Title of Invention	FABRIC LAUNDERING
Abstract	Relatively low levels of polysaccharides in combination with small, deformable, water-insoluble particles of a size in the range 0.05-5 microns are capable of giving benefits in a wash liquor in terms of reduced fabric abrasion.

Full Text

C4398/C FORM-2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) FABRIC LAUNDERING HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India The following specification particularly describes the invention and the manner in which it is to be performed WO 2006/027087 PCT7EP2005/008862 FABRIC LAUNDERING Technical Field 5 The present invention relates to improved products and processes for fabric laundering- 10 Background of the Invention Most people are aware that washing and wearing clothes is not good for them. Clothes suffer damage due to abrasion in the wash, particularly around seams and hems. On dark 15 cellulosics (such as black or navy 'jeans', for example) this damage exposes fibrillated regions of the textile which scatter light differently than undamaged regions. While the damaged regions may have lost relatively small 20 quantities of dye, they are very easy to perceive and produce a strong visual impact. It has been suggested to reduce the incidence of such damage by using lubricating agents in wash liquors. However the skilled worker is faced with a problem when asked to choose the right lubricant. 25 Prior proposals have included acrylic materials, dextrans, oily and waxy materials. Hydroxy ethyl cellulose (HEC) is widely commercially available and is well known as a viscosity modifier in a 30 range of surfactant-containing products as well as in paints and other coatings. It is generally produced by the WO 2006/027087 PCT/EP2005/008862 - 2 - treatment of cellulose with ethylene oxide to give materials with a specified degree of substitution of the hydroxyl groups of the glucose rings with hydroxy ethyl groups. Related materials are known which comprise other short alkyl 5 chains (typically C2-4). Other- known materials are hydroxy- alkyl derivatives of. other beta 1-4 linked polysaccharides. In order to bring about viscosity changes cellulose ethers 10 are generally required to be present- at levels of l-2%wt on liquor, depending on the molecular weight of the polymer. It is known that bulk viscosity increases in a wash liquor can have beneficial effects on fabrics being laundered, as the increase in viscosity reduces certain fabric-fabric 5 interactions which can cause degradation of the fabrics through such mechanisms as abrasion etc. However, viscosity increases have negative consequences as well. They can significantly reduce cleaning. 20 WO 99/61479 discloses the use of hydrophobically modified cellulose ether in, for example, detergents. WO 00/65015 discloses the use of cellulose-ether as a finishing agent, which is replenished during washes. 25 WO 98/29528 discloses the use of 0.1-8%wt of modified cellulose ether, which 'associates with the fibres of the fabric being laundered' and 'reduces the tendency of the fabrics to deteriorate in appearance'. 30 C4398 (C) WO (Amended 4 July 06) -3- Brief Description of the Invention We have now determined that relatively low levels of polysaccharides in combination with small, deformable, water 5 insoluble particles, are capable of giving benefits in a wash liquor in terms of reduced fabric abrasion. Accordingly, the present invention provides a method of treating fabrics with a wash liquor which comprises: 10 a) a beta 1,4 polysaccharide, with a degree of substitution in the range of 1.5-2.0, b) deformable, water-insoluble particles of a size in the 15 range 0.05-0.5 microns, and c) a textile compatible carrier which is a detergent- active compound chosen from soaps and synthetic non- soap anionic and non-ionic compounds. 20 The method is preferably applied to coloured fabrics with a luminance (L*) less than 50 in a wash liquor, more preferably to black fabric articles. 25 Typically, the wash liquor comprises 0.001-0.1 g/L of the polysaccharide. The invention also provides a washing composition comprising: 30 (Amended 4 July 06) 3a a) a beta 1,4 polysaccharide with a degree of substitution in the range of 1,5-2.0, 5 b) deformable, water-insoluble particles of a size in the range 0.05-0.5 microns, and c) a textile compatible carrier which is a detergent-active compound chosen from soaps and synthetic non- 10 soap anionic and nonionic compounds. WO 2006/027087 PCT/EP2005/008862 - 4 - Luminance (also known as lightness) is the measure of the brightness of a surface on a black-white scale. It is one of the triplet of independent measurements, the other two being chroma (C*, which measures saturation) and hue (H*, 5 which measures chromatic tone), which can be used to characterize any colour by locating it in a 'colour space'. Changes in these three values can be combined to give the well known measure 'delta E' which is often used to determine the change in colour of an article when it is 10 washed. In this specification the colour space used as a referent is the CIELAB (International Lighting Commission) system, also known as the CIE 1976 colour space. This is an 15 internationally recognized standard. When L* is 0 the surface being considered is black. When L* is 100, the surface is a white standard. Such a white standard is supplied for use with the Datacolor™ Spectraflash SF600+ reflectance spectrometer. 20 Colours with luminance (L*) less than 50 are also known herein as 'Class 3' colours. There are three sets of Class 3 colours - high chroma (C*), saturated colours such as bright purple, and intense blue, low chroma muted tones such as 25 browns and olives and those with little or no chroma e.g. black/dark grey. Class 3 colours are very sensitive to fading. Uneven colour changes occur very readily on Class 3 colours because the lightness differences between areas are large and thus particularly amenable to human perception. 30 (Amended 4 July 06) - 5 - While not wishing to limit the scope of the invention by reference to a theory of operation, it is believed that the particles, which have a low tendency to abrade due to their deformable nature (and are typically rounded in shape) 5 lubricate the relative movement of fabric fibres (which are typically cellulosic) and are held in place by the polysaccharide. The polysaccharide is a beta 1-4 polysaccharide; preferably 10 a cellulose derivative. Cellulose derivatives are widely available and many show excellent cellulose self recognition. Preferably the polysaccharide is a hydroxy C2-C4 alkyl 15 derivative. Preferably the hydroxy C2-C4 alkyl derivative is a hydroxy ethyl derivative. In a preferred embodiment the polysaccharide is the hydroxy-alkyl ether of cellulose. This material is not only commonly 20 available, but also shows excellent lubrication benefits. The degree of substitution (DS) of the polysaccharide is in the range 1.5-2.0. Lower DS levels have poor water solubility, which appears to be important for the 25 lubricating effect. Higher levels appear to lead to problems with particulate soil redeposition. Preferably the molecular weight of the polysaccharide is 100,000 to 500,000 Dalton, preferably less than 300,000 30 Dalton. The polysaccharide is preferably such that viscosity WO 2006/027087 PCT/EP2005/008862 - 6 - of the material is 300-400 cps at 2% solution (measured on a Brookfield viscometer using ASTM D2364). The solution viscosity under standard conditions is related to the molecular weight of the polysaccharide, and the preferred 5 materials have nearly Newtonian viscosity profiles between 1 and 10 reciprocal seconds. Suitable hydroxy C2 alkyl derivatives of cellulose are available in the marketplace from Dow under the trade name 10 "Cellosize" and from Hercules under the trade name "Natrasol". Preferred dosage levels are such that the in wash concentration of the 1-4 beta polysaccharide is 0.01-0.06 15 g/L. In typical European was conditions the dosage of a laundry product is 7g/L in about 8-15 litres of water depending on the machine and load. Preferably the level of polysaccharide is 0.1-3%wt on full 20 formulated product, more preferably 0.2-0.8%wt. In this specification, all percentages are weight percentages unless otherwise stated. A typical product would contain 0.5%wt of the polysaccharide which would give an in use concentration of around 0.035g/L. 25 The deformable, water-insoluble particles of a size in the range 0.05-0.5 microns are preferably a wax, more preferably a micro-crystalline wax. Suitable waxes comprise hydrocarbons which are either branched, or cyclic or a 30 mixture of both. Typical chain lengths are C40-C50. WO 2006/027087 PCT/EP2005/008862 - 7 - Particularly preferred particulate materials are elastic. Hardness of the materials can be measured by ASTM D-1321 (at 25°C). Typical values are 10-20. 5 Typically the particles are prepared by an emulsification method and therefore they can contain surfactant species. Typical dosage levels of the particles (on wash liquor) are 10 0.001-0.5 g/L. The melting point of suitable particulate materials for use in a domestic washing process (which may typically be performed at 40 Celsius) will typically be above 60 Celsius 15 and preferably be 70-90 Celsius. It is however only important that the particles retain their particulate nature at the temperature of the wash. Typically, melting points will be below 85 Celsius, preferably below 65 Celsius. 20 Suitable particulate materials are available from Hercules under the trade name ‘Paracol’ and from Lubrizol under the trade name ‘Thermol’. 25 Detailed Description of the Invention Carriers and Product Form: The compositions of the invention will generally be used in 30 conjunction with a textile compatible carrier. (Amended 4 July 06) - 8 - In the context of the present invention the term "textile compatible carrier" includes a component which can assist in the interaction of the polymer with the textile. The carrier can also provide benefits in addition to those 5 provided by the first component e.g. softening, cleaning etc. The carrier is a detergent-active compound. Many of these fall within the more general definition 'surfactant' as used herein. The surfactant may comprise the entire carrier or other, non-surfactant carrier materials may be 10 present. In a washing process, as part of a conventional textile washing product, such as a detergent composition, the textile-compatible carrier is a detergent-active compound. 15 The polymer is used to treat the textile in the wash cycle of a laundering process. The composition of the invention may be in the form of a 20 liquid, solid (e.g. powder or tablet), a gel or paste, spray, stick or a foam or mousse. Examples include a soaking product, or a main-wash product. Liquid compositions may also include an agent which produces 25 a pearlescent appearance, e.g. an organic pearlising C4398 (C) WO (Amended 4 July 06) - 9 - compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (TiO2) coated mica. Liquid compositions may be in the form of emulsions or emulsion precursors thereof. 5 Detergent Active Compounds: Many suitable detergent active compounds are available and are fully described in the literature, for example, in 10 "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The textile-compatible carriers that can be used are soaps and synthetic non-soap anionic and nonionic compounds. 15 Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkylsulphates, 20 particularly C8-C18 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. 25 Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from i to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic copied from AMENDED SHEET 13-07-2006 07/07/2007 C4398 (C) WO (Amended 4 July Go; - 10 - alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide). 5 The total quantity of detergent surfactant in the composition is suitably from 0.1 to 60 wt% e.g. 0.5-55 wt%, such as 5-50wt%. 10 Preferably, the quantity of anionic surfactant (when present) is in the range of from 1 to 50% by weight of the total composition. More preferably, the quantity of anionic Copied from AMENDED SHEET 13-07-2006 07/07/2006 WO 2006/027087 PCT/EP2005/008862 - 11 - surfactant is in the range of from 3 to 35% by weight, e.g. 5 to 30% by weight. Preferably, the quantity of nonionic surfactant (when 5 present) is in the range of from 2 to 25% by weight, more preferably from 5 to 20% by weight. Amphoteric surfactants may also be used, for example amine oxides or betaines. 10 Builders: The compositions may suitably contain from 10 to 70%, preferably from 15 to 70% by weight, of detergency builder. 15 Preferably, the quantity of builder is in the range of from 15 to 50% by weight. The detergent composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal 20 aluminosilicate, more preferably a sodium aluminosilicate. The aluminosilicate may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis) , preferably from 25 to 50%. Aluminosilicates are materials having the 25 general formula: 0.8-1.5 M2O. AI2O3. 0.8-6 Si02 where M is a monovalent cation, preferably sodium. These 30 materials contain some bound water and are required to have (Amended 4 July 06) - 12 - a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as 5 amply described in the literature. Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. Copied from AMENDED SHEET 13-07-2006 07/07/2006 (Amended 4 July 06) - 13 - The compositions may alternatively or additionally contain nonionic textile softening agents such as lanolin and derivatives thereof. 5 Lecithins are also suitable softening compounds. Nonionic softeners include Lb phase forming sugar esters (as described in M Hato et al Langmuir 12, 1659, 1666, (1996)) and related materials such as glycerol monostearate or 10 sorbitan esters. Often these materials are used in conjunction with cationic materials to assist deposition (see, for example, GB 2 202 244). Silicones are used in a similar way as a co-softener with a cationic softener in rinse treatments (see, for example, GB 1 54 9 180). Copied from AMENDED SHEET 13-07-2006 :07/0772006 WO 2006/027087 PCT/EP2005/008862 -14- The compositions may also suitably contain a nonionic stabilising agent. Suitable nonionic stabilising agents are linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof. 5 Advantageously the nonionic stabilising agent is a linear Cs to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably 10 from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1:1, preferably within the range from 18:1 to about 15 3:1. The composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in 20 particular, hardened tallow C16 to C18 fatty acids. Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more 25 than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10. WO 2006/027087 PCT/EP2005/008862 -15- Other Components Compositions according to the invention may comprise soil release polymers such as block copolymers of polyethylene 5 oxide and terephthalate. Other optional ingredients include emulsifiers, electrolytes (for example, sodium chloride or calcium chloride) preferably in the range from 0.01 to 5% by weight, pH 10 buffering agents, and perfumes (preferably from 0.1 to 5% by weight). Further optional ingredients include non-aqueous solvents, perfume carriers, fluorescers, colourants, hydrotropes, 15 antifoaming agents, enzymes, optical brightening agents, and opacifiers. Suitable bleaches include peroxygen bleaches. Inorganic peroxygen bleaching agents, such as perborates and 20 percarbonates are preferably combined with bleach activators. Where inorganic peroxygen bleaching agents are present the nonanoyloxybenzene sulphonate (NOBS) and tetra-acetyl ethylene diamine (TAED) activators are typical and preferred. 25 Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof. In addition, compositions may comprise one or more of anti- 30 shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers WO 2006/027087 PCT7EP2005/008862 -16- (sunscreens), heavy metal sequestrants, chlorine scavengers, dye fixatives, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids. The lists of optional components are not intended to be exhaustive. 5 The preferred mode of delivery of the compositions of the invention is in the form of a fabric washing powder. These are typically dosed at around 7 g/litre, into 15-20 litres of wash water. 10 In order that the invention may be further and better understood it will be described below with reference to the following non-limiting examples. 15 Examples: Table 1 below shows delta E results (change in colour) from new. These are Quickwash TM experiments using 6g/l Persil 20 Original Non-Bio, ex Lever Bros UK (Spring 2004). Lower values of delta E indicate a reduction in the magnitude of the colour change as compared with higher values. A Datacolor™ Spectraflash SF600+ reflectance spectrometer 25 was calibrated using white tile and black trap standards prior to measurement of the reflectance over the wavelength range 400-720nm on each fabric piece. The test fabrics (red, green, black and blue woven cotton) 30 were washed in a Quickwash™ apparatus using the following protocol. WO 2006/027087 PCT7EP2005/008862 - 17 - Apparatus Raitech™ Quickwash™ Plus. Powder 6g/L Fabrics One coloured fabric piece was place in each 5 of the five compartments of the Quickwash™. Wash Conditions The Quickwash programme was executed as follows: 10 1. 30 second drain 2. Fill with 3 litres of 15°FH water at 40°C 3. Machine paused and powder added 4. Programme resumed 5. Agitated for 15 minutes at 40 C 15 6. Drain for 30 seconds 7. Fill with 3 litres of 15°FH water at 40°C. 8. Agitate for 5 minutes (Rinse) 9. Drain for 30 seconds 10. Dry at 4.0 bar for 1 minute 20 11. Dry at 3.5 bar for 1 minute 12. Dry at 3.0 bar for 2 minutes 13. Cool-down These steps were repeated five times. After the completion 25 of the five washing and drying cycles the reflectance of each fabric was recorded at the same points using the calibrated spectrometer and the delta E value recorded. ‘95%c' values are the +/- limits of the confidence interval based on a statistical analysis of results. 30 WO 2006/027087 PO7EP2005/008862 - 18- Table 1: Delta E from new mean mean mean mean 95%c 95%c 95%c 95%c Black Red Blue Green Black Red Blue Green 0.125g/lCellosizeQP300 3.71 8.82 3.32 5.10 0.15 0.28 0.20 0.13 0.25g/lCellosizeQP300 3.85 10.14 4.21 5.46 0.15 0.23 0.08 0.07 0.125g/lParacol1324C 4.50 9.83 3.33 5.93 0.14 0.25 0.13 0.09 0.25g/l Paracol 1324C 3.98 11.12 3.69 5.67 0.10 0.15 0.18 0.16 0.125g/l QP300 + 0.125g/l 1324C 3.40 8.92 2.68 5.02 0.18 0.22 0.08 0.15 5 From the results it can be seen that the wax alone (Paracol 1324C ex. Hercules) is worse than HEC (Cellosize QP300, ex Dow), even when used at twice the level (0.25g/l wax compared to 0.125g/l HEC). However, when the two are used 10 together, the benefit increases rather than decreases. Table 2 below shows some further results using the black coloured fabric pieces only and the same etherimental conditions as above. This time ‘Delta 1/ is being measured 15 (i.e. the change in luminance). WO 2006/027087 PCT/EP2005/008862 - 19 - Table 2; Delta L from new (after five washes) Rep 1 Rep 2 Rep 3 Rep 4 Average s.d. 95% conf Black Black Black Black Black Black Black Persil Non Bio 5.09 5.86 6.72 4.80 5.62 0.86 0.84 + 0.25g/l QP300 3.51 3.88 3.98 3.79 0.25 0.28 + 0.25g/l 1324C 3.8 4.61 3.59 4.00 0.54 0.61 +0.125g/l QP300 +0.125g/l 1324C 2.91 2.79 3.40 3.03 0.32 0.37 5 Again it can be seen that the greatest benefit (lowest change in luminance) is found when both the wax and the cellulose derivative are present and that the same amount in total of either of these materials taken alone shows less benefit. C4398 (c) wo Amended 4 July 06) -20- CLAIMS 1. A method of treating fabrics with a wash liquor which comprises: 5 a) a beta 1-4 polysaccharide with a degree of substitution in the range of 1.5-2.0, b) deformable, water-insoluble particles of a size in 10 the range 0.05-5 microns, and c) a textile compatible carrier which is a detergent- active compound chosen from soaps and synthetic non-soap anionic and non-ionic compounds. 15 2. A method according to claim 1 wherein the fabrics have a luminance (L*) less than 50. 3. A method according to claim 2 wherein the fabrics are 20 black. 4. A laundry washing composition comprising: a) a beta 1-4 polysaccharide, with a degree of 25 substitution in the range of 1.5-2.0, b) deformable, water-insoluble particles of a size in the range O.O5-5 microns, and Copied from AMENDED SHEET 13-07-2006 07/07/2006 C4398 (C) WO (Amended 4 July 06) -21- c) a textile compatible carrier which is a detergent-active compound chosen from soaps and synthetic non-soap anionic and non-ionic compounds. 5 5. A composition according to claim 4 wherein the polysaccharide is cellulose derivative. 6. A composition according to claim 4 wherein the polysaccharide is a hydroxy C2-C4 alkyl derivative. 10 7. A composition according to claim 4 wherein the polysaccharide is a hydroxy ethyl derivative. 8. A composition according to claim 4 wherein the 15 molecular weight of the polysaccharide is 100,000 to 500,000 Dalton. 9. A composition according to claim 4 wherein the polysaccharide is such that viscosity of the material 20 is 300-400 cps at 2% solution (measured on a Brookfield viscometer using ASTM D2364). 10. A composition according to claim 4 wherein the deformable, water-insoluble particles of a size in the 25 range 0.05-5 microns are a wax. 11. A composition according to claim 10 wherein the wax is a micro-crystalline wax. 30 12. A composition according to claim 10 wherein the wax particles comprise surfactant. Dated this 2nd day of March 2007 Copied from AMENDED SHEET

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