WO2010003792A1 - Laundry compositions - Google Patents

Laundry compositions Download PDF

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Publication number
WO2010003792A1
WO2010003792A1 PCT/EP2009/057537 EP2009057537W WO2010003792A1 WO 2010003792 A1 WO2010003792 A1 WO 2010003792A1 EP 2009057537 W EP2009057537 W EP 2009057537W WO 2010003792 A1 WO2010003792 A1 WO 2010003792A1
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WO
WIPO (PCT)
Prior art keywords
alginate
agents
granule
citric acid
fabric
Prior art date
Application number
PCT/EP2009/057537
Other languages
French (fr)
Inventor
Andrew Philip Parker
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to BRPI0914211A priority Critical patent/BRPI0914211A2/en
Priority to EP09793904.5A priority patent/EP2297288B1/en
Priority to ES09793904T priority patent/ES2424793T3/en
Priority to CN200980126208.5A priority patent/CN102083952B/en
Publication of WO2010003792A1 publication Critical patent/WO2010003792A1/en
Priority to ZA2010/08049A priority patent/ZA201008049B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • This invention relates to an alginate granule. More particularly, the invention is directed to an alginate granule comprising citric acid. The invention further relates to laundry detergent compositions comprising the alginate granules of the invention, to a process to make the alginate granules and to the use of said granules to deliver benefit agents to the fabric.
  • Encapsulation or immobilisation of active materials is a well known technique which can offer advantages such as the stabilisation/protection of active materials that are otherwise unstable or reactive.
  • Alginates are known as encapsulation materials.
  • WO 00/46337 Quest International B. V.
  • This document relates to a liquid detergent composition containing greater than 5% by weight of surfactant and an encapsulate containing greater than 10% by weight of active material and a cross-linked anionic gum.
  • the anionic gum can be an alginate, and the active material can be a fragrance.
  • WO 2007/009621 discloses fabric softening particles which incorporate a fabric softening emulsion into an alginate or carrageenan polysaccharide matrix. These particles do not contain any sequestrant. The alginate particles leave residues on fabric due to the reliance on sequestrants present in detergent formulations to aid dissolution of the softening particle.
  • alginate encapsulates/beads A problem that exists with such alginate encapsulates/beads is that they leave visible residues on laundered clothes. Such visible residues are not only problematic for consumers, but are also indicative that the alginate matrix has not released the encapsulated benefit agent or other active material.
  • citric acid in the granulation process provides alginate granules that exhibit a reduced level of visible residues in laundry use.
  • the present invention provides an alginate granule comprising:
  • a second aspect of the invention provides a laundry detergent composition comprising from 0.1 to 25 wt . % of the alginate granule of the first aspect, from 2 to 70 wt . % of a surfactant, and from 1 to 70 wt . % of a builder.
  • a third aspect of the invention provides the use of the alginate granule of first aspect, to deliver a fabric benefit agent to a textile during the laundering process.
  • a fourth aspect of the invention provides a process for making the alginate granules of the first aspect, wherein the process includes the steps of:-
  • the alginate granules preferably have a size range of from 0.05 to 10mm. More preferably the particle size is between 0.1 and 2mm. The granule size can be measured for example using graded sieves.
  • the alginate granule preferably comprises:
  • Alginate is the general name for alginic acid and its salts. Alginates are linear polysaccharides made up from ⁇ - 1,4 linked D-mannuronate (M) residues and its C-5 epimer, ⁇ - 1,4 linked L-guluronate (G) residues. The alginates have a block polymeric arrangement of these M and G residues along the linear chain. The arrangement of these blocks can be described as being blocks of repeating M residues, repeating G residues, or alternating M and G residues.
  • the ratio of mannuronate to guluronate residues present in the alginate is well known in the art as the M:G ratio.
  • the M:G ratio of the alginate can vary due to the source or growth conditions of the alginate.
  • One common alginate source is brown seaweed (Phaeophyceae) .
  • the M:G ratio of the alginate used in the present invention is preferably from 0.1:1 to less than 1:1, for example 0.1:1 to 0.99:1. This means that the alginates used herein preferably contain a greater number of G residues than M residues.
  • the M:G ratio is more preferably 0.1:1 to 0.8:1, even more preferably from 0.2:1 to 0.8:1.
  • Certain embodiments of the alginate granules of the present invention may comprise alginate having an M:G ratio of from 0.25 to 0.75. Suitable sources for these alginates are those obtained from the fronds and stipes of Laminaria hyperborea .
  • the alginate granules comprise preferably alginate with a M:G as defined above. More preferably all of the alginate present in the granule has the aforementioned M:G ratios.
  • the molecular weight of the alginate can be between 1,000 to 3,000,000 Daltons.
  • the alginate is used in the form of a sodium salt.
  • Suitable alginates with the preferred M:G ratio are available under the "Manugel” trade name from International Speciality Products, for example “Manugel GMB”; “Protonal” from FMC Biopolymer; and, “Satialgine”, “Cecalgum” and “Algogel” from Texturant Systems.
  • the alginate is present in the granule at a level of from 30 to 80 wt . % .
  • the cationic species form the gelled cross-linked matrix with the alginate.
  • the cationic species is a divalent or polyvalent metal cation.
  • the cationic species forms a gelled network with alginate.
  • the cationic species is a calcium salt (e.g. calcium chloride) .
  • the cationic species is present in the granule at a level of from 10 to 30 wt . % .
  • Citric acid as used herein incorporates the free acid itself as well as its various anionic forms.
  • the citric acid is incorporated in the alginate granule as the free acid.
  • the citric acid is present in the granule at a level of from 5 to 30 wt . % .
  • the fabric benefit agent is selected from the group consisting of: chlorine/oxygen scavengers, antioxidants, non-calcium binding sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants, UV absorbers, shading dyes, fluorescent whitening agents, dispersants, anti-redeposition agents, soil release agents, enzymes (for removing fuzz or pills or preventing staining) , dye transfer inhibitors, dye binders, dye fixers, softeners, or crystal growth inhibitors.
  • the fabric benefit agent may also be a mixture of two or more of the aforementioned benefit agents.
  • the fabric benefit agent is selected from the group consisting of: mild reducing agents, non-calcium binding sequestrants, perfumes, fluorescent whitening agents, shading dyes, antimicrobial agents or mixtures thereof .
  • the inclusion level of the fabric benefit agent (s) in the granules is dependant on the amount that is required to achieve the benefit required, the release profile of the agent (s) and the calcium level. Typical ranges of fabric benefit agents in the alginate granule are from 0.001 to 60wt.% of the granule.
  • the inclusion level can preferably be between 0.001% to 20wt.% of the granule.
  • the inclusion level could be as high as 60wt.% of the granule.
  • a suitable process for making the alginate granules of the invention includes the steps of:-
  • citric acid is also present in the second solution.
  • the solution can use any suitable solvent. Water is preferred.
  • the alginate granule is suitably delivered to the fabric via incorporation into laundry detergent composition.
  • Suitable laundry detergent compositions comprise from 0.1 to 25 wt .% of the alginate granule and from 2 to 70 wt . % of a surfactant and from 1 to 70 wt . % of a builder.
  • the alginate granules are present in the laundry detergent composition at a level of from 0.1 to 25 wt.%, preferably from 0.5 to 10 wt.%.
  • the laundry treatment composition may take the form of an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry-blended powder, a tablet, a paste, a molded solid or any other laundry detergent form known to those skilled in the art.
  • the composition is preferably a liquid or granular laundry composition, most preferably a granular laundry composition.
  • Preferred laundry detergent composition forms which are particularly suitable in combination with the alginate granules of the invention are granular, spray-dried or dry- blended powder compositions.
  • the laundry detergent composition comprises between 2 to 70 wt.% of a surfactant, most preferably 10 to 30 wt.%.
  • a surfactant most preferably 10 to 30 wt.%.
  • the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • the surfactants used are saturated.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are Ce to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl Cio to Ci 5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the preferred anionic detergent compounds are sodium Cu to Ci 5 alkyl benzene sulphonates and sodium C12 to Cis alkyl sulphates.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .
  • Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) .
  • surfactant system that is a mixture of an alkali metal salt of a Ci ⁇ to Cis primary alcohol sulphate together with a C12 to Ci 5 primary alcohol 3 to 7 EO ethoxylate .
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt . % of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from about 5 wt . % to about 40 wt . % of the surfactant system.
  • the laundry detergent composition may comprise from 1 to 70 wt .% of a builder.
  • the level of builder is preferably from 1 to 40 wt . % .
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. It is preferred that when an insoluble inorganic builder, e.g., zeolite is used, the size is in the range 0.1 to 10 microns (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex MalvernTM) .
  • calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra- acetic acid.
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-O, 384, 070.
  • zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-O, 384, 070.
  • the composition may also contain 0-50 wt . % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
  • Zeolite and carbonate are preferred builders.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt . % .
  • Aluminosilicates are materials having the general formula:
  • M is a monovalent cation, preferably sodium.
  • These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • the ratio of surfactants to aluminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
  • phosphate builders may be used.
  • ⁇ phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) .
  • the laundry detergent formulation is a non- phosphate built laundry detergent formulation, i.e., contains less than 1 wt . % of phosphate.
  • the laundry detergent composition preferably comprises a blue or violet shading agent in the range from 0.0001 to 0.01 wt . % .
  • the shading agents reduce the perception of damage to many coloured garments and increase whiteness of white garments.
  • the shading agents are preferably selected from blue and violet dyes of the solvent disperse basic, direct and acid type listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) .
  • a direct violet or direct blue dyes is present.
  • the dyes are bis-azo, tris-azo dyes or triphendioxazine dye.
  • the carcinogenic benzidene based dyes are not preferred.
  • Bis-azo copper containing dyes such as direct violet 66 may be used.
  • the most preferred bis-azo dyes have the following structure :
  • ring D and E may be independently naphthyl or phenyl as shown;
  • Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
  • R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
  • R 3 and R 4 are independently selected from: hydrogen and Cl-
  • C4-alkyl preferably hydrogen or methyl
  • Preferred bis-azo dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
  • Preferred solvent and disperse dyes are selected from, mono-azo or anthraquinone dyes, most preferably, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
  • a preferred pigment is pigment violet 23.
  • the laundry detergent composition preferably comprises one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, - lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase.
  • the aforementioned additional enzymes may be present at levels from about 0.00001 wt . % to about 2 wt.%, from about 0.0001 wt .% to about 1 wt.% or even from about 0.001 wt.% to about 0.5 wt.% enzyme protein by weight of the composition.
  • Preferred enzymes are cellulases.
  • the laundry detergent composition preferably comprises a fluorescent agent (optical brightener) .
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt . % .
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Diamine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl) -2H-napthoi [l,2-d]trazole, disodium 4, 4 ' -bis ⁇ [ (4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1, 3, 5-triazin-2-yl) ] amino ⁇ stilbene-2-2 ' disulfonate, disodium 4, 4 ' -bis ⁇ [ (4-anilino-6-morpholino-l, 3, 5-triazin-2- yl) ] amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis (2-sulfoslyryl) biphenyl .
  • the laundry detergent composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2) : 80 [1955]) .
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol .
  • Perfume and top note may be used to cue the whiteness benefit of the invention.
  • the laundry detergent composition may comprise one or more polymers.
  • Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • compositions in the form of a liquid it is useful to include a hydrotrope, which prevents liquid crystal formation.
  • Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate.
  • Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine .
  • the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance.
  • the amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
  • the laundry detergent compositions may also suitably contain a bleach system. If bleach is present, then it is preferred that the compositions of the invention contain peroxy bleach compounds capable of yielding hydrogen peroxide in aqueous solution, for example inorganic or organic peroxyacids, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
  • Bleach ingredients are generally post-dosed as powders.
  • the peroxy bleach compound for example sodium percarbonate
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt. %, preferably from 10 to 25 wt . % .
  • the peroxy bleach compound for example sodium percarbonate, 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 wt . % .
  • 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 may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) , ethylenediamine disuccinate (EDDS) , and the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP) .
  • Hardening bath 500ml demineralised water + 1.75g CaCl2.2H 2 O + 0.2533g Acid Blue 80
  • Hardening bath 500ml demineralised water + 1.75g CaCl 2 .2H 2 O + 2.5g citric acid + 0.2533g Acid Blue 80 Batch 3 :
  • Hardening bath 500ml demineralised water + 1.75g CaCl2.2H2 ⁇ + 10. Og citric acid + 0.2533g Acid Blue 80
  • the granules were then removed from the hardening bath using a lmm sieve and oven dried at 60 0 C to constant weight.
  • the benefit agent release profile of the three batches of the alginate granules was then measured by placing Ig of granules into 500ml demineralised water adjusted to either pH 4, 7 or 10. The solution was pumped thorough a 10mm quartz flowcell mounted in a Hewlett-Packard 8453 diode array Uv/Vis Spectrophotometer ® . The release of Acid Blue 80 was measured by absorption at 629nm over a period of 90 minutes at room temperature.
  • Granule dissolution in a washing machine was assessed using the "black sachet" test, which reproduces the conditions experienced by a granule if it becomes caught in a pocket and is thus suffers less mechanical abrasion than if it was mobile inside the drum.
  • Ig of the various alginate granules was placed in between two pieces of black woven cotton and all edges overlocked, thus preventing the alginate granules from escaping.
  • the sachet was then attached to a 100x50cm panel of woven cotton sheeting to prevent it becoming lodged in the door seal of the washing machine.
  • the panel was then placed in a washing machine along with 80Og woven cotton sheeting, 80Og of knitted cotton and 80Og of 65:35 woven cotton ipolyester .
  • the particles of batch 1 are considered a fair representation of the disclosure of WO 2007/009621, in that they contain alginate, benefit agent and calcium.
  • the particles of batches 2 and 3 are according to the invention, and show the benefit of adding citric acid as part of the actual particle, as opposed to relying on sequestrant present in the detergent compositions to aid dissolution of the particle.
  • the alginate granules that contained citric acid as part of the granule itself exhibited significantly improved performance in that there were reduced or no residues after washing. This the technical advantage in terms of reduced residues for the incorporation of citric acid in a granule according to the invention as opposed to the prior art disclosures .

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Abstract

According to the invention there is provided an alginate granule comprising: (a) alginate; (b) one or more cationic species which is a divalent or polyvalent metal cation; (c) citric acid; and (d) one or more fabric benefit agents. The invention further relates to laundry detergent compositions comprising the alginate granules of the invention, to a process to make the alginate granules and to the use of said granules to deliver benefit agents to the fabric.

Description

LAUNDRY COMPOSITIONS
FIELD OF INVENTION
This invention relates to an alginate granule. More particularly, the invention is directed to an alginate granule comprising citric acid. The invention further relates to laundry detergent compositions comprising the alginate granules of the invention, to a process to make the alginate granules and to the use of said granules to deliver benefit agents to the fabric.
BACKGROUND
Encapsulation or immobilisation of active materials is a well known technique which can offer advantages such as the stabilisation/protection of active materials that are otherwise unstable or reactive. Alginates are known as encapsulation materials.
Our co-pending application PCT/EP2007/063046 relates to gelled alginate beads comprising alginate with a M:G ratio of from 0.1:1 to less than 1:1; one or more cationic species and one or more benefit agents. These are used to slowly release a benefit agent.
Another example of encapsulate use of alginate can be found in WO 00/46337 (Quest International B. V.) . This document relates to a liquid detergent composition containing greater than 5% by weight of surfactant and an encapsulate containing greater than 10% by weight of active material and a cross-linked anionic gum. The anionic gum can be an alginate, and the active material can be a fragrance.
WO 2007/009621 discloses fabric softening particles which incorporate a fabric softening emulsion into an alginate or carrageenan polysaccharide matrix. These particles do not contain any sequestrant. The alginate particles leave residues on fabric due to the reliance on sequestrants present in detergent formulations to aid dissolution of the softening particle.
A problem that exists with such alginate encapsulates/beads is that they leave visible residues on laundered clothes. Such visible residues are not only problematic for consumers, but are also indicative that the alginate matrix has not released the encapsulated benefit agent or other active material.
SUMNLARY OF INVENTION
We have found that inclusion of citric acid in the granulation process provides alginate granules that exhibit a reduced level of visible residues in laundry use.
In one aspect the present invention provides an alginate granule comprising:
(a) alginate;
(b) one or more cationic species which is a divalent or polyvalent metal cation; (c) citric acid; and
(d) one or more fabric benefit agents. A second aspect of the invention provides a laundry detergent composition comprising from 0.1 to 25 wt . % of the alginate granule of the first aspect, from 2 to 70 wt . % of a surfactant, and from 1 to 70 wt . % of a builder.
A third aspect of the invention provides the use of the alginate granule of first aspect, to deliver a fabric benefit agent to a textile during the laundering process.
A fourth aspect of the invention provides a process for making the alginate granules of the first aspect, wherein the process includes the steps of:-
a) provision of a first solution comprising an admixture of alginate, citric acid, and one or more benefit agents; b) forming droplets of the first solution; and, c) contacting said droplets with a second solution comprising a cationic species which is a divalent or polyvalent metal cation.
DETAILED DESCRIPTION OF THE INVENTION
The amounts of components present in the various compositions quoted herein are given as wt . % of the composition unless otherwise stated.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about".
Alginate Granules
The alginate granules preferably have a size range of from 0.05 to 10mm. More preferably the particle size is between 0.1 and 2mm. The granule size can be measured for example using graded sieves.
The alginate granule preferably comprises:
(a) 30-80 wt. % of alginate;
(b) 10-30% of one or more cationic species which is a divalent or polyvalent metal cation; (c) 5-30% citric acid; and,
(d) one or more fabric benefit agents.
Alginate
"Alginate" is the general name for alginic acid and its salts. Alginates are linear polysaccharides made up from β- 1,4 linked D-mannuronate (M) residues and its C-5 epimer, α- 1,4 linked L-guluronate (G) residues. The alginates have a block polymeric arrangement of these M and G residues along the linear chain. The arrangement of these blocks can be described as being blocks of repeating M residues, repeating G residues, or alternating M and G residues.
The ratio of mannuronate to guluronate residues present in the alginate is well known in the art as the M:G ratio. The M:G ratio of the alginate can vary due to the source or growth conditions of the alginate. One common alginate source is brown seaweed (Phaeophyceae) .
The M:G ratio of the alginate used in the present invention is preferably from 0.1:1 to less than 1:1, for example 0.1:1 to 0.99:1. This means that the alginates used herein preferably contain a greater number of G residues than M residues. The M:G ratio is more preferably 0.1:1 to 0.8:1, even more preferably from 0.2:1 to 0.8:1. Certain embodiments of the alginate granules of the present invention may comprise alginate having an M:G ratio of from 0.25 to 0.75. Suitable sources for these alginates are those obtained from the fronds and stipes of Laminaria hyperborea .
The alginate granules comprise preferably alginate with a M:G as defined above. More preferably all of the alginate present in the granule has the aforementioned M:G ratios.
Depending on the nature of the benefit agents and the release profile required, the molecular weight of the alginate can be between 1,000 to 3,000,000 Daltons.
Conveniently, the alginate is used in the form of a sodium salt.
Suitable alginates with the preferred M:G ratio are available under the "Manugel" trade name from International Speciality Products, for example "Manugel GMB"; "Protonal" from FMC Biopolymer; and, "Satialgine", "Cecalgum" and "Algogel" from Texturant Systems. Preferably the alginate is present in the granule at a level of from 30 to 80 wt . % .
Cationic Species
The cationic species form the gelled cross-linked matrix with the alginate. The cationic species is a divalent or polyvalent metal cation. The cationic species forms a gelled network with alginate. In a preferred embodiment, the cationic species is a calcium salt (e.g. calcium chloride) .
Preferably the cationic species is present in the granule at a level of from 10 to 30 wt . % .
Citric acid
Citric acid as used herein incorporates the free acid itself as well as its various anionic forms. Preferably the citric acid is incorporated in the alginate granule as the free acid.
Preferably the citric acid is present in the granule at a level of from 5 to 30 wt . % .
Fabric benefit agents
Preferably the fabric benefit agent is selected from the group consisting of: chlorine/oxygen scavengers, antioxidants, non-calcium binding sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants, UV absorbers, shading dyes, fluorescent whitening agents, dispersants, anti-redeposition agents, soil release agents, enzymes (for removing fuzz or pills or preventing staining) , dye transfer inhibitors, dye binders, dye fixers, softeners, or crystal growth inhibitors. The fabric benefit agent may also be a mixture of two or more of the aforementioned benefit agents.
Most preferably the fabric benefit agent is selected from the group consisting of: mild reducing agents, non-calcium binding sequestrants, perfumes, fluorescent whitening agents, shading dyes, antimicrobial agents or mixtures thereof .
The inclusion level of the fabric benefit agent (s) in the granules is dependant on the amount that is required to achieve the benefit required, the release profile of the agent (s) and the calcium level. Typical ranges of fabric benefit agents in the alginate granule are from 0.001 to 60wt.% of the granule.
For certain fabric benefit agents such as perfumes, fluorescent whitening agents or shading dyes which are effective at low levels, the inclusion level can preferably be between 0.001% to 20wt.% of the granule.
For other fabric benefit agents such as mild reducing agents and non-calcium binding sequestrants, the inclusion level could be as high as 60wt.% of the granule. Process for making the granules
A suitable process for making the alginate granules of the invention includes the steps of:-
a) provision of a first solution comprising an admixture of alginate, citric acid, and one or more benefit agents; b) forming droplets of the first solution; and, c) contacting said droplets with a second solution comprising a cationic species which is a divalent or polyvalent metal cation.
This is an example of a diffusion setting method and can suitably be carried out at neutral pH.
In an alternative process, citric acid is also present in the second solution.
The solution can use any suitable solvent. Water is preferred.
Laundry Detergent Composition
The alginate granule is suitably delivered to the fabric via incorporation into laundry detergent composition.
Suitable laundry detergent compositions comprise from 0.1 to 25 wt .% of the alginate granule and from 2 to 70 wt . % of a surfactant and from 1 to 70 wt . % of a builder. The alginate granules are present in the laundry detergent composition at a level of from 0.1 to 25 wt.%, preferably from 0.5 to 10 wt.%.
The laundry treatment composition may take the form of an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry-blended powder, a tablet, a paste, a molded solid or any other laundry detergent form known to those skilled in the art. The composition is preferably a liquid or granular laundry composition, most preferably a granular laundry composition.
Preferred laundry detergent composition forms which are particularly suitable in combination with the alginate granules of the invention are granular, spray-dried or dry- blended powder compositions.
SURFACTANT
The laundry detergent composition comprises between 2 to 70 wt.% of a surfactant, most preferably 10 to 30 wt.%. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated. Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are Ce to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl Cio to Ci5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cu to Ci5 alkyl benzene sulphonates and sodium C12 to Cis alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .
Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a Ciε to Cis primary alcohol sulphate together with a C12 to Ci5 primary alcohol 3 to 7 EO ethoxylate .
The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt . % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5 wt . % to about 40 wt . % of the surfactant system.
BUILDERS OR COMPLEXING AGENTS
The laundry detergent composition may comprise from 1 to 70 wt .% of a builder.
For laundry compositions in the form of granular, spray- dried or dry-blended powders, the level of builder is preferably from 1 to 40 wt . % .
Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. It is preferred that when an insoluble inorganic builder, e.g., zeolite is used, the size is in the range 0.1 to 10 microns (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern™) .
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra- acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-O, 384, 070.
The composition may also contain 0-50 wt . % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
Zeolite and carbonate (including bicarbonate and sesquicarbonate) are preferred builders. The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt . % . Aluminosilicates are materials having the general formula:
0.8-1.5 M2O. Al2O3. 0.8-6 SiO2
where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have 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 amply described in the literature. The ratio of surfactants to aluminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term λphosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) .
Preferably the laundry detergent formulation is a non- phosphate built laundry detergent formulation, i.e., contains less than 1 wt . % of phosphate. SHADING AGENT
The laundry detergent composition preferably comprises a blue or violet shading agent in the range from 0.0001 to 0.01 wt . % . The shading agents reduce the perception of damage to many coloured garments and increase whiteness of white garments.
The shading agents are preferably selected from blue and violet dyes of the solvent disperse basic, direct and acid type listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) .
Preferably a direct violet or direct blue dyes is present. Preferably the dyes are bis-azo, tris-azo dyes or triphendioxazine dye. The carcinogenic benzidene based dyes are not preferred.
Bis-azo copper containing dyes such as direct violet 66 may be used.
The most preferred bis-azo dyes have the following structure :
R2
Figure imgf000015_0001
or
R^2
Figure imgf000016_0001
wherein: ring D and E may be independently naphthyl or phenyl as shown;
Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen; R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
R3 and R4 are independently selected from: hydrogen and Cl-
C4-alkyl, preferably hydrogen or methyl; X and Y are independently selected from: hydrogen, C1-C4- alkyl and Cl-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
Preferred bis-azo dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
Preferred solvent and disperse dyes, are selected from, mono-azo or anthraquinone dyes, most preferably, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
A preferred pigment is pigment violet 23.
ENZYMES
The laundry detergent composition preferably comprises one or more enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, - lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a cleaning composition, the aforementioned additional enzymes may be present at levels from about 0.00001 wt . % to about 2 wt.%, from about 0.0001 wt .% to about 1 wt.% or even from about 0.001 wt.% to about 0.5 wt.% enzyme protein by weight of the composition.
Preferred enzymes are cellulases.
FLUORESCENT AGENT
The laundry detergent composition preferably comprises a fluorescent agent (optical brightener) . Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt . % . Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Diamine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl) -2H-napthoi [l,2-d]trazole, disodium 4, 4 ' -bis { [ (4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium 4, 4 ' -bis { [ (4-anilino-6-morpholino-l, 3, 5-triazin-2- yl) ] amino} stilbene-2-2' disulfonate, and disodium 4,4'- bis (2-sulfoslyryl) biphenyl .
PERFUME
Preferably the laundry detergent composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International
Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the - I i
present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt . % are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2) : 80 [1955]) . Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol .
Perfume and top note may be used to cue the whiteness benefit of the invention.
POLYMERS
The laundry detergent composition may comprise one or more polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
HYDROTROBE
For compositions in the form of a liquid, it is useful to include a hydrotrope, which prevents liquid crystal formation. The addition of the hydrotrope thus aids the clarity/transparency of the composition. Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate. Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine . Preferably, the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance. The amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
BLEACH
The laundry detergent compositions may also suitably contain a bleach system. If bleach is present, then it is preferred that the compositions of the invention contain peroxy bleach compounds capable of yielding hydrogen peroxide in aqueous solution, for example inorganic or organic peroxyacids, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates . Bleach ingredients are generally post-dosed as powders.
If present, the peroxy bleach compound, for example sodium percarbonate, is suitably present in an amount of from 5 to 35 wt. %, preferably from 10 to 25 wt . % . The peroxy bleach compound, for example sodium percarbonate, 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 wt . % .
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) , ethylenediamine disuccinate (EDDS) , and the aminopolyphosphonates such as ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP) .
Experimental
Example 1
Three granules were prepared using the diffusion setting process .
Batch 1: Alginate solution - 200ml demineralised water + 4.5g Manugel GMB + 0.1013g Acid Blue 80
Hardening bath - 500ml demineralised water + 1.75g CaCl2.2H2O + 0.2533g Acid Blue 80
Batch 2:
Alginate solution - 200ml demineralised water + 4.5g Manugel
GMB + Ig Citric acid + 0.1013g Acid Blue 80
Hardening bath - 500ml demineralised water + 1.75g CaCl2.2H2O + 2.5g citric acid + 0.2533g Acid Blue 80 Batch 3 :
Alginate solution - 200ml demineralised water + 4.5g Manugel
GMB + Ig Citric acid + 0.1013g Acid Blue 80
Hardening bath - 500ml demineralised water + 1.75g CaCl2.2H2θ + 10. Og citric acid + 0.2533g Acid Blue 80
The granules were then removed from the hardening bath using a lmm sieve and oven dried at 600C to constant weight.
Release of Benefit Agent Test
The benefit agent release profile of the three batches of the alginate granules was then measured by placing Ig of granules into 500ml demineralised water adjusted to either pH 4, 7 or 10. The solution was pumped thorough a 10mm quartz flowcell mounted in a Hewlett-Packard 8453 diode array Uv/Vis Spectrophotometer®. The release of Acid Blue 80 was measured by absorption at 629nm over a period of 90 minutes at room temperature.
Figure imgf000023_0001
[Acid Blue 80] released in g/ml - 2. Og/ml = 100% release
Thus, at pH 10, where the citric acid is converted to sodium citrate, dye release increases significantly compared to pH 4 and pH 7.
Example 2 - Visible Residues Test
Granule dissolution in a washing machine was assessed using the "black sachet" test, which reproduces the conditions experienced by a granule if it becomes caught in a pocket and is thus suffers less mechanical abrasion than if it was mobile inside the drum.
Ig of the various alginate granules was placed in between two pieces of black woven cotton and all edges overlocked, thus preventing the alginate granules from escaping. The sachet was then attached to a 100x50cm panel of woven cotton sheeting to prevent it becoming lodged in the door seal of the washing machine. The panel was then placed in a washing machine along with 80Og woven cotton sheeting, 80Og of knitted cotton and 80Og of 65:35 woven cotton ipolyester .
lOOg of Persil® Biological washing powder which comprises sodium citrate was placed in the detergent compartment and a 400C cotton wash cycle carried out (Prenton water, 26°FH) . On completion of the wash, the load was removed and tumble dried. The sachet was then opened and the degree of residues assessed on a scale of 1 to 5 (1 = no residues, 5 = high residues) .
Batch 1 (no citric acid) Ranking = 5
Batch 2 (low citric acid) Ranking = 2
Batch 3 (high citric acid) Ranking = 1
As Persil® Biological powder contains sodium citrate, it is clear that inclusion of the sodium citrate (a sequestrant) in the detergent composition is insufficient to stop residues. This confirms the disclosure of WO 2007/009621. The particles of batch 1 are considered a fair representation of the disclosure of WO 2007/009621, in that they contain alginate, benefit agent and calcium. The particles of batches 2 and 3 are according to the invention, and show the benefit of adding citric acid as part of the actual particle, as opposed to relying on sequestrant present in the detergent compositions to aid dissolution of the particle. The alginate granules that contained citric acid as part of the granule itself exhibited significantly improved performance in that there were reduced or no residues after washing. This the technical advantage in terms of reduced residues for the incorporation of citric acid in a granule according to the invention as opposed to the prior art disclosures .

Claims

1. An alginate granule comprising:
(a) alginate;
(b) one or more cationic species which is a divalent or polyvalent metal cation;
(c) citric acid; and
(d) one or more fabric benefit agents.
2. An alginate granule according to claim 1 comprising:
(a) 30-80 wt. % of alginate;
(b) 10-30% of one or more cationic species which is a divalent or polyvalent metal cation;
(c) 5-30% of citric acid; and
(d) one or more fabric benefit agents.
3. An alginate granule according to claim 1 or claim 2, wherein the alginate has a ratio of mannuronate to guluronate residues (the M:G ratio) of from 0.1:1 to less than 1:1, preferably from 0.1:1 to 0.8:1, more preferably from 0.2:1 to 0.8:1.
4. An alginate granule according to any one of claims 1 to 3, wherein the cationic species is calcium.
5. An alginate granule according to any preceding claim, wherein the fabric benefit is selected from the group consisting of: chlorine/oxygen scavengers, antioxidants, non-calcium binding sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants, UV absorbers, shading dyes, fluorescent whitening agents, dispersants, anti- redeposition agents, soil release agents, enzymes (for removing fuzz or pills or preventing staining) , dye transfer inhibitors, dye sequestrants, dye fixers, softeners, crystal growth inhibitors, or mixtures thereof .
6. An alginate granule according to claim 5, wherein the fabric benefit is selected from the group consisting of: mild reducing agents, sequestrants, perfumes, fluorescent whitening agents, shading dyes, antimicrobial agents or mixtures thereof.
7. An alginate granule according to any preceding claim wherein the fabric benefit agent is water soluble.
8. A laundry detergent composition comprising: -
(i) from 0.1 to 25 wt . % of the alginate granule of any one of claims 1 to 7,
(ii) from 2 to 70 wt . % of a surfactant; and, (iii) from 1 to 70 wt . % of a builder.
9. Use of the alginate granule of any one of claims 1 to 7, to deliver a fabric benefit agent to a textile during the laundering process.
10. A process for making the granule of any one of claims 1 to 7, comprising the following steps:- a) provision of a first solution comprising an admixture of alginate, citric acid, and one or more benefit agents; b) forming droplets of the first solution; and, c) contacting said droplets with a second solution comprising a cationic species which is a divalent or polyvalent metal cation.
11. A process according to claim 10, wherein the alginate has a ratio of mannuronate to guluronate residues (the M:G ratio) of from 0.1:1 to less than 1:1.
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