327 Al © (54) Title: COLOURED SPECKI (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date 7 February 2002 (07.02.2002) (10) International Publication Number WO 02/10327 Al (1) International Patent Classification CIID 3/40, M04, 3/12 21) International Application Number: PCT/EPOW/O7I77 (22) International Filing Date: 25 June 2001 (25.06.2001) 25) Filing Language: English (26) Publi ton Language: English (80) Priority Data: 00187740 31 July 2000 (31.07.2000) GB (71) Applicant (or AF, AG, AU BB, BZ. CA. CY, GB, GD. Git, GM, IE, 11, KE, LC, LK, LS, MN, MIF, NZ, SD, SG, Sl. SZ. TT, TZ, UG, ZA, ZW only: UNILEVER PLC (GB/GB]; Unilever House, Blackirars, London ECAP 4BQ (GB). (71) Applicant (for AL, AM, AT: AZ, BA, BE, BE BG, BU, BR, BY. CE CG, CH, Cl, CM, CN, CO, CR, CU, CZ. DE, DK, DM, DZ, BC, BE, ES, FI, FR. Ga, GE, GN, GR. GW, HR. HU, ID, IS, 1 JP. KG, KP. KR. KZ, LR. LE, LU, LY. MA, MC. MD, MG, MK, ML, MR, MK, MZ, NE, NI, NO, PL, PT, RO, RU, SE, SI, SK, SN, TD, TG, 1, TM, TR, UA, UZ, VN, YU only: UNILEVER NV [NLINLJ; Ween 455, NL-3OL3 AL Rotterdam (NL) (71) Applicant gor IN only): HINDUSTAN LEVER LIM- ITED [IN/IN]; Hindustan Lever Houso, 165/166 Backhay Reclamation, Mumbai 400 020, Maharashtra (IN) (72) Inventors: CARRIEL, Soledad, Searlet, Ri; Lever Division, Avenida Manvel Domingos Pinto, 481, Vila Anastacio, CEP-05120-900, Parque Anhanguera, SP (BR). NUNZIO, del, Mario, Jovelino; Av. Cidade Jardim, CEP 12233.900 Sao Jose dos Campos (BR). SCHIOZER, Adriana, Lopes: Lever Division, Valinhos Factory, Av. Gessy Lever, 99, Centro, Valinbos, CEP-13271-000 Val inos, SP (BR), (74) Agents: FRANSELLA, Mary; Evelyn ot al; Unilever PLC, Patent Department, Colworlh House, Sharnbrook, Bediond, Bedfordshire MK 1LQ (GB) (81) Designated States (national): AE, AG, AL, AM, AT, AU, 1, GB, GD, GE, GH, IP. KE, KG, KP. KR, KZ,LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW GM, HR, HU,ID IL, IN, 8p Designated States regional): ARIPO patent (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), Buropean patent (AT, BE, #, DK, ES, F1, FR, GB, GR, IE ~ PI, SE,'TR), OAPI patent (BE, BJ, CP, GN, GW, ML, MR, NE, SN, TD, TG) with international search report For nvo-leter codes and other abbreviation, refer tothe "Guid ‘ance Notes on Codes and Abbreviations” appearing atthe begin hing of each regular issue ofthe PCT Gazette. S Tang 1r COMPOSITION AND PARTICULATE LAUNDRY DETERGENT COMPOSITIONS CON. 02 (57) Abstract: A coloured speckle composition for use in laundry detergent powders and tablets is hased on sodium chloride, The speckles exhibit excellent dissolution behaviour and flow properties, and no staining of fabri in the wash is observed. The speckle composition i used both in white powders and in powders having a contrasting colour, for example, red speckles may be used in a ‘white or blue powder s10 15 20 25 30 Wo 02/10327 PCT/EPO1/07177 COLOURED SPECKLE COMPOSITION AND PARTICULATE LAUNDRY DETERGENT COMPOSITIONS CONTAINING IT TECHNICAL FIELD The present invention relates to a coloured particulate material and its use as speckles in particulate laundry detergent compositions for use in laundering fabrics by hand or machine. BACKGROUND AND PRIOR ART It is well known to include visually contrasting particles, laundry detergent powders. These may be included as a cue to the for example, coloured speckles or noodles, consumer, to indicate the presence of some specific ingredient, for example, bleach, or may simply be present to give the product an attractive appearance. Problems that have been observed with previously proposed speckle compositions include poor dissolution, poor flow properties, and a tendency for the colourant to stain fabrics in the wash. Speckles based on various carrier materials have been disclosed in the prior art. GB 1 546 139 (Procter & Gamble) discloses coloured speckles in which a colourant is carried on hydratable alkaline inorganic salt, for example, sodium tripolyphosphate, sodium carbonate or sodium tetraborate.10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 US 5 606 883 (Bernard et al) discloses coloured speckle agglomerates comprising zeolite, nonionic surfactant, colourant, binding agent and water. EP 19413A (Unilever) discloses coloured speckles based on a solid surfactant, for example, a highly-ethoxylated nonionic surfactant. EP 60728A (Unilever) discloses coloured speckles prepared by spraying a detergent base powder with an aqueous colourant solution which also contains a hydratable salt, preferably a phosphate, carbonate or sulphate. GB 2 199 338A (Unilever) discloses coloured speckles prepared by mixing a detergent base powder with a dyestuff and treating with a binder which is preferably a water- soluble polymer (e.g. acrylic/maleic copolymer) or a nonionic surfactant. WO 99/51714A (Unilever) discloses coloured speckles in which the principal carrier material is an alpha-hydroxy carboxylic acid, preferably citric acid. Other materials that have been proposed as bases for coloured speckles include soap, sodium metasilicate, and clays. WO 90 00006A (PPG Industries Inc) discloses a particulate halogen bleaching composition, for example, calcium hypochlorite, containing about 0.1 to 10 wt% of a colourant-10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 treated particulate inorganic water-soluble salt, for example, sodium chloride. US 4 992 193 (Lever Brothers) discloses a conventional detergent powder containing soap-based noodles (but not speckles) which comprise 2-5 wt% inorganic salt (sodium chloride is specifically disclosed) and optionally up to 0.1 wt% dyestuff. US 3850833 (Colgate-Palmolive) discloses coloured particles consisting of sodium chloride, potassium chloride and/or sodium sulphate for incorporation into a scouring cleanser composition. SUMMARY OF THE INVENTION The present inventors have now discovered that coloured speckles for use in laundry detergent compositions may advantageously be based on sodium chloride. Sodium chloride is stable, inert, highly water-soluble, and compatible with all ingredients used in laundry detergent compositions. The speckles exhibit excellent dissolution behaviour and flow properties, and no staining of fabrics in the wash is observed. DEFINITION OF THE INVENTION The present invention accordingly provides a particulate laundry detergent composition comprising a minor proportion of a coloured speckle composition having a colour10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 contrasting with that of the major proportion of the composition, wherein the coloured speckle composition comprises sodium chloride and a colourant. The present invention also provides a coloured particulate composition for use as a speckle composition in a particulate laundry detergent composition, which coloured particulate composition comprises: (a) from 90 to 99.5 wt%, preferably from 95 to 99 wt%, of sodium chloride, (b) from 0.01 to 6 wt%, preferably from 0.02 to 0.5 wt%, of a colourant, and at least one of: (cl) from 0.1 to 10 wt%, preferably from 0.2 to 5 wt%, of silica, (c2) from 0.1 to 10 wt%, preferably from 0.2 to 1 wtt, of a flow aid other than a silica, (c3) from 0.01 to 3 wt, preferably from 0.02 to 0.5 wt%, of an opaque white pigment and, (c4) from 0.05 to 5 wt, preferably from 0.1 to 1 wt%, of a binder.10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 DETAILED DESCRIPTION OF THE INVENTION The Speckle Composition The coloured speckle composition of the invention contains a major proportion, preferably at least 90 wt%, of sodium chloride. Preferably the speckle composition contains from 90 to 99.5 wt’, more preferably from 95 to 99 wt%, of sodium chloride. Also essential is a colourant. This may be a pigment, or a water-dispersible dye. Preferred colours are red and blue. A preferred pigment is Pigment Red CI 12490. suitable blue colourants are phthalocyanines. The colourant is suitably present in an amount of from 0.01 to 6 wt%, preferably from 0.02 to 0.5 wt%, based on the speckle composition. Preferably an opaque white pigment present to give the speckle particles sufficient opacity. A suitable material is titanium dioxide. The opaque white pigment is suitably present in an amount of from 0.01 to 3 wt%, preferably from 0.02 to 0.5 wie. According to a preferred embodiment of the invention the speckle composition contains silica, to provide a protective outer coating on the speckles and to improve flow. Silica is suitably present in an amount of from 0.1 to 10 wt%, preferably from 0.2 to 5 wtt.10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 ‘The speckle composition preferably also contains a flow aid other than a silica. Suitable flow aids are selected from silicates and aluminosilicates. The flow aid is suitably present in an amount of from 0.1 to 10 wt%, preferably from 0.2 to 1 wet. Preferably the speckle composition also contains a binder. Preferred binders are polymers, for example, cellulosic materials, for example, sodium carboxymethyl cellulose, or acrylic polymers, for example, acrylic/maleic copolymers such as Sokalan (Trade Mark) CP5 ex BASF. Other organic film-forming materials may be envisaged, for example, polyethylene glycols or highly ethoxylated nonionic surfactants. an especially preferred binder is sodium carboxymethyl cellulose. The binder is suitably present in an amount of from 0.05 to 5 wtt, preferably from 0.1 to 1 wet. Preparation of the Speckle Composition ‘The speckle composition may be prepared by any convenient method for treating the sodium chloride with the colourant. any suitable mixing apparatus may be used. The mixer should have a stainless steel or other inert interior surface in view of the corrosive properties of sodium chloride. In a preferred procedure, the sodium chloride is dosed into a mixer, and a premix of the colourant, the opaque white pigment and the binder then added. If silica is incorporated, a minor proportion of the silica is preferably added with the sodium chloride, and the major proportion10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 added after addition of the colourant premix. Flow aid is preferably added last. After thorough mixing to ensure homogeneity, the composition is dried. Detergent Compositions The coloured speckle composition of the invention is suitable for use in both white and coloured detergent compositions, provided that there is sufficient contrast between the colour of the major proportion of the powder and the colour of the speckles. Thus the detergent composition may comprise a major proportion of white or light-coloured particles and a minor proportion of the coloured speckle composition. Alternatively, the detergent composition may comprise a major proportion of particles having a first colour, for example, blue, and a minor proportion of the coloured speckle composition having a second colour contrasting with the first colour, for example, red. ‘The speckle composition is preferably present in an amount of from 0.01 to 15 wt%, preferably from 0.1 to 10 wt%, more preferably from 1 to 10 wt’ and most preferably from 2 to B wts. Detergent compositions according to the invention contain, as well as the speckle composition, conventional detergent ingredients, notably detergent-active materials (surfactants), and preferably also detergency builders.10 20 25 30 Wo 02/10327 PCTEPOW/07177 Heavy-duty laundry detergent compositions in accordance with the invention may suitably comprise from 5 to 60 wt% of detergent-active material, from 10 to 80 wt% of detergency builder, from 0.1 to 10 wt% of the speckles, and optionally other detergent ingredients to 100 wt’. The detergent compositions will contain, as essential ingredients, one or more detergent active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof. Many suitable detergent active compounds are available and are fully described in the literature, for example, in “Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. ‘The preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds. Non-soap anionic surfactants are especially preferred. Non-soap 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 Cg-Cis; primary and secondary alkylsulphates, particularly Cg-Cis primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. A preferred anionic surfactant is linear alkylbenzene sulphonate.10 15 20 Wo 02/10327 PCTEPOW/07177 Nonionic surfactants may optionally be present. ‘These include the primary and secondary alcohol ethoxylates, especially the Cg-C29 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Cio-Cis primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpoly- glycosides, glycerol monoethers, and polyhydroxyamides (glucamide) . Cationic surfactants may optionally be present. These include quaternary ammonium salts of the general formula RURQR3RN’ X wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising anion (for example, compounds in which Ri is a Cg-Cg2 alkyl group, preferably a Cg-Cio or Ci2-Cia alkyl group, Rz is a methyl group, and R3 and Rq, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters). In an especially preferred cationic surfactant of the general formula RiR2R3RaN° xX", Ri represents a Cg-Cio or Cr2~ Cig alkyl group, Rp and R3 represent methyl groups, Re presents a hydroxyethyl group, and x represents a halide or methosulj10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 eo Optionally, amphoteric surfactants, for example, amine oxides, and zwitterionic surfactants, for example, betaines, may also be present. Preferably, the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 8 to 35 wt%, most preferably from 10 to 30 wes Nonionic surfactant, if present, is preferably used in an amount within the range of from 1 to 20 wts. The total amount of surfactant present is preferably within the range of from 5 to 60 wt. The compositions may suitably contain from 10 to 80 wtt, preferably from 15 to 70 wtt, of detergency builder. Preferably, the quantity of builder is in the range of from 15 to 50 wt. The detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) . The zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders. Alternatively, the zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever), and commercially10 1s 20 25 30 Wo 02/10327 PCTEPOW/07177 -a- available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK. Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20. Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used. Also preferred according to the present invention are phosphate builders, especially sodium tripolyphosphate. This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate. Other inorganic builders that may be present additionally or alternatively include sodium carbonate, layered si: amorphous aluminosilicates. Most preferably, the builder is selected from sodium tripolyphosphate, zeolite, sodium carbonate, and combinations thereof. Organic builders may optionally be present. These include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric polycarboxylates such as citrates, gluconates,10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 - 12 - oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates, hydroxyethyl iminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites. Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt’. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form. Detergent compositions according to the invention may also suitably contain a bleach system, although non-bleaching formulations are also within the scope of the invention. The bleach system is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution. Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. ‘The peroxy bleach10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt’, preferably from 2 to 5 wtt. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N‘,N‘- tetracetyl ethylenediamine (TAED). A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP. The detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. preferred proteolytic enzymes (proteases) are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 - 4 - Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable. Other enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as Carezyme ex Novo. In particulate detergent compositions, detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wtt. However, any suitable physical form of enzyme may be used in any effective amount. Antiredeposition agents, for example, cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present. ‘The compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22. Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie). The detergent compositions may also include one or more inorganic salts other than builder salts. These may include, for example, sodium bicarbonate, sodium silicate,10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 - 15 - sodium sulphate, magnesium sulphate, calcium sulphate, calcium chloride and sodium chloride. Preferred inorganic salts are sodium sulphate, sodium chloride, and combinations thereof. The coloured speckle composition is especially suitable for incorporation in detergent compositions which contain sodium chloride in addition to that present in the speckle composition. The detergent compositions may also contain other inorganic materials, for example, calcite, silica, amorphous aluminosilicate, or clays. Other ingredients that may be present include solvents, hydrotropes, fluorescers, dyes, photobleaches, foam boosters or foam controllers (antifoams) as appropriate, fabric conditioning compounds, and perfumes. An especially preferred detergent composition according to the invention comprises: (4) from 10 to 30 wk% of linear alkylbenzene sulphonate, (4i) from 5 to 60 wt of detergency builder selected from sodium tripolyphosphate, sodium carbonate, zeolite and combinations thereof, (4ii) from 0 to 50 wt of sodium chloride, (iv) from 1 to 10 wk’ of the coloured speckle composition,10 20 25 Wo 02/10327 PCTEPOW/07177 - 16 - (v) optionally other minor ingredients to 100 wts, preferably selected from sodium carboxymethyl cellulose, sodium sulphate, bentonite clay, fluorescer, dye of a contrasting colour to that of the coloured speckle composition, and perfume. The detergent compositions of the invention may be in powder or tablet form. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry- mixing) further ingredients. "Concentrated" or "compact" powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes. In both types of powder, the speckle composition may be incorporated by postdosing (dry mixing). The detergent composition of the invention may alternatively be in tablet form. Tablets may be prepared by compacting powders, especially "concentrated" or "compact" powders, prepared as described above. ‘The speckle composition is then included in the powder prior to compaction. EXAMPLES The invention will now be illustrated in further detail by means of the following Examples, in which parts and percentages are by weight unless otherwise stated.10 15 20 Wo 02/10327 PCTEPOW/07177 -at- Example nk Speckle Composition A speckle composition was prepared to the following formulation: Ingredient Weight % Sodium chloride 98.50 Silica 1.00 |—~__—} 0.16 0.35 Sodium carboxymethyl cellulose Zeolite ‘Titanium dioxide, dispersed CI 77891 Pigment Red CI 12490 ‘The composition was prepared as follows. The ingredients were introduced into a stainless steel mixer in the following order: 1. Sodium chloride 2. Silica (0.33 wt) 3. Pigment solution (titanium dioxide, red colourant, sodium carboxymethyl cellulose) 4, Silica (rest) 5. Zeolite The ingredients were mixed for a period of time sufficient to ensure homogeneity, and the resulting particulate material then dried. The speckles were of an attractive pink colour.10 Wo 02/10327 PCTEPOW/07177 - 18 - Comparative Examples A to C Speckles using the same colourant were prepared using the following materials instead of sodium chloride: Comparative Example | Carrier material BR ‘Soap B Sodium metasilicate c Sodium carbonate Detergent Compositions The speckle compositions of Example 1 and Comparative Examples A, B and C were introduced, at a level of 4 wtt, into samples of a laundry detergent powder having the following formulation:10 15 Wo 02/10327 PCTEPOW/07177 - 19 - Ingredient Weight & Linear alkylbenzene sulphonate 14.700 Sodium tripolyphosphate 1.024 Zeolite (100%) 7.863 Sodium carbonate 24.200 Speckie composition (1, A, B or C) 4.000 Sodium chloride [45.7486 | Sodium sulphate 0.0205 Bentonite clay 2.6621 Fluorescers (Tinopal* CBS-x, DMS) 0.1822 Sodium carboxymethyl cellulose 0.1184 Blue dye 0.0124 Perfume 0.2700 Water and minor ingredients ‘balance The pink speckles of Example 1 had a strong visual impact giving the product an attractive appearance. On storage no loss of colour from the speckles was observed. Dissolution and Staining Test ‘The detergent compositions and speckle compositions were tested for dissolution and for fabric staining. Dissolution was measured by a conductivity method. Staining was measured using hand bowl wash methodology. The fabrics used were knitted cotton, and polyester (67%) /cotton (338) .15 20 25 Wo 02/10327 PCTEPOW/07177 = 20 - Three different handwash methods were used: (a) the powder was dissolved in water in a bowl and the fabrics then added, (ii) the fabrics were placed in the water in the bowl and the powder then added, (iii) the fabrics were thoroughly wetted and a concentrated paste (powder and a little water) applied directly. In methods (i) and (ii), the detergent compositions were used at a concentration in the wash liquor of 3.5 g/l. The fabrics were allowed to soak for 1 hour and for 2 hours, and the fabrics were then washed and rinsed. The speckle compositions were also placed directly onto wet fabrics for 1 hour and 2 hours of soak. The results were as follows: Example 5 B B ¢ Dissolution Good Poor | Good ‘Good Staining ‘No No. Yes Yes Only the sodium-chloride-based speckles of Example 1 gave good dissolution without any fabric staining. No staining was observed even under the most stressed conditions.10 15 20 25 30 Wo 02/10327 PCTEPOW/07177 =~ 21 - CLAIMS A particulate laundry detergent composition comprising a minor proportion of a coloured speckle composition having a colour contrasting with that of the major proportion of the composition, characterised in that the coloured speckle composition comprises sodium chloride and a colourant. A detergent composition as claimed in claim 1, characterised in that the coloured speckle composition comprises at least 90 wtt of sodium chloride. A detergent composition as claimed in claim 1 or claim 2, characterised in that the coloured speckle composition comprises: (a) from 90 to 99.5 wt%, preferably from 95 to 99 wt8, of sodium chloride, (b) from 0.01 to 6 wtt, preferably from 0.02 to 0.5 wt, of a colourant, (c) optionally from 0.1 to 10 wt’, preferably from 0.2 to 5 wt, of silica, (a) optionally from 0.1 to 10 wt%, preferably from 0.2 to 1 wt%, of a flow aid other than a silica, (e) optionally from 0.01 to 3 wt%, preferably from 0.02 to 0.5 wt®, of an opaque white pigment,10 15 20 25 Wo 02/10327 PCTEPOW/07177 ~ 22 - (£) optionally from 0.05 to 5 wt’, preferably from 0.1 to 1 wt®, of a binder. A detergent composition as claimed in any preceding claim, characterised in that it comprises from 0.01 to 15 wtt, preferably from 0.1 to 10 wt%, more preferably from 1 to 10 wt%, of the coloured speckle composition. A detergent composition as claimed in any preceding claim, characterised in that it further comprises sodium chloride additional to that present in the coloured speckle composition. A detergent composition as claimed in any preceding claim, characterised in that it comprises a major proportion of white or light-coloured particles and a minor proportion of the coloured speckle composition. A detergent composition as claimed in any one of claims 1 to 5, characterised in that it comprises a major proportion of particles having a first colour and a minor proportion of the coloured speckle composition having a second colour contrasting with the first colour. A detergent composition as claimed in claim 7, characterised in that the major proportion of particles is blue and the coloured speckle composition is red.10 15 20 25 30 Wo 02/10327 10. a1 PCTEPOW/07177 ~ 23 - A detergent composition as claimed in any preceding claim, characterised in that it comprises from 5 to 60 wt% of detergent-active material, from 10 to 80 wt% of detergency builder, from 0.1 to 10 wtt of the coloured speckle composition, and optionally other detergent ingredients to 100 wtt. A detergent composition as claimed in claim 9, characterised in that it comprises: (i) (14) (iv) (v) from 10 to 30 wt’ of linear alkylbenzene sulphonate, from 5 to 60 wt% of detergency builder selected from sodium tripolyphosphate, sodium carbonate, zeolite and combinations thereof, from 0 to 50 wt of sodium chloride, from 1 to 10 wt% of the coloured speckle composition, optionally other minor ingredients to 100 wt, preferably selected from sodium carboxymethyl cellulose, sodium sulphate, bentonite clay, fluorescer, dye of a contrasting colour to that of the coloured speckle composition, and perfume. A detergent composition as claimed in any preceding claim, characterised in that it is in powder or tablet form.10 15 20 30 Wo 02/10327 PCTEPOW/07177 12. 13. - 24 - A coloured particulate composition for use as a speckle composition in a particulate laundry detergent composition, characterised in that the coloured particulate composition comprises: (a) from 90 to 99.5 wt%, preferably from 95 to 99 wtt, of sodium chloride, (b) from 0.01 to 6 wtt, preferably from 0.02 to 0.5 wt%, of a colourant, and at least one of (cl) from 0.1 to 10 wt%, preferably from 0.2 to 5 wt%, of silica, ({c2) from 0.1 to 10 wt%, preferably from 0.2 to 1 wt%, of a flow aid other than a silica, (c3) from 0.01 to 3 wt, preferably from 0.02 to 0.5 wt%, of an opaque white pigment, (c4) from 0.05 to 5 wt, pr 1 wt, of a binder. ably from 0.1 to A coloured particulate composition as claimed in claim 12, characterised in that comprises a flow aid (c2) selected from silicates, aluminosilicates and mixtures thereof.10 15 Wo 02/10327 PCT/EPO1/07177 14, 15. 16. aye = 25 - A coloured particulate composition as claimed in claim 12 or claim 13, characterised in that the colourant (b) is a red or blue pigment. A coloured particulate composition as claimed in any one of claims 12 to 14, characterised in that it comprises titanium dioxide as an opaque white pigment (c3). A coloured particulate composition as claimed in any one of claims 12 to 15, characterised in that it comprises a polymeric binder (c4). A coloured particulate composition as claimed in claim 16, characterised in that the polymeric binder (c4) is sodium carboxymethyl cellulose.INTERNATIONAL SEARCH REPORT ‘nie Appleton No PCT/EP 01/07177 7% SUSSTCRTON OF SUB IECT eee erTbs/ae "CTibs/oa—c113/12 According ontario Paton Gaston (°C) ot eh lon casteton an FIELDS SEARCHED Tian datnaain esarched(Gesaiaon sata feowad by Sanaa aBOB) irc 7 CliD Daan sara oer an Rion aA TT aT a GOSS as RGUGST Fa HS Sa iT as CaSO GT HTT SST Pa TA Ua, Ws PRA Sa a WPI Data, EPO-Internal, PAJ {. DOCUMENTS CONSIERED TO BE RELEVANT cited in the application example T Categry* | Craton of decametwth neater, wore appropri, tev passages Febrero aaa, x Us 5 605 883 A (ILIFF ROBERT J ET AL) au 25 February 1997 (1997-02-25) abstract column 4, line 58 - line 64 A column 6, line 50 - line 58 2-4, 6-10 12-14, 16,17 A GB 1 546 139 A (PROCTER & GANBLE) 1,3,4, 16 May 1979 (1979-05-16) 612,14 TZ] Faeries ar ited inthe contrast of bX. Fk ] Pats ta members art in aro. 7 Spach cao ced canis “dosent ering to gut i ofthe at whi not ‘unlored ba prious france “se ear donamant ul pbleed ona aer hematin! tng Se “1 dicuent wich mayo dubioon pry cla) ‘tnch cede ceapicn to fubcatn ee of aar ie rer pact uso o> epost) “0 cneumert refering to sna cout, we, extibtoe of ‘shor ears “Poumon pene pose Eatna Hing de bak ‘ior pny ce cairo a ier ocure pbb air ne eral tng date very da ananot testis witha aplaetan at isnt wasn ie pncoctheoy yee he invention *eoeument of par evans: to eines invnton 7% ere be cate ov” Cama Cone fnvavoan iene sphere Secret twee lone + cneunont opal claranes bw etn invention aot be enede vcs anette saga ne ‘Gouna combed wt on ror de ac Sc ‘ees snbson br cons fa ee ed “1 cacumont ome hase ptt fy Da oho eae clon es lomo ar Taso tga ns erat aaah pa | | 22/10/2001 15 October 2001 Tie and ring ares ot ho SA | rans oe Sera tla a. eepamtent | }__ Saunders, Fam POET saa DTINTERNATIONAL SEARCH REPORT tnt Appletion No PCT/EP 01/0717 ‘(Gontncaon) DOCUMENTS CONSIDERED TOBE RELEVANT 26 November 1974 (1974-11-26) cited in the application example I ‘Cae | Clan a doer wih dean heo ppp Oe RTA PaCS pos A DATABASE WPT 1,3-12, Section Ch, Neek 197623 14,16,17 Derwent Publications Ltd., London, G8; Class A97, AN 1976-42484% xP002032900 & OP 49 033905 A (DAINICHISEIKA COLOR & CHEM MFG), 28 March 1974 (1974-03-28) abstract A Us 3 850 833 A (KOCEICH M ET AL) 12,14INTERNATIONAL SEARCH REPORT Inert ‘Application Ne PCT/EP 01/07177 Patent document Publication Patent family | Publication ced in soar report ae ‘marnoats) ae Us 5605883 ‘A 25-02-1997 NONE 6B 1546139 A 16-05-1979 BE 844493 Al 24-01-1977 DE 2632367 Al 17-02-1977 FR 2318924 AL 18-02-1977 IT 1075019 8 22-04-1985 oP 52049208 A 20-04-1977 NL. 7608122 A 25-01-1977 Us 4097418 A 27-06-1978 oP 49033905 = A 28-03-1974 JP 866451 C 23-06-1977 ap 51040571 B 04-11-1976 Us 3850833 26-11-1974 AT 319442 B 27-12-1974 AU 473970 B 08-07-1976 AU 3822572 A 26-07-1973 cA 943428 AL 12-03-1974 cH 569083 A5 14-11-1975 DE 2203141 AL 17-08-1972 FR 2123356 AS 08-09-1972 6B 1378923 A 27-12-1974 NL 7201035 A,B, 27-07-1972 BE 778472 AL 16-05-1972 ES. 399140 AL 01-05-1975 IE 36019 B1 21-07-1976 IT 949682 B 11-06-1973 JP 84119505 A 17-09-1979 JP 56017400 B 22-04-1981 PH 12775 A 17-08-1979 SE 414049 B 07-07-1980 SE 423406 B 03-05-1982 SE 7506189 A 30-05-1975 aA 7200436 A Fam RETR yan aT) 26-09-1973