EP2859079A1 - Granulated foam control composition - Google Patents

Abstract

A granulated foam control composition comprises a foam control agent based on a polydiorganosiloxane fluid, an organic additive of melting point 45°C to 100°C comprising a polyol ester, a water-soluble particulate inorganic carrier, a polymer having a net cationic charge and a surfactant. The mean number of carbon atoms in the organo groups of the polydiorganosiloxane fluid is at least 1.3. The foam control agent includes a hydrophobic filler dispersed in the polydiorganosiloxane fluid, and optionally an organosilicone resin. The polyol ester is miscible with the polydiorganosiloxane fluid.

Description

GRANULATED FOAM CONTROL COMPOSITION

[0001] This invention relates to silicone-based foam control compositions for use in aqueous compositions which are liable to foam. The foam control compositions of the invention can be added to detergent compositions, particularly detergent powders, to inhibit excessive foaming when the detergent is used in washing.

[0002] In some countries, washing laundry by hand is common practice. This process requires a lot of water, water that can be scarce or difficult to access. Hence developing suitable granulated antifoam that can be added in laundry detergent powder in order to reduce foam during the rinses would benefit consumers by reducing the number of rinses and thus water consumption. However in order not the change the consumers' habits, such granulated antifoam should not greatly reduce the foam generated during the washing steps. When washing by hand, or in washing machines which are not fully automatic so that the user sees separate washing and rinsing steps, the consumer expects to see foam during the washing step. The antifoam should be substantially more active in reducing foam during the rinsing step than during the washing steps.

[0003] A foam control granule according to the invention comprises:

(A) a foam control agent comprising

(i) a polydiorganosiloxane fluid comprising units of the formula

R

-(Si-O)- R where each group R, which may be the same or different, is selected from an alkyl group having 1 to 36 carbon atoms or an aryl group or aralkyl group having 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;

(B) an organic additive of melting point 45 to 100°C comprising a polyol ester which is a polyol fully or partially esterified by carboxylate groups each having 7 to 36 carbon atoms and which is miscible with the polydiorganosiloxane fluid (A)(i); (C) a water-soluble particulate inorganic carrier;

(D) a polymer having a net cationic charge; and

(E) a surfactant.

[0004] The invention also includes the use of a granulated foam control composition comprising granules as defined above to reduce foam during the rinsing step when the granulated foam control composition is incorporated in a laundry detergent powder.

[0005] A method according to the invention of manufacturing a granulated foam control composition comprises:

- mixing

(A) a foam control agent comprising

(i) a polydiorganosiloxane fluid comprising units of the formula

R

-(Si-O)- R

where each group R, which may be the same or different, is selected from an alkyl group having 1 to 36 carbon atoms or an aryl group or aralkyl group having 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 melting point 45°C to 100°C comprising a polyol ester which is a polyol fully or partially esterified by carboxylate groups each having 7 to 36 carbon atoms and which is miscible with the polydiorganosiloxane fluid (A)(i); 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 polymer (D) having a net cationic charge and (E) a surfactant on the water- soluble particulate inorganic carrier either simultaneously with the mixture of (A) and (B) or subsequently to the mixture of (A) and (B).

[0006] The polydiorganosiloxane fluid (i) preferably has no more than 5 mole % branching units such as RS1O3/2 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 polydiorganosiloxane fluid is free from non-silicone polymer chains such as polyether chains.

[0007] One preferred example of a polydiorganosiloxane fluid is a polysiloxane comprising at least 10% diorganosiloxane units of the formula

Y

-(s'i-O)- Y'

and up to 90% diorganosiloxane units of the formula

Y

-(Si-O)- X-Ph

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

EP1075864. The diorganosiloxane units containing a -X-Ph group preferably comprise 5 to 60%) of the diorganosiloxane units in the fluid. The group X is preferably a divalent alkylene group having from 2 to 10 carbon atoms, most preferably 2 to 4 carbon atoms, but can alternatively contain an ether linkage between two alkylene groups or between an alkylene group and -Ph, or can contain an ester linkage. Ph is most preferably a phenyl group, but may be substituted for example 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 together form an aromatic ring, resulting in conjunction with the Ph group in e.g. a naphthalene group. A particularly preferred X-Ph group is 2-phenylpropyl -CH^-CH^CIT^-CgH^. The group Y is preferably methyl but can be ethyl, propyl or butyl. The group Y preferably has 1 to 18, most preferably 2 to 16, carbon atoms, for example ethyl, methyl, propyl, isobutyl or hexyl. Mixtures 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 direct to Si. [0008] The polysiloxane fluid (A)(i) 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 trivalent, organic or silicon-organic moiety linking polymer chains, as described in EP-A- 1075684.

[0009] An alternative example of a preferred polydiorganosiloxane fluid is a polysiloxane comprising 50-100% diorgano siloxane units of the formula

Y

-(s'i-O)- z

and optionally up to 50% diorgano siloxane units of the formula

Y

-(Si-O)- 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.

[0010] It is preferred that the number of siloxane units (DP or degree of polymerisation) in the average molecule of the polysiloxane fluid of either of the above types is at least 5, more preferably from 10 to 5000. Particularly preferred are polysiloxanes with a DP of from 20 to 1000, more preferably 20 to 200. The end groups of the polysiloxane can be any of those conventionally present in siloxanes, for example trimethylsilyl end groups.

[0011] The polydiorganosiloxane fluid containing -X-Ph groups, or the

polydiorganosiloxane fluid containing -Z groups, is preferably present as at least 80%> by weight of the polysiloxane fluid content of the foam control composition, most preferably as 100% or more than 95% of the polysiloxane fluid.

[0012] The polydiorganosiloxane fluid (i) can alternatively be a polydiorganosiloxane in which the organic groups are substantially all alkyl groups having 2 to 4 carbon atoms, for example polydiethylsiloxane. Such polydiorganosiloxane fluids are however not preferred, since foam control agents based on them are less efficient in controlling foaming from laundry detergent powders than those described in EP-A- 1075684.

[0013] The foam control composition contains a hydrophobic filler (ii) dispersed in the polydiorganosiloxane fluid. Hydrophobic fillers for foam control agents are well known and are particulate materials which are solid at 100°C, such as silica, preferably with a surface area as measured by BET measurement of at least 50 /g., titania, ground quartz, alumina, an aluminosilicate, zinc oxide, magnesium oxide, a salt of an aliphatic carboxylic acids, a reaction product of an isocyanate with an amine, e.g. cyclohexylamine, or an alkyl amide such as ethylenebisstearamide or methylenebisstearamide. Mixtures of two or more of these can be used.

[0014] 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 silica 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 to 50μπι, preferably 2 to 30 and most preferably 5 to 25μπι. 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

dimethylsiloxane polymers which are end-blocked with silanol or silicon-bonded alkoxy groups, hexamethyldisilazane, hexamethyldisiloxane or organosilicon resins containing (CH₃)₃SiOi/2 groups and silanol groups. Hydrophobing is generally carried out at a temperature of at least 100°C. Mixtures of fillers can be used, for example a highly hydrophobic silica filler such as that sold under the Trade Mark 'Sipernat D10' can be used together with a partially hydrophobic silica such as that sold under the Trade Mark Aerosil R972'.

[0015] The amount of hydrophobic filler (A)(ii) in the foam control composition of the invention is preferably 0.5-50% by weight based on the polysiloxane fluid (A)(i), more preferably from 1 up to 10 or 15% and most preferably 2 to 8% by weight.

[0016] The foam control composition preferably contains an organosilicon resin (A)(iii) which is associated with the polydiorganosiloxane fluid. Such an organosilicon resin can enhance the foam control efficiency of the polysiloxane fluid. This is particularly true for polysiloxane fluids containing -X-Ph groups, as described in EP-A- 1075684, and is also true for polysiloxane fluids containing -Z groups. In such polysiloxane fluids, the resin modifies the surface properties of the fluid.

[0017] The organosilicon resin (A)(iii) is generally a non-linear siloxane resin and preferably consists of siloxane units of the formula R'_aSi04-_a/2 wherein R' denotes a hydroxyl, hydrocarbon or hydrocarbonoxy 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

R"3Si01/2 and tetrafunctional (Q) groups Si04/2 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_aSi0₄-_a/2 of 0.86 to 2.15), more preferably 0.4: 1 to 1.1 : 1 and most preferably 0.5: 1 to 0.8: 1 (equivalent to a=1.0 to a=l .33).

[0018] The organosilicon resin (A)(iii) is preferably a solid at room temperature. The molecular weight of the resin can be increased by condensation, for example by heating in the presence of a base. The base can for example be an aqueous or alcoholic solution of potassium hydroxide or sodium hydroxide, e.g. a solution in methanol or propanol. A resin comprising M groups, trivalent R"Si03/₂ (T) units and Q units can alternatively be used, or up to 20% of units in the organosilicon resin can be divalent units R"2Si0₂/₂. The group R" is preferably an alkyl group having 1 to 6 carbon atoms, for example methyl or ethyl, or can be phenyl. It is particularly preferred that at least 80%, most preferably substantially all, R" groups present are methyl groups. The resin may be a trimethyl-capped resin.

[0019] The organosilicon resin (A)(iii) is preferably present in the antifoam at 1-50% by weight based on the polysiloxane fluid (A)(i), particularly 2-30% and most preferably 4-15%. The organosilicon resin may be soluble or insoluble in the polysiloxane fluid. If the resin is insoluble in the polysiloxane fluid, the average particle size of the resin may for example be from 0.5 to 400μπι, preferably 2 to 50μπι.

[0020] The organic additive (B) of melting point of 45°C to 100°C is miscible with the polydiorganosiloxane fluid (A)(i). By 'miscible', we mean 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 remains as one phase. If the liquids are immiscible the mixture is opaque and separates into two phases upon standing.

[0021] The organic additive (B) increases the foam control efficiency of the supported composition. We have found that additives of melting point at least 45°C are particularly effective in increasing foam control efficiency in the rinse. Most preferably, the mixture of the organic additive (B) and the polydiorganosiloxane fluid (A)(i) has a melting point of 45°C to 100°C.

[0022] The organic additive (B) comprises a polyol ester which is a polyol partially or fully esterified by carboxylate groups each having 7 to 36 carbon atoms. The polyol ester is preferably a glycerol ester or an ester of a higher polyol such as pentaerythritol or sorbitol. The polyol ester is preferably a monocarboxylate or polycarboxylate (for example a dicarboxylate, tricarboxylate or tetracarboxylate) in which the carboxylate groups each having 18 to 22 carbon atoms. Such polyol carboxylates tend to have a melting point at least 45°C. The polyol ester can be a diester of a glycol such as ethylene glycol or propylene glycol, preferably with a carboxylic acid having at least 14 carbon atoms, more preferably having 18 to 22 carbon atoms, for example ethylene glycol distearate. Examples of preferred glycerol esters include glycerol tristearate and glycerol esters of saturated carboxylic acids having 20 or 22 carbon atoms such as the material of melting point 54°C sold under the Trade Mark ' Synchrowax HRC, believed to be mainly triglyceride of C22 fatty acid with some C20 and C\ § chains. Alternative suitable polyol esters are esters of pentaerythritol such as pentaerythritol tetrabehenate and pentaerythritol tetrastearate.

[0023] The polyol ester can contain fatty acids of different chain length, which is common in natural products. The organic additive (B) can be a mixture of polyol esters, for example a mixture of esters containing different carboxylate groups such as glycerol tripalmitate and glycerol tristearate, or glycerol tristearate and Synchrowax HRC, or ethylene glycol distearate and Synchrowax HRC.

[0024] The organic additive (B) of melting point of 45 to 100°C can also comprise a more polar polyol ester. Preferred polar polyol esters include partially esterified polyols including monoesters or diesters of glycerol with a carboxylic acid having 8 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.

[0025] The organic additive (B) is preferably present in the granulated foam control composition at 10-200% by weight based on the polydiorganosiloxane fluid (A)(i), most preferably at 20 up to 100 or 120% based on the polydiorganosiloxane fluid.

[0026] The polymer having a net cationic charge (D) is a cationic or amphoteric polymer. The amphoteric polymers of the present invention will have a net cationic charge, i.e. the total cationic charges on these polymers will exceed the total anionic charge. The cationic charge density of the polymer ranges from about 0.05 milliequivalents/g to about 12

milliequivalents/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 can be on the backbone of the polymers or the side chains of polymers. For polymers with amine monomers, the charge density depends on the pH of the carrier. For these polymers, charge density is measured at a pH of 7. Preferably the charge density of the polymer ranges from about 0.05 milliequivalents/g to about 7 milliequivalents/g.

[0027] The weight-average molecular weight Mw of the cationic polymer is generally between 80,000 and 4,000,000, preferably from 100,000 or 200,000 up to 4,000,000 and even more preferably from 200,000 up to 1,500,000 or 2,000,000, as determined by size exclusion chromatography relative to polyethyleneoxide standards with RI detection. The mobile phase used is a solution of 20% methanol in 0.4M aqueous MEA, 0.1 M NaN0₃, 3% acetic acid on a Waters Linear Ultrahydrogel column, 2 in series. Columns and detectors are kept at 40°C. Flow is set to 0.5 mL/min.

[0028] The polymers having a net cationic charge which are most suitable for the present invention have a molecular weight and charge density which are inversely related. Lower charge density polymer usually is most suitable at a higher molecular weight, while higher charge density polymer usually is most suitable at a lower molecular weight. The present charged polymer has a cationicity parameter of up to 50 dalton meq/g, wherein the cationicity parameter is defined as the product of molecular weight as defined above and charge density as defined above divided by 1000 (Mw x CD/ 1000).

[0029] The polymer having a net cationic charge significantly enhances suppression of foam in the rinse compared to suppression of foam during the wash. [0030] Nonlimiting examples of deposition enhancing agents are cationic or amphoteric polysaccharides, proteins and synthetic polymers. Cationic polysaccharides include but not limited 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 4 million, preferably from about 100,000 or 200,000 up to 4,000,000.

[0031] One group of preferred cationic polysaccharides is shown in Formula I below:

(I)

wherein R1, R^, R3 are each independently H, C_1-24 alkyl (linear or branched),

R^

I

-^-CH₂CH-0^-Rx wherein n is from about 0 to about 10; Rx is H, C_1-24 alkyl (linear or branched) or or mixtures thereof, wherein Z is a water soluble anion, preferably chloride, bromide, iodide, hydroxide, phosphate, sulfate, methyl sulfate and acetate; R^ is selected from H, or Ci-C₆ alkyl _or mixtures thereof; R^, R^ and R^ are selected from H, or Ci- C₂8 alkyl, benzyl or substituted benzyl or mixtures thereof.

[0032] R4 is H or - (P)_m-H , or mixtures thereof; wherein P is a repeat unit of an addition polymer formed by a cationic monomer. In one embodiment, the cationic monomer is selected from methacrylamidotrimethylammonium 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-soluble 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 polymer ranges from about 0.01% to 5% per sugar unit, more preferably from about 0.05% to 2% per glucose unit, on average in the polysaccharide.

[0033] Preferred cationic polysaccharides include cationic hydroxyalkyl celluloses.

Examples of cationic hydroxyalkyl cellulose include those with the INCI name

Polyquaternium 10 such as those sold under the trade names Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquaternium 67 sold under the trade name Softcat

SK™, all of which are marketed by Amerchol Corporation Edgewater NJ; and

Polyquaternium 4 sold under the trade name Celquat H200 and Celquat L-200 available from National Starch and Chemical Company, Bridgewater, NJ. Other preferred polysaccharides include Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl C12-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 Lauryldimonium Chloride sold under the trade name Crodacel LM, PG-Hydroxyethylcellulose Cocodimonium Chloride sold under the trade name Crodacel QM and , PG-Hydroxyethylcellulose stearyldimonium Chloride sold under the trade name

Crodacel QS and alkyldimethylammonium hydroxypropyl oxyethyl cellulose.

[0034] In one embodiment of the present invention, the cationic polymer comprises cationic starch. Cationic starches are described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986) and in U.S. Pat. No. 7, 135,451, col. 2, line 33 - col. 4, line 67. The cationic starch used in the present invention can for example comprise amylose at a level of from about 0% to about 70% by weight of the cationic starch. The cationic starch can for example comprise cationic maize starch, which comprises from about 25% to about 30%) amylose by weight of the cationic starch. The remaining polymer in the above embodiments comprises amylopectin. [0035] Further preferred polysaccharides include cationic galactomannans, such as cationic guar gums or cationic locust bean gum. An example of cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar sold under the trade name Jaguar C13 or Jaguar Excel available from Rhodia, Inc of Cranburry NJ or N-Hance by Aqualon, of

Wilmington, DE.

[0036] A detailed description of synthetic cationic polymers can be found in an article by M. Fred Hoover that was published in the Journal of Macromolecular Science-Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference. Examples of suitable cationic polymers are those used as retention aids in the manufacture of paper. They are described in "Pulp and Paper, Chemistry and Chemical Technology Volume III edited by James Casey (1981). The molecular weight of these polymers is in the range of 2,000 to 5,000,000. The synthetic cationic polymers of this invention will be better understood when read in light of the Hoover article and the Casey book.

[0037] Synthetic cationic polymers useful in the present invention include but are not limited to s nthetic addition polymers of the general structure (II) below

wherein R1, R2, and Z are defined herein below. Preferably, the linear polymer units are formed from linearly polymerizing monomers. Linearly polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a linear or branched polymer chain or alternatively which linearly propagate polymerization. The linearly polymerizing monomers of the present invention have the formula:

however, those of skill in the art recognize 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, linear polymer units may be directly introduced, i.e. via linearly polymerizing units, or indirectly, i.e. via a precursor as in the case of vinyl alcohol cited herein above.

[0038] In formula (II) above, each R1 is independently hydrogen, C₁-C₁₂ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -ORa, or -C(0)ORa wherein Ra is selected from hydrogen, and Ci-C₂₄ alkyl and mixtures thereof; each R^ is independently hydrogen, hydroxyl, halogen, Ci-Ci₂ alkyl, -ORa, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. ; each Z is independently hydrogen, halogen; linear or branched C₁-C30 alkyl, nitrilo, -N(R³)₂; -

C(0)N(R³)₂; - HCHO (formamide); -OR³; -0(CH₂)_nN(R³)₂; -0(CH₂)_nN⁺(R³)₃X ^" i

- C(0)OR⁴; -C(0)0(CH₂)_nN(R³)₂; -C(0)0(CH₂)_nN+(R³)₃X ^" ;

-CO(CH₂)_nN(R³)₂; -OCO(CH₂)_nN+(R³)₃X -;-C(0) H-(CH₂)_nN(R³)₂;

-C(0) H(CH₂)_nN+(R³)₃X-; -(CH₂)_nN(R³)₂; or -(CH₂)_nN+(R³)₃X-;

in which each R₃ is independently hydrogen, Ci-C₂₄ alkyl, C₂-C₈ hydroxyalkyl, benzyl;

substituted benzyl and mixtures thereof; each R4 is independently hydrogen or Ci-C₂₄ alkyl,

and ; X is a water soluble anion; n is from 1 to 6; R₅ is independently hydrogen or Ci-C₆ alkyl, or mixtures thereof. Z can also be selected from non-aromatic nitrogen heterocycles comprising a quaternary ammonium ion, heterocycles comprising an N- oxide moiety, an aromatic nitrogen-containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen-containing heterocycle wherein at least one nitrogen is an N-oxide; or mixtures thereof. Preferably R1 is hydrogen, Ci-C₄ alkyl, or -

OR_a, or - C(0)OR_a . Preferred R^ is hydrogen, Ci-C₄ alkyl, and mixtures thereof. Non- limiting examples of addition polymerizing monomers comprising a heterocyclic Z unit include l-vinyl-2-pyrrolidinone, 1-vinylimidazole, quaternized vinyl imidazole, 2 -vinyl- 1,3- dioxolane, 4-vinyl-l-cyclohexenel,2-epoxide, and 2-vinylpyridine, 2-vinylpyridine N-oxide, 4-vinylpyridine N-oxide.

[0039] 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 formamide units some of which are subsequently hydrolyzed to form vinyl amine equivalents. [0040] The synthetic cationic polymers and co-polymers used in the present invention comprise Z units which have a cationic charge or which result in a unit which forms a cationic charge in situ. For example, at least one Z group per molecule may be selected from

-0(CH₂)_nN+(R³)₃X - , - C(0)OR⁴; -C(0)N-(R³)₂, -C(0)0(CH₂)_nN(R³)₂, -

C(0)0(CH₂)_nN+(R³)₃X -, -OCO(CH₂)_nN(R³)₂, -OCO(CH₂)_nN+(R³)₃X -C(0)NH-

(CH₂)_nN(R³)₂, -C(0) H(CH₂)_nN+(R³)₃X -(CH₂)_nN(R³)₂, -(CH₂)_nN+(R³)₃X or a non- aromatic nitrogen heterocycle comprising a quaternary ammonium ion, heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide. When the co-polymers of the present invention comprise more than one Z unit, at least about 1% of the monomers which comprise the copolymers will comprise a cationic unit.

[0041] The synthetic cationic polymers or co-polymers used in the present invention can comprise one or more cyclic 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 cyclic 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 independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R^ unit; R⁵ is Ci-C i₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion. Non-limiting examples of R^ units include allyl and alkyl substituted allyl units. Preferably the resulting cyclic residue is a six-member ring comprising a quaternary nitrogen atom. R5 is preferably C₁-C4 alkyl, preferably methyl. An example of a cyclically polymerizing monomer is a dimethyl diallyl ammonium salt having the formula:

which results in a polymer or co-polymer having units with the formula:

wherein the index z, which indicates the degree of polymerisation, is from about 10 to about 50,000.

[0042] Nonlimiting examples of preferred synthetic cationic polymers for use in the present invention include homopolymers and copolymers made from one or more cationic monomers selected from the group consisting of

a) Ν,Ν-dialkylaminoalkyl methacrylate, Ν,Ν-dialkylaminoalkyl acrylate, N,N- dialkylaminoalkyl acrylamide, Ν,Ν-dialkylaminoalkylmethacrylamide , quaternized N,N- dialkylaminoalkyl methacrylate, quaternized Ν,Ν-dialkylaminoalkyl acrylate, quaternized Ν,Ν-dialkylaminoalkyl acrylamide, quaternized N,N-dialkylaminoalkylmethacrylamide b) vinylamine and its derivatives, allylamine and its derivatives,

c) vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride.

Optionally the copolymer comprises a second monomer selected from a group consisting of acrylamide, Ν,Ν-dialkyl acrylamide, methacrylamide, Ν,Ν-dialkylmethacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate, polyalkylene glycol acrylate, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate, , polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) and their salts.

[0043] The polymer may optionally be cross-linked. Crosslinking monomers include, but are not limited to, ethylene glycol diacrylate, divinylbenzene, butadiene. [0044] Preferred cationic monomers include Ν,Ν-dimethyl aminoethyl acrylate, N,N- dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]tri- methylammonium chloride (QDMAM), Ν,Ν-dimethylaminopropyl acrylamide (DMAPA), Ν,Ν-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium chloride, methacrylamidopropyl trimethylammonium chloride (MAPTAC), quaternized vinyl imidazole and diallyldimethylammonium chloride and derivatives thereof. Preferred nonionic comonomers include acrylamide, Ν,Ν-dimethyl acrylamide, C1-C4 alkyl acrylate, C1-C4 hydroxyalkylacrylate, hydroxy ethyl acrylate (HEA), hydroxypropyl acrylate, vinyl formamide, vinyl acetate, and vinyl alcohol, and derivatives thereof.

[0045] The most preferred synthetic polymers are poly(acrylamide-co- diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride) (PAM-MAPTAC), poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate), poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate),

poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate),

poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate),

poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), and

poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid).

[0046] Further alternative synthetic cationic polymers suitable for use in the present invention are polyethyleneimine and its derivatives. These are commercially available under the trade name Lupasol ex. BASF AG of Ludwigschaefen, Germany. In one embodiment, the polyethylene derivative is an amide derivative of polyetheyleneimine sold under the trade name Lupoasol SK. Also included are alkoxylated polyethleneimine; alkyl

polyethyleneimine and quaternized polyethyleneimine.

[0047] Further alternative synthetic cationic polymers suitable for use in the present invention are polyamidoamine-epichlorohydrin (PAE) resins, which are condensation products of polyalkylenepolyamine with polycarboxylic acid further reacted with

epichlorhydrin. The most common PAE resins are the condensation products of

diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. 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' edited by L. L. Chan, TAPPI Press(1994).

[0048] The surfactant (E) can be selected from non-ionic, cationic, anionic and zwitterionic surfactants, or mixtures thereof.

[0049] 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 4.1 5 alcohol, 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 include siloxane polyoxyalkylene copolymers, fatty acid alkylol amides, fatty amine oxides, esters of sucrose, glycerol or sorbitol and fluoro- surfactants.

[0050] Suitable non-ionic surfactants include alkyl polyglucoside and/or an alkyl alkoxylated alcohol. Preferred non-ionic alkyl alkoxylated alcohols include C_8-18 alkyl alkoxylated alcohol, preferably a C_8-18 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 C_8-18 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 nonionic surfactants can be selected from the group consisting of: C₈-Ci₈ alkyl ethoxylates, such as, EODOL® non-ionic surfactants from Shell; C₆-Ci2 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C₁₂-C₁₈ alcohol and C₆-Ci2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C14-C22 mid-chain branched alcohols; C14-C22 mid-chain branched alkyl alkoxylates, preferably having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, preferably alkylpolyglycosides; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants. Mixtures of two or more non ionic surfactants may be used.

[0051] Anionic surfactants can include sulphate and sulphonate surfactants. Preferred sulphonate surfactants include alkyl benzene sulphonate, preferably C₁₀-i₃ alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under 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 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_8-18 alkyl sulphate, or predominantly C₁₂ alkyl sulphate. Another preferred sulphate surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate (AES), preferably a C_8-18 alkyl alkoxylated sulphate, preferably a C_8-18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C_8-18 alkyl ethoxylated sulphate having an average degree 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 may be linear or branched, substituted or un-substituted.

[0052] Suitable 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, sulphonated or sulphated ethoxylate alcohols, sulphosuccinates, alkane sulphonates, alkali metal soaps of higher fatty acids, phosphate esters, alkyl isethionates, alkyl taurates and/or alkyl sarcosinates. Mixtures of two or more anionic surfactants may be used.

[0053] Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof. Preferred cationic surfactants are quaternary ammonium compounds having the general formula:

(R¹⁰)(R! !)(R¹²)(R¹³)N⁺ X- wherein, RIO is a linear or branched, substituted or unsubstituted C_6-18 alkyl or alkenyl moiety,

R^{1 1} and R¹² are independently selected from methyl or ethyl moieties, R^ is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include: halides, preferably chloride; sulphate; and sulphonate. Preferred cationic detersive surfactants are mono-C6-i₈ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-Cg-io alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-Cio-₁₂ alkyl mono- hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono- hydroxyethyl di-methyl quaternary ammonium chloride.

[0054] A cationic surfactant can for example be an alkylamine salt, a quaternary ammonium salt, a sulphonium salt or a phosphonium salt. Mixtures of two or more cationic surfactants may be used.

[0055] A zwitterionic (amphoteric) surfactant can for example be an imidazoline compound, an alkylaminoacid salt or a betaine. Mixtures of two or more zwitterionic surfactants may be used.

[0056] The surfactant (E) enhances the effect of the polymer (D) having a net cationic charge in suppression of foam in the rinse compared to suppression of foam during the wash, and also improves storage stability.

[0057] The weight ratio of the polymer (D) having a net cationic charge to the surfactant (E) can in general be from 1 : 10 to 100: 1 and is preferably between 1 :9 and 9: 1, more preferably between 1 :5 and 9: 1.

[0058] The polymer (D) having a net cationic charge and the surfactant (E) can

conveniently be mixed together before being mixed with the other components of the foam control granule, although they can be added separately if desired.

[0059] Examples of water soluble inorganic carriers (C) are phosphates, for example powdered or granular sodium tripolyphosphate; sulphates, for example sodium sulphate and potassium sulphate; carbonates, for example sodium carbonate, such as anhydrous sodium carbonate or sodium carbonate monohydrate, sodium sesquicarbonate and sodium

bicarbonate, potassium carbonate and potassium bicarbonate; silicates, for example sodium silicate; citrates, for example sodium citrate and potassium citrate; acetates, for example sodium acetate, and chlorides, for example sodium chloride and potassium chloride.

Preferred carriers (C) include sodium sulfate, sodium carbonate and sodium bicarbonate. The particle size of the water-soluble inorganic carrier is preferably in the range 1 to 40μιη, more preferably from 1 up to 20 or 30μιη.

[0060] We have found that the use of a water-soluble particulate inorganic carrier markedly improves the performance of the granulated foam control composition of the present invention compared to a water-insoluble carrier. In particular, the granulated foam control compositions comprising a water-soluble particulate carrier are more effective in reducing foam in the rinse stage. A water-insoluble particulate carrier can however be used as part of the carrier component of the granule of the invention. Examples of suitable water-insoluble carriers include zeolites, for example Zeolite A or Zeolite X, other alumino silicates or silicates such as magnesium silicate and silica. A zeolite is the preferred water-insoluble particulate carrier. If a water-insoluble particulate carrier is used in the granules of the invention, it preferably forms no more than 20% by weight, more preferably no more than 10%, of the total particulate carrier,. The water-soluble particulate carrier and the water- insoluble particulate carrier can conveniently be mixed in dry particle form before being mixed with the other components of the foam control granule.

[0061] The foam control agent (A), the organic additive (B), the cationic polymer (D) and the surfactant (E) can in general be added separately to the carrier particles or premixed in any combination. The foam control agent (A) comprising polysiloxane fluid (i) containing the hydrophobic filler (ii) and optionally the organosilicon resin (iii) is preferably mixed with the organic additive (B). The mixture may preferably be deposited on the carrier particles in non-aqueous liquid form.

[0062] The cationic polymer (D) and the surfactant (E), separately or together, can be deposited on the carrier particles (C) simultaneously with the mixture of (A) and (B) or subsequently. If the cationic polymer (D) and surfactant (E) are deposited on the carrier particles simultaneously with the mixture of (A) and (B), they can be premixed with (A) and (B) or deposited on the carrier particles (C) simultaneously with the mixture of (A) and (B), from the same or separate nozzles. For example the mixture of (D) and (E) can be first prepared followed by the addition of the mixture of (A) and (B) into (D) and (E). The mixture of cationic polymer (D) and surfactant (E) is generally deposited in liquid form, for example from an aqueous solution or dispersion. Drying of the cationic polymer solution aids in binding carrier particles together to form granules.

[0063] The foam control agent (A), organic additive (B), cationic polymer (D), surfactant (E) and carrier particles (C) are preferably mixed in such proportions that the content of polydiorganosiloxane fluid (A)(i) in the foam control granule is between 1 and 25% by weight of the foam control granule. Preferably the polydiorganosiloxane fluid content of the granule is between 1 and 15%, preferably between 2 and 15%, preferably between 5 and 15%, preferably between 7 and 12%.

[0064] The mixture of (A) and (B) is preferably deposited on the carrier particles at a temperature at which the organic additive (B) is liquid, for example a temperature in the range 45-100°C. As the mixture cools on the carrier particles, it solidifies to a structure which contributes to the increased efficiency of the foam control composition. The solidified mixture of (A) and (B) also serves to bind carrier particles together to form granules. The supported foam control composition is preferably made by an agglomeration process in which the foam control composition comprising the foam control agent (A) and the organic additive (B) is sprayed onto the carrier particles while agitating the particles. The particles are preferably agitated in a high shear mixer through which the particles pass continuously.

[0065] Optionally, the carrier particles (C) can conveniently be heated before or during the agglomeration process, that is, before or during deposition of the foam control agent (A), the organic additive (B), the cationic polymer (D) and the surfactant (E). Heating of the carrier particles may range at a temperature > 30°C, alternatively > 40°C, alternatively > 50°C, alternatively > 70°C.

[0066] One type of suitable mixer is a vertical, continuous high shear mixer in which the foam control composition is sprayed onto the particles. One example of such a mixer is a Flexomix mixer supplied by Hosokawa Schugi. If the mixture of (D) and (E) and the mixture of (A) and (B) are deposited onto the water-soluble particulate inorganic carrier via a spray nozzle, the mixture of (D) and (E) and the mixture of (A) and (B) can for example be mixed together in the tip of the nozzle just prior to being sprayed.

[0067] Alternative suitable mixers which may be used include horizontal high shear mixers, in which an annular layer of the powder - liquid mixture is formed in the mixing chamber, with a residence time of a few seconds up to about 2 minutes. Examples of this family of machines are pin mixers (e.g. TAG series supplied by LB, RM- type machines from Rubberg- Mischtechnik or pin mixers supplied by Lodige), and paddle mixers (e.g. CB series supplied by Lodige, Corimix (Trade Mark) from Drais-Manheim, Conax (Trade Mark) machines from Ruberg Mischtechnik).

[0068] Other possible mixers which can be used in the process of the invention are Glatt granulators, ploughshare mixers, as sold for example by Lodige GmbH, twin counter-rotating paddle mixers, known as Forberg (Trade Mark)-type mixers, intensive mixers including a high shear mixing arm within a rotating cylindrical vessel, such as "Typ R" machines sold by Eirich, Zig-Zag (Trade Mark) mixers from Patterson-Kelley, and HEC (Trade Mark) machines sold by Niro.

[0069] Another possible granulation method is fluidized bed. Examples of fluid bed granulation machines are Glatt fluidized bed and Aeromatic/Niro fluidized bed units. In fluidized bed, agglomeration take place by atomizing the liquid dispersion (solution, suspension or emulsion) onto the suspended bed of particles to make the granules.

[0070] Whichever granulation method is used, the carrier particles become bonded together, by the liquid ingredients of the foam control composition to form granules. Each foam control granule comprises a plurality of water soluble inorganic carrier particles (C) coated and bonded together by the liquid composition, comprising the foam control agent (A), the organic additive (B), the polymer (D) having a net cationic charge and the surfactant (E). The granulated foam control composition can readily be incorporated in a detergent powder. The granules produced according to the invention generally have a mean particle diameter of at least 0.1mm, preferably over 0.25 or 0.5mm, up to a mean diameter of 1.2 or 1.5 or even 2mm. We have found that granules according to the invention of this particle size,

particularly 0.5 to 1mm, have good flow properties and resistance to compaction.

[0071] The granulated foam control compositions of the invention can contain additional ingredients such as a density adjuster, a colour preservative such as a maleate or fumarate, e.g. bis (2-methoxy-l -ethyl) maleate or diallyl maleate, an acetylenic alcohol, e.g. methyl butynol, or cyclooctadiene, a thickening agent such as carboxymethyl cellulose, polyvinyl alcohol or a hydrophilic or partially hydrophobed fumed silica, or a colouring agent such as a pigment or dye.

[0072] The granulated foam control compositions of the invention are typically added to detergent powders at 0.1 to 10% by weight, preferably 0.2 to 0.5 or 1.0%. The detergent compositions may for example be those having high levels of anionic surfactants, e.g. sodium dodecyl benzene sulphonate. The granulated foam control compositions of the invention, when used in a laundry detergent (such as a laundry detergent powder), were found to have some impact on the foam during the wash (for example less than 30% foam reduction) while greatly impacting the foam in the first rinse (for example more than 50% foam reduction). This was found true when laundering by hand but also when using semi-automatic machines.

[0073] The invention is illustrated by the following Examples in which parts and

percentages are by weight and in which the following test methods were used.

Wash Suds Index and Rinse Suds Index

[0074] Wash Suds Index is used to compare the suds volume generated 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 composition as a control. Herein, the suds volume is measured by the suds height following a standardized washing process described below.

[0075] 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 standardized rinsing process described below.

[0076] The present laundry detergent used to conduct the experiments includes by weight of the laundry detergent, 0.5% of present and comparative granulated foam control composition, 11%) of linear alkyl benzene sulphonate, 1% of alkyl dimethyl hydroxyl ethyl ammonium chloride, 3.5% of CI 4- 15 alkyl ethoxylated alcohol having a molar average degree of ethoxylation of 9, 20% sodium alumino silicate (Zeolite), 15% sodium carbonate, 28% sodium sulphate, 2% sodium silicate, 1.5% carboxy methyl cellulose, 4% of poly acrylic acid, 2% sodium percarbonate, 0.5% of tetraacetylethylenediamine (TAED), and includes enzymes et.al which make the total amount of all the components add up to 100%.

[0077] 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 a piece of fabric into the laundry liquor and soak for 5 min.

3) For each piece of fabric, scrub it 5 times, dip back into the laundry liquor between each scrub.

4) Wring the scrubbed fabric gently, not disturbing the suds produced. 5) Measure the total height of the suds and laundry liquor, by taking a average from five measures including one center point and four edge points of the basin;

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

7) Get suds height by deducting the measurement in step 6) from step 5).

[0078] 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 control 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 from the water.

[0079] As a summary, the conditions set for the washing and rinsing process are provided in below Table 1.

TABLE 1

EXAMPLES

Example 1 and Comparative Example 1

[0080] A granulated foam control composition according to the present invention was made as follows:

[0081] Six percent (6%) by weight treated precipitated silica available under the name Sipernat D10 from Evonik and 1% partially hydrophobic silica available under the name R972 from Evonik were dispersed in 86.3% polydi organosiloxane fluid having a degree of polymerisation of 65 and comprising 80 mole % methyl dodecyl siloxane groups and 20 mole % methyl 2-phenylpropyl (derived from a-methylstyrene) siloxane groups. 6.7% by weight of a 60% by weight solution of an organosiloxane resin having trimethyl siloxane units and Si02 units in a M/Q ratio of 0.65/1 in octyl stearate was added. The mixture is homogenized through a high shear mixer to form a foam control agent FC1.

[0082] First pass: 62.00 parts by weight of the foam control agent FC1 was mechanically mixed with 38.00 parts of glyceryl tristearate provided by Sasol. The FC1 and molten glyceryl tristearate were mixed at 90°C. The glyceryl tristearate and polydiorganosiloxane fluid were miscible and the mixture had a melting point of 74°C.

[0083] 18.25 parts of the mixture of glyceryl tristearate and FC1, and 4.20 parts water were sprayed at the same time on two separate nozzles onto 77.55 parts of sodium sulfate powder in a Schugi Flexo mixer to generate a granular particulate material. The water contained in this granulated foam control composition was removed in a fluidized bed.

[0084] Second pass: 47.15 parts of polyacrylamide methacrylamidopropyl

trimethylammonium chloride (PAM MAPTAC) cationic polymer, 5.70 parts of CI 4- 15 AE7 nonionic surfactant, and 47.15 parts of water were mechanically mixed.

[0085] The obtained granular particulate material from the first pass was put back into the Schugi Flexo mixer at 97.32 parts, where 2.68 parts of the aqueous solution of PAM

MAPTAC/nonionic surfactant solution were sprayed onto it. The water contained in this granulated foam control composition was removed in a fluidized bed. The resultant granulated foam control composition was labeled Example 1. [0086] A laundry detergent containing a granulated foam control composition according to the present invention was tested versus laundry detergents outside of the scope of the present invention for rinse suds removal.

[0087] Comparative Example 1 : A granulated foam control composition outside of the present invention was made using the process as described above, however, no CI 4- 15 AE7 nonionic surfactant was added in the second pass. Instead, 50 parts of PAM MAPTAC cationic polymer, and 50 parts of water were mechanically mixed (Premix 4). The obtained granular particulate material from the first pass was put back into the Schugi Flexo mixer at 97.32 parts, where 2.68 parts of the aqueous solution of PAM MAPTAC were added. The resultant granulated foam control composition was labeled Comparative Example 1. An overview of the granule compositions can be seen in Table 2.

TABLE 2

[0088] Example 1 and Comparative Example 1 (0.5 wt%) were independently added to existing Off the shelf granular laundry detergent compositions comprising anionic detersive surfactant. For the purpose of this test, Ariel brand granular laundry detergent available in China was used. A control of just Ariel laundry detergent was also included.

[0089] The compositions were then tested for wash suds index and rinse suds index following the test method described herein. Results can be seen in Table 3.

TABLE 3 [0090] As can be seen from Table 3, laundry detergents according to the present invention exhibit a wash suds index that is comparable to, or lower than, the control comprising no foam reduction agent, but also exhibit a lower rinse suds index. Laundry detergent

compositions according to the present invention also exhibited improved ageing stability.

Example 2

[0091] This example describes an alternative granulated foam control composition according to the present invention.

[0092] A mixture of 4 parts of glyceryl tristearate, 6 parts of a silicone antifoam FC1 described previously (in Example 1), 0.2 parts of a solution containing PAM-MAPTAC at 3% in water and 0.2 parts of E07 nonionic surfactant was prepared by mechanically mixing the silicone antifoam FC1 and the PAM-MAPTAC solution and the nonionic surfactant with the molten glyceryl tristearate at 85°C. This mixture and 8.5 additional parts of water were then simultaneously poured slowly into a mixer onto 81 parts of sodium sulfate already present. The mixture was stirred continuously until a particulate material was obtained = Example 2. The water contained in the granular material was removed in a fluidized bed using air at 65°C.

Example 3

[0093] A first premix of 2.9 parts of glyceryl tristearate, 4.7 parts of a silicone antifoam FC1 described previously (in Example 1) is prepared and maintained at 85°C. A second premix of 7.3 parts of a PAM-MAPT AC solution at 6.2 % and 0.3 parts of a 20% active LAS solution is prepared using a high shear mixer and maintained at 85°C. The two premixes are then mixed together using a high shear mixer, and subsequently granulated onto 84.8 parts of anhydrous sodium sulfate in a high shear horizontal agglomerator. The obtained agglomerates are then fed into a fluidized bed with drying air set at 50°C in order to remove water. Composition of Example 3 is disclosed in Table 4.

Example 4

[0094] A first premix of 2.8 parts of glyceryl tristearate, 4.6 parts of a silicone antifoam FC1 described previously (in Example 1) is prepared and maintained at 85°C. A second premix of 7.2 parts of a PAM-MAPT AC solution at 6.2 % and 0.3 parts of a 20% active LAS solution is prepared using a high shear mixer and maintained at 85°C. The two premixes are then fed simultaneously in a horizontal high shear agglomerator containing 85 parts of anhydrous sodium sulfate. The obtained agglomerates are then fed into a fluidized bed with drying air set at 50°c in order to remove water. Composition of Example 4 is disclosed in Table 4.

Example 5

[0095] A first premix of 2.7 parts of glyceryl tristearate, 4.3 parts of a silicone antifoam FC1 described previously (in Example 1) is prepared and maintained at 85°C. A second premix of 6.8 parts of a PAM-MAPTAC solution at 6.2 % and 0.2 parts of a 20% active LAS solution is prepared using a high shear mixer and maintained at 85°C. The two premixes are then mixed together using a high shear mixer and granulated onto 79.6 parts of anhydrous sodium sulfate in a high shear vertical agglomerator. The obtained agglomerates are then fed into a fluidized bed with drying air set at 50°C. In the fluidized bed, 6.4 parts of a solution containing respectively 3 parts of the PAM-MAPTAC solution at 6.2 %, 3 parts of water and 0.4 parts of CI 4- 15 AE7 nonionic surfactant, is sprayed on the obtained granules and then dried.

Composition of Example 5 is disclosed in Table 4.

TABLE 4

[0096] Examples 3 to 5 (1.5 wt%) were independently added to existing Off the shelf granular laundry detergent compositions comprising anionic detersive surfactant. For the purpose of this test, Ariel brand granular laundry detergent available in China was used. A control of just Ariel laundry detergent was also included.

[0097] The compositions were then tested for wash suds index and rinse suds index following the test method described herein. Results can be seen in Table 5. TABLE 5

[0098] As can be seen from Table 5, laundry detergents according to the present invention exhibit a wash suds index that is lower than the control comprising no foam reduction agent, but also exhibit a lower rinse suds index. Laundry detergent compositions according to the present invention also exhibited improved ageing stability.

Claims

1. A foam control granule comprising

(A) a foam control agent comprising

(i) a polydiorganosiloxane fluid comprising units of the formula

R

-(Si-O)- R where each group R, which may be the same or different, is selected from an alkyl group having 1 to 36 carbon atoms or an aryl group or aralkyl group having 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;

(B) an organic additive of melting point 45°C to 100°C comprising a polyol ester which is a polyol fully or partially esterified by carboxylate groups each having 7 to 36 carbon atoms and which is miscible with the polydiorganosiloxane fluid (A)(i);

(C) a water-soluble particulate inorganic carrier;

(D) a polymer having a net cationic charge; and

(E) a surfactant.

2. The foam control granule according to claim 1, wherein the foam control granule comprises a plurality of water soluble inorganic carrier particles (C) coated and bonded together by a liquid composition comprising the foam control agent (A), the organic additive (B), the polymer (D) having a net cationic charge and the surfactant (E).

3. The foam control granule according to claim 1 or claim 2, wherein the weight ratio of the polymer (D) having a net cationic charge to the surfactant (E) is between 1 : 10 and 100: 1.

4. The foam control granule according to any of claims 1 to 3, wherein the surfactant (E) is selected from non-ionic, cationic, anionic and zwitterionic surfactants, or mixtures thereof.

5. The foam control granule according to any of Claims 1 to 4, wherein the polysiloxane fluid (A)(i) is a polysiloxane comprising either (a) at least 10% diorganosiloxane units of the formula

Y

-(Si-O)- Y'

and up to 90% diorganosiloxane units of the formula

Y

-(Si-O)- X-Ph

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; or (b) 50-100%) diorganosiloxane units of the formula

Y

-(Si-O)- z

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

Y

-(Si-O)- 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.

6. The foam control granule according to any of Claims 1 to 5, wherein the mixture of the organic additive (B) and the polydiorganosiloxane fluid (A)(i) has a melting point of 45°C to 100°C.

7. The foam control granule according to any of Claims 1 to 6, wherein the polyol ester is a glycerol triester substantially fully esterified by carboxylate groups each having 14 to 22 carbon atoms.

8. The foam control granule according to any of Claims 1 to 7, wherein the polyol ester is a monocarboxylate or polycarboxylate in which the carboxylate groups each having 18 to 22 carbon atoms.

9. The foam control granule according to any of Claims 1 to 8, wherein the particulate carrier is selected from sodium sulfate, sodium carbonate and sodium bicarbonate.

10. The foam control granule according to any of Claims 1 to 9, wherein the polymer having a net cationic charge has a net charge density of from 0.05 to 12 meq/g, a weight average molecular weight in the range 80,000 to 4,000,000 and a cationicity parameter as herein defined of greater than 50 dalton meq/g.

11. The foam control granule according to any of Claims 1 to 10, wherein the polymer having a net cationic charge is either (c) a cationic polysaccharide or (d) a synthetic addition olymer of the general structure

wherein each R1 is independently hydrogen, C₁-C₁₂ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -OR_A> or -C(0)OR_A wherein R_A is selected from hydrogen and C1-C24 alkyl and mixtures thereof; each R^ is independently hydrogen, hydroxyl, halogen, C1-C12 alkyl, -OR_a> substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic or heterocyclic; and each Z is independently hydrogen, halogen; linear or branched C1-C30 alkyl, nitrilo, -N(R³)₂ -C(0)N(R³)₂; - HCHO (formamide); -OR³, -

0(CH₂)_nN(R³)₂, -0(CH₂)_nN+(R³)₃X ^" , - C(0)OR⁴; -C(0)N-(R³)₂, -C(0)0(CH₂)_nN(R³)₂,

-C(0)0(CH₂)_nN+(R³)₃X -, -OCO(CH₂)_nN(R³)₂, -OCO(CH₂)_nN+(R³)₃X -C(0)NH-

(CH₂)_nN(R³)₂, -C(0) H(CH₂)_nN+(R³)₃X -(CH₂)_nN(R³)₂, -(CH₂)_nN+(R³)₃X or a non- aromatic nitrogen heterocycle comprising a quaternary ammonium ion, heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; each R₃ being independently hydrogen, Ci-C₂₄ alkyl, C₂-C₈ hydroxyalkyl, benzyl or substituted benzyl; each R being independently hydrogen or Ci-C₂₄ alkyl or -(CH₂-CHR₅-0)_m-R³, where R5 is independently hydrogen or Ci-C₆ alkyl; X being a water soluble anion; and n being from 1 to 6; provided that at least one Z group per molecule is selected from -0(CH₂)_nN⁺(R³)₃X ^" > - C(0)OR⁴; -C(0)N-

(R³)₂, -C(0)0(CH₂)_nN(R³)₂, -C(0)0(CH₂)_nN+(R³)₃X -OCO(CH₂)_nN(R³)₂, -

OCO(CH₂)_nN+(R³)₃X -, -C(0)NH-(CH₂)_nN(R )₂, -C(0)NH(CH₂)_nN+(R³)₃X -

(CH₂)_nN(R³)₂, -(CH₂)_nN⁺(R³)₃X ^", or a non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide.

12. The foam control granule according to any of Claims 1 to 11, wherein the foam control agent comprises an organosilicon resin (A)(iii) which is a siloxane resin consisting of monovalent trihydrocarbonsiloxy (M) groups of the formula R"3Si01/2 and tetrafunctional (Q) groups Si04/2 wherein R" denotes an alkyl group and the number ratio of M groups to Q groups is in the range 0.4: 1 to 1.1 : 1.

13. The foam control granule according to any of claims 1 to 12, wherein the

polydiorganosiloxane fluid content of the foam control granule is between 1 and 25%, preferably between 1 and 15%, by weight of the foam control granule.

14. A foam control composition comprising foam control granules according to any of claims 1 to 13, wherein the foam control composition has a mean particle size of between 150 and 700μιη, preferably between 150 and 500μιη, most preferably between 200 and 500μιη.

15. A method of manufacturing a granulated foam control composition comprising:

- mixing

(A) a foam control agent comprising

(i) a polydiorganosiloxane fluid comprising units of the formula

R

-(Si-O)- R where each group R, which may be the same or different, is selected from an alkyl group having 1 to 36 carbon atoms or an aryl group or aralkyl group having 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 melting point 45°C to 100°C comprising a polyol ester which is a polyol fully or partially esterified by carboxylate 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 polymer (D) having a net cationic charge and a surfactant (E) on the water- soluble particulate inorganic carrier either simultaneously with the mixture of (A) and (B) or subsequently to the mixture of (A) and (B).

16. A method according to Claim 15 in which a mixture of polymer (D) having a net cationic charge and surfactant (E) is mixed with the foam control agent (A) and the organic additive (B) prior to being deposited on the particulate carrier.