LAUNDRY DETERGENTS

FIELD OF THE INVENTION

The present invention relates to laundry detergents containing granulated foam control compositions.

BACKGROUND OF THE INVENTION

Laundry detergents comprising anionic detersive surfactants for cleaning fabrics such as clothing have been known for many years. Laundry detergents typically create suds during their use including hand- ash use . During hand washing of clothes and fabrics, a large volume of suds is initially desirable as it indicates to the user that sufficient surfactant is prese t working and cleariing the fabrics. However, during the linse cycle, consumers tend to b lieve that if suds are still present then there is surfactant residue that remains on the clothes, and therefore believe that the clothes are not yet "clean" They thus tend to rinse more times until the suds are not seen in the rinse.

Hence, while a large volume of suds is desirable during cteaning, it paradoxically is undesirable during rinsing. As water is often a limited resource, especially in hand washing countries, the use of water for rinsing reduces the amount available for other possible uses, such as irrigation, drinking, bal ing, etc.

A suds suppressor which is selectively active during rinsing can eliminate unwanted e cessive suds during rinsing and thus change the consumer's perception of the sufficiency and efficac y of a single rinse, the reby saving wate r and effort utilise d on repeated rinse s.

Suds suppressors are well-known in, for example, automatic dishwashing detergents and laundry detergents for front -loading washing machines. S mple suds suppressors are disclosed in for example, EP1075o ^" 83A, EP 1070526 A, US 7ό ^" 32890Β, and EP 210731 A. However, as typical suds suppressors do not distinguish between the wash and rinse conditions, they do not solve the probl m of providing suds during washing and yet reducing suds during rinsing. Particularly, in a hand wash situation, the consumers are used to seeing suds during the wash, and if no suds are present, then consumers think that the laundry detergent contains insufficient surfactant to perform up to expectations.

WO2012075611 discloses laundry detergent compositions comprising foam control compositions that provide suds in the wash, but reduce d suds in the rinse . Bui, there is a need in the art for a suds control composition which provides a satisfying suds volume during the washing stage and improved suds reduction volume after a single rinse process. Furthermore, there is a need for a laundry detergent composition comprising a foam control composition, where in the foam c ontrol composition e xhibits improved storage stability

The Inventors surprisingly found that a laundry detergent comprising a granulated foam control composition and an anionic surfactant wherein said granulated foam control composition comprises a foam control agent comprising a polydiorganosiloxane fluid, hydrophobic filler, and said granulated foam control composition also comprises an organic additive, a water soluble inorganic particulate carrier a cationic polymer and an anionic surfactant exhibited improved suds retention during the wash but improv d suds reduction during the rinse as compared to a laundry detergent outside of the present invention. It was also surprisingly found that laundry detergent compositions according to the present invention also exhibited improved ageing stability

SUMMARY OF THE INVENTION

The present invention relates to a laundry detergent comprising a granulated foam control composition and an anionic detersive surfactant wherein said granulated foam control composition comprises:

(a) a foam control agent comprising: i. a polydiorganosiloxane fluid c omprising units of the formula

R

I

-CSi-O)- I

R where each group R, which maybe the same or different, is selected from an alkyl group having 1 to 36 rbon atoms or an aryl group or aralkyl group having 1 to 36 carbon atoms, the mean number of c arbon atoms in the groups R be ing at least 1 .3 ; ii. a hydrophobic filler dispers d in the polydiorganosiloxane fluid; (b) an organic additive having a melting point of from about 45°C to about lOtTC comprising a polyol ester which is a polyol esterifiedby caiboxykte groups each having 7 to 36 carbon atoms, and whi is miscible with said polydiorganosiloxane fluid;

(c) a water soluble inorganic particulate carrier;

(d) a cationic polymer,

(e) an anionic surfactant.

DETAILED DESCRIPTION OF THE INVENTION

All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All conditions herein are at 20°C, and atmospheric pressure unless oth rwise sp cifically stated. All polymer molecular weights are by average number molecular weight unless otherwise specifically noted.

As used herein, "suds" indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid. The terms like "suds", "foam" and 'lather" can be used interchangeably in the present specification.

The present invention relates to a laundry detergent comprising a granulated foam control composition and an anionic detersive surfactant wherein said granulated foam control composition comprises a foam control agent comprising a polydio^anosiloxane fluid, hydrophobic filler, and said granulated foam control composition also comprises an organic additive, a water soluble inorganic particulate carrier, a cationic polymer and an anionic surfactant.

Laundry dete rgent

The laundry detergent powder is suitable for any laundry detergent application, for e ample : laundry, including automatic washing nrachine kundering and hand kundering, and even bkach and kundry additives.

The kundry detergent is preferably a powder or granular laundry detergent. It can be a fully formulated detergent product such as a fully formuk ted laundry detergent product or it can be combined with other parti ks to form a fully form ukted detergent product such as a fully formulated kundry detergent product. The granulated foam control composition maybe combined with other particles su h as: enzyme particles; perfume particles including agglomerates or ex trudate s of pe rfume microcapsules, and perfume enc apsuktes sue h as starch enc apsukted perfume accord particles; surfactent particles, such as non- ionic detersive surfactant particles including aggbme rates or extrudates. anionic detersive surfactant particles in luding agglomerates and extrudates, and cationic detersive surfactant particles in luding agglomerates and extrudates; poller particles mcluding soil release polymer parti les, cellulosic polymer particles; buffer particles including carbonate salt and/or silicate salt particles, preferably a particle comprising carbonate salt and silic te salt such as a sodium carbonate and sodium silicate co-particle, and particles and sodium bicarbonate; other spray-dried particl s; fluorescent wMtening particles;

aesthetic particles such as cobured noodles or needles or lamellae particles; bleaching particles such as percaibonate particles, especiallycoated percaibonate particles, including carbonate and/or sulphate coated percaibonate, silicate coated pe rcarbonate, borosilicate coated percaibonate, sodium perborate c oate d percarb onate ; bleach catalyst particle s, such as transition metal c atalyst bleach particles, and inline bleach boosting particles; performed perac id particles; hueing dye particles; and any mixture thereof.

It may also be especially preferred for the laundry detergent powder to comprise bw levels, or even be essentially free, of builder. By essentially free of it is typically me ant herein to mean: "comprises no deliberately added". In a preferred embodiment, the laundry detergent comprises no builder.

A mo I un detersive surfactant

The anionic detersive surfactant present in the detergent omposition is separate to the granulated foam control composition. Preferably, the aitionic surfactant present in the detergent composition is a granulated form. The anionic detersive surfactant present in the detergent composition can be alkyl benzene sul phonic acid or salt thereof, alkyl etho ylated sulphate, or a mixture thereof Preferably, the attionic detersive surfactant is a mixture of alkyl benzene sulptonic ac id or salt there of and alkyl ethoxylated sulphate .

Suitable amonic deteisive surfactants include sulphate and sulphonate detersive surfactants.

Preferred sul phonate detersive surfactants include alkyl benzene sulphonate, pref rablyCio-i; alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating comm rcially available linear alkyl benzene (LAB), suitable LAB inc hides low 2-phenyl LAB, sue h as those supplied b y Ξ asol unde r the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®. other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®. A suitable amonic detersive surfactant is alkyl b nzene sulphonate that is obtained by DETAL catalyzed proc ss, although other synthesis routes, such as HF. may also b suitable.

Preferred sulphate deteisive surfactants include alkyl sulphate, preferably C _h alk ! sulphate, or predominantly Ci2 alkyl sulphate .

Another pre ferred sulphate detersive surfac tant is alkyl alkox ylate d sulphate , preferably alkyl ethoKylated sulphate, preferably a C _¾ s alkyl alko-iylated sulphate, preferably a C _¾ s alkyl etho-iylated sulphate, preferably the alkyl alkox ylate d sulphate has an average de ree of

alko-iylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a Cg-is alkyl ethoxylated sulphate having an average degree of ethoxylauon of from 0.5 to 10, preferably from 0.5 to 7, more preferably from 0.5 to 5 and most preferably from 0.5 to 3.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates maybe linear or bran hed, substituted or un-substituted.

The anionic detersive surfactant typically has a sudsing profile of at least about 5 cm, or from about 8 cm to 25 cm, as measured by the below Suds Testing Protocol herein. The level of anionic surfactant is from about 0.5%, 1%, 2%, 5 ¾ or 8% to about 20%, 30%, 40%, 50%, by weight of the laundry detergent.

In one embodiment, the anionic detersive surfactant comprises an anionic moiety, or multiple anionic moieties. Without being bound by theory, it is believed that an anionic moiety allows the anionic detersive surfactant to bind with the canonic polymer and form a coacervate in the wash liquor during the wash. The oacervate is believed to be able to adhere and deposit onto a fabric during washing, then selectively break down when the concentration of anionic detersive surfactant drops during the rinsing stage as compared to the concentration in a laundry liquor during washing, thereby releasing the anufoaming composition.

In an enitoodiment, the present laundry detergent can comprise a mixture of anionic surfactants. The anionic surfactant maybe a water-soluble salt, or an alkali metal salt, or a sodium and/or potassium salt.

Suds boosting co-surfactants may also be used to boost suds during washing. Many such suds boosting co-surfactants are often also anionic surfactants, and are includ d in the total anionic surfactant above.

Granulated foam control composition The granulated foam control compositions are topically added to the laundry detergents at a level of from about 0.1%, 0.2%, 0.5% to about 1.0%, 10% by weight. The granulated foam control compositions of the invention were found to have a minimum impact on the foam during the wash.

The granulated foam control composition may comprise a foam control parti le comprising a core comprising the foam control agent, the organic additive and the water soluble inorganic particulate carrier, and the core being at least partially coated with a coating comprising a polymer and a surfactant.

Alternatively the granulated foam control composition may comprise a plurality of water soluble inorganic carrier particles (C) coated and bonde d together by a liquid composition comprising the foam control agent (A), the organic additive (B), the cationic polymer (D) and the anionic surfactant (E).

It is preferred that the foam control composition is an homogenous mix of the foam control agent organic additive, soluble inorganic carrier, cationic polymer and anionic surfactant. a) Foam control agent

The foam control agent comprises (i) a polydiorganosiloKane fluid, (ii) a hydrophobic filler and optionally an organosilicone resin. The polydiorganosiloxane fluid can be a polyiiorganosilo-iane fluid comprising units of the formula:

R

I

- S i-O)- I

R

where each group R, which maybe the same or different, is selected from an alkyl group having 1 to 36 carbon atoms or an aryl group or aralkyl group having 1 to 36 carbon atoms, the mean number of carbon atoms in the groups R being at least 1 .3. In one embodiment, the polyJiorganosilo-iane fluid preferably has no more than 5 mole % branching units such as RSiO^ units or crosslink sites, most preferably less than 2 mole % branching units. The mean number of carbon atoms in the groups R is preferably at least 1.3, and is more preferably at least 2.0, most preferably at least 2.5, if the groups R do not include aryl or aralkyl groups. The polyJiorganosilo-iane fluid is free from non-silicone polymer chains such as polyether chains.

One preferred example of a polydiorganosilo-iane fluid is a polysiloxane comprising at least 10% diorganosiloxane units of the formula Y

I

-(Si-O)-

I

Y

and up to 90% diorganosiloxane units of the formula

Y

I

-CS i-O)- I

P -X

wherein X denotes a divalent aliphatic organic group bonded to silicon through a carbon atom; Ph denotes an aromatic group; Y denotes an alkyl group having 1 to 4 carbon atoms; and Y' denotes an aliphatic hydrocarbon group having 1 to 24 carbon atoms, as described in EP 1075864. The diorganosiloxane units containing a -X-Ph group preferably comprise 5 to o ^" 0% of the diorganosilDxane units in the fluid. The group X is preferably a divalent alkylene group having from 2 or 4 to 10 carbon atoms, but can alternatively contain an ether linkage between two alkylene groups or betwee n an alkylene group and -Ph, or c an contain an ester linkage .

In one embodiment, Ph is a phe yl group, but may be substituted for e mple by one or more methyl, methoxy, hydroxy or chloro group, or two substituents on the Ph group may together form a divalent alkylene group, or may togethe r form an aromatic ring, resulting in conjunction with the Ph group in e.g. a naphthalene group. In another embodiment X-Ph group is 2-phenylpropyl - CH2-CH(CHj)-C(Hj. The group Y can be methyl but can be ethyl, propyl or butyl as well. The group Y has from 1 or 2 to 16 or IS carbon atoms, for example it is ethyl, methyl, propyl, isobutyl or hexyi. xtures of alkyl groups Y' can be used, for example ethyl and methyl, or a mixture of dodecyl and tetradecyl. Other groups may be present, for example haloalkyl groups such as chloropropyL, acyloxyalkyl or alkoxyalkyl groups or aromatic groups such as phenyl bonded directly to Si.

The polysiloxane fluid containing -X-Ph groups may be a substantially linear siloxane polymer or may have some branching, for example branching in the siloxane chain by the presence of some tri- functional siloxane units, or branching by a multivalent, e .g. divalent or trrvalent, organic or silicon-organic moiety knking polymer chains, as described in EP 1075684A. s

An alternative example of a preferred polydiorganosiloxane fluid is a polysiloxane comprising 50-100% diorganosiloxane units of the formula

Y

I

-CS i-O)- I

Z and optionally up to 50% diorganosiloxane units of the formula

Y

I

- S i-O)- I

Y

wherein Y denotes an alkyl group having 1 to 4 carbon atoms and Z denotes an alkyl group having 6 to 18 carbon atoms. The groups Y in such a polydiorganosiloxane are preferably methyl or ethyl. The alkyl group Z may preferably have from 6 to 12 or 14 carbon atoms, for example octyl, hexyl, heptyl, decyl, or dodecyL, or a mixture of dodecyl and tetradecyl.

In one embodiment, the number of siloxane units (DP, degree of polymerisation) in the average molecule of the polysiloxane fluid of either of the above types is at least 5, more preferably from about 5, 10 and 20 to about 200, 1000 and 5000. The end groups of the polysiloxane can be any of those conventionally present in siloxanes, for example trimethylsilyl end groups.

The polydiorganosiloxane fluid containing -X-Ph groups, or the polydiorganosiloxane fluid containing -Z groups, is preferably present as at l ast 80%, 95% by weight of the polysiloxane fluid content of the foam control composition, more preferably as 100% of the polysiloxane fluid.

The polydiorganosibxane fluid can alternatively be a polydiorganosibxane in which the organic groups are substantially all alkyl groups having 2 to 4 carbon atoms, for example polydiethylsilDxane .

The foam control composition may comprise between 1 and 25%, or even 2 and 20%, or even 2 and 15%, or even between 4 and 12% by weight of the foam control composition of polydiorganosiloxane fluid.

The foam control agent contains an hydrophobic filler dispersed in the polydiorganosiloxane fluid. Hydrophobic fillers for foam control agents are well known and are particulate materials which are solid at 100 ^o C, such as silica, preferably with a surface area as measured by BET measurement of at least 50 m /g., titania, ground quartz, durnina, an alumLnosilicate, zinc oxide, magnesium oxide, a salt of an aliphatic caiboxylic acids, a reaction product of an isocyanate with an amine, e.g. cyclotaxykmine, or an alkyl amide such as emylenebisstearamide or n thylenebisstearamide. Mixtures of two or more of these can be used.

Some of the fillers mentioned above are not hydrophobic in nature, but can be used if made hydrophobic . This can be done either in situ (i.e. when dispersed in the polysiloxane fluid), or by pre-treatment of the filler prior to mixing with the polysiloxane fluid. A preferred filler is sili which is made hydrophobic . Preferred silica materials are those which are prepared by heating, e .g. fumed silica, or precipitation. The silica filler may for example have an average particle size of 0.5, 2 and 5 to about 25, 30 and 50μιη. It can be made hydrophobic by treatment with a fatty acid, but is preferably made hydrophobic by the use of methyl substituted organosilicon materials such as dimethylsibxane polymers which are end-bbcked with silanol or siliconJ-ionded alkoxy groups, hexan¾thyldisilazane,examethyidisi xane or organosilicone resins containing groups and silanol groups. Hydrophobing is generally carried out at a temperature of at least lOO^C. Mixtures of fillers can be used, for example a highly hydrophobic sili a filler which is commercially available under the name Sipemat D10 from Evonik together with a partially hydrophobic silica such under the name Aerosil R972 from Evonik.

The amount of hydrophobic filler in the foam control agent of the invention is preferably from 0.5 to 50% by weight based on the foam control ag nt, more preferably from 1 up to 10 or up to 15% and most pref rably 2 to 8% by weight.

The foam control agent optionally contains an organosilic one resin which is associated with the polydiorganosibxane fluid. Such an organosilicone resin can enhance the foam control efficiency of the polysibxane fluid. This is particularly true for polysiloxane fluids containing -X-Ph groups, as described in EP 1075684A, and is also true for polysiloxane fluids containing -Z groups. In such polysiloxane fluids, the re sin modifies the surface properties of the fluid.

The organosilicone resin is generally a non- linear siloxane resin and preferably consists of siloxane units of the formula R'a3iO+-4j2 wherein R' denotes a hydroxyl, hydrocarbon or hydrocaibonoxy group, and wherein 'a' has an average value of from 0.5 to 2.4. It preferably consists of monovalent trihydrocarbonsiloxy(M) groups of the formula ^SiC^ and tetrafunctional (Q) groups SiO+j5 wherein R" denotes a monovalent hydrocarbon group. The number ratio of M groups to Q groups is preferably in the range 0.4: 1 to 2.5: 1 (equivalent to a value of a in the formula R' _* SiC of O.S≤ to 2.15), more preferably 0.4:1 to 1.1 :1 and most preferably 0.5: 1 to 0.8:1 (equivale t to a=l .0 to a=l .33).

The oiganosilicone resin is preferably a solid at room temperature . The molecular weigh of the resin can be increased by condensation, for example by heating in the prese ce of a base. The base can for example be an aqueous or al oholic solution of potassium hydroxide or sodium hydroxide, e.g. a solution in methanol or propanol. A resin comprising M groups, trivalent R"SiOjja (T) units and Q units can alternatively be used, or up to 20% of units in the organosilicone resin can be divalent units R"jSiOjjd. The group R" is preferably an alkyl group having 1 to 6 caibon atoms, for example methyl or ethyl, or can be phenyl. It is particularly preferred that at least 80%, most pref rably substantially all, R" groups present are methyl gioups. The resin maybe a trimethyl- capped resin.

The oiganosilicone resin is preferably present in the foam control agent at 1-50% by weight based on the polysiloxane fluid, particularly 2-30% and most preferably 4- 15%. The oiganosilicone resin may be soluble or insoluble in the polysibxane fluid. If the resin is insoluble in the polysiloxane fluid, the average particle siae of the resin may for example be from about 0.5 and 2 to about 50 and 400 m.

The granulated foam control composition of the invention can contain additional ingredients such as a density adjuster, a color preservative such as a male ate or fumarate, e.g. bis(2-methoxy-l- ethyljmaleate or diallyl maleate, an acetylenic alcohol, e.g. methyl butynoL or cyclooctadiene, a thickening agent such as caiboxymethyl cellulose, polyvinyl alcohol or a hydrophi c or partially hydrophobed fumed silica, or a coloring agent su h as a pigm nt or dye. b) Organic additive

The organic additive living a melting point of from about 45°C to about 100°C is miscible with the polydioiganosiloxane fluid. By 'miscible', it me ns that materials in the liquid phase (i.e., molten if necessary) mixed in the proportions in which they are present in the foam control composition do not show phase separation. This can be judged by the clarity of the liquid mixture in the absence of any filler or resin. If the liquids are miscible, the mixture is clear and re mains as one phase. If the liquids are immiscible, the mixture is opaque and separates into two phases upon standing. The organic additive increases the foam control efficiency. We have found that additives of melting point at least about 45°C are effective in increasmg foam control efficiency in the rinse. The organic additive comprises a polyol ester, which is a polyol, partially or fully esterified by carboxyiate groups each having 7 to 3D ^" carbon atoms. The polyol ester is preferably a glycerol este r or an este r of a higher polyol sue h as pentaerythritol or sorbitol. The polyol e ster is preferab ly a monocarboxylate or polycarboxylate (for example a dicarboxylate, tricarboxylate or tetrac rboxylate) in which the carboxyiate groups each having IS to 22 carbon atoms. Such polyol carboxylates tend to have a melting point of at least 45 C. The polyol ester can be a diester of a glyjol such as ethylene glycol or propylene glycol, preferably with a carboxyiic acid having at least from 14, IS to 22 carbon atoms, for example ethylene glycol distearate . Examples of glycerol esters include glycerol triste rate and glycerol sters of saturated carboxyiic acids having 20 or 22 carbon atoms sue h as the mate rial of melting point about 54°C commercially available unde r the trade name Synchro wax HRC from Croda, believed to be mainly a triglyceride of Cji fatty acid with some Cjo and C is chains. Alternative suitable polyol esters are esters of pentaerythritol such as pentaerythritol tetrabehenate and entae ryLhritol tetrastearate .

The polyol ester can contain fatty acids of different chain length, which is common in natural products. The organic additive can be a mixture of polyol esters, for example a mixture of esters containing different carboxyiate groups such as glycerol tripalmitate and glycerol tristearate, or glyj erol tristearate and Ξ ync hro ax HRC , or e thyle ne glyc ol diste arate and Ξ ynchro wax HRC .

The organic additive can also comprise a more polar polyol ster. In one mbodimenl, the polar polyol esters include partially esterified polyols including monoesters or diesters of glycerol with a carboxyiic acid having S to 30 carbon atoms, for example glycerol monostearate, glycerol monolaurate, glycerol distearate or glycerol monobehanate . Mixtures of monoesters and diesters of glycerol can be used. Partial esters of other polyols are also useful, for example propylene glycol monopalmitate, sorbitan monostearate or ethylene glycol monostearate. c) Water-soluble inorganic particulate carrier

Examples of water-soluble inorganic particulate carriers are phosphates, for example powdered or granular sodium tri olyphosphate; sulphates, for example sodium sulphate; carbonates, for example sodium carbonate, anhydrous sodium carbonate or sodium carbonate monohydrate ; silicates, for example sodium silicate; citrates, for example sodium citrate; acetates, for example sodium acetate ; sodium s squicarbonate; sodium bicarbonate ; and mixtures thereof. The water soluble inorganic particulate carrier in the granulated foam control composition may be selected from the group consisting of sodium or potassium chloride, sodium or potassium sulfate, sodium or potassium carbonate, sodium or potassium citrate, sodium or potassium bicarbonate, and combinations thereof.

The particle size of the water-soluble inorganic earner is preferably in the range of about 1 to about 30μιη, more preferably about 1 to about 20 ιη. In one aspect, the granulated foam control composition maybe covered by wate r-soluble inorganic particulate carriers, forming a granulated foam control composition which can readily be incorporated in a detergent powder.

Water-insoluble inorganic ingredient

In one embodiment th granulated foam control composition comprises a water-insoluble inorganic ingredient preferably the water- insoluble inorganic ingredient being zeolite or silica, most pref rably zeolite . In one aspect the water-insoluble inorganic ingredient is blended with the water- soluble inorganic carrier. The water- insoluble inorganic ingredient comprises no more than 0wt%, or 20wt¾, or 10wt¾, or 5wt¾ of the granulated foam control composition. d) Cationic polymer

The cationic polyme r is a polymer having a net c ationic c harge . The cationic polymer can be an amphoteric polymer. The amphoteric polymers of the present invention will also have a net cationic charge, i. . the total cationic charges on these polymers will exceed the total anionic charge. The charge density of the charged polymer ranges from about 0.05, 0.5 and 2.5 to about 7, 12 and 23 milliequivalents/g (her inafter, briefly, "meq/g' The charge density is calculated by dividing the number of net charge per repeating unit by the molecular weight of the repeating unit. The positive charges could be on the backbone of the polyme rs o r the side chains of polyme E . For polymers with amine monomers, the charge density depends o the pH of the carrier. For these polymers, charge density is measured at a pH of 7.

The weight-average molecular weight of the cationic polymer will generally be from about 80,000, about 150,000, about 200,000 to about 3,000,000, about 4,000,000, as determined by size exclusion chromatography relative to polyethyleneoxide standards with R detection. The mobile phase use d in the chromatography is a solution of 20% methanol in 0.4M ME A, 0.1 M NaNOj, 3% acetic acid on a Waters Linear Ultrahdyrogel column, 2 in series. Columns and detectors are kept at 40°C. Flow rate is set to 0.5 iuL/min.

The molecular weight and charge density of the cationic polymer can act to "compensate" for each other. Lower charge density polymers will work provided their molecular weight is sufficiently high, and lower molecular weight polymers will work provided their harge d sity is sufficiently high. Ξο, there appears to be an optimum cauonicity parameter, where the cauonicity parameter is defined as the produ t of mole ular weight * harge density/1000 (MW*CD/1000). Preferred charged polymers have a cauonicity parameter of from about 50, about 100, about 150 to about 50,000, about 70,000, about 90,000 me q*Da/g .

Nordiiniting examples of the cationic polymer can include;

a. Cationic Polysaccharides:

Cationic polysaccharides include but not hmited to cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches. Cationic polysaccharides have a molecular weight from about 50,000 to about 2 million, preferably fiom about 100,000 to about 1,500,000.

One group of prefe rred cat Ξ tructural Formula I as follows :

Wherein R ¹ , R ² , R ³ are each independently H, CI -24 alkyl (linear or branched),

R ⁵

^C¾CH-O^R wherein n is from about 0 to about 10; R ^T is H, CI -24 alkyl (linear or branched) or or mixtures thereof, wherein Z is a water soluble anion, preferably chloride, biomide, iodide, hydroxide, phosphate, sulfate, methyl sulfate and acetate ; R ^J is selected from H, or CI -Co ^" alkyl or mixtures thereof; R ⁷ , R ⁸ and R ^s are selected from H, or C1-C2S alkyl, benzyl or substituted benzyl or mixtures thereof

R ⁺ is H or -(P)m-H , or mixtures thereof, wherein P is a repeat unit of an addition polymer form d by a cationic monomer. In one embodiment, the cationic monomer is selected from n^thacrylamidoMmethylammonium chloride, dimethyl diallyl ammonium having the formula: which results in a polymer or co -polymer having units with the formula:

wherein Z' is a water-solu le anion, preferably chloride, bromide iodide, hydroxide, phosphate sulfate, methyl sulfate and acetate or mixtures thereof and m is from about 1 to about 100.

Alkyl substitution on the saccharide rings of the polyme r ranges from about 0.01 to 5% per sugar unit, more preferably from about 0.05% to 2% per glucose unit, of the polymeric material.

Preferred cationic polysaccharides include cationic hydroxyalkyl celluloses. Examples of cationic hydroxyalkyl cellulose include those with the INCI name PolyquaterniumlO such as those sold unde r the trade names Ucare Polyme r JR 30M, JR 400, JR 125, LR 400 and L 400 polyme rs; Polyquaternium 6Ί sold under the trade name Softcat ΞΚ TM, all of which are available from Amer hol Corporation Edge water NJ; and Polyquaternium 4 available under the trade name Celquat H200 and Celquat L-200 from National Starch and Chemical Company, Bridge water, NJ. Other pref rred polysa harides include hydroxyethyl cellulose or hydoxypropyi ellulose quaternised with glycidjii C 1 -C22 alkyl dimethyl ammonium chloride . Examples of such polysaccahrides include the polymers with the INCI names Polyquaternium 24 sold under the trade name Quaternium LM 200, PG-hydroxyethylcellulose kuryldimonium chloride sold under the trade name Crodacel LM, PG-hydroxyethylcellulose cocodimonium chloride sold under the trade name Crodacel QM and, PG-hydroxyethyl llulose stearyldimonium chloride sold under the trade name Crodacel QS and alkyldmemylammonium hydroxypropyl ox ye thyl cellulose.

In ore embodiment of the present invention, the cationic polymer compris s cationic starch. The se are de scribed by D. B . Ξ olarek in Modified Ξ tarche s, Properties and Use s publishe d by CRC Press ( 1926) and in U .Ξ . Pat . No . 7, 135,451 , c ol. 2, line 33 - c ol. 4, line o ^~ 7. In another embodime nt, the cationic starch of the present invention comprises amylose at a level of from about 0% to about 70% by weight of the cationic starch. In yet another embodiment, when the cationic starch comprises cationic maiae starch, the cationic starch comprises from about 25% to about 30% amybse. by weight of the cattonic starch. In the above mentioned embodiments, other polymers comprising amylopec tin c an present in said cationic stare h to fill the remainder pe rcentages .

A u td group of preferred polysaccharides are cationic gakctoniar-nans, such as cationic guar gums or cationic bcust bean gum. Examples of cationic guar gum are qua ternary ammonium derivatives of hydroxypropyl guar sold under the trade names Jaguar C13 and Jaguar Excel available from Rhodia, Inc of Cranburry NJ and N-Hance byAquaton, Wilmington. DE. b. Synthetic Cationic Polyme κ

Synthetic cat nic polymers in general and their method of manufacture are known in the literatur . For example, a de tailed descriptbn of cationic polyme rs can be found in an article by M. Fred Hoover that was published in the Journal of Ivlacromolecular Science-Chemistry, A4(o ^" ), pp 1327-1417, October, 1970. The entire discbsure of the Hoover article is incorporated herein by reference . Other suitable cationic polymers are those used as retention aids in the manufacture of paper. They are described in 'Rulp and Paper, Chemistry and Chemical Technobgy Volume III edited by James Casey (1981). The molecular weight of these polymers is in the range of about 80,000 to about 4,000,000 Da.

i. Additbn Polymers

Synthetic polymers include but are not limited to synthetic addition polymers of the general structure

wherein R , R , and Z are defined herein bebw. Preferably, the linear polymer units are formed from linearly polymerizing monomers. Linearly polyme rizing monomers are defined herein as monomers whic under standard polymerising condittons result in a linear or branched polymer chain or alternatively which linearly propagate polymerisation. The linearly polymerising monomers of the pre sent invention have the formula: However, those of skill in the art recognise that many useful linear monomer units are introduced indirectly inter alia, vinyl amine units, vinyl alcohol units, and not by way of linearly polymerizing monomers. For example, vinyl acetate monomers once incorporated into the backbone are hydrolyzed to form vinyl alcohol units. For the purposes of the present invention, lin ar polymer units ma b e dire ctly introduced, i .e . via linearly polyme rising units, or indire ctly i.e . via a precursor as in the case of vinyl alcohol cited her in above .

Each R ¹ is independently hydrogen, CI -CI 2 alkyl, substituted or unsubsututed phenyl, substituted or unsubsututed benzyl, -ORa, or -C(0)ORa wherein Ra is selected from hydrogen, and C 1 -C24 alkyl and mixture s thereof. Prefe rably Rl is hydrogen, C 1 -C4 alkyl, -ORa, or

- C(0)ORa.

Each R is independently hydrogen, hydroxy!, halogen, CI -CI 2 alkyl, -ORa, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, hetero yclic, and mixtures thereof. Preferred R ^J is hydrogen, C1-C4 alkyl, and mixtures thereof.

Each Z is independently hydrogen, halogen; linear or branched C1-C30 alkyl, nitrilo, - N(R ^J )j ; -C(0)N(R ³ )j ; -NHCHO (formamide);-OR ⁵ ,-0(CH _J ) _I ^(R ³ ) _J ,-0(CH _i )nN-KR ⁱ )3X ^" _J - C(0)ORVC(0)N-(R¾,-C(0)C*CH2)^(R¾,

-C(0)NH(CHj)Ji(R ³ )j.C(0)NH(CHj)Ji ⁺ (R ³ )3X ^" ,-(CHj)iiN( ³ )2, -(C¾)rLN ⁺ (R ^s ) ₅ X ^" ,

each R ³ is independently hydrogen, C1 -C24 alkyl, C2-C8 hydioxyalkyl, benzyl; substituted benzyl and mixture s thereof; each R is lnde pendently hydrogen or CI -C24 alkyl, and

X is a water soluble anion; the index n is from 1 to 6.

R ^J is independently hydrogen, CI -Co ^" alkyl,

and mixtures thereof

Z can also be selected from non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, heterocycle comprising a N-oxide moiety an aromatic nitrogen contdning heterocyclic wherein one or more of the nitrogen atoms is quatemized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is a N-oxide , or mixtures thereof. Non-kmiting examples of addition polymerizing monomers comprising a heterocyclic Z unit includes l-vinyl-2- pynOhdinone, 1-vmylimidazole, quate naze d vinyl imidazole, 2-vinyl- 1, 3-dioxolane, -vinyl-l- cy lohexenel,2-epoxide, and 2-vinyl yridine, 2-vinyl yridine N-oxide, -vmylpyridme N-oxide .

A non- limiting example of a Z unit which can be made to form a cationic charge in situ is the -NHCHO unit formamide. The formulator can prepare a polymer or co-polymer comprising fonitamide units some of whic are subsequently hydrolyae d to form vinyl amine equivalents.

The polymers and co-polymers of the present invention comprise Z units which have a cationic charge or which result in a unit which forms a cationic charge in situ. When the copolymers of the pre se nt inve ntion c omprise more than one Z unit, for e xample, Zl , Z2, ... Zn units, at least about 1% of the monomers which comprise the co-polymers will comprise a cationic unit.

The polymers or co-polymeis of the present invention can comprise one or more yclic polymer units which are derived from cyclically polymerizing monomers. Cyclically polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a cy lic polymer residue as well as serving to linearly propagate polymerization. Preferred cyclically polymerizing monomers of the present invention have the formula: wherein each R ⁺ is inde ndently an ole fin-comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R ⁺ unit; R ^J is CI -CI 2 linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion.

Non- limiting examples of R ⁺ units include ally! and alkyl substituted allyl units. Preferably, the resulting cyclic residue is a six-member ring comprising a quaternary nitrogen atom.

R ^J is preferablyCl-C4 alkyl, preferably methyl.

An example of a c y lie ally polyme rizing monomer is dimethyl diallyl ammonium having the formul

which re suits in a polymer or co -polymer having units with the formula: IS

wherei preferably the index z is from about 10 to about 50,000.

Nonlinriting examples of preferred polymers according to the present invention include copolymers made from one or more cationic monomers selected from the group consisting

Ν,Ν-diaJiylaminoalkyl methacrylate, N,N-dialkylanuroalkyl acrylate, N,N- dklkykntinoalkyl acrykmide, Ν,Ν-dialkyfentinoalkylmetta^ qraternized N,N- dkltykminoaltyl methacrylate, quale rnized N.N-dklkykminoalkyl acrylate, quaternized N,N- dhlkykntinoalkyl acrykmide, quaternized Ν,Ν-dialkylaniinoaliyln^tl^rylardde vinykmine and its derivatives, allylamine and its derivatives, vinyl imidazole, quate rnized vinyl imidazole and diallyl dialkyi ammonium chloride, and combinations the reof.

Optionally a second monomer is selected from a group consisting of acrylamide, N,N- dklkyl acrylamide, methacrylamide, N,N-dial yln¾thacrylamide, CI -CI 2 alkyl acrylate, CI -CI 2 hydro-iyalkyl acrylate, polyalkykne glyol acrylate, CI -CI alkyl methacrylate, CI -CI 2 hydro-iyalkyl methacrylate, polyalkylene glycol methacrylate, vinyi acetate, vinyl alcohol, vinyl formamide , vinyl acetamide, vinyl alkyl ethe r, vinyl pyridine, vinyl pyrrolidone , vinyl imidazole and derivatives, acrylic acid, met acrylic acid, maleic acid, vinyl sulfonic acid, styt ne sulfonic acid, a rylamidopropylniethane sulfonic acid (ΑΜΡΞ) and their salts, and combinations thereof.

The polymer may optionally be crosslinked. Crosslinking monomers include, but are not limited to, ethylene glycoldiacrylatate, divinylbenzene and butadiene.

Preferred cationic monomers in lude N,N-dimethyl aminoethyl acrylate, N,N-dimethyl aminoethyl methacrylate (DMA ), P-(n¾thacryloylamino)emyi]tri-n^ chloride (QDMA ), N _j N-dmet ylanunopropyl acrylamide (D APA), Ν,Ν-dimethylaminopropyl n¾1 acrykmide (DMAPMA), acrylaniidopropyl trimethyl ammonium chloride, n¾1 acrylamidopropyl trimethylanunonium chloride (MAPTAC), quaternized vinyl imidazole and dkUyldime thylaminonium chloride and de rivatives the reof.

Preferred second monomers include acrylamide, N, N-dimethyl acrylamide, C1-C4 alkyl acrylate, C1-C4 hydroxyalkylacrylate , vinyl formamide, vinyl acetate, and vinyl alcohol. Most preferred nonionic monomers are acrykmide, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate and derivative thereof,

The most preferred synthetic polymeis are poly acryknu^-co-diaUyldimem^

chloride), poly(acrylamide-n¾thacrylarti ammonium chloride), poly(ac rylamide- co-N,N-dime hyl anunoethyl methacrylate), polyacrykmide-co-N,N-dimethyl aminoethyl methacrylate), polyhydroKyemykcrykte -co-dimethyl aminoethyl methacrylate), polyihydroxpropylacrylate -co-dimethyl anunoethyl methacrylate), poly(hydroxpropyIacryiate-co- n^lhacrylamidopropyltri^ chloride), polyacrykmide-co- dkUyldmwmyknmTDnium chJjoride-co-acryhc acid), poly(acryiamide- me thac rylamidQpropyltrime thyl ammonium chloride-c o-acry c ac id) .

ii . Polye thyle neimine and its derivatives .

These are commercially available under the trade name of Lupasol from BASF AG of Ludwigschaefen, Germany. In one embodiment, the polyethylene derivative is an amide derivative of polyetheyleneimine sold under the trade name Lupoasol ΞΚ. Also included are alkoxylated polye tide neimine ; alkyl polyeftyieneimine and quaternized polyethyle neimine .

iii. Polyamidoamine-e pichlorohydrin (PAE) Re sins

PAE resin is a condensation product of polyaltylenepolyamine with poly arboxyic acid.The most common PAE resins are the condensation products of diemylenetriamine with adipic acid followed by a subsequent reaction with epich rohydrin. They are available from Hercules Inc. of Wilmington DE under the trade name Kymene or from BASF A.G. under the trade name Luresin. These polymers are described in Wet Strength Resins And Their Applications editedbyL. L. Chan, TAPPI Press (1994). e) Anionic surfactant

Anionic surfactants can include sulphate and sulphonate surfactants. Preferred sulphonate surfactants include alkyl be nzene sulphonate, pre ferablyCio-u alkyl be nzene sulphonate . Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, bysulphonatrng commercially available linear alkyl benze ne (LAB) ; suitable LAB include s low 2-phe nyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petre lab®, other suitable LAB include high 2-phenyl LAB, such as those supplied b y Ξ asol unde r the tradename Hyblene®. A suitable anionic surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable. Preferred sulphate surfactants include alkyl sulphate, preferably C _h lky! sulphate, or predominantly Cij alkyl sulphate. Another pref rred sulphate surfactant is alkyl alkoxylated sulphate, preferably alkyl e thoKylated sulphate, preferably a C _H8 alkyl alkoxylated sulphate, preferably a C _¾ s alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an ave rage de gree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a Cg-is lkyl ethoxylated sulphate having an average degr of ethoxylation of from 0.5 to 10, preferably from 0.5 to 7, more preferably from 0.5 to 5 and most preferably from 0.5 to 3. The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates maybe linear or bran hed, substituted or un-substituted.

S itable organic anionic surfactants include alkyl aryl sulphonates, for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefin sulphates and sulphonates, sulphated monoglycerides, sulphated esters, sulphonate d or sulphated etho yiate alcohols, sulphosuccinates, alkane sulphonates, alkali metal soaps of higher fatty acids, phosphate esters, alkyl isethionates, alkyl ta urate s and/or alkyl sarcosinates.

The anionic surfactant present in the foam control composition maybe selected from a sulphate surfactant, a sulphonate surfactant or a mixture thereof, preferably selected from alkyl benzene sulphonate, an alkyl alkoxylated sulphate, or a mixture thereof.

Without being bound by theory, the anionic surfactant (e) enhances the effect of the canonic polymer (d) in suppression of foam in the rinse compared to suppression of foam during the wash.

The ratio of anionic surfactant to canonic polymer in the foam control composition can be from 10:1 to 1 :100.

The foam control agent may comprise the anionic surfactant and a second surfactant. In one embodiment the foam control agent may comprise the anionic surfactant and at least a second surfactant. The surfactant maybe a non-ionic surfactant, an anionic surfactant a. cationic surfactant a zwitterionic surfactant or a mixture thereof. The surfactant maybe a non-ionic surfactant ^{or evBn} an alkoxylated non-ionic surfactant.

The nonionic surfactant can for example be an alkoxylated non- ionic surfactant such as a condensate of ethylene oxide with a long chain (fatty) alcohol or (fatty) acid, for example C 1 _15 alcohot condensed with 7 moles of ethylene oxide, a condensate of ethylene oxide with an amine or an amide, or a condensation product of ethylene and propylene oxides. Further suitable nonionic surfactants in lude siloxane polyoxyalkylene copolymers, fatty acid alkylol amides, fatty amine oxides, esters of sucrose, glycerol or sorbitol and fluoro-surfactants. Suitable non-ionic surfactants include alkyl polyglucoside and/or an alkyl alkoxylated al ohol. Preferred non- ionic alkyl alkoxylated alcohols include Cs-is alkyl alkoxylated alcohol, preferably a Cs- _! salkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C^is alkyl ethoxylated alcohol living an average degree of

ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7. The alkyl alkoxyla ted alcohol can be linear or branched, and substituted or un-substituted. Suitable non-ionic surfactants can be selected from the group consisting of: Cs-Cis alkyl ethoxylates, such as, NEODOL® non- ionic surfactants from Shell; d-Cu alkyl phenol alkoxyktes whe rein preferably the alkoxykte units are ethylene oxy units, propyleneoxy units or a mixture thereof; Cu-Cis alcohol and Ct-Ci2 alkyl phenol condensates with ethylene oxide/propylene oxide bbck polymers such as Pluronic® from BASF, Ci+-Cji mid-chain branched al ohols; Ci+-Cij mid-chain branched alkyl alko ylates, preferably having an average degree of alkoxylation of from 1 to 30; alkyl polysaccharid s, preferablyalkylpolygly osides; polyhydroxy fatty ac id amides; ether capped polyoxyalkylated) alcohol surfactants; and mixtures thereof.

A cationic surfactant can for example be an alkylamine salt, a quaternary ammonium salt, a sulphonium salt or a phosphonium salt.

A zwitterionic (amphoteric) surfactant can for example be an imidazoline compound, an alkylaminoac id salt or a betaine . Coating

In one embodiment the granulated foam control composition comprises a coating, wherein the coating comprises a polymer and a surfactant. In this embodiment, the granulated foam control composition as described above forms the core, which is then at least partially coated with the coatin . The c oating may c over all of the surface of the granulated foam c ontrol agent or may c over only a small part. It is preferred that the core comprising a homogenous mix of the foam control ag nt, organic additive, soluble inorganic arrier, c tionic polymer and anionic surfactant, and that this is then at least partially oated with the coating.

The coating comprises a polymer and a surfactant. The polymer can be any polymer. However, it is preferred that the polymer is sele ted from polymers described above in relation to the granulated foam control composition. The surfactant in the coating can be anysurfactant. The surfactant can be selected from non- ionic, cationic, anionic, zwitterionic surfactants and mixtures thereof. The anionic surfactant can be the same as des ribed above in relation to the granulated foam control composition. The nonionic surfactant can for example be an alkoxylated non-ionic surfactant such as a condensate of ethylene oxide with a long chain (fattyj alcohol or (fatty) acid, for example C 1^15 alcohol, condensed with 7 moles of ethylene oxide, a conde nsate of e thyle ne oxide with an amine or an amide, or a

condensat n product of ethylene and propylene oxides. Further suitable nonionic surfactants include siloxane polyoxyalkylene copolymers, fatty ac id alkylol amides, fatty amine oxides, esters of sucrose, glyc erol or sorbitol and fluoio -surfac tants.

Suitable non-ionic surfactants include alkyl polyglucoside and/or an alkyl alkoxylated alcohol. Preferred non- ionic alky, alkoxylated alcohols include Cs-is alkyl alkoxylated alcohol, preferably a Cs-is alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C¾s alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7. The alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted. Suitable non-ionic surfactants can be selected from the group consisting of: Cs-Cis alkyl ethoxylates, suc as, NF-ODOL® non- ionic surfactants from Shell; Ci-Cij alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethylene oxy units, propyleneoxy units or a mixture thereof, Cu-Cis alcohol and d- u alkyl phenol condensates with ethylene oxide/propylene oxide bbck polymers such as Pluronic® from BASF; Ci+-C¾2 mid-chain branched alcohols; Ci+-Ci2 mid-chain branched alkyl alko ylates, preferably liv an average degree of alkoxylation of from 1 to 30; all l polysaccharid s, preferablyalkylpolyglycosides; polyhydroxy fatty ac id amides; ether capped polyoxyalkyl ted) alcohol surfactants; and mixtures thereof.

Suitable cationic surfactants include alkyl pyridinium compounds, alkyl qua ternary ammonium compounds, alkyl quaternary phosphoni urn compounds, alkyl ternary sulphonium compounds, and mixtures thereof. Preferred cationic surfactants are quaternary ammonium compounds having the general formula:

(RXRi)(Ra)(R3jN ⁺ X: wherein, R is a linear or branched, substituted or unsubstituted C i.isalkyl or alkie nyl moiety, Ri andRj are independently sel ted from methyl or ethyl moieties, Rj is a hydroxy!,

hydroxymethyl or a hydroxys thyl moiety, X is an anion whic h provides charge neutrality, preferred anions include : halides, preferably chloride; sulphate; and sulphonate. Preferred canonic detersive surfactants are mono-C t-is lkyl mono-hydroxyethyl di-methyl qu te rnary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-C _¾ o alkyL mono-hydroKydthyl di-methyl quaternary ammonium chloride, mono-C^u alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

A cationic surfactant can for example be an alkylamine salt, a quaternary ammonium salt, a sulphonium salt or a phosphonium salt.

A zwitterionic (amphoteric) surfactant can for example be an imidazoline compound, an dkylaminoae id salt or a betaine .

Additional Detergent Ingredients

The balance of the laundry detergent topically contains from about 5% to about 70%, or about 10% to about o ^~ 0% adjunct ingredients. Suitable detergent ingredients include: transition metal catalysts; imine bleach boosters; enzymes such as amylases, carbohydrases, cellulases, lac cases, lipases, bleaching enzymes such as oxidases and peroxidases, proteases, pectate lyases and mannanases; source of peroxygen such as per arbonate salts and/or perborate salts, preferred is sodium percarbonate, the source of peroxjjgen is preferably at least partiallycoated, preferably completely coated, by a coating ingredient such as a carbonate salt a sulphate sail, a silicate salt borosilicate, or mixtures, including mixed salts, thereof; bleach activator such as tetraacetyl ethylene dkmine , oxybenze ne sulphonate bleach ac tivators sue h as nonanoyl oxybe nzene sulphonate, caprolac tarn bleach activators, imide bleach activators such as N-nonanoyl-N-methyl acetamide, preformed peracids such as Ν,Ν-ptha ykmino peroxycaproic acid, nonykmido p roxyadipic acid or dib nzoyl peroxide; suds suppressing systems such as silicone based suds suppressors;

brighteners; hueing agents; photobleach; fabri -softening agents such as clay, silicone and/or quaternary ammonium compounds; flocc ulants such as polye thyle ne oxide ; dye transfe r inhibitors such as polyvinylpyrrolidone, poly -vinyl pyridine N-oxide and/or co-polymer of vinyl pytiOlidone andvinylimidazole; fabric integrity components such as oligomers produced by the condensation of imidazole and epicl^rhydrin; soil dispersants and soil anti-redeposition aids such as alkoxyl ted polydmines and ethoxylated emyleneimine polymers; anti-re deposition compon ts such as polyesters and/or terephthalate polymers, polyethylene glycol including polyethylene glycol substituted with vinyl alcohol and/or vinyl acetate pendant groups; perfumes such as p rfume microcapsules, polymer assisted perfume delivery systems including Schiffbase perfume /polymer complexe s, starch enc apsulated perfume acc ords; soap rings ; ae sthetic particles including coloure d noodles and/or needles; dyes; fillers such as sodium sulphate, although it maybe preferred for the composition to be substantially free of filleis; carbonate salt including sodium c arbonate and/or sodium bicarbonate; silicate salt such as sodium silicate, including 1.o ^~ R and 2. OR sodium silicate, or sodium metasili ate ; co-polyesters of di-carboxylic acids and diols; cellulosic polymers such as me thyl c ellulose, carboxymethyl cellulose, hydrox ye thoxyce llulose , or other alkyl or alkylalkoxy cellulose, and hydrophobic ally modified cellulose; carboxylic ac id and/or salts thereof, including citric acid and/or sodium citrate, and any combination thereof.

Other surfactants useful herein include cationic surfactants, nonionic surfactants, and amphoteric surfactants. Such surfactants are well known for use in laundry detergents and are tj cally present at levels of from about 0.2% or 1 % to about 40% or 50% .

Process for washing fabrics

The present invention is also to a method of cle aning fab ric, said method c omprising the steps of: a) providing a laundry dete rgent according to the present invention ;

b) forming a laundry liquor by diluting the laundry detergent, wherein the anionic surfactant level of the l undry liquor is at l ast SO ppm,

c) washing the fabric in the kundry liquor;

d) rinsing the fabric in water, wherein the anionic surfa tant detersive oncentration is no more than 25wt% of the anionic detersive surfactant concentration in stepb).

The anionic detersive surfactant concentration in the laundry liquor during washing is preferably at least about SO ppm, or 140 ppm, or 200 ppm, or 400 ppm, or 600 ppm, and the concentration of anionic detersive surfactant during rinsing is no more than 25 wt% of the anionic detersive surfactant concentration during the wash step, for example it is no more than 200 ppm, or 150 ppm, or 100 ppm, or SO ppm, or 50 ppm. Process for Ivkking

The present kundry detergents may be prepared by mixing the granulated foam control composition with the anionic surfactant. The anionic surfactant is typically in a form of a water- soluble granule formed by agglomeration and/or spray drying and/or extrusion, and manufacturing proce sses the reof maybe e ither batch or continuous proc ess, both of which are we 11 known in the art.

One aspe t of the present invention is a method of manukcturing a granulated foam control composition comprising:

Preparing a foam control particle, omprising mixing

(a) a foam control agent comprising

(i) a polydiorganosiloxane fluid comprising units of the formula

R

I

-(Si-O).

I

R where each group R, which maybe the same or different i≤ sele ted from an alkyL group having 1 to 36 carbon atoms or an aryl group or aralkyl group living up to 36 carbon atoms, the mean number of carbon atoms in the groups R being at least 1.3;

(ii) a hydrophobic filler dispersed in the polydiorganosiloxane fluid; and

(iii) optionally an organosilicon resin; and

(b) an organic additive of me lting point 45 to 100°C c omprising a polyol este r which is a polyol fully or partially esterified by carboxjjiate groups each having 7 to 36 carbon atoms; and

depositing the mixture of (a) and (b) on a water-soluble particulate inorganic carrier, the mixture of (a) and (b) being in non-aqueous liquid form prior to depositing it on the water- soluble particulate inorganic carrier; and

depositing a mixture of (d) a polymer having a net cationic arge and an anionic surfa tant (e) on the water-soluble particulate inorganic carrier,

wherein the mixture of (a) andb) and the mixture of (d) and (e) are deposited onto the water- soluble inorganic carrier either simultaneously or sequentially.

In a subsequent step, the granulated foam control composition can be add d to kundry detergent composition. In one aspect the anionic surfactant (e) maybe added independently or as a mixture together with the polymer having a net canonic charge.

In one embodiment, the mixture of canonic polymer (d) and surfactant (e) is mixed with the foam control agent (a) and the organic additive (b) prior to being deposited on the particulate carrier. The mix ture of (d) and (e ) may first be prepared followed b y the addition of the nuxture of (a) and (b) into (d) and (e). Preferably the mixture of (a) and (b) is kept molten, and the mixture of (d) and (e) is ke pt at ele ate d temperature (approximate ly 70*0) . Without wishing to be bound by theo ry mamteirring the two mixtures at elevated temperatures provides for better mixing. If the temperature drops, then the mixture of (a) and (b) begins to solidify and so mixing of the two mixtures becomes more diffi ult.

In one en iodiment a co-aceivate of anionic surfactant and cationic polymer is prepared before addition to foam control agent and organic additive.

The percentage of active anionic surfactant present in a cationic polymer (d)/anionic surfactant (e) ombination can less than o ^~ 0%, preferably l ss than 40%, most preferably less than 30%. The cationic polymer (d) and the anionic surfactant ( e) can c onvenie ntlybe mixe d together before be ing mixed with the other components of the foam control granule, although they can be added separately if desired.

In one en^odiment the anionic surfactant is LAS, and the cationic polymer is PAM MAPTAC, (preferably, from Lubrizio having a molecular w ight of 1,100,000 Da, comprising 33 parts of polydcrykmide monome r units and 12 parts of n^tliacrykmidopropyi irfmemylammonium c hloride monomer units), and wherein the percentage of active LAS present in a LAS PAM MAPTAC combination does not e xceed 33%, pre ferably not exc eed 25%, most pie ferably not exc eed 17% . In another embodime t, the anionic surfactant is ΑΕΞ, and the cationic polymer is PAM MAPTAC, and wherein the percentage of active ΑΕΞ present in an ΑΕΞ ΡΑΜ MAPTAC combination does not ex ceed 33%, pre ferably not exc eed 25%, most pre ferably not exc eed 17% . In another embodime nt, the anionic surfactant is LAS, and the cationic polymer is a copolymer comprising diallyl dimethyl ammonium chloride monomer units and acrylamide monome r units, (Merquat 550 provided by Lubrizio), and wherein the percentage of active LAS in the LAS Merquat 550 combination does not exceed 33%, preferably not exceed 25%, most preferably not exceed 17%. In another

embodime nt, the anionic surfactant is LAS, and the cationic polymer is a homopolymer of diallyl dimethyl ammonium clnoride monomer units (Merquat 100 provided by Lubrizio), and wherein the percentage of active LAS present in an LAS /Merquat 100 combination will not exceed 60%, prefe rabl not exce ed 40%, most prefe rably not exce ed 27% . In yet another e mbodimenl, the anionic surfa tant is LAS, and the cationic polymer is a polymeric quaternary ammonium salt formed by reacting hydroxyethyi cellulose with a trimethyl ammonium substituted epoxide, and has a Mw of 300,000 and a c harge density of 1.25 meq/g .cationic polyme r (JR. 30M provide d by Do w Chemicals), and wherein the pe rcentage of ac tive LAS pre se nt in a LAS JR. 30M combination will not exceed 25%, preferably not ex eed 20%, most preferably not exceed 14%.

The mixture of foam control agent and organic additive is preferably deposited on the particulate carriers at a temperature at whi the organic additive is liquid, for example a

temperature in the range of about 45-100^ As the mixture cools on the particulate carriers, it solidifies to a structure which contributes to the inc reased e fficiency of the foam c ontrol

composition. The foam control composition is preferably made by an agglome ration process in which the foam control composition comprising the tbam control agent and the organic additive is sprayed onto the particulate carriers while agitating the particles. In one embodiment the particles are agitated in a high shear mixer through which the particles pass continuously The mixture of (d) and e ) and the mixture of a) and flb ) can be de posited onto the water-soluble particulate inorganic carrier via a spray nozzle . In one aspect, the mixture of (d) and (e) and the mixture of (a) and (b) are mixed toge ther in the tip of the nozzle just prior to being spraye d.

It maybe pr ferred that the particulate water-soluble inorganic carrier is present at an elevated temperature when the mixture of (a) and (b) and the mixture of (d) and (e) are deposited on to it. The temperature of the particulate water-soluble inorganic carrier maybe greater than 30^ or eve n greater than 40 ^i' C or even greater than 50* . Without wishing to be bound by the ory, the particles produced when the particulate water-soluble inorganic material is at an elevated

te mperature when the mixture of (a) and (b) and the mix ture of (d) and (e ) are deposited on to it have a different appearance to the particles produced when the particulate water-soluble inorganic material is not at an elevate d tempe rature whe n the mixture of (a) and (b) and the mixture of (d) and (e) are deposited on to it.

In a preferred embodiment, the particulate water-soluble inorganic carrier is sodium sulphate. One type of suitable mixer is a verti l, continuous high shear mixer in which the foam control composition is sprayed onto the particles. One example of such a mixer is available under the name Flexomix mixer from Hosokawa Schugi.

Alternative suitable mixers which may be used include horizontal high shear mixers, in which an annular layer of the powder-hquid mixture is formed in the mixing chamber, with a 23 residence time of a few seconds up to about 2 minutes. Examples of this family of n^lunes are pin mixers, e.g.. TAG series from LB, RM-tjpe machines from Rubberg-Mischtechnik or other pin mixers supplied by Lodige, and paddle mixers, e.g. CB series from Lodige, Corimix from Drais- Manheim and Conax from Ruberg Ivnschtechnik.

Other possible mixers which can be used in the process of the invention are Gktt granulators, ploughshare mix rs, as sold for example by Lodige GmbH, twin counter- rota ting paddle mixers commercially available under the name Forberg, mtensive mixers including a high shear mixing arm within a rotating cyhndrical vessel, commercially available under the name Typ R from Eirich, under the name Zig-Zag from Patterson-Kelley, and under the name HEC from Niro.

Wash Suds Index and Rinse Suds Index

Wash Suds Index is used to compare the suds volume gene rated during the washing stage by the present laundry detergent comprising a granulated foam control composition versus a laundry detergent alone without the present granulated foam control omposition as a control. Herein, the suds volume is measured by the suds height following a standardised washing process described below.

Rinse Suds Index is used to compare the suds volume remaining after rinsing of the present laundry detergents comprising granulated foam control composition versus the laundry detergents alone as a control. Herein the suds volume is measured by the surface area of suds in a rinsing basin following a standardise d rinsing process describ d below.

The present laundry detergent used to conduct the experiments in ludes by weight of the laundry det rgent 0.5% of present and comparative granulated foam control composition, 1 1% of linear alkylbensene sulphonate, 1% of alkyl dimethyl hydroxy! ethyl anmwmum chtoride, 3.5% of CI - 15 alkyl ethoxykted alcohol having a molar average degree of ethoxylation of 9, 20% sodium dumino silicate (Zeolite), 15% sodium carbonate, 28% sodium sulphate, 2% sodium silicate, 1.5% carboxy methyl cellulose, 4% of poly acrylic acid, 2% sodium p rcarbonate, 0.5% of tetraacetylethylenediamine (TAED), and includes enzymes t.al which make the total amount of all the components add up to 100%.

Standard Washing process:

1) Fill a basin with 2 L DI water (4 gpg) and dissolve the laundry detergents to reach a concentration of 3500 ppm in the water and swirl for 2 min until it fully dissolves and forms a laundry liquor. 2) Put 3 pie es of fabric into the laundry liquor and soak for 10 nun.

3) For eac h piec e of fabric, scrub it 5 times, dip bac k into the laundry liquor bet we en each scrub .

4) Wring the scrubbed fabric gently not dislurbing the suds produ ed.

5) Measure the total height of the suds and laundry liquor, by taking a average from five measures in luding one center point and four edge points of the basin;

6) Measure the laundry liquor he ight in the basin by removing suds from the basin;

7) Get suds height by deducting the measurement in step 6 ^" ) from ste p 5) .

Standard Rinsing process:

1) Put the washed and wringed piece of fabric into a new basin comprising 2 L of fresh DI water (4 gpg) by controlling the laundry liquor carryover to be 200 ±5 g (carryover = total weight after wash - dry fabric weight). Rinse each piece of fabric through 3 gentle scrubs.

2) Take a picture for the suds coverage on the rinse water surface on 5-10 sec after removing the piece of fabric ftoin the water.

As a summary the conditions set for the washing and rinsing process are provided in below table 1. Table 1

EXAMPLES

A comparison was made be tween laundry dete rgent c omposiuons c omprising foam control composition, where in the foam c ontrol composition c omprised an anionic surfactant and laundry detergent compositions comprising loam control compositions, wherein the foam control composition does not comprise an anionic surfactant. Example 1 :

Six perce nt (o ^" %) by we ight treated prec ipitate d silic a available under the name Ξ ipernat D10 from Evonik and 1% partially hydrophobic silica available under the name R972 from Evonik are dispersed in 86.3% polydiorganosilox ne fluid having a degree of polymerisation of 65 and comprising SO mole % methyl dodecyl siloxane groups, 20 mole % methyl ..-phenyl propyl (derived from [alpha] -methylstjTene) siloxane groups. by weight of a o ^" 0% by weight solution of an organosiloxane re sin having trime thyi silox ane units and Ξ i02 units in a MQ ratio of 0.65S1 in octyl stearate (70% solid) is added. The mixture is homogenized through a high shear mixer to form a foam control intermediate PCI .

6.6 parts by weight of the foam control inte rmediate PC 1 was me chani ally mix d with

4.05 parts of glyceryl tristearate provided byOle on to give x l . The FCl and molten glyceryl tristearate were mix d at S0°C. The glyc rol tristearate and polydiorganosiloxane fluid were misc Jble and the mixture had a melting point of 70°C . 10.3 parts by we ight of a 6.2% active aque ous solution of P AM MAPTAC cationic polyme r was mechanically mixe d with 0.37 parts of a 20.0% active aqueous solution of LAS to give Mix 2. Mix 2 was then mdntained t 70 ^i" C. ίΰ.65 parts by weight of molten Mix 1 was the n mec hanic ally mixed with 10.65 parts by weight of Mx 2 at 70 ^o C to give an homogenous mix. 1 .3 parts by weight of the homogenous mixture were poured sbwly into a mixer where 7S.7 parts of sodium sulfate powder was already being stirred. The mixture was stirred continuously until a granular particulate material was obtained. The water containe d in this granulated foam control composition was re moved in a fluidize d bed using air at 50°C. A granulated foam control composition was achieved.

Ex mple A:

6.2 parts by weight of the foam control intermediate FC1 was mechanically mixed with 10.0 parts of glycerol tristearate provided byOle on. The FC1 and molten glycerjji tristearate were mixed at S0°C. The gly eryl tristearate and polydiorganosiloxane fluid were miscible and the mixture had a melting point of 70^. 16.8 parts by we ight of the mixture of glycerjji triste arate and FC 1 we re poured sbwly into a mixer where 7S.7 parts of pre-heated sodium sulfate (70^) powder was already being stirred. The mixture was SUITE d continuously until a granular particulate material was obtained. 3.3 parts by we ight of a il .2% aqueous solution of P AM MAPTAC was poured slowly into the mix er on top of the aire ady formed granular i rue ulate material. The mixture was stirred continuously until the polymer was evenly dispersed on the granular particulate material. The water contained in this granulated foam control composition was removed in a fluidned ed using air at 30°C. A granulated foam control composition was achieved.

Example B:

7.8 parts by weight of the foam control intermediate FC1 was mechanically mixed with 12.63 parts of gly; eryl tristearate provided by Oleon. The FC 1 and molten glyceryl triste arate we re mixed at S0°C. The glyceryl tristearate and polyiLorganosiloxane fluid were mis ible and the mixture had a melting point of 70°C. 20.43 parts by weight of the mix ture of gly: eryl tristearate and FC1 were poured slowly into a mixer where 74.2 parts of sodium sulfate powder was already being stirred. The mix ture was stirred c ontinuously until a granular partic ulate material was obtained. 5.4 parts b y weight of a 6.2% aque ous solution of P AM MAPTAC was poure d slo wLy into the mixer on top of the already formed granular particulate material. The mixture was stirred continuously until the polymer was evenly dispersed on the granular parti late material. The water contained in this granulated foam control composition was removed in a fluidiaed bed using air at 30 ^o C. A granulated foam control composition was achieved.

The foam c ontrol c ompositions were added to c omme rcially available Ariel laundry detergent powder as available on-shelf in China. The standard wash and rinse protocol as detailed above were used. Wash suds index and rinse suds index was measured as detailed above.

Samples were then stored at room temperature, and periodically tested using the same wash suds index and rinse suds inde tests described abov . The results were compared to those done when the sample was fre sh. If a greater than 10% decrease in wash suds or a greater than 10% increase in rinse suds was seen, then the sample was defined to have a loss of stability

Results can be seen in Table 2.

Table 2

25

from Table 2, detergent compositions comprising a foam control composition according to the present invention exhibited excellent wash suds index comparable to that of foam control compositions outside of the present invention. However, detergent compositions comprising a foam control composition according to the pres nt inv ntion exhibited redu d rinse suds as compared to compositions outside of the present invention. Finally, compositions comprising foam control compositions according to the present invention ex ibited improved storage stability as compared to compositions outside of the present invention.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact num rical values recited. Instead, unless otherwise specified, each suc dimension is intended to me an both the recited value and a functionally equivalent range surrounding that value. For example, a dime nsion disclosed as "40 mm" is inte nded to me an "about 40 mm ."