The present invention relates to a granular composition and in particular to a granular composition for delivering silicones rapidly to an aqueous medium. Silicones have found wide use in a range of aqueous-based applications. For example silicones may be used as fabric softeners, as antifoam agents and as surface treatments. In each case, the silicone is typically presented to the end-user as an aqueous silicone formulation. The aqueous silicone formulation is then introduced into the washing medium in the case of fabric softeners, or the aqueous solution/suspension in the case of antifoam agents and surface treatments. Presenting the silicone in an aqueous formulation permits the rapid mixing of the silicone with the washing medium or the aqueous solution/suspension.

However, aqueous silicone formulations produced on an industrial scale necessarily require the presence of large quantities of water. In addition, large quantities of plastics materials are used in the manufacture of suitable containers. As a result, the use and subsequent transport of this added water is costly and has an associated negative environmental impact.

One solution has been to make solid silicone formulations which use less water in manufacture and in the final product. By way of an example, WO 2004/069981 relates to a solid silicone formulation where the solid formulation is a granular composition.

Solid formulations tend to weigh less than the aqueous formulations, do not require the use of robust plastics containers, have a longer shelf- life, and require fewer biocides and preservatives. The reduction in the quantity of water used results in lower production and transport costs, and results in a lower environmental impact. Additionally, solid formulations are preferred by the user as they are easier to store and handle.

However, such formulations suffer from a poor release rate of the silicone. This is disadvantageous in many applications. In addition, granular compositions also have problems related to caking and ageing of the solid formulations. For example, a hygroscopic material in the granular composition can increase the tendency for the granular composition to cake or clump in the presence of atmospheric moisture with prolonged storage. -?-

There remains a need, therefore, for a formulation that is capable of delivering the silicone rapidly, whilst also being storage stable.

Accordingly, the present invention provides a granular composition comprising a plurality of granules wherein each of the granules comprises (i) a silicone; (ii) a disintegrant present at at least 50% by weight based on the total weight of the granular composition; and (iii) an effervescent couple comprising a first compound and a second compound capable of reacting to produce effervescence, wherein the first compound and the second compound are dispersed in the disintegrant.

Thus, the present invention provides a granular composition where each of the granules contains a silicone, a disintegrant and an effervescent couple, such that the components of the effervescent couple are dispersed throughout the dispersant to prevent premature reaction. This provides storage stability to the composition whilst allowing the rapid delivery of the silicone in the presence of water.

Embodiments of the invention will now be described with reference to the accompanying drawings, in which:

Fig. 1 shows a granule forming the granular composition; and

Fig. 2 shows a comparison between the defoaming effect of an antifoaming effervescing granular composition and non-effervescing antifoaming formulations.

A granular composition is provided comprising a plurality of granules. A granule is a discrete particle formed as an aggregate of smaller particles. The granular composition typically takes the form of a free flowing powder.

The individual granules preferably have a minimum mean particle size of 100 microns, more preferably 200 microns and most preferably 300 microns; and preferably a maximum mean particle size of to 3,000 microns, more preferably 1,000 microns and most preferably 700 microns. The mean particle size may be determined by sieving and weighing or by using a laser granulometer.

As shown in Fig. 1, the granular composition is characterised in that the individual granules 1 will each comprise a silicone 2, a disintegrant 3 and an effervescent couple 4,5. However, this is a property of the bulk composition, and it should be understood that the composition is subject to usual manufacturing tolerances which may lead to some incompletely formed granules, for example by incomplete mixing of the liquid feed and the solid phase used in their manufacture (see hereinbelow for further details of the manufacturing method) or by some deaggregation occurring with prolonged storage. Thus, it is not necessary for every granule in the granular composition necessarily to have all of these components, but substantially all of the granules will comprise these components. By "substantially all" it is meant that greater than 75% of the granules by mass of the granular composition will contain all of these components. Preferably at least 80, 90 or 95% of the granules by mass of the granular composition will comprise these components.

The granules comprise a silicone, i.e. an organopolysiloxane-containing component. The silicone may be solely an organopolysiloxane or it may be a copolymer or a terpolymer of organosiloxane units bearing different organic substituents or of an organic polymer and an organopolysiloxane. Such materials are well known in the art. An organopolysiloxane is a silicon-containing polymer based on repeat siloxane units independently selected from (R ₃ Si0 _1/2 ), (R ₂ SiO), (RSiO _3/2 ), or (SiO ₂ ) siloxy units, commonly referred to as M, D, T, and Q siloxy units, respectively, where R is usually an organic group. The silicone may be any organopolysiloxane having the general formula R _n Si0 ₍₄ _ _n y ₂ in which n has an average value of one to three and R is an alkyl radical of 1-20 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, phenyl, tolyl, and xylyl, more preferably methyl, or aryl groups such as phenyl, or alkylaryl groups such as 2-phenylpropyl. Illustrative polysiloxanes are polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. The organopolysiloxane can be cyclic, linear, branched, or a mixture thereof.

In one embodiment, the silicone can be a volatile methyl siloxane (VMS) which includes low molecular weight linear and cyclic volatile methyl siloxanes. Volatile methyl siloxanes conforming to the CTFA definition of cyclomethicones are considered to be within the definition of low molecular weight siloxane.

Linear VMS have the formula (CH ₃ ) ₃ Si0 { (CH ₃ ) ₂ Si0 } _f Si(CH ₃ ) ₃ . The value of f is 0-7. Cyclic VMS have the formula {(CH ₃ ) ₂ Si0} _g . The value of g is 3-6. Preferably, these volatile methyl siloxanes have a molecular weight of less than 1,000; a boiling point less than 250 ⁰ C; and a viscosity of 0.65 to 5.0 mmV ¹ (centistokes), generally not greater than 5.0 mm Y ¹ (centistokes).

Representative linear volatile methyl siloxanes are hexamethyldisiloxane (MM) with a boiling point of 100 ⁰ C, viscosity of 0.65 mmY ¹ , and formula Me ₃ SiOSiMe ₃ ; octamethyltrisiloxane (MDM) with a boiling point of 152°C, viscosity of 1.04 mmV ¹ , and formula Me ₃ SiOMe ₂ SiOSiMe ₃ ; decamethyltetrasiloxane (MD ₂ M) with a boiling point of 194°C, viscosity of 1.53 mmV ¹ , and formula Me ₃ SiO(Me ₂ SiO) ₂ SiMe ₃ ; dodecamethylpentasiloxane (MD ₃ M) with a boiling point of 229°C, viscosity of 2.06 mmV ¹ , and formula Me ₃ SiO(Me ₂ SiO) ₃ SiMe ₃ ; tetradecamethylhexasiloxane (MD ₄ M) with a boiling point of 245 ⁰ C, viscosity of 2.63 mm Y ¹ , and formula Me ₃ SiO(Me ₂ SiO) ₄ SiMe ₃ ; and hexadecamethylheptasiloxane (MD ₅ M) with a boiling point of 270 ⁰ C, viscosity of 3.24 mmY ¹ , and formula Me ₃ SiO(Me ₂ SiO) ₅ SiMe ₃ .

Representative cyclic volatile methyl siloxanes are hexamethylcyclotrisiloxane (D ₃ ), with a boiling point of 134°C, a molecular weight of 223, and formula ((Me ₂ )SiO) ₃ ; octamethylcyclotetrasiloxane (D ₄ ) with a boiling point of 176°C, viscosity of 2.3 mmY ¹ , a molecular weight of 297, and formula ((Me ₂ )SiO) ₄ ; decamethylcyclopentasiloxane (D ₅ ) with a boiling point of 210 ⁰ C, viscosity of 3.87 mmY ¹ , a molecular weight of 371, and formula ((Me ₂ )SiO) ₅ ; and dodecamethylcyclohexasiloxane (D ₆ ) with a boiling point of 245°C, viscosity of 6.62 mmY ¹ , a molecular weight of 445, and formula ((Me ₂ )SiOJo. The silicone may also be selected from any of the volatile methyl siloxane structures listed hereinabove where some of methyl groups are replaced with a hydrocarbon group containing 2-12 carbon atoms, such as ethyl or propyl groups, for example; [(CH ₃ ) ₃ Si0] ₂ RSi0 where R is an alkyl group such as ethyl, propyl, hexyl, octyl (that is; ethyl, propyl, hexyl, octyl -heptamethyltrisiloxane, CTFA/INCI names ethyl, propyl, hexyl, and octyl trimethicone, respectively).

Alternatively to volatile methyl siloxanes, the silicone oil may be selected from volatile ethyl siloxanes.

The silicone oil may also be selected from one of the following volatile methyl siloxanes VMS: TM ₃ structures, such as [(CH ₃ ) ₃ Si0] ₃ SiR or [(CH ₃ ) ₃ SiO] ₂ RSiOSiR[OSi(CH ₃ ) ₃ ] ₂ , where R is alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, or cyclohexyl; QM ₄ structures, such as [(CH ₃ ) ₃ Si0] ₄ Si. The silicone can be alkylmethylsiloxane materials. These materials include liquids and waxes. The liquids can be either cyclic having a structure comprising: [MeRSiO] _a [Me ₂ SiO]b

or linear having a structure comprising:

R ⁵ Me ₂ SiO(MeRSiO)W(Me ₂ SiO) _x SiR ⁵ Me ₂

wherein each R is independently a hydrocarbon of 6 to 30 carbon atoms, R' is methyl or R, a is 1-6, b is 0-5, and w and x are 0-100, preferably 1-5. These liquids may be either volatile or non- volatile and they can have a wide range of viscosities such as from about 0.65 to about 50,000 HIm ² S ^"1 . These alkylmethylsiloxane materials are known in the art and can be produced by known methods. They may be liquid or waxy at ambient temperature (25°C). The silicone may also be a silicone oil in combination with other organopolysiloxanes, such as resins, gums or elastomers. Most of these elastomers can gel volatile silicones fluids as well as low polarity organic solvents such as isododecane. Representative examples of such silicone elastomers are taught in US 5,880,210, and US 5,760,116, both referred to herein for their teaching of suitable silicone elastomer compositions that may be used in practicing embodiments of the present invention. To improve compatibilities of silicone elastomers with various ingredients, alky Is, polyether, amines or other organofunctional groups have been grafted onto the silicone elastomer backbone. Representative examples of such organofunctional silicone elastomers are taught in US 5,811,487, US 5,880,210, US 6,200,581, US 5,236,986, US 6,331,604, US 6,262,170, US 6,531,540, and US 6,365,670 which are referred to herein for their teaching of organofunctional silicone elastomers suitable for use in the present invention.

The silicone may be a gum. Polydiorganosiloxane gums are known in the art and are available commercially. They consist of generally insoluble polydiorganosiloxanes having a viscosity in excess of 1,000,000 mmY ¹ (centistokes) at 25°C, alternatively greater than 5,000,000 mmV ¹ (centistokes) at 25°C. These silicone gums are typically sold as compositions already dispersed in a suitable solvent to facilitate their handling. Ultra-high viscosity silicones can also be included as optional ingredients. These ultra-high viscosity silicones typically have a kinematic viscosity greater than 5 million mmV ¹ (centistokes) at 25°C, to about 20 million mmV ¹ (centistokes) at 25°C. Compositions of this type in the form of suspensions are most preferred, and are described for example in US 6,013,682. Silicone resins may be included in the present compositions. These resin compositions are generally highly crosslinked polymeric siloxanes. Crosslinking is obtained by incorporating trifunctional and/or tetrafunctional silanes with the monofunctional silane and/or difunctional silane monomers used during manufacture. The degree of crosslinking required to obtain a suitable silicone resin will vary according to the specifics of the silane monomer units incorporated during manufacture of the silicone resin. In general, any silicone having a sufficient level of trifunctional and tetrafunctional siloxane monomer units, and hence possessing sufficient levels of crosslinking to dry down to a rigid or a hard film can be considered to be suitable for use as the silicone resin. Commercially available silicone resins suitable for applications herein are generally supplied in an unhardened form in low viscosity volatile or non- volatile silicone fluids. The silicone resins should be incorporated into compositions of the invention in their non-hardened forms rather than as hardened resinous structures.

Silicone acrylates may be included in the present compositions. Representative examples are described in EP 0 963 751.

Silicone carbinol fluids may be included in the present compositions. These materials are described in WO 03/101412, and can be commonly described as substituted hydrocarbyl functional siloxane fluids or resins.

Fluorosilicone fluids may be included in the present compositions. The fluorosilicone fluid has the average formula R ₃ Si0(RR'Si0) _x SiR ₃ or R ₃ SiO(RR'SiO)χ(R ₂ SiO) _y SiR ₃ wherein R is a monovalent hydrocarbon radical, R' is a fluoroalkyl radical, x is an integer having a value of 5 to 100 and y is an integer having a value of zero to about fifty. The monovalent hydrocarbon radical R can be an alkyl radical such as methyl, ethyl, butyl, propyl and the like; an alkenyl or cycloalkenyl radical such as vinyl, allyl, cyclopentenyl and the like; an aryl radical such as phenyl, tolyl, xylyl and the like; an arylalkyl radical such as beta-phenylethyl, beta-phenylpropyl and the like; or a cycloaliphatic radical such as cyclohexyl, cyclopentyl, cycloheptyl and the like. Most preferably R is a methyl radical. The fluoroalkyl radical R' in the above formula has the general formula (C _m F _2m+ i)(CH ₂ CH ₂ ) _z wherein m is an integer having a value of 1 to 4 and z is an integer having a value of 1 to 3. Suitable fluoroalkyl radicals include CF ₃ CH ₂ CH ₂ -, CF ₃ CF ₂ CH ₂ CH ₂ - and CF ₃ CF(CF ₃ )CH ₂ CH ₂ -. The preferred fluoroalkyl radical is CF ₃ CH ₂ CH ₂ -. Such fluorosilicone fluids can be made by methods described in US 2,961,425.

Water-soluble or water-dispersible silicone polyether compositions may be included in the present compositions. These are also known as polyalkylene oxide silicone copolymers, silicone poly(oxyalkylene) copolymers, silicone glycol copolymers, or silicone surfactants. These can be linear rake or graft type materials, or ABA and ABn types where the B is the siloxane polymer block, and the A is the poly(oxyalkylene) group. The poly(oxyalkylene) group can consist of polyethylene oxide, polypropylene oxide, or mixed polyethylene oxide/polypropylene oxide groups. Other oxides, such as butylene oxide or phenylene oxide are also possible.

The silicone component may comprise a silicone material having at least one nitrogen containing substituent. Although silicone materials may be silanes, preferably the silicone material is a siloxane polymer having units of the general formula R _a Si0( ₄ _a/ ₂ ), wherein each R is independently selected from hydrocarbon groups having from 1 to 12 carbon atoms, preferably alkyl, alkenyl, alkynyl, aryl, alkaryl or aralkyl and a has a value of from 0 to 3, and units of the general formula R _b R'Si0( ₃ _b/ ₂ ), where R is as defined above, R' is a nitrogen containing group and b has a value of from 0 to 2. Preferably R is an alkyl group having from 1 to 6 carbon atoms or an aryl or substituted aryl group having from 6 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, phenyl, tolyl, and xylyl. Preferably the nitrogen in R' is part of an amino functionality, amido functionality, imide functionality or quaternary ammonium functionality and most preferably amino or amido functionality. These are well known and have been described in many patent applications.

Suitable silicone materials include polyorganosiloxanes of the unit general formula R _n Si0 ₍₄ _ _n/2) wherein n has an average value of from 1.9 to 2.1 and R represents an organic radical attached to silicon through a silicon to carbon bond, from 0.25 to 50 per cent of the R substituents being monovalent radicals having less than 30 carbon atoms and containing, in a position at least 3 carbon atoms distance from the silicon atom, at least one -NH- radical and/or at least one -NHX radical, wherein X represents a hydrogen atom, an alkyl radical of 1 to 30 carbon atoms or an aryl radical, the remaining R substituents being monovalent hydrocarbon radicals, halogenated hydrocarbon radicals, carboxyalkyl radicals or cyanoalkyl radicals of 1 to 30 carbon atoms, at least 70 per cent of these remaining R substituents being monovalent hydrocarbon radicals of from 1 to 18 inclusive carbon atoms. In the polyorganosiloxanes at least 0.25 per cent and up to 50 per cent of the total R substituents may consist of the specified amino containing monovalent radicals. The preferred polyorganosiloxanes are, however, those in which the amino-containing substituents comprise from 1 to 5 per cent of the total R substituents. Preferably also the alkyl and aryl radicals represented by X are those having less than 19 carbon atoms and are e.g. methyl, ethyl, propyl, butyl, nonyl, tetradecyl and octadecyl, aryl radicals e.g. phenyl and naphthyl aralkyl radicals e.g. benzyl and beta- phenylethyl, alkaryl, e.g. ethylphenyl and alkenyl e.g. vinyl and allyl. A proportion of the remaining R substituents may be other than monovalent hydrocarbon radicals, for example hydrogen atoms, halogenated hydrocarbon radicals, e.g. chlorophenyl and other substituted hydrocarbon radicals, e.g. carboxyalkyl and cyanoalkyl. However, preferably substantially all of the remaining R substituents are methyl radicals. The amino- containing substituents may contain up to 30, preferably from 3 to 11, carbon atoms. The nitrogen atom of any amino radical in R is linked to the silicon atom through a chain of at least 3 carbon atoms. The nitrogen can also be present as a cycloalkylamino group.

Examples of the operative amino-containing substituents are the -(CH ₂ ) ₃ NH ₂ , -(CH ₂ ) _S NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH-CH ₃ -CH ₂ NHCH ₂ CH ₂ NH ₂ and -(CH ₂ ) ₃ NH(CH ₂ ) ₆ NH.CH ₃ radicals, piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl or 1,2,3,4-tetrahydroquinolinyl Also operative are polyalkyleneimine radicals, e.g. those of the general formula R" ₂ NCH ₂ CH ₂ (NHCH ₂ CH ₂ ) _X NH ₃ R- where R" is a hydrogen atom, an alkyl radical or an aryl radical, x has a value from 1 to 10 inclusive, y is 1 or 2 and R' is a saturated divalent or trivalent hydrocarbon radical having at least 3 carbon atoms. The preferred polyorganosiloxanes therefore include copolymers of dimethvlsiloxane units with delta-aminobutyl(methyl)siloxane units or gamma- aminopropyl(methyl)siloxane units, copolymers of dimethylsiloxane units with methyl(N- beta-aminoethyl-gamma-aminopropyl) siloxane units and copolymers of dimethvlsiloxane units with methyl(N-betaaminoethyl-gamma-aminoisobutyl) siloxane units. If desired the copolymers may be end-stopped with suitable chain terminating units, for example trimethylsiloxane units, dimethylphenylsiloxane units or dimethylvinylsiloxane units. Also if desired at least some of the amino-containing substituents may be present in the chain terminating units.

Suitable also are polydiorganosiloxanes which may be linear (unbranched) or substantially linear siloxane polymers having at least one silicon-bonded -R X group in the molecule. The group R* is a divalent moiety, such as alkylene, alkenylene, arylene, or substituted alkylene, alkenylene or arylene, X may be NQC(O)R' wherein Q represents hydrogen, alkyl, alkenyl, aryl or substituted alkyl, alkenyl or aryl, R' represents e.g. H, methyl, ethyl, propyl] , octyl, stearyl] , vinyl or phenyl, or may be -C(O)NR" ₂ wherein R" represents e.g. hydrogen, methyl, ethyl, butyl, octyl, dodecyl, octadecyl or phenyl, or may be the group -[NZ(CH ₂ )J _p NZ(CH ₂ ) _n NZQ, wherein Z represents hydrogen or R ¹ C(O)-, n is an integer of from 2 to 6 and p is 0, 1 or 2. Examples of X groups therefore are NH.C(0)CH ₃ ; -NHC(O)C ₄ H ₉ ; -NRC(O)C ₈ H ₁₇ ; -C(O)NH ₂ ; -C(O)NH(C ₄ H ₉ ); -C(O)NH(Ci ₈ H ₃₇ ); -C(O)N(C ₂ H ₅ ) ₂ ; -NC(O)CH ₃ (CH ₂ ) ₂ NHC(O)CH ₃ ; -NH(CH ₂ ) ₂ NHC(O)CH ₃ ; -NC(O)CH ₃ N(CH ₂ ) ₆ NC(O)C ₂ H ₅ ; -NH(CH ₂ ) ₂ NHC(O)Ci ₇ H ₃ 5; and -NH(CH ₂ ) ₂ NC(O)CH ₃ .(CH ₂ ) ₂ NHC(O)CH ₃ . At least 50 percent of the silicon-bonded substituents in the polydiorganosiloxane may be methyl groups, any substituents present in addition to the -RX groups and the methyl groups being monovalent hydrocarbon groups having from 2 to 20 carbon atoms or the groups -RNH ₂ , -RCOOH and - R[NH(CH ₂ ) _n ] _p NH(CH ₂ ) _n NH ₂ . The exemplified polydiorganosiloxane may comprise 1 % RX groups of the total number of substituents in the polydiorganosiloxane. The polydiorganosiloxanes are preferably terminated with triorganosiloxy, e.g. trimethylsiloxy, groups but may be terminated with groups such as hydroxy or alkoxy. Although the polydiorganosiloxanes are preferably those consisting of diorganosiloxane units, with or without triorganosiloxane units, they may contain small proportions of chain-branching units, that is mono-organosiloxy units, and SiO ₂ units. The molecular size of the suitable polydiorganosiloxanes is not critical and they may vary from freely flowing liquids to gummy solids. The preferred polydiorganosiloxanes are, however, those having a viscosity in the range from about 5.10 ^" to about 5.10 ² mV ¹ at 20 ⁰ C. Such polydiorganosiloxanes are more easily emulsified than the higher viscosity materials.

Suitable aminosilanes have the general formula R' _z Si(OR) ₄ _ _z where R can be an alkyl group such as methyl, ethyl, n-propyl, isopropyl, and t-butyl or an aromatic group such as phenyl, tolyl, and xylyl, but is preferably methyl. R' is an amine-containing group, and z is an integer with a value of 1 to 3, preferably 1 or 2. R' has the general formula -R ⁸ R ⁷ , wherein each R ⁷ is independently selected from a hydrogen atom and a group of the formula -R ⁸ NH ₂ , and each R ⁸ is independently a divalent hydrocarbon group. Typically, R' is an aminoalkyl group or cycloalkylamino group, such as -(CH ₂ ) _W NH ₂ or - (CH ₂ ) _W NH-(CH ₂ ) _W NH ₂ , wherein w is an integer, preferably with a value of 2 to 4. Examples of suitable aminosilanes include aminoethylaminoisobutylmethyldimethoxysilane, (ethylenediaminepropyl)- trimethoxysilane, and gammaaminopropyltriethoxysilane. Aminosilanes are known in the art and are commercially available. US 5,117,024, discloses aminosilanes and methods for their preparation.

Suitable silicone quaternary ammonium compounds are disclosed by US 5,026,489 entitled, "Softening Compositions Including Alkanolamino Functional Siloxanes." The patent discloses monoquaternary ammonium functional derivatives of alkanolamino polydimethylsiloxanes. The derivatives are exemplified by (R ⁹ ₃ Si0) ₂ SiR ⁹ - (CHR ¹⁰ XNR ¹⁰ _I3 R ¹ V _b wherein R ⁹ is an alkyl group, R ¹⁰ is H, alkyl, or aryl, R ¹¹ is (CHR ¹⁰ )OH, a is 1 to 10, and b is 1 to 3.

The silicone can be a saccharide-siloxane copolymer having a saccharide component and an organosiloxane component and linked by a linking group. The saccharide-siloxane copolymer has the following formula:

R ² _a R ¹ ₍ 3-a)Si0-[( SiR ² R ¹ O) _m -( SiR^O) _n ] _y -SiRV _a) R ² _a

wherein each R ¹ can be the same or different and comprises hydrogen, Ci-Ci ₂ alkyl, an organic radical, or R ³ -Q, Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality, m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3, y is an integer such that the copolymer has a molecular weight less than 1 million, R ² has the formula Z-(G ¹ ) _b -(G ² ) _c , and there is at least one R ² per copolymer, wherein G ¹ is a saccharide component comprising 5 to 12 carbons, b+c is 1- 10, b or c can be 0, G ² is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals, Z is the linking group and is independently selected from: -R ³ -NHC(O)-R ⁴ - ; -R ³ -NHC(O)O- R ⁴ - ; -R^NH-C(O)-NH-R ⁴ - ; -R^C(O)-O-R ⁴ -; -R ³ -O-R ⁴ - ;

-R ³ -CH(OH)-CH ₂ -O-R ⁴ - ; -R ³ -S-R ⁴

-R ³ -CH(OH)-CH ₂ -NH-R ⁴ - ; and -R ³ -N(R ¹ )-R ⁴ , where

R ³ and R ⁴ are divalent spacer groups comprising (R ⁵ ) _r (R ⁶ ) _s (R ⁷ ) _t , where at least one of r, s and t must be 1 , and R and R ⁷ are either Ci-Ci ₂ alkyl or ((Ci-Ci ₂ )O) _p where p is any integer 1-50 and each (Ci-Cn)O may be the same or different, R ⁶ is -N(R ⁸ )-, where R is H or Ci-Ci ₂ alkyl, or is Z-X where Z is previously defined or R .

X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R ³ and R ⁴ must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.

The organopolysiloxane may contain any number or combination of M, D, T, or Q units, but has at least one substituent that is a sulfonate group having the general formula:

-R ¹ O-(CO)-C ₆ H ₄ SO ₃ M ⁺ where R ¹ is a divalent organic group bonded to the organopolysiloxane, M is hydrogen, an alkali metal, or a quaternary ammonium, and G is an oxygen atom, NH, or an NR group where R is a monovalent organic group. The sulfonate group substituent is bonded to the organopolysiloxane via a Si-C bond by the R ¹ moiety. The sulfonate group substituent can be present in the organopolysiloxane via linkage to any organosiloxy unit, that is, it may be present on any M, D, or T siloxy unit. The sulfonate functional organopolysiloxane can also contain any number of additional M, D, T, or Q siloxy units of the general formula (RsSiOm), (R ₂ SiO), (RSiθ3β), or (SiO ₂ ), where R is a monovalent organic group, providing that the organopolysiloxane has at least one siloxy unit with the sulfonate functional group present.

The monovalent organic groups represented by R in the organopolysiloxanes may have from 1 to 20 carbon atoms, alternatively 1 to 10 carbon atoms, and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; amine functional organic groups such as aminopropyl and aminoethylaminoisobutyl; a poly alky lene oxide (polyether) such as polyoxyethylene, polyoxypropylene, polyoxybutylene, or mixtures thereof, and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl. Typically, at least 50 percent, alternatively at least 80%, of the organic groups in the organopolysiloxane may be methyl (denoted as Me).

The R ¹ group in the sulfonate group substituent can be any divalent organic group, but typically is a divalent hydrocarbon group containing 2 to 6 carbon atoms. Divalent hydrocarbons are represented by an ethylene, propylene, butylene, pentylene, or hexylene group. Alternatively, R ¹ is a propylene group, -CH ₂ CH ₂ CH ₂ - or an isobutylene group, -CH ₂ CH(CH ₃ )CH ₂ -.

G in the general formula for the sulfonate substituent group above is an oxygen atom, NH, or an NR group where R is a monovalent organic group. When G is an NR group, R can be any of the monovalent organic groups described above. Typically, G is the NH chemical unit forming an amide group in the sulfonate substituent formula above. The silicone may be an organosilicon component of the formula Si(OZ' ) ₄ , ZSi(OZ' ) ₃ or Z ₂ Si(OZ' ) ₂ in which Z represents an alkyl, substituted alkyl, aryl or substituted aryl group having 1 to 20 carbon atoms and each Z' represents an alkyl group having 1 to 6 carbon atoms. Preferably Z represents an alkyl, substituted alkyl, aryl or substituted aryl group having 6 to 18 carbon atoms.

The organosilicon component may comprise a condensation compound obtained by the hydrolysis -condensation of any combination of compounds of the formula Si(OZ' ) ₄ , ZSi(OZ') ₃ or Z ₂ Si(OZ') ₂ , in which Z represents an alkyl, substituted alkyl, aryl or substituted aryl group having 1 to 20 carbon atoms and each Z' represents an alkyl group having 1 to 6 carbon atoms.

Preferably, the organosilicon component comprises alkoxysilyl groups having 1 or 2 carbon atoms, preferably 1 carbon atom (methoxysilyl groups).

The organosilicon component can contain an organopolysiloxane. This may be chosen from any known organopolysiloxane materials, i.e. materials which are based on a Si-O-Si polymer chain and which may comprise mono-functional, di-functional, tri- functional and/or tetra-functional siloxane units, many of which are commercially available. It is preferred that the majority of siloxane units are di-functional materials having the general formula RR' SiO _2/2 , wherein R or R' independently denotes an organic component or an amine, hydroxyl, hydrogen or halogen substituent. Preferably R will be selected from hydroxyl groups, alkyl groups, alkenyl groups, aryl groups, alkyl-aryl groups, aryl-alkyl groups, alkoxy groups, aryloxy groups and hydrogen. More preferably a substantial part, most preferably a majority of the R substituents will be alkyl groups having from 1 to 12 carbon atoms, most preferably methyl or ethyl groups. The organopolysiloxane can for example be polydimethylsiloxane (PDMS). Alternatively the organopolysiloxane may comprise methylalkylsiloxane units in which the said alkyl group contains 2-20 carbon atoms. Such methylalkylsiloxane polymers, particularly those in which the said alkyl group contains 6-20 carbon atoms, may confer even higher water resistance than PDMS. Blends of organopolysiloxanes can be used, for example a blend of a methylalkylsiloxane polymer with a linear PDMS. In a preferred embodiment, the organosilicon component comprises a dialkoxysilane, trialkoxysilane, or a mixture of these with each other or with an organopolysiloxane. The dialkoxysilane generally has the formula Z ₂ Si(OZ') ₂ and the trialkoxysilane generally has the formula ZSi(OZ' ) ₃ in which Z in each formula represents an alkyl, substituted alkyl, aryl or substituted aryl group having 1 to 20 carbon atoms and each Z' represents an alkyl group having 1 to 6 carbon atoms. The group Z can for example be substituted by a halogen, particularly fluoro, group, an amino group or an epoxy group, or an alkyl group can be substituted by a phenyl group or a phenyl group can be substituted by an alkyl group. Preferred silanes include those in which Z represents an alkyl group having 6 to 18 carbon atoms and each Z' represents an alkyl group having 1 to 4, particularly 1 or 2, carbon atoms, for example n-octyl trimethoxysilane, 2-ethylhexyl triethoxysilane or n-octyl triethoxysilane.

Preferably, the silicone is present at 0.5 to 45% by weight based on the total weight of the granular composition. Preferably, the silicone is present at 1 to 35%, and most preferably at 3 to 30% by weight based on the total weight of the granular composition. Preferably the silicone is a fabric softener, an antifoam agent or a surface treatment.

A fabric softener (or fabric softening agent) is a compound that delivers softness to the touch, reduces tangling, knotting or wrinkling, or gives ease of ironing or static control to a fabric that is treated with this compound during a washing cycle. An antifoam agent (or defoamer) is a material which is effective in breaking or otherwise controlling foaming in aqueous media. The antifoam agent equilibrates the rate of foam collapse with the rate of foam formation. Such materials, in addition, remove unsightly and troublesome surface foam, improve filtration, watering, washing, and drainage, of various types of suspensions, mixtures, and slurries. Antifoam agent have found application traditionally in areas of use such as detergents, the pulp and paper industry, paints and latex, coating processes, fertilizers, textiles, fermentation processes, metal working, adhesive, caulk and polymer manufacture, the sugar beet industry, oil well, cement, cleaning compounds, cooling towers, and in chemical processes of varied description such as municipal and industrial primary and secondary waste water treatment facilities. Foam is a mass of bubbles formed in or on the surface of a liquid, produced chemically or by mechanical agitation. The silicone may be in the form of foam control agents/antifoams. Silicone foam control agents generally comprise one or more polyorganosiloxane materials and preferably also a hydrophobic particulate filler. The polyorganosiloxane material may be linear or may be branched as described for example in EP 0 217 501, US 5,674,938, US 6,150,488 and GB 2 257 709. The organic groups in the polyorganosiloxane fluid generally comprise methyl groups, it may also comprise a silicon-bonded substituent of the formula Y-Ph, wherein Y denotes a divalent aliphatic organic group bonded to silicon through a carbon atom and Ph denotes an aromatic group, examples of such fluids being described in EP 1 075 864, or a higher (C8+) alkyl group, examples of such fluids being described in EP 0 578 423. The polyorganosiloxane may be also comprise a one or more oxyalkylene-modified organosiloxanes as described in JP 56-139107 and JP 2001-81016. A preferred hydrophobic filler is silica, made hydrophobic by treatment with a methyl substituted organo-silicon material such as polydimethylsiloxane, hexamethyldisilazane, hexamethyldisiloxane or an organosilicon resin comprising monovalent groups (CH ₃ ) ₃ SiOi/ ₂ , or with a fatty acid, preferably at a temperature of at least 80 ⁰ C. Alternative hydrophobic fillers include titania, ground quartz, alumina, aluminosilicates, organic waxes, e.g. polyethylene wax or microcrystalline wax, and/or alkyl amides such as ethylenebisstearamide or methylenebisstearamide. The silicone antifoam preferably also contains a silicone resin, for example a MQ resin comprising groups of the formula R*3SiOi/ ₂ and SiO ₄ ^ groups, wherein R* denotes a monovalent hydrocarbon group. The silicone resin can be soluble, partially soluble or insoluble in the polysiloxane fluid.

Suitable Dow Corning silicones include Dow Corning® Antifoam 1500, Pulpaid® 3056 compound, Dow Corning® 3431 polymer, Dow Corning® 8040 fluid , Dow Corning® Q2-8166 polymer, Dow Corning® 2-8211, Dow Corning® 8500 conditioning agent, Dow Corning® 2-8630 polymer, Dow Corning® 8813 polymer, Dow Corning® 2-8822A polymer, Dow Corning 200® fluid 1000 CST, Dow Corning® 5-0299 polymer 60,000 CST, and are preferably 1500, 3056, 8630 and 8500, and most preferably 8630 or 3056. It should be noted that 1500 and 3056 are antifoams; 8040, 8630, 8813, 8822, 8166, 8211 are amino siloxanes; 8500 is an amido siloxane; and 3431, PDMS 1000 cst and 5-0299 are PDMS fluids. The granules also contain a disintegrant and an effervescent couple. The disintegrant forms at least 50% of the granule by weight and the effervescent couple is present as at least two components which react to produce effervescence. On contact with water, the disintegrant and the effervescent couple rapidly cause the granule to disintegrate into its component particles. This releases the silicone rapidly into the aqueous medium.

The disintegrant is a compound which, when in contact with water, facilitates in the breaking down of the granules, thereby releasing of the contents of a granule into the aqueous medium. That is, the chemical and physical interactions that hold the disintegrant particles together within a granule, are broken down when the granule is in contact with water.

This disintegration may be by dissolution and/or dispersion of the disintegrant.

Preferably the disintegrant is finely divided having a mean particle size of 1 to 500 microns, more preferably 5 to 100 microns, and most preferably 10 to 80 microns.

The disintegrant is present in at least 50% by weight based on the total weight of the granular composition or more preferably, at least 60 or 70% by weight of the granular composition, but wherein the disintegrant is present at no more than 95% by weight, more preferably no more than 90% by weight based on the total weight of the granular composition. The disintegrant disperses the other contents of the granule, thereby separating the other components of the granule. Preferably the disintegrant is an inert compound, that is, chemically unreactive with the other contents of the granule.

The disintegrant serves multiple functions. The disintegrant separates the first and second compounds of the effervescent couple, thereby preventing premature reaction, during formulation of the granular composition and within the granule when the granule is formed. The disintegrant also prevents instability of the effervescent couple with storage. That is, the disintegrant prevents any atmospheric moisture absorbed by the granule from initiating a reaction between the reagents of the effervescent couple, which would lead to a degradation of the granule. The disintegrant also prevents other possible side reactions occurring, both during formulation of the granular composition and when the granule is stored. The disintegrant also allows for some control over the effervescent reaction, as overly vigorous effervescence can be detrimental in some applications, such as where overly vigorous effervescence would lead to some of the effervescing mixture escaping from a mixing container, for example, from a relatively shallow washing machine powder dispensing drawer. As the disintegrant also allows some water to be tolerated in formulation, this increases the options in formulating the granular composition, in terms of processes and compounds that can be used, for example, water-soluble surfactants can be incorporated into the liquid feed, which would otherwise be difficult to achieve. The dispersant also allows for some control of the physical/bulk properties of the granules, for example the solubility, cake strength and compressibility of the granular composition can be modified.

The nature of the disintegrant is not critical provided that it is capable of disintegrating in the presence of water, either by dissolution or dispersion. Accordingly, it is preferably water soluble or water dispersible. Examples of suitable materials are organic compounds, polymers, salts and minerals.

The organic compound is preferably a carbohydrate and more preferably a water- soluble carbohydrate. The carbohydrate may be a mono-, di-, tri-, oligo- or polysaccharide, including hydrogenated oligo- and polysaccharides. Preferably the carbohydrate is selected from lactose, dextrose (e.g. dextrose monohydrate M), sucrose (preferably icing sugar which is finely ground (about 4-110 microns) sucrose), maltodextrin or hydrogenated dextrin (e.g. Glucidex 47, Glucidex IT19, neosorb P60, cargill A, cargill C Dry), starch (preferably native starch, such as native corn starch), or cellulose derivatives (e.g. sodium carboxymethylcellulose). Preferably the carbohydrate is dextrose or starch.

Examples of salts include water-soluble salts such as sodium sulfate, sodium acetate, sodium silicate, magnesium sulfate, phosphates, such as powdered or granular sodium tripolyphosphate and sodium citrate. The mineral may be silica, titania, ground quartz, alumina, a clay or an aluminosilicates/zeolite, e.g. zeolite 4M. Preferably the particulate mineral is a zeolite.

The disintegrant may be present as a single material or a mixture of disintegrants. Examples of water-soluble disintegrants include water soluble salts (e.g. sodium sulfate, sodium acetate, sodium silicate, magnesium sulphate), phosphates (e.g. powdered or granular sodium tripolyphosphate), sodium citrate and water-soluble carbohydrates (e.g. cellulose derivatives, for example sodium carboxymethylcellulose, or sugars, for example lactose, dextrose, or maltodextrin, for example that sold under the trade mark Glucidex IT). Examples of water-dispersible disintegrants include water-dispersible clays, such as those sold under the trade mark Laponite RD, starch, for example granulated starch or native starch, and calcium sulfate. Examples of water-insoluble disintegrants include zeolites, for example Zeolite 4A or Zeolite X, and other aluminosilicates or silicates, for example magnesium silicate or silica.

Preferably, the disintegrant is a carbohydrate or a zeolite, and most preferably starch. The disintegrant is selected such that the granular composition releases at least

50%, more preferably at least 70%, by weight of the silicone within 2 minutes of contacting the granular composition with distilled water. The test may be performed by adding 2 g of the granular composition to 200 mL of water (soft water or preferably distilled water) under stirring with a mechanical stirrer at a rate of 200 rpm at 25 ⁰ C. The amount which has been dispersed or dissolved is determined by filtering the resulting suspension/solution and weighing the amount of residual solid.

The disintegrant may be water soluble or water insoluble depending on the application. The disintegrant is preferably water soluble where there is a requirement to minimise or avoid a residue, for example, where the granular composition is used for delivering a fabric softener directly to a washing machine drawer. By water soluble is meant that the disintegrant has a water solubility of greater than 10 g/L measured at 20 ⁰ C. In a preferred embodiment, the disintegrant is water soluble and has a dispersion rate such that at least 30%, preferably at least 50%, by mass of the granular composition has dissolved in the water within a time of two minutes. The test may be performed by adding 2 g of the granular composition to 200 mL of water (soft water or preferably distilled water) under stirring with a mechanical stirrer at a rate of 200 rpm at 25 ⁰ C. After 2 minutes, the aqueous medium is filtered, the undissolved residue is dried and the amount determined by weighing the dried residue.

The granules also contain an effervescent couple. The effervescent couple contains at least two compounds (a first compound and a second compound) that react together in the presence of water to produce a gas. The gas produced by the effervescent couple may be, for example, carbon dioxide, nitrogen, oxygen or chlorine dioxide. Suitable effervescent couples are known in the art. However, in the granular composition, the first and second compounds are dispersed throughout the disintegrant thereby holding them separate from one another. In other words, each granule is formed of an intimate blend of the disintegrant and the first and second compounds of the effervescent couple. The intimate blend of the disintegrant and the effervescent couple provides improved water tolerance to the composition (compared, for example, to a granule formed in layers of different components). This allows small amounts of water to be used in the manufacture of the granular composition which assists in the manufacturing process. It also leads to improved shelf-life in the resultant product (the consumer product). For example, the granular composition may tolerate up to 10%, preferably 1-10 wt% and more preferably 1-5 wt% of water based on the total weight of the granular composition.

The amount, chemical and physical nature of the effervescent couple will affect the rate at which the granules of the present invention will disintegrate. Effervescence will increase the disintegration rate of the granular composition relative to the rate obtainable from the diffusion of water alone. The more effervescent couple that is present in a granule, the more effervescence will result. The effervescence should not be too vigorous, as overly vigorous effervescence may lead to some escape of the effervescing mixture from the mixing container. In some applications, the bubbles formed should not be too small as this can lead to stable foams, which may be difficult to disperse. Also, if the bubbles are too large, residue may be deposited on the sides of the mixing container.

The effervescence serves two principle functions. The first is to assist in the break down of the structure of the granules of the granular composition, as the gas escapes from the granule. The second is that the gas formed produces propulsion of the granule in the aqueous solution, i.e. causing some motion of the granules, leading to greater water- granule interaction, and thus mixing. In some applications this motion of the granules also serves to aid in delivery of the granule. In a washing machine dispensing drawer, this motion can assist in the granule being transferred into the washing machine drum. Without such motion, non-effervescing granules may remain at the bottom of the washing machine dispensing drawer. This is particularly true of a softening compartment of a washing machine dispensing drawer which is designed for liquids softeners, and so often contains a siphon. Without such additional motion the granules may not be carried with the siphoned solution into the washing machine drum.

An example of an effervescent couple is an organic acid as the first compound and a carbonate salt as the second compound. Preferably the acid is citric, malic, maleic, fumaric, aspartic, glutaric, tartaric, malonic, succinic, adipic, boric, benzoic, oleic acid, citramalic and 3-chetoglutaric acids, a polymeric acid, such as poly aery lie acid, or a mixture thereof. Preferably, the base is a sodium, potassium or the ammonium salt of carbonate or bicarbonate, or mixtures thereof. Most preferably the acid is citric acid monohydrate and the base is sodium bicarbonate. The reaction between these components may be represented as follows:

3 NaHCO ₃ + HOC(CH ₂ COOH) ₂ COOH-H ₂ O + 4 H ₂ O -» HOC(CH ₂ COONa) ₂ COONa + 3 CO ₂ + 8 H ₂ O.

Preferably, the effervescent couple is present at 1 to 45% by weight based on the granular composition. More preferably the effervescent couple is present at 5 to 20%. Preferably the molar ratio of acidic functional groups (of the first compound) to the basic functional groups (of the second compound) in the effervescent couple in the granular composition is 3:1 to 1:3, more preferably 2:1 to 1:2 and most preferably 1.5:1 to 1:1.5. The amounts will be determined by, amongst other things, the nature of the consumer product being produced. For example, a skin care composition will have a lower pH and a detergent will have a higher pH.

Preferably, the granules additionally comprise a binder (reference numeral 6 in Fig. 1). The binder facilitates the adhesion of particles to form a granule, and hence may increase the amount of silicone that can be formulated in a granule. Preferably the binder is water soluble and most preferably the binder is a polyethylene glycol.

Preferably the binder is selected from polyethylene glycol Mw 8000 (PEG 8000), polyethylene glycol Mw 6000 (PEG 6000), polyethylene glycol Mw 4000 (PEG 4000), polyethylene glycol Mw 3000 (PEG 3000), polyethylene glycol Mw 2000 (PEG 2000), polyethylene glycol Mw 1550 (PEG 1550), or mixtures thereof. Most preferably the binder is PEG 8000. The binder may also include a co-binder such as polysorb, cationic polymer (Merquat 100) and/or polyvinylpyrrolidone (PVP Kl 5).

Preferably the binder is present at 0.1 to 40%, more preferably at 3 to 35% and most preferably at 4 to 20% by weight based on the weight of the granular composition. Preferably the binder is present in a ratio of up to 50%, preferably 20% by mass relative to the liquid feed used in the manufacture of the granules. The liquid feed comprises at least the silicone and optionally a surfactant and/or a softening booster.

Preferably, the granules additionally comprise a co-binder (reference numeral 7 in Fig. 1) or are treated with a co-binder after granulation. Preferably, the co-binder is a water soluble film forming polymer. Preferably, the co-binder is selected from PVP, Sokalan CP5, Sokalan PA25 or Polysorb, or a mixture thereof. Most preferably the co- binder is Polysorb. Preferably the co-binder is present at 0.1 to 10%, more preferably at 0.2 to 6% and most preferably at 0.3 to 4%, by weight based on the weight of the granular composition. Preferably, the granules additionally comprise a surfactant. The surfactant facilitates the formation of an emulsion. Preferably this emulsion is formed with the silicone and other compounds used to make the liquid feed that is used to manufacture of the granular composition. Preferably the surfactant is an ethoxylated fatty acid or alcohol. Preferably the surfactant is selected from ethoxy (7) tridecanol (Volpo T7/85), C16-18 EO(80) fatty alcohol ethoxylated (Lutensol AT80), Steareth-2 (Volpo S2), Steareth-20 (Volpo S20), Ceteareth-20 (Volpo CS20), glycol stearate (Cithrol IOMS (Fatty acid ester)), glyceryl monostearate (Cithrol DGMS NfE), PEG-40 stearate (Crodet S40 LD), pareth-4 (Volpo L4) and pareth-23 (Volpo L23).or mixtures thereof. The more preferred surfactants are Volpo S2, Volpo S20 or Volpo T7, most preferably Volpo T7. Preferably the surfactant is present at 0.1 to 20%, more preferred at 0.5 to 15% and most preferably at 1.5 to 8% by weight based on the weight of the granular composition. Preferably the surfactant is present in a ratio of up to 80% relative to the silicone. More preferably, the surfactant is present in a ratio of up to 70, 45 or 20% relative to the amount of silicone.

Additionally the granules may comprise a softening booster which is a compound which increases the softening effect. Preferably, the softening booster is a cationic fabric softening agent, more preferably a quaternised ester-amine (esterquat). More preferably the softening booster is Tetranyl AOT-I (from Kao). Preferably the softening booster is present at 0.1 to 10% by weight based on the weight of the granular composition.

Additionally the granules may also comprise an anti-spotting agent. Preferably, the anti-spotting agent is selected from benzoic and oleic acid, or a mixture thereof. Preferably the anti-spotting agent is present at 0.1 to 10% by weight based on the weight of the granular composition.

The granules may further comprise a herbicide (e.g. a glyphosate such as Roundup®), a pesticide, a fertiliser, a pharmaceutically active ingredient or a cosmetic powder. They may further comprise a thickener, a dye, perfume, a deposition agent, a foam booster, a biocide or other conventional additives.

In an embodiment of the present invention, the granular composition is included as part of a consumer product further comprising a discrete powder. That is, a product containing the discrete individualised particles are intermixed with the individualised granules. Preferably, the discrete powder is substantially the same size as the granules of the granular composition, to avoid segregation during storage. This discrete powder may be selected from a herbicide (e.g. a glyphosate such as Roundup®), a pesticide, a fertiliser, a pharmaceutically active ingredient, a cosmetic powder, an anti-caking agent (e.g. calcium carbonate or magnesium carbonate), a powder for home care, a washing powder, a dishwasher powder and a lavatory cleaning powder. The granules are essentially present as an additive. Accordingly, the discrete powder is preferably present at 50% or above, more preferably at 80% or above, more preferably at 90% or above, and most preferably at 95% or above, based on the weight of the composition as a whole (i.e. the consumer product). The maximum amount of the discrete powder is less critical and is based on commercial considerations balancing the cost of the discrete powder and the additive; however, for example, the discrete powder may be present at a maximum of 99.9%, or 99.5% by weight based on the weight of the composition as a whole. The consumer product may be in the form of a compressed tablet.

The present invention also provides a method of delivering a silicone to an aqueous medium comprising contacting the aqueous medium with the granular composition. The granular composition is added as a solid to the aqueous medium, thereby causing water to diffuse into the granule. This leads to the effervescent couple being contacted by the water causing the first and second components of the couple to react, causing effervescence. This effervescence greatly accelerates the disintegration of the granule as the gas released in the reaction breaks up the structure of the granules exposing fresh effervescent couple to the water. The effervescence also results in propulsion of the granule (and the disintegrating parts of the granule) through the aqueous solutions increasing the interaction of the granule (and the disintegrating parts of the granule) with the aqueous medium, compared to aqueous diffusion alone. This continues until the effervescent couple is expended.

The present invention also provides a method of manufacturing the granular composition comprising forming a liquid feed which comprises the silicone and forming a solid phase comprising the disintegrant and the effervescent couple, adding the liquid feed to the solid phase, mixing the liquid feed and solid phase and optionally drying the resultant mixture. The liquid feed may optionally contain a binder, a co-binder, a surfactant and/or water. The granules so formed can be treated with additional agents to impregnate or coat the granules with these additional agents.

The liquid feed which comprises the silicone is contacted with the solid phase comprising the disintegrant and the effervescent couple in a mixer in which droplets of the liquid feed become agglomerated with the solid phase. This contact may be in a granulating mixer, an extruder, a compactor or in a high- or low-shear mixer. Preferably the liquid feed is contacted with the solid phase in a granulating mixer in which the agglomerated product is kept in particulate form. The granulating mixer is generally a high-shear mixer such as an Eirich (trade mark) pan granulator, a Schugi (trade mark) mixer, a Paxeson- Kelly (trade mark) twin core blender, a Lodige ploughshare mixer, an Aeromatic (trade mark) fluidised bed granulator or a Pharma (trade mark) drum mixer. In most granulating mixers, the liquid feed is sprayed onto the solid phase while the solid phase is being agitated. The liquid feed can alternatively be poured into the mixer instead of spraying.

The granular composition is collected from the granulating mixer and packaged. The product from a vertical continuous granulating mixer may be fed to a fluidised bed which cools and/or dries the granules and fluidises them for transport to a packing station. If the particle size distribution of granular composition at the outlet of the granulating mixer is larger than desired, including fines and oversize material, the fines may be recovered in a filter coupled with the fluidised bed cooler and/or in a classification unit and recycled with fresh particles feeding the mixer, and oversize material can be collected, crushed and mixed with the granular composition in a fluidised bed. If the liquid feed and the solid phase are agglomerated in an apparatus which does not maintain the agglomerated mixture as separate granules, for example an extruder or a compactor, the agglomerated mixture can be converted into granules by flaking, by comminuting an extruded strand or by spheronisation after extrusion.

One preferred form of granulating mixer is a vertical continuous granulating mixer comprising blades rotating within a tubular housing and having an inlet for solid phase and a spray inlet for the liquid feed to contact the solid phase above the blades. The blades are mounted on a substantially vertical shaft aligned with the housing and rotating within the housing. The blades have a predetermined clearance from the inner wall of the housing. Contact with the liquid agglomerates the particles into granules; the liquid acts as a binder by absorbing the kinetic energy of colliding particles. The blades maintain the solid particles and granules in motion and prevent agglomeration into granules which are too large. Examples of such vertical continuous granulating mixers are described in US 4,767,217, EP 0 744 215 and WO 03/059520. Vertical continuous granulating mixer technology has the advantage that the residence time in the mixing chamber is very short, for example about 1 second, giving the possibility of high throughput.

Embodiments of the invention will now be described, by way of example, with reference to the following examples.

Examples Example 1 (comparative)

Granules were prepared following the protocol described hereinbelow.

75 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 18 g of aqueous Volpo T7/85 was then added under mechanical agitation. When the mixture again reached 65-70 ⁰ C, 160 g of 1500 antifoam compound (PDMS based antifoam compound containing hydrophobic silica) was added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 76.8 g of this emulsion was poured onto 110 g of zeolite in a mixer under strong agitation. The mixture was stirred continuously until a particulate material was obtained. The particulate material was then passed over an Aeromatic® fluidized bed at 35°C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1,400 microns).

Example 2

75 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 18 g of aqueous Volpo T7/85 was then added under mechanical agitation. When the mixture reached again 65-70 ⁰ C, 160 g of 1500 antifoam compound was added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 70.72 g of this emulsion was poured onto a mixture of powders containing 8 g of citric acid, 8 g of sodium bicarbonate and 84 g of zeolite in a mixer under strong agitation. The mixture was stirred continuously until a particulate material was obtained. The particulate material was then passed over an Aeromatic® fluidized bed at 35°C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1,400 microns).

Example 3

75 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 18 g of aqueous Volpo T7/85 was then added under mechanical agitation. When the mixture again reached 65-70 ⁰ C, 160 g of 1500 antifoam compound was added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 64.07 g of this emulsion was poured onto mixture of powders containing 16 g of citric acid, 16 g of sodium bicarbonate and 68 g of zeolite and mixed under strong agitation. The mixture was stirred continuously until a particulate material was obtained. The particulate material was then passed over an Aeromatic® fluidized bed at 35°C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1,400 microns).

Example 4

140 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 42.3 g of aqueous Volpo T7/85 was added under mechanical agitation. When the mixture again reached 65-70 ⁰ C, 70.4 g of 8630 (amino siloxane) was added with agitation for several minutes to give a homogeneous, white liquid feed. 190 g of this emulsion was then poured onto a mixture of powders containing 128 g of citric acid, 128 g of sodium bicarbonate and 544 g of dextrose monohydrate M, in a mixer with strong agitation. When the expected particle size was achieved, 39 g of diluted aqueous Polysorb 70 at 52% solid was poured onto the granules whilst agitation was maintained. After drying in a fluid bed at 35 ⁰ C for 10 minutes, the granules were sieved to remove the fines (below 212 microns) and the coarse fraction (above 1,400 microns).

Example 5

The process described in Example 4 was used to formulate an antifoam granule, with the following quantities of raw materials:

Example 6

The process described in Example 4 was used to formulate an antifoam granule, with the following quantities of raw materials:

Example 7

Example 8

Example 9

Example 10 (comparative)

The process described in Example 2 was used to formulate an antifoam granule with the following quantities of raw materials:

Example 11 (comparative) Example 12

Example 13

Example 14

Example 15 Rate of dispersion

The granular compositions (2 g) from Examples 1 to 3 were added to 200 mL of distilled water and stirred at 200 rpm at 25 ⁰ C for 2 minutes. The aqueous solution was then filtered using a Buchner funnel apparatus containing a filter. The filter was recovered and dried for 24 hours. The weight of residue was then measured. The results were as follows:

Example 1 (comparative): 1.66 g (83 % residue) Example 2: 1.22 g (61 % residue)

Example 3: 0.36 g (18 % residue)

These results show that the effervescent couple increases the rate of dispersion of the granular composition of the present invention. That is, Examples 2 and 3 have less residue remaining from the disintegration of the granules after two minutes than the comparative Example 1 , which has no effervescent couple.

Furthermore, the rate of dispersion increases as the proportion of effervescent couple present in the granular composition increases, that is, Example 3 with more effervescent couple gives less residue than the Example 2.

Example 16

Antifoaming

The aim of this experiment was to evaluate the antifoam performance of the effervescent granules compared to the non-effervescing granules.

Example 16a (comparative)

60 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 13 g of aqueous Volpo T7/85 and 55 g of aqueous Crodasinic LS35 were then added under mechanical agitation. When the mixture reached again 65-70 ⁰ C, 65 g of organo-modified antifoam compound was added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 57.8 g of this emulsion was poured onto 100 g of zeolite in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 6 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35 ⁰ C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

Example 16b (invention)

60 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 13 g of aqueous Volpo T7/85 and 55 g of aqueous Crodasinic LS35 were then added under mechanical agitation. When the mixture reached again 65-70 ⁰ C, 65 g of organo-modified antifoam compound was added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 56 g of this emulsion was poured onto a mixture of powders containing 8 g of citric acid, 8 g of sodium bicarbonate and 84 g of zeolite in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 6 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35 ⁰ C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

To determine the antifoam performance of the effervescent granules compared to the non-effervescing granules, a shake test was performed in a model foaming solution. The granules were tested at 50 ppm of silicone in 100 ml of an aqueous solution of LAS (1 % concentration of surfactant). They were shaken in a glass bottle for 8, then 32, then 48 and finally 96 seconds. After each shake cycle, the height foam and collapse time were recorded. Height foam is the level of foam when the shaking period has stopped. The collapse time is the time needed for the foam produced to collapse to 10% of the free volume above the solution (the measurements were stopped after 2 minutes). If the level of the foam is much higher than 10% after 2 minutes, an arbitrary value of 120 seconds was given for the collapse time.

A comparison was made between a zeolite containing an antifoam compound (no effervescent couple) and an effervescing granular composition of the present invention. The results of the collapse time are shown in the Fig. 2. From Fig. 2, it can be seen that the use of the effervescing granule (right column) significantly increase the active release of the silicone, thus showing better performance. Example 17 Ageing

Granules were stored in humidity chamber at 35 ⁰ C and 70% RH. The flowability and the hardness of the granules were inspected before and after ageing. The results are summarised as follows:

It can be seen that the granules of the present invention are more stable to environmental moisture over time, whereas the reference example (where there was no disintegrant in the granules) was not. Accordingly, the granules were subject to aging caused by the harsh environmental conditions, which were designed to mimic prolonged storage of the granules. It should be noted that the Polysorb present in the composition of Example 5 is included to assist the handling of the raw materials and does not have a material effect on the results described in this example.

Example 18

Amount of effervescing couple Example 18a

48 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 64 g of aqueous Volpo T7/85, 104 g of amino fluid 8630 and 36.4 g of esterquat Tetranyl AOT-I were added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 55 g of this emulsion was poured onto a mixture of powders containing 8 g of citric acid, 8 g of sodium bicarbonate and 184 g of dextrose in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 4.6 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35 ⁰ C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

Example 18b

18 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 21 g of aqueous Volpo T7/85, 41 g of amino fluid 8630 and 15.3 g of esterquat Tetranyl AOT-I were added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 38.17 g of this emulsion are poured onto a mixture of powders containing 24 g of citric acid, 24 g of sodium bicarbonate and 152 g of dextrose in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 7.3 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35 ⁰ C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

Example 18c

18 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system,

21 g of aqueous Volpo T7/85, 41 g of amino fluid 8630 and 15.3 g of esterquat Tetranyl AOT- 1 were added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 39.93 g of this emulsion was poured onto a mixture of powders containing 32 g of citric acid, 32 g of sodium bicarbonate and 136 g of dextrose in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 6 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35°C during 10 minutes. The granules were then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

Effervescence of the granular compositions was investigated as follows.

A washing machine rinse drawer was removed from a Miele washing machine and connected to a source of tap water. 10 g of effervescent granule was added. 2 litres of water within 2 min approximately were poured in the drawer (rinse compartment equipped with its original siphon). The foam generation, the motion of the granule and the residues left in the drawer were visually observed.

The use of excess effervescent couple, in some applications, can result in too much effervescence, leading to residue being left in the mixing container.

Example 19

Influence of softening booster Example 19a

50 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 60 g of aqueous Volpo T7/85 and 120 g of amino fluid 8630 ware added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 41.6 g of this emulsion was poured onto a mixture of powders containing 12 g of citric acid, 12 g of sodium bicarbonate and 126 g of icing sugar in a mixer with strong agitation. The mixture was stirred continuously until a particulate material was obtained. 3.4 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35°C during 10 minutes. The granules are then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

Example 19b

25 g of PEG 8000 was melted at 65-70 ⁰ C. While maintaining the heating system, 30.2 g of aqueous Volpo T7/85, 36.4 g of amino fluid 8630 and 29.5 g of esterquat Tetranyl AOT-I were added and the agitation was maintained during several minutes to get a homogeneous, white liquid feed. 42.3 g of this emulsion was poured onto a mixture of powders containing 12 g of citric acid, 12 g of sodium bicarbonate and 126 g of icing sugar in a mixer under strong agitation. The mixture was stirred continuously until a particulate material was obtained. 0.6 g of aqueous polysorb (35%) was added under agitation. The particulate material was then passed over an Aeromatic® fluidized bed at 35 ⁰ C during 10 minutes. The granules are then sieved to remove the fines (below 212 microns) and the coarse fraction (above 1400 microns).

This evaluation was divided into two steps, a washing machine cycle and then an evaluation by panellists.

a. Wash test condition: Washing machine: Miele WM 934

20 g of a commercial powder (Dash) Temperature: 40 ⁰ C Drying: 600 rpm

4 cotton towels

5 pillow cases

The softening agent was added in the rinse drawer of the washing machine. The amount of residues left in the drawer at the end of the rinse cycle was visually observed. Water may be added right after the rinse cycle in order to ensure that the same amount of silicone active is present in the drum. After drying at room temperature during 24 hours under controlled humidity, the towels were evaluated by the panelists.

b. Panel evaluation

The panellist evaluated the treated towels with a reference towel. The reference was assigned a value of 5 points. The panellist gave their opinion for the treated towel (+ or - softer than the reference treated towel). In the present case, Example 19a was taken as reference (5 points).

In both examples, the granular composition of the present invention delivers the silicone effectively. It is also observed that, the use of esterquat tetranyl AOT-I showed an additional increase in softening, scoring a mark of 7.72 compared to 5.00.