably, the textile substrate is or comprises a cellulosic material and optionally a polyester material.

[0022] Preferably, the textile substrate is or comprises cotton, polyester, or a mixture thereof, more preferably the textile substrate is or comprises cotton.

[0023] Preferably, the textile substrate is or comprises a cellulosic fibre. Examples of suitable cellulosic fibres include hemp, linen, flax, jute, ramie, sisal and especially cotton.

[0024] Preferably, the textile substrate is or comprises denim.

[0025] The colourant present in the coloured textile substrate can be a pigment or dye, more preferably a dye, preferably wherein the dye is an azo compound, more preferably an indigo dye.

[0026] Denim may be dyed using an indigoid dye, or preferably with an indigo dye.

[0027] The textile substrate may be a plurality of textile substrates.

[0028] The textile substrate may be in the form of garments, towels, sheets, bead-linen, furniture coverings and bags. The textile substrate be in the form of shirts, jackets, hats, scarves, socks, skirts, underwear or especially trousers.

[0029] Agitating

[0030] Agitation in the method according to the first aspect of the present invention can be performed by stirring, rotating, shaking, vibrating and sonicating the textile substrate along with the solid particles and the liquid. Agitation is preferably performed by rotating, especially by rotating a textile treatment compartment in which is contained the textile substrate, the solid particles and the liquid.

[0031] Rotating preferably is tumbling. In tumbling the centrifugal force experienced by the textile substrate during rotation is preferably from 0.01 to 0.99G, more preferably from 0.1 to 0.9G. and even more preferably from 0.2G to 0.8G. The G force can be calculated from rpm2x r x 1.118x10-5wherein rpm means revolutions per minute and r is the radius of the rotation in centimetres. The radius of rotation is preferably the radius of a rotatable drum present in an apparatus suitable for performing the method of the present invention.

[0032] Preferably the solid particles and the liquid form a mixture during the agitation. Preferably, the solid particles and the liquid contact the textile substrate during the agitation.

[0033] Ceramic material

[0034] The ceramic material preferably is or comprises a metal oxide which is selected from aluminum oxide, zirconium oxide, titanium dioxide, magnesium oxide, yttrium oxide and cerium dioxide or a mixture thereof.

[0035] The present inventors have found that these types of ceramics are especially effective in the present invention. In particular, these ceramics provide good abrasion and / or fading performance and can be re-used many times without any detectable degree of damage or wear to the ceramic solid particles.

[0036] Preferably, the metal oxide is or comprises a metal oxide which is selected from aluminum oxide, zirconium oxide, titanium dioxide, magnesium oxide, yttrium oxide and cerium dioxide or a mixture thereof.

[0037] Metal oxides have been found to provide especially suitable solid particles for fading and / or abrading in the method of the present invention over other ceramics.

[0038] Preferably, metal oxide is or comprises aluminum oxide, zirconium oxide or a mixture thereof.

[0039] Optionally, the metal oxide is or comprises a mixture of zirconium oxide and yttrium oxide. The combination of zirconium oxide and yttrium oxide provides more robust and tougherceramic solid particles which can be used even more times in the method of the present invention more times.

[0040] Optionally, the ceramic material is or comprises a sintered metalloid oxide which is or comprises silicon dioxide.

[0041] Optionally, the ceramic material is or comprises a sintered metal oxide and metalloid oxide mixture, wherein the metal oxide is or comprises aluminium oxide and a metalloid oxide is or comprises silicon dioxide.

[0042] Ceramic solid particles comprising sintered silicon dioxide tend to be especially environmentally friendly since the sintering temperatures tend to be somewhat lower than several other ceramic materials.

[0043] Sintering can be performed by heat and / or pressure, more preferably by heat and optionally pressure. Sintering temperatures and durations do vary though often they are at least 600°C, more typically at least 800°C and even more typically at least 1000°C.

[0044] Sintering temperatures above the melting point of the oxides or metalloid oxides are not usually employed. Thus, sintering temperatures generally do not exceed 2000°C, more generally they do not exceed 1800°C and most generally they do not exceed 1600°C.

[0045] The ceramic material is preferably man-made that is to say that the sintering process is not done by nature.

[0046] The ceramic material is preferably synthetic.

[0047] The ceramic material preferably comprises at least 80wt%, at least 90wt%, at least 95wt%, at least 99wt% or 100% of metal oxide and / or metalloid oxides.

[0048] Shape of the solid particles

[0049] Preferably, the solid particles and more preferably the solid particles which are a ceramic material have a spheroidal, ellipsoidal, potato, cylindrical, cuboidal, prismatic or pyramidal shape. Of these spheroidal shapes are especially preferred. Shapes without edges or vertices are preferred.

[0050] By spheroidal we preferably mean approximating to or including a spherical shape. Thus spheroidal shapes include those not exactly or precisely spherical.

[0051] Preferably spheroidal, encompasses shapes having a 2D degree of roundness of from 0.8 to 1.0, more preferably from 0.9 to 1.0 and especially from 0.95 to 1.0. Roundness is defined as the Perimeter2 / (4π x Area) wherein the perimeter and the area are established for each particle for example by digital image analysis of a 2D projection of the solid particles of the ceramic material.

[0052] The present inventors have found that spheroidal solid particles which are a ceramic material work especially well in the method the present invention and they can be dispensed and collected very effectively when the method is performed by an apparatus.

[0053] Also, spheroidal solid particles which are a ceramic material have been found to be long lasting, provide uniform surface fading and / or abrasion and tend not to damage the textile substrate.

[0054] The solid particles which are a ceramic are optionally neither lapped nor polished. Lapping and polishing are abrasive methods to smooth the surface of the solid particles which are a ceramic material. The present inventors have found that better abrasion and / or fading of the textile substrate is achieved without such lapping or polishing. Indeed, lapping or polishing was found to reduce the abrasion and fading performance of the ceramic material. The solid particles which are a ceramic are optionally lapped and / or polished. Lapping and / or polishing can provide a smooth surface which whilst not abrading or fading quite so well has the advantage of being more easily cleanable.

[0055] Preferably, the solid particles which are a ceramic have a matte appearance.

[0056] Size of the solid particles of the ceramic material

[0057] The solid particles of the ceramic material have a size of from 1 mm to 30 mm.

[0058] The solid particles of the ceramic material preferably have a smallest size of at least 2 mm, at least 3 mm, at least 4 mm, or at least 5mm.

[0059] The solid particles of the ceramic material preferably have a largest size of no more than 25mm, no more than 23mm, no more than 20mm, no more than 18 mm, no more than 16mm, no more than 14mm and no more than 12mm.

[0060] The size of any solid particles can be established by vernier calipers. The size of any solid particles can also be obtained from light obscuration and image analysis. An example of a suitable apparatus for performing light obscuration and image analysis is a CamsizerTM. Preferably, the size is the longest linear dimension, in the case of a sphere this is the same as the diameter.

[0061] The size is preferably a mean size and especially an arithmetic mean size.

[0062] Where the size is a mean size this is preferably established for 100, more preferably 1,000 and most preferably 10,000 solid particles. Of course, establishing the mean size for numbers of particles greater than these numbers of particles produces essentially the same number but just to higher degrees of precision. Thus, alternatively the mean size may be established for at least 100, more preferably at least 1,000 and most preferably at least 10,000 solid particles. There is little benefit in establishing a mean size for a number of solid particles beyond 100,000.

[0063] Uniformity of the solid particles of the ceramic material

[0064] In order of increasing preference at least 50 % by number, at least 60 % by number, at least 70% by number, at least 80% by number, at least 90% by number, at least 95% by number and at least 99% by number of the solid particles of the ceramic material have the same shape, more preferably they have the same spheroidal shape.

[0065] The present inventors have found that having a uniformity of shape is advantageous in permitting the dispensing and collection of the particles when the method is performed in an apparatus.

[0066] In order of increasing preference at least 50 % by number, at least 60 % by number, at least 70% by number, at least 80% by number, at least 90% by number, at least 95% by number and at least 99% by number of the solid particles of the ceramic material have approximately the same size. By the word approximately in this context it is preferably meant that the size can be within + / - 20%, + / - 10%, + / - 5% or + / - 1%. So as an example if the arithmetic mean size of the ceramic material is 10 mm then + / - 10% would mean a size between 9 mm and 11 mm.

[0067] The present inventors have found that having a uniformity of size is advantageous in permitting the dispensing and collection of the particles when the method is performed in an apparatus.

[0068] Density of the solid particles of the ceramic material

[0069] Preferably, the solid particles of the ceramic material have an apparent density of at least 1.1g / cm3, at least 1.2g / cm3, at least 1.3g / cm3, at least 1.4g / cm3, at least 1.5g / cm3, at least 1.75g / cm3, at least 2g / cm3or at least 2.5g / cm3.

[0070] Preferably, the solid particles of the ceramic material have an apparent density of no more than 10g / cm3, no more than 8g / cm3, no more than 6g / cm3, no more than 5g / cm3or no more than 4g / cm3.

[0071] The apparent (which is the same as the bulk) density can be obtained by pouring the solid particles of the ceramic material into a container of a known volume and establishing the weight of the solid particles of the ceramic material in that volume. Preferably, the volume is 100cm3, 500cm3, 1,000cm3or 5,000cm3. The larger volumes simply provide more accurate results.

[0072] Optional solid particles

[0073] Optionally, all of the solid particles present during the method can be solid particles which are a ceramic material. Accordingly, the solid particles in the range of from 1mm to 30mm in size are all ceramic materials.

[0074] More preferably, at least some of the solid particles are not a ceramic material, more preferably at least some of the solid particles or comprise a polymeric material.

[0075] The polymeric material may be a thermoset or more preferably a thermoplastic material.

[0076] The polymeric material may be or comprise a polyolefin, polyamide, a polyester, a polycarbonate, a polyurethane, a polyacrylic, a polystyrenic or a mixture thereof. Polyamide and polyolefin are preferred, more especially polyamides. A preferred polyamide is nylon. Preferred polyamides include Nylon 6,6 and Nylon 6. Preferred polyolefins include polyethylene, polybutylene and especially polypropylene.

[0077] When at least some of the solid particles are or comprise a polymeric material then the weight ratio of solid particles which are a ceramic material to those which are or comprises a polymeric material is preferably from 1:99 to 70:30, more preferably from 5:95 to 50:50 and especially from 10:90 to 50:50. The present inventors have found that a surprisingly advantageous performance enhancement of the abrasion and / or fading of the solid particles as a whole is achieved at the abovementioned ratios.

[0078] Preferably, the solid particles which are a ceramic material are at least 1 weight percent, at least 5 weight percent, at least 10 weight percent, at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent or at least 35 weight percent of all of the solid particles present during the method. The remaining solid particles preferably comprise a polymeric material.

[0079] The size of the solid particles which are not a ceramic material (especially which are or comprise a polymeric material) is preferably the same as that described for the solid particles which are a ceramic material.

[0080] Amounts

[0081] Preferably, the weight ratio of the solid particles to the dry textile substrate is at least 0.01:1, at least 0.05:1, at least 0.1:1, at least 0.2:1, at least 0.5:1, at least 0.7:1 or at least 1:1.

[0082] Preferably, the weight ratio of the solid particles to the dry textile substrate is no more than 100:1, no more than 20:1, no more than 10:1, no more than 7:1, no more than 5:1 or no more than 4:1.

[0083] Preferably, the weight ratio of the solid particles to the dry textile is from 0.1:1 to 10:1, or from 0.5:1 to 5:1 or from 0.7:1 to 4:1.

[0084] Preferably, the weight ratio of liquid to textile substrate is at least 0.1:1, at least 0.3:1, at least 0.5:1, at least 0.7:1, at least 1:1 or at least 1.5:1.

[0085] Preferably the weight ratio of the liquid to textile substrate is no more than 100:1, no more than 50:1 no more than 20:1, no more than 10:1, no more than 7:1, no more than 5:1, no more than 4:1, no more than 3:1 or no more than 2:1.

[0086] Duration

[0087] The method according to the first aspect of the present invention is preferably performed for at least 1 minute, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 30 minutes or at least 45 minutes.

[0088] The method according to the first aspect of the present invention is preferably performed for no more than 24 hours, no more than 16 hours, no more than 10 hours, no more than 8 hours, no more than 6 hours, no more than 4 hours or no more than 2 hours.

[0089] The method may be carried out for a period of from 15 minutes to 4 hours.

[0090] Temperature

[0091] The method is preferably performed at a temperature of at least 0°C, at least 10°C, at least 15°C, at least 20°C, at least 25°C or at least 30°C.

[0092] The method is preferably performed at a temperature of no more than 100°C, no more than 90°C, no more than 80°C, no more than 70°C or no more than 60°C.

[0093] The method is preferably performed at a temperature of from 20°C to 80°C.

[0094] The temperature is preferably the temperature of the liquid present in the method.

[0095] Liquid

[0096] The liquid is preferably aqueous, that is to say the liquid preferably is or comprises water.

[0097] The liquid may be organic and may comprise alcohols, ketones, aldehydes, esters, alkanes, amides, sulphones and mixtures thereof.

[0098] When the liquid is aqueous it preferably consists of water or it comprises a mixture of water and one or more water-miscible organic liquids. Suitable water-miscible organic liquids include alcohols, aldehydes, ketones and amides.

[0099] The amount of liquid may be sufficient to moisten the textile substrate and the solid particles, alternatively the amount of liquid may be sufficient such that the textile substrate and solid particles are dispersed in the liquid during the method.

[0100] Optional components

[0101] In addition to the textile substrate, the solid particles and the liquid one or more optional components may be present during the method. Typically, the liquid comprises these one or more optional components. Typically, the one or more optional components are dispersed and / or dissolved in the liquid.

[0102] Optional components include an oxidant, a surfactant, an enzyme, an antifoaming agent, a biocide, a buffer, an acid, a base, a anti-back staining agent.

[0103] Preferably, the liquid comprises an oxidant. This is especially so where fading of the textile substrate is desired alone or in addition to abrasion.

[0104] The oxidant is preferably a hypohalite, a peroxide, a permanganate, a chromate, ozone or an enzyme.

[0105] The hypohalite is typically hypochlorite which is typically in the sodium salt.

[0106] The peroxide is preferably hydrogen peroxide.

[0107] The permanganate is preferably potassium permanganate.

[0108] The chromate is preferably potassium chromate.

[0109] Ozone is preferably generated as a gas and is bubbled into the liquid.

[0110] Enzymes suitable as oxidants include peroxidase, tyrosinase and laccase, especially peroxidase.

[0111] The surfactant can be cationic, anionic, non-ionic or zwitterionic. Of these anionic and / or non-ionic surfactant tend to be preferred. Preferred anionics surfactants are the sulphate functional anionics such as sodium laureth sulfate (SLS). Preferred non-ionic surfactants are the polyethylene glycol containing surfactants.

[0112] Builders are materials that soften the liquid when it is water. That is to say builders help to remove metal ions (especially calcium and magnesium) from aqueous liquids.

[0113] Suitable builders include the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, aluminosilicates, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with acrylic acid, ethylene or vinyl methyl ether, 1 ,3, 5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 13,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and salts thereof. Suitable builders also include zeolites.

[0114] Back staining is the undesirable transfer of coloration from one region of a textile substrate to another. So as an example the intense blue indigo coloration of denim jeans can be undesirably transferred to the white pockets.

[0115] Anti-back staining agents help to reduce this back staining. Many anti-back staining compositions are commercially available. Often, they comprise a chelating agent, a dispersing agent and an emulsifying agent.

[0116] Where the textile substrate comprises a cellulosic material and where abrading is desired it is preferred that one optional component is an enzyme, more preferably one optional component is an enzyme which is a cellulase.

[0117] The cellulase enzyme may comprise one or more enzymes capable of degradation of cellulose.

[0118] The cellulase enzyme may be or comprise an endo-cellulase. Endo-cellulases are cellulases that cleave polysaccharide polymer chains internally by breaking 1,4-β(beta)-D- glycosidic bonds in the cellulose backbone.

[0119] The cellulase enzyme may comprise an exo-cellulase (also referred to as exoglucanases or cellobiohydrolases). Exo-cellulases are cellulases that cleave cellobiose from the reducing and non-reducing ends of cellulose and molecules generated by the action of endo-cellulases.

[0120] The cellulase enzyme may include any of, cellobiohydrolases, endoglucanases and beta-glucosidases.

[0121] In particular, the cellulase enzyme may comprise an enzyme that catalyses the hydrolysis of 1,4-β(beta)-D-glycosidic linkages. Any suitable textile application cellulase may be used. Suitable cellulases include the Cellusoft® LT, Denimax® Core and Novoprime® ranges (Novozymes), IndiAge® (DuPont), Ecostone® LT (AB Enzymes), and LavaTMCell NSY (DyStarTM).

[0122] The use of cellulase enzymes with textile substrates which are or comprise a cellulosic material enhances the abrasion and may additionally partially or completely remove pilling from the textile surface. Partial or complete removal of pilling is sometimes called depilling.

[0123] Typically, the enzyme may be present in the liquid at a concentration of from 0.1wt% to 10wt%, more preferably from 0.1wt to 5wt% relative to the liquid.

[0124] Re-use

[0125] The method according to the first aspect of the present invention is preferably repeated one or more times using the same solid particles which are a ceramic material.

[0126] Preferably, the method can be repeated at least 5, 10, 20, 50, 100, 200, 500, or 1000 times using the same solid particles which are a ceramic material. Preferably, whilst repeating the method with the same solid particle which are a ceramic the solid particles of the ceramic material show no visible signs of damage. That is to say the solid particles of the ceramic material do not show any one or more of cracks, chips or breaks. Preferably, after such repeated uses the solid particles which are ceramic material show a mass loss of less than 1%, less than 0.5% or less than 0.1% by weight.

[0127] Apparatus

[0128] The method according to the first aspect of the present invention is preferably performed in an apparatus. The apparatus is preferably a textile treatment apparatus which typicallycomprises a rotatable drum. Preferably, the apparatus is configured to automatically dispense the solid particles into a textile treatment and then to collect the solid particles from the textile treatment compartment.

[0129] The apparatus preferably comprises a rotatable drum, said drum comprising a textile treatment compartment and a storage compartment and wherein the apparatus is configured such that it can dispense the solid particles from the storage compartment into the textile treatment compartment before the method and such that it can collect the solid particles from the textile treatment compartment and return them to the storage compartment after the method.

[0130] The apparatus will also typically comprise a door for permitting the loading and unloading of the textile substrates into and out of the apparatus.

[0131] The apparatus will also typically comprise one or more pipes or conduits to supply the liquid into and out of the textile treatment compartment.

[0132] The storage compartment stores the solid particles when the method is not being performed.

[0133] The storage compartment is preferably located at the rear of the rotatable drum, typically furthest from the door.

[0134] Preferably the drum comprises: i. a dispensing flow path which permits the transport of the solid particles from the storage compartment to the textile treatment compartment; and ii. a collecting flow path which permits the transport of the solid particles from the textile treatment compartment to the storage compartment. Suitable apparatus include those described in the following PCT patent publications, WO2018 / 172725, WO2020 / 012026, WO2020 / 012027 and WO2020 / 064830 which are incorporated herein by reference thereto.

[0135] Further Method

[0136] Also disclosed herein is a method of abrading and / or fading a textile substrate, comprising: agitating a textile substrate with liquid and a plurality of solid particles that each comprise a ceramic body manufactured from a ceramic material that is or comprises a sintered metal oxide or a metalloid oxide or a mixture of a sintered metal oxide and a metalloid oxide; whereby the ceramic body of each solid particle has a length dimension of from 1 mm to 30 mm and an apparent density of at least 1g / cm3.

[0137] Aptly the method further comprises agitating the textile substrate with liquid and only said a plurality of solid particles.

[0138] Aptly the method further comprises agitating the textile substrate with liquid and a plurality of solid particles that include said a of solid particles.

[0139] Aptly the method further comprises agitating the textile substrate with liquid and a plurality of solid particles that include said a plurality of solid particles and a further plurality of solid particles that each comprise a polymeric body manufactured from a polymeric material.

[0140] Aptly the ceramic body is spheroidal and the length dimension comprises a diameter of the spheroidal body.

[0141] Aptly the ceramic body is cylindrical and the length dimension comprises a diameter of a circular cross section of the body or a length of the cylindrical body.

[0142] Examples

[0143] The present invention will now be illustrated by the following non-limiting examples.

[0144] Apparatus

[0145] An apparatus having a rotatable drum was provided in the form of XDrumTM500 from Jiangsu Sea-lion Machinery Co which was a washing machine made in accordance with PCT publications WO2020 / 012026 and WO2020 / 012027, this was used to provide the agitation in the form of rotation and more specifically in the form of tumbling, herein after referenced as XDrum.

[0146] Materials

[0147] The liquid used was water which had been softened to pCa < 5ppm, herein referenced as the Softened water.

[0148] The solid particles used in Example 1, 2 and 3 and Comparative example 1 comprise a polymeric material made of Nylon 6 and an inorganic filler namely barium sulfate. They were prepared by hot melt extrusion and had an average size of around 7mm and an apparent density of 0.89g / cm3, herein referenced as the Nylon 6 particles. The solid particles used in Example 4 and Comparative examples 2, 3 and 4 comprise a polymeric material made of Polypropylene and an inorganic filler namely barium sulfate. They were prepared by hot melt extrusion and had an average size of around 7mm and a specific density of 1.63g / cm3, herein referenced as the Polypropylene particles.

[0149] Solid particles which were a ceramic material were: Sintered alumina (92% Al2O3) particles having an apparent density of around 1.65g / cm3, having a size of approximately 10mm, the particles were unpolished and unlapped and had a matte appearance, they were obtained from Baan Machines herein referenced as Alumina particles.Sintered zirconia / yttrium oxide (95% ZrO2 / 5% Y2O3) particles having an apparent density 3.7 g / cm3, having a size of approximately particles were lapped and polished and had a shiny appearance, they were obtained from Pingxiang Nanxiang Chemical Packing Co. Ltd herein referenced as Zirconia particles. Sintered metal oxide (Al203) / metalloid oxide (SiO2) particles having an apparent density of 1.32g / cm3, having a size of approximately 10mm, the particles were unpolished an unlapped and had a matte appearance, they were obtained from ASDA herein referenced as Clay particles. Sintered silicon carbide (≥99% SiC) particles having a specific density 3.2 g / cm3, having a size of approximately 10 mm, the particles were unpolished and had a matte appearance, they were obtained from Shanghai Rampart Import and Export Co. Ltd herein referenced as Silicon carbide particles.

[0150] A cellulase used in Examples 1, 2 and 3 and Comparative example 1 was Lava® Cell NSY (obtained from DyStar®). A second cellulase, Cellusoft® LT 19500 L (Novozymes), was used in Examples 4 and 5 and Comparative examples 2 and 3.

[0151] Denydet CL9 is an anti-backstaining agent obtained from Denykem. It was used to help reduce the tendency of removed indigo dye to backstain on e.g. pockets etc, hereinafter referred to as Denydet.

[0152] Denyzyme LT is an amylase enzyme obtained from Denykem. It was used to remove starch sizing from textiles.

[0153] The textile substrate for Examples 1, 2 and 3 and Comparative example 1 was indigo dyed denim jeans manufactured by Thaimid. The jeans had been previously desized using an amylase enzyme to remove starch sizing. For the desizing step, 50 litres of Softened water was heated to 60℃ in the drum of the XDrum , 75 grams (1.5%, on the weight of the jeans.) Denyzyme and 50 grams (1.0% on the weight of the jeans) of Denydet were added to 5 kilograms (equivalent dry weight) denim jeans, loaded into the XDrum and the composition was agitated by rotating the rotatable drum in an XDrum apparatus for a period for 10 minutes in the absence of any solid particles. The liquid was retained after the desizing step, herein Retained water. This yielded the textile substrate for use in the examples and comparative examples, herein the Desized denim Jeans.

[0154] The textile substrate for Examples 4 and 5 and Comparative examples 2 and 3 was Swissatest denim (E-277) obtained from Swissatest Testmaterialien AG.

[0155] Example 1

[0156] The following components were loaded into the drum of the XDrum apparatus, namely the Desized denim jeans (equivalent to 5 Kg dry weight); the Retained water (50 litres) at an initialtemperature of 60°C; 10 kilograms of solid particles comprising of 7 kilograms of the Nylon 6 particles and 3 kilograms of the Clay gms (1% on weight of Desized denim jeans) of the cellulase (Lava® Cell NSY) was added to the Softened water and allowed to thoroughly mix.

[0157] The abrasion / fading step was then performed for 90 minutes, whilst the drum of the XDrum rotated to cause a tumbling motion for the solid particles, the Softened water and the Desized denim jeans.

[0158] The solid particles were removed by the XDrum apparatus from the Desized denim jeans and were stored in the rear of the drum away from the denim jeans.

[0159] A rinse step was then performed using 30 L of fresh Softened water at ambient temperature for a period of 2 minutes. The Softened water was then drained after the rinse.

[0160] A wash-off step was then performed using 30 L of softened water at ambient temperate containing 50 grams (1.0% on weight of denim) of Denydet CL9 for 7 minutes. The liquid was drained after the wash-off step.

[0161] A water extraction step was then performed for 3 minutes by rotating the drum at a speed of 500 rpm.

[0162] The resulting Denim samples were dried at a temperature of 80 °C for 30 minutes.

[0163] The degree of colour fading of the Denim samples was determined using the CIE Lab colour space system by measuring the DE 2000 (DE00) colour differentiation from the raw denim (untreated denim) reference (before any desizing or method of the present invention), and the brightness value (L*), using a pre-calibrated Konica Minolta CM-3600A spectrometer. Four readings were taken for each sample in different locations on the Denim samples.

[0164] Example 2

[0165] Example 2 was performed exactly as described in Example 1 with the exception that instead of Clay particles the Alumina particles were used.

[0166] Example 3

[0167] Example 3 was performed exactly as described in Example 1 with the exception that instead of Clay particles the Zirconia particles were used.

[0168] Comparative example 1

[0169] Comparative example 1 was performed exactly as described in Example 1 except that 10 kg of the Nylon 6 particles were used and no Clay particles were used (i.e. no ceramic particles as defined in the first aspect of the present invention were present).

[0170] Comparative Example 2

[0171] Four Swissatest denim swatches were cut to into rectangles having a length of 11.5 cm long and a width of 8 cm. Each denim swatch was rolled forming a tube with a length of 9.5 cm and a weight of about 3 g thus equating to a total fabric weight of 12 g. The tubes were placed into a 1 L rotary tumbler (KT-6808 MIN-TUMBLER) with the blue surface facing outwards of the tube. To the tumbler, 200mL of pre-heated softened water (60°C, pH 6) and 1.2g (10% of weight of dry fabric (o.w.f.)) of cellulase (Cellusoft® LT 19500 L) was added.120g of solid particles were then added into the tumbler, this weight was made up of a 50:50 wt% blend of Polypropylene particles and Silicon carbide particles. 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.

[0172] After a period of 1 hour of agitating by tumbling, the tumbler was stopped, and the denim swatches were removed.

[0173] The denim swatches were then rinsed twice with cold tap water before the water was wrung out and the swatches were air dried overnight.

[0174] The fading level of each of the denim swatches was determined using the same methodology as Example 1.

[0175] Examples 4 and 5 and Comparative Example 3

[0176] Examples 4 and 5 and Comparative Example 3 were performed exactly as described in Comparative Example 2 except that the solid particles were replaced as follows: Example 4 used 60g of Polypropylene particles and 60g Clay particles; Example 5 used 60g of Polypropyene particles and 60g of Alumina particles; Comparative example 3 used 120g of Polypropylene particles.

[0177] Results

[0178] The results of the experiments carried out in the above Examples and Comparative examples are shown in the following Table.

[0179] Table 1 - Results of Example 1, 2 and 3 and Comparative Example 1 Example DE00 L* Example 1 Clay / Nylon 6 particles 6.74 21.32 Example 2 Alumina / Nylon 6 6.71 21.2 particles Example 3 Zirconia / Nylon 6 6.93 21.77 particles Comparative Example 1 Nylon 6 particles 6.45 20.35

[0180] The higher the value for L* and DE00, the greater the degree of colour fading and the more successful the fading / abrading method. Table 1 clearly shows that the method of the present invention is superior to a fading / abrading method using Nylon 6 particles in the absence of any ceramic particles as defined in the first aspect of the invention.

[0181] Table 1 also shows that a 30% weight utilisation of these ceramic particles gives a superior fading / abrading effect compared to Nylon 6 particles in the absence of any ceramic particles. In other words, the benefits of the present invention only require the presence of at least some of the ceramic particles as defined in the first aspect of the present invention. It is not required that all of the solid particles present are ceramic particles as defined in the first aspect of the present invention to obtain the benefits of the present invention.

[0182] The zirconia particles were noted to be particularly effective, very robust to mechanical damage and were readily cleanable.

[0183] The clay particles were effective but were less robust to mechanical damage.

[0184] The alumina particles were effective and were robust to mechanical damage, they were however somewhat harder to clean than the zirconia particles perhaps because of their matte finish.

[0185] Table 2 - Results of Comparative Example 2 and 3 and Examples 4 and 5 DE00 L* Comparative Example 2 Silicon 9.73 35.61 particles / Polypropylene particles Example 4 Clay particles / 12.72 39.39 Polypropylene particles Example 5 Alumina particles / 11.3 37.59 Polypropylene particles Comparative Example 3 Polypropylene 10.1 36.17 particles

[0186] The higher the value for L* and DE00, the greater the degree of colour fading and the more successful the stonewashing process. Table 2 clearly shows that the method of the present invention (Examples 4 and 5) is superior to a fading / abrading method using a blend of Silicon carbide particles and Polypropylene particles (Comparative example 2), or Polypropylene particles alone (Comparative example 3).

[0187] General

[0188] In the present invention items in the singular also include items in the plural unless stated to the contrary. Thus, as examples, a textile substrate includes a plurality of textile substrates, a ceramic material includes a plurality of ceramic materials, a metal oxide includes a plurality of metal oxides and a metalloid oxide includes a plurality of metalloid oxides.

[0189] Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of them mean “including but not limited to” and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps.

[0190] Features, integers, characteristics or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of the features and / or steps are mutually exclusive. The invention is not restricted to any details of any foregoing embodiments. The invention extends to any novel one, or novel combination, of the featuresdisclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of steps of any method or process so disclosed.

[0191] The reader’s attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

Claims

Claims:

1. A method of abrading and / or fading a textile substrate comprising agitating said textile substrate with solid particles and a liquid, wherein: at least some of the solid particles are a ceramic material; the solid particles of the ceramic material have a size of from 1 mm to 30 mm; the ceramic material is or comprises a sintered metal oxide, metalloid oxide or a mixture thereof; and the solid particles of the ceramic material have an apparent density of at least 1g / cm3.

2. A method according to claim 1 wherein the ceramic material is or comprises a metal oxide which is selected from aluminum oxide, zirconium oxide, titanium dioxide, magnesium oxide, yttrium oxide and cerium dioxide or a mixture thereof.

3. A method according to claim 2 wherein the metal oxide is or comprises aluminum oxide, zirconium oxide or a mixture thereof.

4. A method according to claim 2 wherein the metal oxide is or comprises a mixture of zirconium oxide and yttrium oxide.

5. A method according to claim 1 wherein the ceramic material is or comprises a sintered metalloid oxide which is or comprises silicon dioxide.

6. A method according to claim 1 wherein the ceramic material is or comprises a sintered metal oxide and metalloid oxide mixture, wherein the metal oxide is or comprises aluminium oxide and a metalloid oxide is or comprises silicon dioxide.

7. A method according to any one of the preceding claims wherein the solid particles which are a ceramic material have a spheroidal shape.

8. A method according to any one of the preceding claims wherein the solid particles which are a ceramic material are neither lapped nor polished.

9. A method according to any one of the preceding claims wherein the solid particles of the ceramic material have an apparent density of at least 1.5 g / cm3.

10. A method according to any one of the preceding claims wherein the solid particles of the ceramic material have an apparent density of no more than 6g / cm3.

11. A method according to any one of the claims wherein some of the solid particles are or comprise a polymeric material.

12. A method according to claim 11 wherein the polymeric material is or comprises a polyamide or a polyolefin.

13. A method according to claim 11 or claim 12 wherein the weight ratio of solid particles which are a ceramic material to those which are or comprises a polymeric material is from 1:99 to 70:

30.

14. A method according to claim 13 wherein the weight ratio is from 5:95 to 50:

50.

15. A method according to any one of the preceding claims which is performed for a period of from 15 minutes to 4 hours.

16. A method according to any one of the preceding claims which is carried out at a temperature of from 20°C to 80°C.

17. A method according to any one of the preceding claims wherein the liquid comprises an oxidant.

18. A method according to claim 17 wherein the oxidant is a hypohalite, a peroxide, a permanganate or chromate, ozone or an enzyme.

19. A method according to claim 19 wherein the oxidant is a peroxide which is hydrogen peroxide.

20. A method according to any one of the preceding claims which is performed in an apparatus which comprises a rotatable drum, said drum comprising a textile treatment compartment and a storage compartment and wherein the apparatus is configured such that it can dispense the solid particles from the storage compartment into the textile treatment compartment before the method and such that it can collect the solid particles from the textile treatment compartment and return them to the storage compartment after the method.

21. A method according to claim 20 wherein the drum comprises:i. a dispensing flow path which permits the transport of the solid particles from the storage compartment to the compartment; and ii. a collecting flow path which permits the transport of the solid particles from the textile treatment compartment to the storage compartment.

22. A method according to any one of the preceding claims which is repeated one or more times using the same solid particles which are a ceramic material.

23. A method according to any one of the preceding claims wherein the liquid is or comprises water.

24. A method according to any one of the preceding claims wherein the textile substrate is or comprises a cellulosic material.

25. A method according any one of the preceding claims wherein the textile substrate is or comprises cotton.

26. A method according to any one of the preceding claims wherein the textile substrate is in the form of Denim.