WO2009156233A1

WO2009156233A1 - Laundry treatment compositions

Info

Publication number: WO2009156233A1
Application number: PCT/EP2009/056119
Authority: WO
Inventors: Andrew Paul Chapple; Lesley Ebbrell; Peter Graham; David Andrew Ross Jones
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2008-06-25
Filing date: 2009-05-20
Publication date: 2009-12-30
Also published as: CN102076836A; BRPI0914753A2; ZA201008966B; EP2294169B1; EP2294169A1; ES2398425T3; CN102076836B

Abstract

According to the invention there is provided a solid softening granule comprising an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof, and a softening system comprising of a locust bean gum polysaccharide and a softening silicone; a process to make the granule is also provided, as well as a laundry treatment composition comprising the softening granule and use of the laundry composition and a method of treating a textile with said laundry composition.

Description

LAUNDRY TREATMENT COMPOSITIONS

FIELD OF INVENTION

The present invention relates to solid softening granules for incorporation into a wash added laundry treatment composition, to a process for the preparation of the fabric softening granules, to a domestic method of treating a textile, and to the use of the fabric softening granules.

BACKGROUND

To impart a soft feel to laundered clothes is desirable to consumers. One way of achieving this is to use a separate rinse conditioner in addition to the detergent. However, it is more convenient to use a single product that provides both the cleaning and softness requirements, these are known as "softening in the wash" products.

WO 04/111169 discloses hydrolytically stable polysaccharides which are covalently linked to a first polymeric textile softening species and optionally emulsified with a second polymeric textile softening species.

A problem that exists in the softening in the wash field is the formulation of such softening in the wash products.

Many useful softener ingredients are liquids or emulsions.

Various methods are utilised to incorporate these liquids or emulsions into powder formulations. An encapsulation route is proposed in WO 2006/117385. Disclosed is a solid redispersible emulsion, comprising an oil-in-water emulsion consisting of a laundry care constituent, which is encapsulated in an enclosure stabilised by polyvalent metal ions. The enclosure material is preferably a polysaccharide such as alginate.

A granulation route is proposed in WO 2007/009621 to provide softening particles. Disclosed is a process in which a silicone oil emulsion is granulated with a kappa carrageenan or alginate polymer matrix.

However, a problem with such alginate encapsulates and granules are that they are unstable when stored at high temperature and humidity due to leakage of silicone oil. A further problem is that when incorporated in laundry products they leave visible residues on the laundered clothes .

SUMMARY OF INVENTION

We have found that granulation using a soluble inorganic carrier provides softening granules that overcome one or more of the aforementioned problems and further provide acceptable fabric softening.

In one aspect the present invention provides a solid softening granule comprising: (i) from 1 to 30 wt . % of a softening system which comprises a locust bean gum polysaccharide and a softening silicone in a weight ratio of from 1:200 to 1:5; and, (ϋ) from 70 to 99 wt . % of an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof.

A second aspect of the invention provides a laundry treatment composition comprising from 0.1 to 25 wt . % of the solid softening 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 an effective amount of the laundry treatment composition of the second aspect to soften fabric in the wash.

A fourth aspect of the invention provides a domestic method treating a textile, comprising the steps of:

(i) treating a textile with an aqueous solution of from 1 to 20 g/1 of the laundry treatment composition of the second aspect; and, (ii) rinsing and drying the textile.

A fifth aspect of the invention provides a process for making the solid softening granules of the first aspect, wherein the process includes the steps of:- a) provision of an emulsion comprising water and a softening system which comprises a locust bean gum polysaccharide and a softening silicone in a weight ratio of from 1:200 to 1:5; b) granulation of the emulsion with an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof in a high shear mixer; and, c) drying the resulting granules.

DETAILED DESCRIPTION OF THE INVENTION

The amount of components present in the laundry treatment composition quoted herein are wt . % of total composition unless otherwise stated.

Solid Softening Granules

The solid softening granules are in the form of granules. The granules preferably have a size range of from 0.1 to

5mm, more preferably from 0.2 to 3mm, most preferably from 0.25 to 1.5mm. The granule size can be measured for example using graded sieves.

Softening System

The solid softening granule comprises from 1 to 30 wt.%, preferably from 2.5 to 27.5 wt.%, more preferably from 5 to 25 wt.% of a softening system. The softening system comprises a locust bean gum polysaccharide and softening silicone . Polysaccharide

The weight ratio of the polysaccharide to the softening silicone in the softening system is in the range of 1:200 to 1:5, preferably 1:50 to 1:5, more preferably 1:20 to 1:5 parts by weight.

The polysaccharide is present in the granule at a level of from 0.005 to 5 wt.%, preferably from 0.05 to 3 wt . % .

A polysaccharide comprises a plurality of saccharide rings which have pendant hydroxyl groups. The polysaccharide is locust bean gum. This is a polysaccharide having an affinity for cellulose.

The polysaccharide may be straight or branched. Many naturally occurring polysaccharides have at least some degree of branching, or at any rate at least some saccharide rings are in the form of pendant side groups on a main polysaccharide backbone.

The polysaccharide may optionally have hydrolytically releasable esterified pendant groups attached, for example acetate groups. However preferably the polysaccharide is a non-hydrolysable polysaccharide (NHP) , which is free of hydrolytically releasable esterified pendant groups.

Locust bean gum is an example of a polysaccharide having a β-1,4 linked polysaccharide backbone with various levels of branchpoints to saccharide or polysaccharide side chains. Locust bean gum is a galacto-mannan polysaccharide and has a β-1,4 linked backbone with galactose branches.

The locust bean gum polysaccharide is a non-charged polysaccahride .

In a preferred locust bean gum polysaccharide at least some of these hydroxyl groups are independently substituted by, or replaced with, one or more silicone groups. The "average degree of substitution" for a given class of substituent means the average number of substituents of that class per saccharide ring for the totality of polysaccharide molecules in the sample and is determined for all saccharide rings.

Preferably, the average degree of substitution for the silicone groups on the polysaccharide backbone is from 0.00001 to 0.5, preferably from 0.001 to 0.5, more preferably from 0.001 to 0.1. A further preferred range is from 0.01 to 0.05.

Preferably the polysaccharide has one or more silicone groups attached to it in a covalent fashion. If one or more silicone groups are attached to the polysaccharide, they are independent of and separate to the softening silicone of the emulsion. The silicone material attached to the polysaccharide may be the same material as the softening silicone, but there is no requirement for that to be the case .

Preferably, the bond between the silicone and the polysaccharide is such that the decay rate constant (k^) of the material in an aqueous solution at 0.01 wt% of the material together with 0.1 wt% of anionic surfactant at 40⁰C

-3 -1 and at a pH of 10.5 is such that k_d<10 s

The silicone material attached to the polysaccharide is preferably a polymeric long chain silicone material, preferably selected from polydialkyl siloxanes, amine derivatives thereof, and mixtures thereof.

In the covalent attachment of the silicone group (s) to the polysaccharide material, one or more hydroxyl groups on the polysaccharide are reacted with a reactive group attached to the silicone chain, or the hydroxyl group (s) of the polysaccharide in question is/are converted to another group capable of reaction with a reactive group attached to the silicone chain as described in WO 04/111169.

Preferred linking groups for attachment of the silicone group to the polysaccharide are by amide linkages, ester linkages, ether linkages, urethane linkages, triazine linkages, carbonate linkages, amine linkages or ester- alkylene linkages.

A further method for silicone functionalisation of polysaccharides is disclosed in WO 2006/117386. This document discloses the chemical modification of polysaccharides using a mechanical device which involves treatment of the polysaccharide with a rolling mill which has at least two adjacent rollers running in opposite directions and rotating at different speeds. One chemical modification agent used can be an epoxy-functionalised polysiloxane, and the polysaccharide is mixed with the chemical modification agent before and/or during the mechanical processing.

The polysaccharide which has one or more silicone groups covalently attached can be conveniently referred to herein as a polysaccharide-silicone conjugate.

The most preferred polysaccharide-silicone conjugate material is locust bean gum substituted with one or more polydimethylsiloxane chains, referred to herein as ^λLBG- silicone' .

Softening Silicone

The weight ratio of the polysaccharide or polysaccharide- silicone conjugate to the softening silicone in the softening system is in the range of 1:200 to 1:5, preferably 1:50 to 1:5, more preferably 1:20 to 1:5 parts by weight.

The softening silicone is present in the granule at a level of from 0.995 to 29.995 wt.%, preferably from 0.91 to 27.3 wt . % . The most preferred level of the softening silicone in the granule is from 10 to 25 wt.% of total weight of the granule.

The softening silicone is selected from polydialkyl siloxanes, amine derivatives thereof, and mixtures thereof. Preferably the softening silicone is an amino-silicone, and is independently selected from any silicone covalently bonded to the polysaccharide. More preferably the softening silicone is a hindered amine silicone. The preferred dynamic viscosity of the softening silicone is > 2,500 mPas (at a shear rate of around 100 reciprocal seconds and a temperature of 20°C).

The solid softening granules comprise polysaccharide and softening silicone. These components can be preferably combined together into an emulsion for ease of processing into the solid softening granules.

When an emulsion is used, the emulsion comprises a softening silicone and a polysaccharide (preferably a polysaccharide- silicone conjugate) both as described above.

The emulsions further comprise another liquid component, preferably a polar solvent, such as water. The emulsion has typically 30 to 99.9%, preferably 40 to 99% of the other liquid component (e.g. water). The emulsion may for example be a high water emulsion, or a low water emulsion. Low water emulsions may be for example 30 to 60% water, preferably 40 to 55% water. High water emulsions may be for example 60 to 99.9% water, preferably 80 to 99% water. Moderate water emulsions may be for example 55 to 80% water. The emulsion can be concentrated to provide a low water emulsion.

The emulsion may also contain an emulsifying agent, preferably an emulsifying surfactant for the softening silicone and polysaccharide or polysaccharide-silicone conjugate. In preferred cases, the polysaccharide-silicone conjugate is itself an emulsifying agent. The emulsifying agent, if present, is preferably one or more surfactants, for example, selected from any class, sub class or specific surfactant (s) disclosed herein in any context.

The emulsifying agent most preferably comprises or consists of a non-ionic surfactant. Additionally or alternatively, one or more selected additional surfactants from anionic, cationic, zwitterionic and amphoteric surfactants may be incorporated in or used as the emulsifying agent.

The emulsion is prepared by mixing the softening silicone, polysaccharide (preferably a polysaccharide-silicone conjugate), polar solvent (e.g. water), and preferably also an emulsifying agent, such as a surfactant, especially a non-ionic surfactant, in a high shear mixer.

Inorganic Carrier

The inorganic carrier is selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof.

As used herein, carbonate and bicarbonate are used to refer to an alkali or alkaline earth metal salt such as for example sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or another salt obtained by full or partial neutralization of carbonic acid. The weight percent of a salt of carbonate or bicarbonate can be expressed either as the weight percent of just the anionic carbonate or bicarbonate, or of the entire salt including the cation. The inorganic carrier may be soluble or insoluble. Preferably the inorganic carrier is soluble. Examples of soluble inorganic carriers are carbonates and bicarbonates, in particular, sodium carbonate and sodium bicarbonate.

By ^λsoluble' used in relation to the soluble inorganic carrier is meant that the inorganic carrier dissolves in water. Such that when Ig of inorganic carrier is placed into an aqueous solution of IL at room temperature and shaken at 100 RPM on a rotator shaker at 293K for 2 hours, then the weight of the inorganic carrier removed (by filtering through a sieve or filter paper of appropriate size and drying) is less than 95% by weight of that added. By ^λinsoluble' used in relation to the solid inorganic carrier means those carriers that do not pass the aforementioned solubility test.

The inorganic carrier is present in the solid softening granule at a level of from 70 to 99 wt.%, preferably 72.5 to 97.5 wt.%, most preferably from 75 to 95 wt.%.

The carbonate carrier is a carbonate salt of a suitable alkali or alkaline earth metal cation. Preferably the carbonate is habit modified carbonate (HMC) . More preferably the carbonate material is habit modified sodium carbonate. These materials have a high surface area and hence high carrying capacity. An advantage of such material is that high loading of the softening silicone can be achieved. Examples of how to modify sodium carbonate in this fashion can be found in WO 2006/081930. Disclosed therein is a process for preparing a modified sodium carbonate carrier material, the process comprising the steps of: (i) preparing an aqueous solution of sodium carbonate; an effective amount of a crystal growth modifier selected from the group comprising polyacrylates, polyaspartates and polyaspartic acids; whereby crystal growth-modified sodium carbonate is formed; (ii) drying the solution by any conventional drying method to form a dry solid carrier material .

Preferred bicarbonate salts are sodium and potassium bicarbonate .

The preferred soluble inorganic carrier is sodium carbonate. The most preferred inorganic carrier is habit modified sodium carbonate.

Process for making the granules

A suitable process for making the solid softening granules of the invention includes the steps of:- a) provision of an emulsion comprising water and a softening system which comprises a locust bean gum polysaccharide and a softening silicone in a weight ratio of from 1:200 to 1:5; b) granulation of the emulsion with an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof, in a high shear mixer; and, c) drying the resulting granules. Preferably the emulsion of step a) is concentrated by water evaporation to provide an emulsion comprising from 30 to 60% water. Suitable apparatus for this concentration step is a

Buchi ¹TM rotary evaporator.

The drying step c) is preferably carried out at a level of from 20 to 100 °C. The granules may by air dried at the lower end of this temperature range, an oven can be used to dry the granules at high temperatures.

The granules can thus be isolated, and optionally passed through sieves to achieve the required sized granules. In a high shear mixer as used herein, mixing is applied using any suitable apparatus such as an ultrasound sonicator, microfluidizer or homogenizer. A suitable homogeniser is a Manton Gaulin homogeniser or any other make of high shear homogenizer such as an Ultra Turrax. A suitable laboratory-scale high shear mixer is the Braun MR4050HC.

Laundry Treatment Composition

The solid softening granule is suitably delivered to the fabric via incorporation into laundry treatment composition.

Suitable laundry treatment compositions comprise from 0.1 to 25 wt .% of the solid softening granule and from 2 to 70 wt . % of a surfactant. The softening granules are present in the laundry treatment 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 a granular, spray-dried or dry-blended powder, a tablet, a molded solid or any other similar laundry detergent form known to those skilled in the art.

Preferred laundry treatment composition forms which are particularly suitable in combination with the solid softening granules of the invention are granular, spray- dried or dry-blended powder compositions.

SURFACTANT

The laundry treatment 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 C_±β 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 treatment 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, - I i

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 treatment 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 :

or

R^2

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 treatment 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 treatment 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 treatment 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 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 treatment 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.

BLEACH

The laundry treatment 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 - Production of carbonate/LBG-silicone granules

Example Ia

Example preparation of Locust Bean Gum Poly Dimethyl Siloxane Conjugate (LBG-silicone conjugate)

LBG-silicone conjugates can be prepared by the methods described in WO 04/111169. An example preparation is as follows .

Lithium chloride (2Iq) was dissolved in anhydrous dimethyl sulfoxide (300cm ) with heating (150 °C) and stirring under nitrogen. Once the lithium chloride was dissolved the solution was cooled to 120 °C before slowly adding locust bean gum (3.5g) over a period of 20 minutes with vigorous stirring.

The viscous solution thus obtained was then further cooled to 70 °C and carbonyl diimidazole (54mg, 0.5mmols) was added and stirring and heating was continued for a further two hours. Diaminopropyl terminated polydimethylsiloxane, 3,000 MWt, (Ig, 0.33mmols) was then added and the solution stirred with heating for 18 hours.

The solution was cooled to room temperature before adding drop-wise to vigorously stirring acetone (3 litres) to precipitate the polymer. The solution was centrifuged to isolate the product which was then washed with acetone (2 x 200cm ) before drying under vacuum (40 "C) overnight to give an off-white solid (3.Ig).

From the IH NMR of the hydrolysed product (heated to 1 hour at 70 °C in 20% DCI/D₂O) the degree of substitution of PDMS groups to sugar units was found to be 5.3 x 10^~4.

Example Ib

Example method for forming emulsions containing the polysaccharide & softening silicone

As softening system (in this case an emulsion) comprising a polysaccharide (i.e. LGB-silicone conjugate) and softening silicone can be prepared by the methods described in WO 04/111169. An example preparation is as follows.

The LBG-silicone conjugate and optional emulsifier (Synperonic A7 was used) were weighed into a bottle along with the required amount of water. This mixture was agitated using an ultrasonic probe (Soniprobe™) at half power until no undissolved polysaccharide is visible (2-3 minutes). The softening silicone (Q2-8220) was then added to the bottle. The mixture was sheared using a Silverson™ L4R high shear mixer fitted with a 25mm diameter shearing head and a square-hole, high shear screen at setting 5 for four minutes.

Synperonic A7™ is a dodecane hexaethoxylate nonionic surfactant Q2-8220™ is an aminosilicone oil from Dow Corning. Its viscosity was measured as 160 mPas with a "Bohlin CV 120 High Resolution" viscometer at 22°C and a shear rate of 100s^'1 using the cone and plate method.

Example Ic Example granulation processes using emulsion softening systems .

Emulsion softening systems were prepared by the methods outlined in WO 04/111169. A commercially available active softening silicone emulsion was modified by addition of the LBG-silicone conjugate. This is the emulsion softening system used for the following granulation processes.

The 20% active content levels of the emulsions used as well as the % active content of the resulting granules indicate total silicone actives, in this case the combination of the LBG-silicone conjugate and softening silicone.

The weight ratio of the LBG-silicone conjugate to the softening silicone for each of the emulsions was 1:9. Thus the 20% active content level of the emulsion was made up of 2% LBG-silicone conjugate + 18% softening silicone.

Granules A

14.7g of the emulsion softening system was granulated with 2Og of habit modified sodium carbonate in a laboratory-scale high shear mixer (Braun MR4050HC) . The resultant granules were then air dried at approximately 25 °C. The dried product was sieved between 180 and 1400 microns. The "active" content of these granules is 8.5%. Granules B

14.7g of the emulsion softening system was granulated with 2Og of habit modified sodium carbonate in a laboratory-scale high shear mixer (Braun MR4050HC) . The resultant granules were then air dried at approximately 45 °C. The dried product was sieved between 180 and 1400 microns. The "active" content of these granules is 11.2%.

Granules C

lOOg of the emulsion softening system was concentrated by removal of water in a Buchi™ rotary evaporator to a final weight of 56.2g (the concentrate now has an active content of 35.6%) .

20.75g of this concentrated emulsion was granulated with 3Og of habit modified sodium carbonate in a laboratory-scale high shear mixer (Braun MR4050HC) . The resultant granules were then oven-dried at 45 °C. The dried product was sieved between 180 and 1400 microns. The "active" content of these granules is 17.4%.

Granules D

lOOg of the emulsion softening system was concentrated by removal of water in a Buchi™ rotary evaporator to a final weight of 56.2g (the concentrate now has an active content of 35.6%) . 20.75g of this concentrated emulsion was granulated with 3Og of habit modified sodium carbonate in a laboratory-scale high shear mixer (Braun MR4050HC) . The resultant granules were then oven-dried at 85 °C. The dried product was sieved between 180 and 1400 microns. The "active" content of these granules is 19.8%.

Granules E

13.3g of this concentrated emulsion was granulated with 25g of commercial grade sodium carbonate (light ash ex. Brunner Mond) in a laboratory-scale high shear mixer (Braun MR4050HC) . The resultant granules were then oven-dried at 85 °C. The dried product was sieved between 180 and 1400 microns. The "active" content of these granules is 15.9%.

Table 1

Example 2 - Softness Benefit

Comparative alginate granules were produced in accordance with WO 2006/117385.

Silicone dosage was based on theoretical silicone levels in the granules. These were calculated to give equivalent silicone dosage on the fabric monitors of 2mg silicone per g of fabric (100% pick-up of silicone is assumed), for each granule type. This level of silicone equates to 4.3% silicone in the Persil powder.

The fabrics used in both the softening test (white cotton terry towelling) and residues test (black jersey cotton interlock), were pre-washed before use. Standard protocols for desizing were used for this pre-washing, generally 2 washes at 60⁰C with a European reference detergent. METHODS

A RotaWash™ was used to simulate conditions in typical full- scale European Front Loading Automatic (FLA) washing machines. The RotaWash™ is a small scale washer with 12 individual wash ^λpots' , each with a capacity of 25OmIs. In these experiments, each wash pot contains a single piece of fabric .

Conditions used below simulate as near as possible those of a standard 40⁰C cotton wash in a European FLA washing machine, using the RotaWash. Four repeat wash pots were ran per granule type. This gives sufficient replicates for the instrumental shear measurements.

Temp 40⁰C

Water Hardness Wirral water (12-14° French Hardness) LiquoriCloth ratio 8:1 (Liquor = 132 mis) Cloth type White terry towelling, 1 piece per pot (21cm²) ~ 16.5g

Ballbearings 25 in each pot Powder Persil™ Bio non-perfumed (pre- dissolved before adding to pots)

Powder dosage 5.8 g/1 (66 mis of 11.6g/l stock, plus

66 mis Wirral water)

Wash time 45 mins Rinses 2 x 10 min rinses (with agitation) , using 250ml Wirral water per rinse

Drying Line dry The following chart (table 2) shows softness delivery measured by Shear Hysteresis (Instrumental Shear measurement) from the Persil™ Bio powder (2006 UK commercially available laundry detergent product) with addition of various LBG-Silicone granules made according to example 1 and in comparison to the alginate softening granules .

Table 2

Reduction in shear hysteresis values when compared to the control show lower friction values for the fabric and hence a softness benefit to the laundered fabric for the alginate granules as well as for the two LBG-silicone/carbonate granules, granules D & C. Subjective assessment of fabrics washed with silicone were significantly softer to the hand than without softener - showing that consumer acceptable softening is delivered from the carbonate granules as well as from the alginate granules.

Example 3 - Improved physical properties on storage

Carbonate granules show improved physical properties (reduction of oil leakage and stickiness) on storage at 28°C/70% RH (8 weeks), compared with alginate granules. After this period the carbonate granules were still free flowing, while the alginate granules were a sticky mass stuck together by leaked silicone, and were unacceptable for use in formulations.

Example 4 - Reduction in visible residues

Conditions used below simulate as near as possible those of the standard 30⁰C residues test in a full scale FLA washing machine, using a black wash load of knitted cotton, low agitation wash (Woollens wash cycle) . Again, the RotaWash™ was used, and two repeat wash pots were run per granule type. Temp 30⁰C

Water Hardness Wirral water (12-14° French Hardness) Liquor : Cloth ratio 8:1 (Liquor = 132 mis) Cloth type Black jersey interlock, 1 piece per pot, 1 piece per pot (21cm²) ~ 16.5g

Ballbearings Not included to reduce agitation Powder Persil™ Bio non-perfumed (pre- dissolved before adding to pots)

Powder dosage 5.8 g/1 (66 mis of 11.6g/l stock, plus

66 mis Wirral water)

Wash time 24 mins Rinses 2 x 10 min rinses (with agitation) , using 250ml Wirral water per rinse

Drying Line dry

Visual assessment of black fabric washed with Persil™ Bio powder + LBG-Silicone/carbonate granules (tested separately with both ^λC and ^λD' granules from table 1) and Persil™ Bio powder + alginate granules showed a considerably lower level of visible residues for the carbonate granules (for both ^ΛC and ^λD' ) compared with the alginate granules. This was based on a visual assessment of the washed and dried black monitor fabrics by 3 people. Unlike the alginate granules, no particle residues were seen with the carbonate granules. The same result was seen for fabrics from both replicate washes .

Claims

1. A solid softening granule comprising:

(i) from 1 to 30 wt . % of a softening system which comprises a locust bean gum polysaccharide and a softening silicone in a weight ratio of from 1:200 to 1:5; and,

(ii) from 70 to 99 wt . % of an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof.

2. A solid softening granule according to claim 1, wherein the softening system is present in the softening granule at a level of from 5 to 25 wt . %

3. A solid softening granule according to claim 1 or claim 2, wherein the inorganic carrier is present in the softening granule at a level of from 75 to 95 wt . % .

4. A solid softening granule according to any preceding claim, wherein the softening silicone is present in the softening granule at a level of from 10 to 25 wt . % .

5. A solid softening granule according to any preceding claim, wherein the locust bean gum polysaccharide is covalently attached to one or more silicone materials chosen from polydialkyl siloxanes, amine derivatives thereof, and mixtures thereof.

6. A solid softening granule according to any preceding claim, wherein the inorganic carrier is soluble.

7. A solid softening granule according to claim 6 wherein the soluble inorganic carrier is sodium carbonate, preferably habit modified sodium carbonate.

8. A solid softening granule according to any preceding claim, wherein the softening silicone present in the emulsion comprises aminosilicone .

9. A solid softening granule according to any preceding claim, wherein the locust bean gum polysaccharide has one or more silicone chains covalently attached, the softening silicone comprises aminosilicone and the inorganic carrier is habit modified sodium carbonate.

10. A laundry treatment composition comprising: -

(i) from 0.1 to 25 wt . % of a solid softening granule of any one of claims 1 to 9, (ii) from 2 to 70 wt . % of a surfactant; and, (iii) from 1 to 70 wt . % of a builder.

11. Use of an effective amount of the laundry treatment composition of claim 10 to soften fabric in the wash.

12. A domestic method of treating a textile, comprising the steps of: (i) treating a textile with an aqueous solution of from 1 to 20 g/1 of the laundry treatment composition of claim 10; and, (ii) rinsing and drying the textile.

13. A process for making the solid softening granules of any one of claims 1 to 10, wherein the process includes the steps of:-

a) provision of an emulsion comprising water and a softening system which comprises a locust bean gum polysaccharide and a softening silicone in a weight ratio of from 1:200 to 1:5; b) granulation of the emulsion with an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof in a high shear mixer; and, c) drying the resulting granules.

14. A process according to claim 13, wherein the emulsion of step a) is concentrated by water evaporation to provide an emulsion comprising from 30 to 60% water.

15. A process according to claim 13 or claim 14, wherein the drying step c) is carried out at a level of from 20 to 100^°C.