FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
LAUNDRY TREATMENT COMPOSITIONS
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed

LAUNDRY TREATMENT COMPOSITIONS
FIELD OF INVENTION
5 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. 10
BACKGROUND
To impart a soft feel to laundered clothes is desirable to consumers. One way of achieving this is to use a separate 15 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.
20 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.
25 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. 30

An encapsulation route is proposed in WO 2006/117385. Disclosed is a solid redispersible emulsion, comprising an oii-in-water emulsion consisting of a laundry care constituent, which is encapsulated in an enclosure 5 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 10 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 15 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.
20 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 25 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, 5 (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.
10 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.
15 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 20 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, 25 (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:-30

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; 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, 10
DETAILED DESCRIPTIOM OF THE INVENTION
The amount of components present in the laundry treatment composition quoted herein are wt.% of total composition 15 unless otherwise stated.
Solid Softening Granules
The solid softening granules are in the form of granules. 20 The granules preferably have a size range of from 0.1 to
5mm, more preferably from 0.2 to 3mm, most preferably from 0.2 5 to 1.5mm. The granule size can be measured for example using graded sieves.
25 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 30 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 5 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.%. 10
A polysaccharide comprises a plurality of saccharide rings which have pendant hydroxyl groups. Th.e polysaccharide is locust bean gum. This is a polysaccharide having an affinity for cellulose.
15
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
20 polysaccharide backbone.
The polysaccharide may optionally have hydrolytically releasable esterified pendant groups attached, for example acetate groups. However preferably the polysaccharide is a 25 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 30 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 5 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 10 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.
15 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.
20
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
25 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.
30 Preferably, the bond between the silicone and the
polysaccharide is such that the decay rate constant (kd) of

the material in an aqueous solution at 0.01 wt% of the
material together with 0.1 wt% of anionic surfactant at 40°C
-3 -1 and at a pH of 10.5 is such that kd<10 s
5 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.
10 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
15 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 20 linkages, ether linkages, urethane linkages, triazine linkages, carbonate linkages, amine linkages or ester-alkylene linkages.
A further method for silicone functionalisation of 25 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 30 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.
5 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 10 material is locust bean gum substituted with one or more polydimethylsiloxane chains, referred to herein as 'LBG-silicone' .
Softening Silicone
15
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.
20
The softening silicone is present in the granule at a level of from 0.995 to 29.395 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
2 5 granule.
The softening silicone is selected from polydialkyl siloxanes, amine derivatives thereof, and mixtures thereof. Preferably the softening silicone is an amino-silicone, and 30 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). 5
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. 10
When an emulsion is used, the emulsion comprises a softening silicone and a polysaccharide {preferably a polysaccharide-silicone conjugate) both as described above.
15 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
20 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 vater emulsions may be for example 55 to 80% water. The emulsion can be concentrated to provide a low water
25 emulsion.
The emulsion may also contain an emulsifying agent, preferably an emulsifying surfactant for the softening silicone and polysaccharide or polysaccharide-silicone 30 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.
5 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.
10
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
15 non-ionic surfactant, in a high shear mixer.
Inorganic Carrier
The inorganic carrier is selected from alkali metal and 20 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
25 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
30 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. 5
By soluble' 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
10 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 'insoluble' used in relation to the solid inorganic
15 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 20 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
25 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
30 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 5 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.
iO Preferred bicarbonate salts are sodium and potassium bicarbonate.
The preferred soluble inorganic carrier is sodium carbonate. The most preferred inorganic carrier is habit modified 15 sodium carbonate.
Process for making the granules
A suitable process for making the solid softening granules 20 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; 25 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.
30

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 Bucn.TM rotary evaporator. 5
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. 10
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 15 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. 20
Laundry Treatment Composition
The solid softening granule is suitably delivered to the fabric via incorporation into laundry treatment composition. 25
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.%
5 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.
10 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.
15 SURFACTANT
The laundry treatment composition comprises between 2 to 7 0 wt.% of a surfactant, most preferably 10 to 30 wt.%. In general, the nonionic and anionic surfactants of the
20 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
25 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 30 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 C6 to C22 alkyl phenol-ethylene oxide 5 condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C9 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
10 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. 15 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 C9 to C20 benzene sulphonates, particularly sodium
2 0 linear secondary alkyl C10 to C15 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 C11 to C15
25 alkyl benzene sulphonates and sodium C12 to C18 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.
30

Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and non.i-onic surfactants pointed out in EP-A-346 995 (Unilever)• Especially 5 preferred is surfactant system that is a mixture of an. alkali metal salt of a C16 to C18 primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.
10 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.
15
BUILDERS OR CQMPLEXING AGENTS
The laundry treatment composition may comprise from 1 to 7 0 wt.% of a builder. 20
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.%.
25 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, 30 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 5 alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium 10 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 15 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 20 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 25 metal ions.
Zeolite and carbonate (including bicarbonate and sesquicarbonate) are preferred builders.
30 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:
5 0.8-1.5 M2O. AI2O3. 0.8-6 Si02
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.
10 The preferred sodium aluminosilicates contain 1.5-3.5 Si02
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
15 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 ^phosphate' embraces diphosphate, triphosphate, and 20 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-25 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 5 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 10 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).
15 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.
20 Bis-azo copper containing dyes such as direct violet 66 may be used.
The most preferred bis-azo dyes have the following structure: 25



5 wherein:
ring D and E may be independently naphthyl or phenyl as
shown;
R1 is selected from: hydrogen and Cl-C4-alkyl, preferably
hydrogen; 10 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 C1-
C4-alkyl, preferably hydrogen or methyl; 15 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, 20 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, 25 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. 5
ENZYMES
The laundry treatment composition preferably comprises one or more enzymes which provide cleaning performance and/or
10 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,-
15 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 2 0 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. 25
Preferred enzymes are cellulases.
FLUORESCENT AGENT
30 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 5 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, Di¬amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS
10 pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1, 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,
15 disodium 4,4'-bis{[(4-anilino-5-morpholino-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
PERFUME
20
Preferably the laundry treatment composition comprises a perfume. The perfume is preferably in the range from 0.0 01 to 3 wt.%, most preferably 0.1 to 1 wt.%. Many suitable examples of perfumes are provided in the CTFA (Cosmetic,
25 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.
30 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 sever^ or more different perfume components.
5 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. 10
Perfume and top note may be used to cue the whiteness benefit of the invention.
POLYMERS
15
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
20 lauryl methacrylate/acrylic acid copolymers.
BLEACH
The laundry treatment compositions may also suitably contain 25 a bleach system. If bleach is present, then it is preferred that the comptjsitions of the invention contain peroxy bleach compounds capi^i;)iQ of yielding hydrogen peroxide in aqueous solution, for example inorganic or organic peroxyacids, and inorganic per^alts such as the alkali metal perborates, 30 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 5 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.%.
10
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
15 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 20 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
5 Example la
Example preparation of Locust Bean Gum Poly Dimethyl Siloxane Conjugate (LBG-silicone conjugate)
LBG-silicone conjugates can be prepared by the methods 10 described in WO 04/111159. An example preparation is as follows.
Lithium chloride (27g) was dissolved in anhydrous dimethyl
3
sulfoxide (300cm ) with heating (150°C) and stirring under
15 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.
20 The viscous solution thus obtained was then further cooled to 70°C and carbonyl diimidazole (54mg, O.Smmols) 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
25 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 30 isolate the product which was then washed with acetone (2 x

2 00cm3) before drying under vacuum (40°C) overnight to give an off-white solid (3.1g).
From the IH NMR of the hydrolysed product (heated to 1 hour 5 at 70°C in 20% DCi/D20) the degree of substitution of PDMS groups to sugar units was found to be 5.3 x lO-4.
Example lb
Example method for forming emulsions containing the 10 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 15 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
20 agitated using an ultrasonic probe (SoniprobeTM) 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 Silversdn™ L4R high shear mixer fitted with a 25mm diameter shearing
25 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 30 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
5 Example granulation processes using emulsion softening systems.
Emulsion softening systems were prepared by the methods outlined in WO 04/111169. A commercially available active 10 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 15 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 20 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
25
14.7g of the emulsion softening system was granulated with 20g 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
30 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 5 20g 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%. 10
Granules C
iOOg of the emulsion softening system was concentrated by removal of water in a Buchi™ rotary evaporator to a final 15 weight of 56.2g (the concentrate now has an active content of 35.6%) .
20.75g of this concentrated emulsion was granulated with 30g of habit modified sodium carbonate in a laboratory-scale 20 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%.
2 5 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 30 of 35.6%) .

20.75g of this concentrated emulsion was granulated with 30g of habit modified sodium carbonate in a laboratory-scale high shear mixer {Braun MR4050HC). The resultant granules were then oven-dried at 850C. The dried product was sieved 5 between 180 and 1400 microns. The "active" content of these granules is 19.8%.
Granules E
10 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%).
15 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 850C. The dried product was sieved between 180 and 1400
20 microns. The "active" content of these granules is 15.9%.

Table 1

Granules Emulsion Inorganic Drying Temp Active
Concentration Step? carrier 'C level
A No Habit
modified
NaCO3 25 8.5
B No Habit
modified
NaCO3 45 11.2%
C Yes Habit
modified
NaCO3 45 17.4%
D Yes Habit
modified
NaCO3 85 19.8%
E Yes NaCO3 85 15.9%
Example 2 - Softness Benefit
5
Comparative alginate granules were produced in accordance with WO 2006/117385.
Silicone dosage was based on theoretical silicone levels in 10 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. 15
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 20 washes at 600C with a European reference detergent.

METHODS
A RotaWashTM was used to simulate conditions in typical full-scale European Front Loading Automatic (FLA) washing 5 machines. The RotaWashTM is a small scale washer with 12 individual wash 'pots', each with a capacity of 250mls. In these experiments, each wash pot contains a single piece of fabric.
10 Conditions used below simulate as near as possible those of a standard 4000 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. 15
Temp 4 0°C
water Hardness Wirral water (12-14° French Hardness)
LiquorrCloth ratio 8:1 (Liquor = 132 mls)
Cloth type White terry towelling, 1 piece per
20 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
25 66 mis Wirral water)
Wash time 45 mins
Rinses 2x10 min rinses (with agitation),
using 250ml Wirral water per rinse
Drying Line dry
30

The following chart (table 2) shows softness delivery measured by Shear Hysteresis (Instrumental Shear measurement) from the Persil™ Bio powder (2 00 6 UK commercially available laundry detergent product) with 5 addition of various LBG-Silicone granules made according to example 1 and in comparison to the alginate softening granules.
Table 2

Composition Shear Hysteresis 2H65
Control (Persil™ Bio Powder) 6.20
Alginate granules, 80% 3.61
silicone
Granules D 4.10
LEG-silicone/Carbonate
granule, 17.4% silicone
Granules C 4.22
LBG-silicone/Carbonate
granule, 19.8% silicone
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 15 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 5 granules.
Example 3 — Improved physical properties on storage
Carbonate granules show improved physical properties 10 (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 wexe a sticky mass stuck together by leaked silicone, and were unacceptable for 15 use in formulations.
Example 4 - Reduction in visible residues
Conditions used below simulate as near as possible those of 20 the standard 30°C 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. 25

Temp 30°C
Water Hardness Wirral water (12-14° French Hardness)
Liquor:Cloth ratio 8:1 {Liquor = 132 mis)
Cloth type Black jersey interlock, 1 piece per
5 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/I (66 mis of 11.6g/l stock, plus
10 66 mis Wirral water)
Wash time 24 mins
Rinses 2x10 min rinses (with agitation),
using 250ml Wirral water per rinse
Drying Line dry
15 ■
Visual assessment of black fabric washed with Persil™ Bio powder + LBG-Silicone/carbonate granules (tested separately with both ,\'C' and 'D' granules from table 1) and Persil™ Bio
20 powder + alginate granules showed a considerably lower level of visible residues for the carbonate granules (for both 'C' and 'D') 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,
25 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:
5 (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
10 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
15 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
20 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.%.
25
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
30 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
5 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
10 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
15 softening silicone comprises aminosilicone and the
inorganic carrier is habit modified sodium carbonate.
10. A laundry treatment composition comprising:-
20 (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, (ill) from 1 to 70 wt.% of a builder.
25 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: 30

(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. 5
13. A process for making the solid softening granules of
any one of claims 1 to 10, wherein the process includes the steps of:-
10 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
15 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.
20 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 25 the drying step c) is carried out at a level of from 20 to 100°C.