FOAM CONTROL COMPOSITIONS

Cross Reference to Related Applications

[0001a] This application claims the benefit of GB National Patent Application Serial No. 17101 73.4 filed on 26 June 2017. GB National Patent Application Serial No. 17101 73.4 is hereby incorporated by reference.

Field of the Invention

[0002] This invention relates to granulated foam control compositions for use in laundry detergents. The granulated foam control compositions of the embodiments of the present invention can be added to detergent compositions to inhibit unwanted foaming when the detergent is used in a washing procedure, specifically, to reduce the foam level at the rinsing stage of said laundry washing procedure.

Description of the Related Art

[0003] Washing of clothes by hand or in semi-automatic machines is widespread in many countries; seventy percent of the world's population still wash their clothes in this way. When doing so, consumers usually like to see a lot of lather (foam) as they associate foaming with detergent efficiency. However, removing the lather requires numerous rinses, generally three or more rinses, which costs a lot of effort and wastes water.

[0004] Most foam control agents are designed for use in automatic washing machines. They are active in the washing stage of the laundry washing procedure, to avoid overflow of foam. They are less suitable for hand washing applications as they eliminate or greatly reduce the lather in the washing stage. A foam control agent that would not greatly reduce the foam level in the washing stage but would cause fast defoaming in the rinse would allow saving of significant quantities of water and reduce the time and efforts needed for rinsing.

Summary of the Invention

[0005] Disclosed is a granulated foam control composition comprising

1 ) a hydrophobic fluid,

2) a hydrophobic filler,

3) a water insoluble carrier

4) a polyethylene glycol of MW ranging of from 100,000 to 10,000,000,

5) an optional binder.

[0006] Further optional ingredients selected from silicone resin, binder, surfactant and plasticizer may also be present in the composition.

[0007] Also disclosed are methods to prepare the granulated foam control compositions.

[0008] Further disclosed is a detergent composition comprising the granulated foam control composition. [0009] The use of polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in a granulated foam control composition is disclosed.

[0010] A method to reduce foam at the rinsing step of a laundry washing procedure is also provided, together with the use of said granulated foam control composition in a laundry washing procedure.

[0011] A washing procedure is understood as comprising at least of one washing step and at least one rinsing step. The washing step is when the detergent is combined with the laundry to be washed. The rinsing step is when water is added to remove the detergent and foam from the laundry to be rinsed. Typically, the present laundry washing procedure occurs primarily by hand, alternatively, it occurs exclusively by hand.

[0012] The present invention allows for a reduction of water consumption during the rinsing step of a laundry hand washing procedure, together with an improved sensory experience for the consumer effecting the washing procedure. The present granulated foam control composition increases the transfer and the efficacy of the foam control agent in the rinse, as it withstands the washing step to be released only during the rinsing step. The foam control composition is thus protected during the washing step and only released upon the rinsing step. The polyethylene glycol of MW ranging of from 100,000 to 10,000,000 is believed to swell and keep the granulated foam control composition cohesive through the washing step. During said washing step, the foam control agent is believed to be transferred onto the laundry and to be

mechanically released during the rinsing step when water and foam are drained out of the laundry by the pressure applied by the washer.

Figures

[0013] Figure 1 illustrates the water uptake profile of compressed disks, where the X axis represents the time in minutes and the Y axis represents the water uptake in percent.

[0014] Figure 2 illustrates the surfaces of the testing basins as explained in the examples section: pictures of the surface of basin 1 is taken after step 2; pictures 3 & 4 are taken at the end of step 5, with step 4 and 5 lasting 4 minutes, where the foam is graded from 0 to 5, 0 corresponding to 'no foam' and 5 to 'surface totally covered by foam'.

Detailed Description of the Invention

[0015] The term "about" as used herein serves to reasonably encompass or describe minor variations in numerical values measured by instrumental analysis or as a result of sample handling. Such minor variations may be in the order of plus or minus 0% to 10% or plus or minus 0% to 5% of the numerical values.

[0016] The term "branched" as used herein describes a polymer with more than two end groups.

[0017] The term "comprising" is used herein in its broadest sense to mean and to encompass the notions of "include" and "consist of." [0018] The term "ambient temperature" or "room temperature" refers to a temperature between about 20°C and about 30°C. Usually, room temperature ranges from about 20 ^S C to about 25°C.

[0019] The use of "for example" or "such as" to list illustrative examples does not limit to only the listed examples. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to" and encompasses other similar or equivalent examples.

[0020] The term "substituted" as used in relation to another group, for example, a hydrocarbon group, means, unless indicated otherwise, one or more hydrogen atoms in the hydrocarbon group has been replaced with another substituent. Examples of such substituents include, for example, halogen atoms such as chlorine, fluorine, bromine, and iodine; halogen atom containing groups such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl; oxygen atoms; oxygen atom containing groups such as (meth)acrylic and carboxyl; nitrogen atoms; nitrogen atom containing groups such as amines, amino-functional groups, amido- functional groups, and cyano-functional groups; sulphur atoms; and sulphur atom containing groups such as mercapto groups.

[0021] All viscosity measurements referred to herein were measured at 25 °C unless otherwise indicated. Typically, viscosity is measured using a Brookfield viscosimeter.

[0022] The granulated foam control composition is based on a typical foam control agent which comprises a hydrophobic fluid, a filler and an optional silicone resin, used in conjunction with a water insoluble carrier, and with a polyethylene glycol of MW ranging of from 100,000 to 10,000,000.

[0023] The hydrophobic fluid may be any type of typical silicone fluid or organic fluid or mixture thereof used in foam control agents.

The silicone fluids may be linear or branched. A wide variety of silicone fluids are known as foam control fluids. There is no particularly specific required hydrophobic fluid, as long as it is compatible with the carrier and other ingredients in the formulation and perform as foam controlling hydrophobic fluid.

[0024] Examples of silicone fluid used in foam control agents include polydialkylsiloxanes such as polydimethylsiloxane or polydiethylsiloxane, branched siloxanes, alkylaryl

polyorganosiloxanes, aryl functional siloxanes, polyorganosiloxanes substituted with amine, amido or polyoxyalkylene functionality, silicone polyether copolymers, organopolysiloxanes having carboxyl-functional organic groups, organopolysiloxanes having pendant esterified carboxyalkyl groups, or mixtures thereof.

[0025] Alkyl groups include those groups having 1 -20 carbon atoms, alternatively 1 -10 carbon atoms.

[0026] Polydialkylsiloxanes include polydimethylsiloxane (PDMS) which may be branched or have a higher viscosity (i.e. above 12,500 mm2 /s at 25°C). Preferably at least 80% of all units in the branched organopolysiloxane, most preferably at least 90%, have the formula R ₂ Si0 ₂ /2, where each group R represents an aliphatic or aromatic hydrocarbon group having up to 18 carbon atoms. It is most preferred that substantially all R groups are methyl or phenyl groups, especially methyl groups. When branched, the organopolysiloxane also contains units of the formula RS1O3/2 or S1O4/2. These other units may be present as individual units in the siloxane chains, or they may be present as little clusters, from which a number of siloxane chains extend. Preferred branching units include small three-dimensional siloxane resin particles which may have a number of pending siloxane polymer units. Thus a very loose network is formed of polyorganosiloxane chains giving a fluid branched organopolysiloxane. Branched

organopolysiloxanes and methods of making them are described for example in EP-A-217501 , US-A-4639489, US-A-5668101 , WO 2007/137948.

[0027] Alternative polydialkylsiloxanes include those having different alkyl groups of varying chain length. For example polysiloxanes comprising 50-100% diorganosiloxane units of the formula -(X'YSi-O)- and optionally up to 50% diorganosiloxane units of the formula -(Y ₂ Si-0)- wherein Y denotes an alkyl group having 1 to 4 carbon atoms and X' denotes an alkyl group having 6 to 20 carbon atoms. The groups Y in such a polydiorganosiloxane are preferably methyl or ethyl. The alkyl group X' 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.

[0028] Alkylaryl polyorganosiloxanes may comprise at least 10% diorganosiloxane units of the formula -(Y'YSi-O)- and up to 90% diorganosiloxane units of the formula -(YZSi-O)- wherein Z denoates a -X-Ph group, were X is 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. 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 -CH2-CH(CH ₃ )-C6H ₅ . 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. [0029] Aryl organopolysiloxanes may be a substantially linear polydiorganosiloxane or can be a branched organopolysiloxane containing for example up to 10 mole% branching units.

[0030] Examples of organopolysiloxanes having a phenyl group include

poly(methylphenylsiloxane), trimethylsiloxy-terminated poly(methylphenylsiloxane), silanol- terminated poly(methylphenylsiloxane).

[0031] Polyorganosiloxanes substituted with amine, amido or polyoxyalkylene functionality have siloxane units of the general formula RaSi0 ₄ - _a /2 in combination with siloxane units of the general formula R R'cSi04- - _c 2, where R denotes a hydrocarbon group, preferably having from 1 to 12 carbon atoms, preferably an alkyl, aryl or alkenyl group, R' is a functional group, selected from an amine containing substituent, an amido containing substituent and a polyoxyalkylene containing substituent, a is an integer with a value from 0 to 3, b is an integer with a value of from 0 to 2, c is an integer with a value of 1 , 2 or 3; b + c having a value of from 1 to 3, preferably with an average of from 1 .6 to 2.4, more preferably 1 .9 to 2.2.

[0032] R' groups with amine functionality are preferably selected from aminoalkyl groups. Suitable aminoalkyl groups have the formula R ¹ -(NH-A') _q -NH-A- wherein A and A' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether linkage; q = 0 to 4; and R ¹ is hydrogen or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. Examples of preferred aminoalkyl groups include -(CH ₂ )3NH ₂ , -(CH ₂ ) ₄ NH2, -(CH2) ₃ NH(CH ₂ )2NH2, -CH ₂ CH(CH3)CH ₂ NH(CH2)2NH2,

-(CH ₂ )3NHCH2CH ₂ NH(CH2)2NH2, -CH ₂ CH(CH3)CH ₂ NH(CH2)SNH2, -(CH ₂ )3NH(CH ₂ )4NH2 and -

[0033] Amido containing substituents R' are provided for example by the group

=NC(0)(CHR ₂ ) _n OH linked to the silicon atom through a divalent linkage R*. Preferably R ² represents a hydrogen atom and n has the value 3, 4, 5 or 6. Preferred materials are those wherein R* represents a divalent hydrocarbon group or a group R ³ (NR ⁴ R ³ ) _S wherein R ³ represents a divalent hydrocarbon group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an aryl group, or a group X, X represents the group CO(CHR ⁵ ) OH, wherein R ⁵ represents a hydrogen atom or an alkyl group and s has a value in the range 0 to 4, more preferably 1 or 2.

[0034] Where the functionality is polyoxyalkylene, the substituent will have the general formula:

where R ³ is as defined above, and t has a value of from 1 to 50, preferably 3 to 10 and u has a value of from 0 to 50, preferably 0 to 8.

[0035] Siloxane polyether copolymers can for example be a silicone polyether block copolymer comprising at least one polydiorganosiloxane block, for example a polydimethylsiloxane block, and at least one polyether block, for example a polyoxyethylene, block. Examples of silicone polyether copolymers include polydimethylsiloxane-polyoxyethylene copolymers, polydimethylsiloxane-polyoxyethylene/polyoxypropylene copolymers, ethoxylated 3- hydroxypropylheptamethyltrisiloxane.

[0036] The organopolysiloxane containing pendant esterified carboxyalkyi groups can, for example, be a substantially linear polydiorganosiloxane or can be a branched

organopolysiloxane containing for example up to 10 mole% branching units. The carboxalkyl groups can, for example, contain 2 to 12 carbon atoms, particularly 2 to 5 carbon atoms, and can, for example, be carboxym ethyl, 2-carboxyethyl, 2-methyl-2-carboxyethyl or 2-ethyl-2- carboxyethyl groups. The carboxyalkyi groups can be esterified by alkyl, aryl, aralkyl or cycloalkyi groups, for example the carboxyalkyi groups can each be esterified by an alkyl group having 1 to 20 carbon atoms. Preferably, all or most of the carboxyalkyi groups are esterified by an alkyl group having 8 to 18 carbon atoms, for example a n-octyl, 2-ethylhexyl, lauryl, tetradecyl, hexadecyl or stearyl group. A mixture of different alkyl groups, for example alkyl groups of different chain length, can be used such as a mixture of C12 and C14 alkyl groups.

[0037] Methods to provide for siloxanes are well known in the art.

[0038] Examples of organic fluid used in foam control agents include oils, e.g. mineral oils, especially hydrogenated mineral oil or white oil, liquid polyisobutene, isoparaffinic oils and vegetable oils, for example peanut oil, coconut oil, olive oil, cottonseed oil and linseed oil.

Further examples of organic liquids include polyoxypropylene glycols, polyoxybutylene glycols, esters of carboxylic acids such as dioctyl phthalate, diethyl succinate, methyl caproate, butyl pelargonate, ethyl stearate, dodecyl laurate or methyl melissate and monohydric alcohols such as decanol. Examples of organic fluids which are not liquid at 25°C but are liquid at higher temperatures include petroleum jelly or Vaseline®, higher alcohols and higher carboxylic acids such as myristic acid.

[0039] The hydrophobic fluid has a viscosity ranging of from 0.005 to 5000 Pa.s, at 25°C.

The hydrophobic fluid is present in the granulated foam control composition in an amount ranging of from 5 to 25% by weight, based on the weight of the granulated foam control composition, alternatively 5 to 20% by weight.

[0040] Hydrophobic fillers for foam control agents are well known and are particulate materials which are solid at 100°C, such as silica (typically having a surface area as measured by BET measurement of at least about 50 m ² /g), titania, ground quartz, alumina, 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.

[0041] 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 hydrophobic fluid), or by pre-treatment of the filler prior to mixing with the hydrophobic fluid. One example of a suitable filler is silica that has been made hydrophobic. Suitable silica materials include those that are prepared by heating, e.g. fumed silica, or precipitation. The silica filler may, for example, have an average particle size of about 0.5 to about 50μιη, alternatively about 2 to about 30, and alternatively about 5 to about 25μιη. It can be made hydrophobic by treatment with a fatty acid or 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 (CH ₃ )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 trademark SIPERNAT® D10 from Evonik Industries (Germany) can be used together with a partially hydrophobic silica such as that sold under the trademark AEROSIL® R972 from Evonik Industries.

[0042] The hydrophobic filler in the foam control agent may be the same or different from the water insoluble carrier in the granulated foam control composition. Typically, the hydrophobic filler is different from the water insoluble carrier in the granulated foam control composition.

[0043] The hydrophobic filler is present in the granulated foam control composition in an amount ranging of from 0.25 to 10% by weight, based on the weight of the granulated foam control composition.

[0044] The foam control agent of the present invention may optionally include one or more organosilicon resins. The organosilicon resin may be a non-linear siloxane resin. In one embodiment, the organosilicon resin includes siloxane units having the formula R' _a SiO( ₄ - _a )/2, wherein R' denotes a hydroxyl, hydrocarbon, or hydrocarbonoxy group, and wherein a has an average value of from about 0.5 to about 2.4. In one embodiment, the organosilicon resin includes monovalent trihydrocarbonsiloxy (M) groups of the formula R"3SiOi 2 and tetrafunctional (Q) groups Si0 ₄ /2, wherein R" denotes a monovalent hydrocarbon group. In one embodiment, the M/Q ratio is in the range about 0.4:1 to about 2.5:1 (equivalent to the value of a in the formula R' _a SiO( ₄ - _a )/2 of about 0.86 to about 2.15) for use in laundry detergent applications. In another embodiment, the M/Q ratio is from about 0.4:1 to about 1 .1 :1 for use in laundry detergent applications. In yet another embodiment, M/Q ratio about 0.5:1 to about 0.8:1

(equivalent to the value of a in the formula R' _a SiO( _{4 a} )/2 of about 1 .0 to about 1 .33) for use in laundry detergent applications.

[0045] The organosilicon resin described herein is generally a solid at room temperature.

However, it is contemplated that liquid organosilicon resins (e.g., those having a M/Q ratio greater than about 1.2) may also be used.

[0046] The organosilicon resin typically includes only M and Q groups, as described above. However, it is contemplated that a resin comprising M groups, trivalent R"Si0 ₃ /2 (T) groups and Q groups may also or alternatively be used. The organosilicon resin may also include divalent units R" ₂ Si0 ₂ /2, e.g., in an amount of about 20% or less of all siloxane units present. The group R" may comprise an alkyl group (e.g., methyl, ethyl, or phenyl) having from about 1 to about 6 carbon atoms. It may be desirable that about 80% to substantially all of the R" groups present be methyl groups. Other hydrocarbon groups may also be present including, but not limited to, alkenyl groups such as dimethylvinylsilyl units (e.g., not exceeding about 5% of the total R" groups). Silicon-bonded hydroxyl groups and/or alkoxy, (e.g. methoxy) groups may also be present. Such organosilicon resins are generally well known and can be made in solvent or in situ, e.g., by hydrolysis of certain silane materials. In one embodiment, the organosilicon resin is made by hydrolysis and condensation in the presence of a solvent (e.g. xylene) of a precursor of the tetravalent siloxy unit (e.g. tetra-orthosilicate, tetraethyl orthosilicate, polyethyl silicate or sodium silicate), and a precursor of monovalent trialkylsiloxy units (e.g. trimethylchlorosilane, trimethylethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane). The resulting MQ resin may, if desired, be further trimethylsilylated so that it is reacted out. Residual Si-OH groups may be heated in the presence of a base to cause self -condensation of the resin by elimination.

[0047] The organosilicon resin is present in the granulated foam control composition in an amount ranging of from 0 to 5 % by weight, alternatively of from 0.1 to 5 % by weight, based on the weight of the granulated foam control composition.

[0048] The water insoluble carrier of the granulated foam control composition may be selected from silicates, aluminosilicates, starches, insoluble clays, or mixtures thereof.

[0049] Examples of silicate include magnesium silicate

[0050] Examples of aluminosilicate include zeolite.

[0051] Examples of starches include starch from rice, potato, wheat, corn.

Typically, the zeolite may be any of those crystalline or amorphous aluminosilicate materials that are known to be beneficial in detergent powder compositions. Suitable zeolites may be pre- treated with e.g. non-ionic surfactants, but are preferably untreated zeolites, as they seem to provide a better stability of the foam control agent when stored in a powder detergent composition.

[0052] The carrier is present in the granulated foam control composition in an amount ranging of from 60 to 94% by weight, based on the weight of the granulated foam control composition.

[0053] A polyethylene glycol of MW ranging of from 100,000 to 10,000,000 is present in the granulated foam control composition.

[0054] The polyethylene glycol has a molecular weight (M _n ) of at least 100,000, preferably at least 300,000, preferably at least 500,000, preferably at least 1 ,000,000, preferably at least 2,000,000, preferably at least 3,000,000; preferably no more than 10,000,000, preferably no more than 8,000,000, preferably no more than 7,000,000. [0055] Typically, the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 may have a viscosity in water as follows: for 5%wt dispersion, the viscosity may range of from 30 to 10,000 mPa/s; and for 1 %wt dispersion, the viscosity may range of from 1 ,000 to 15,000 mPa/s.

[0056] In some instances, it may be critical for the present invention that the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 is processed under its solid, undispersed form and that it is maintained in a solid form throughout the manufacturing process. It then serves as an external cohesive agent for the granulated foam control agent, and may not be processed after dispersion in water.

[0057] In other instances, it may be suitable to the present inventing to process the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in its liquid, dispersed form.

[0058] The polyethylene glycol is typically not miscible with the silicone hydrophobic fluid. The polyethylene glycol is typically not charged.

[0059] The polyethylene glycol of MW ranging of from 100,000 to 10,000,000 is present in the granulated foam control composition in an amount ranging of from 0.4 to 15% by weight, based on the weight of the granulated foam control composition, alternatively of from 0.4 to 12% by weight, alternatively of from 0.4 to 8% by weight.

[0060] A binder may be present in the granulated foam control composition. The binder is a material which can be applied to the carrier as a liquid binding medium and which can be solidified to a solid which binds carrier particles together.

[0061] The binder is different from the polyethylene glycol of MW ranging of from 100,000 to 10,000,000.

[0062] Examples of binder include material having a solid consistency at room temperature, i.e. from 20 to 25°C, for example a waxy material of melting point 35 to 70°C, this type of material may be an organic material such as beeswax, carnauba wax, or a silicone material such as alkyl-functional silicone wax, alkyl-functional silanes, amine-functional silicone wax, amide- functional silicone wax, and any combination thereof.

[0063] Further examples of binder include water-soluble or water-dispersible polymers, preferably a film-forming polymer, which can be applied as an aqueous solution or emulsion to the carrier and can be solidified by drying to agglomerate the carrier, such as polycarboxylate, polyvinyl alcohol, poly(meth)acrylic acid, polyacrylamide or mixtures or salts of these.

[0064] In one embodiment, the binder is chosen from polyvinyl alcohols.

[0065] Polyvinylalcohol (PVA) can be any commercially available polyvinyl alcohol and may for example have a degree of hydrolysis in the range 80% to 99.9%. The viscosity of the PVA, namely of a 4% aqueous solution of PVA in water, may be in the range of from 3 to 60 mPa.s, as measured by a Hoppler viscometer (DIN 53015) at 20°C.

[0066] Various suitable PVAs are sold by Kuraray America Inc. under 'Poval' and "Mowiol' brand name. [0067] The binder may be present in the granulated foam control composition in an amount ranging of from 0 to 15 % by weight, based on the weight of the granulated foam control composition, alternatively of from 0.5 to 15% by weight, alternatively of from 0.5 to 10% by weight.

[0068] The granulated foam control composition may contain further optional ingredients, such as plasticizers, softness agent, surfactants, colorants, preservatives.

[0069] Plasticizers may be used to plastify the binder if necessary, to promote plasticity, flexibility and to reduce brittleness of the binder. Examples of plasticizers include glycerol, glycerin, dipropylene glycol, ethylene glycol, polyethylene glycol, soy lecithin, benzyl butyl phthalate, dipropylene glycol dibenzoate.

[0070] The plasticizer may be present in the granulated foam control composition in an amount ranging of from 0 to 8 % by weight, based on the weight of the granulated foam control composition, alternatively of from 0.1 to 8% by weight.

[0071] Suitable softness agent includes aminofunctional silicone fluid, polydimethylsiloxane (same or different from hydrophobic fluid discussed above).

Suitable surfactants include any of anionic, nonionic and cationic surfactants or mixtures thereof.

[0072] Examples of anionic surfactants include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of 8 to 16 carbon atoms; primary and secondary alkyl sulphates, particularly primary alkyl sulphates having an alkyl chain length of 8 to 16 carbon atoms; alkyl ethersulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. The detergent composition preferably contains an anionic surfactant, optionally with a nonionic surfactant.

[0073] Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially aliphatic alcohols having 8 to 20 carbon atoms ethoxylated with an average of from 1 to 20 moles, preferably 1 to 10 moles, of ethylene oxide per mole of alcohol. Suitable non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides.

[0074] Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, sulphonium salts and phosphonium salts.

[0075] The surfactant may be present in the granulated foam control composition in an amount ranging of from 0 to 10 % by weight, based on the weight of the granulated foam control composition, alternatively of from 0.1 to 10% by weight.

[0076] The present invention also relates to methods for the preparation of a granulated foam control composition. [0077] A first method for the preparation of a granulated foam control composition comprises the sequential steps of

1 ) providing for a liquid foam control composition (i) comprising at least the hydrophobic fluid, the hydrophobic filler, and the binder;

2) providing for a carrier (ii);

3) depositing the liquid foam control composition (i) on the carrier (ii) to produce temporary wet granules;

4) depositing the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form on the temporary wet granules of step 3);

5) drying the temporary wet granules of step 4) to produce the granulated foam control

composition.

[0078] A second method for the preparation of a granulated foam control composition comprises the sequential steps of

1 ) providing for a liquid foam control composition (i) comprising at least the hydrophobic fluid, the hydrophobic filler, and the binder;

2) providing for a carrier composition (ii) comprising at least the carrier and the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form;

3) depositing the liquid foam control composition (i) on the carrier composition (ii) to produce temporary wet granules;

4) drying the temporary wet granules of step 3) to produce the granulated foam control

composition.

[0079] A third method for the preparation of a granulated foam control composition comprises the sequential steps of

1 ) providing for a liquid foam control composition (i) comprising at least the hydrophobic fluid, the hydrophobic filler, the binder and the polyethylene glycol of MW ranging of from

100,000 to 10,000,000 in diluted form;

2) providing for a carrier (ii);

3) depositing the liquid foam control composition (i) on the carrier (ii) to produce temporary wet granules;

4) drying the temporary wet granules of step 3) to produce the granulated foam control

composition.

[0080] The liquid foam control composition (i) may be provided by mixing, and optionally heating, the liquid ingredients which will provide for said liquid foam control composition. The liquid foam control composition may be a dispersion or may be an emulsion. The surfactants described above may this be used to emulsify the hydrophobic ingredients in water. The carrier composition may be provided by mixing the carrier and solid polyethylene glycol of MW ranging of from 100,000 to 10,000,000 and any other suitable solid ingredient, by any means suitable to combine powders.

[0081] The deposition of the liquid foam control composition (i) on the carrier or carrier composition (ii) is carried out by any of the known conventional methods to produce powders. Such methods include spray drying, fluidized bed, agglomeration methods, granulation methods, extrusion methods.

[0082] The granulated foam control composition may be made by an agglomeration process in which the liquid foam control composition 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.

[0083] 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 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-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 from LB, RM-type 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 Mischtechnik.

[0084] 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 commercially available under the name Forberg, intensive mixers including a high shear mixing arm within a rotating cylindrical 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.

[0085] The deposition may be done by pouring the mixture into the mixer, as well as spraying and/or extrusion.

[0086] Once produced and ultimately dried, the granulated foam control composition may comprise

1 ) 5 to 25% by weight of hydrophobic fluid,

2) 0.25 to 10 % by weight of hydrophobic filler,

3) 0 to 5 % by weight of silicone resin,

4) 60 to 94% by weight of water insoluble carrier

5) 0.4 to 15% by weight of polyethylene glycol of MW ranging of from 100,000 to 10,000,000, 6) 0 to 15 % by weight of binder,

7) 0 to 8 % by weight of plasticizer,

8) 0 to 10 % by weight of surfactant, 9) 0 to 2% by weight of residual water,

based on the total weight of the granulated foam control composition (equaling to 100% by weight).

[0087] The present invention also discloses a detergent composition comprising the granulated foam control composition described above.

[0088] The detergent composition of the invention is preferably a laundry detergent, but can alternatively be a detergent for dish washing or a detergent composition for personal care use such as a shampoo, shower gel or soap bar. In all of these applications, the consumer may prefer to see lather during the washing step but rapid defoaming in the rinsing step.

[0089] The detergent composition is typically in a solid form. The detergent composition may be a powder, bar or tablet. Solid bars may be soap-containing bars or synthetic bars. Laundry detergents for hand washing or for use in semi-automatic machines are commonly sold in powder form.

[0090] The detergent composition comprises at least one detersive surfactant, which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active surfactants, and mixtures thereof. Many suitable detergent-active surfactants are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The preferred detersive surfactants that can be used are soaps and/or synthetic non-soap anionic and/or nonionic compounds. The total amount of surfactant present is suitably within the range of from 5 to 40 wt% of the detergent composition.

[0091] The detergent compositions may also contain one or more detergency builders. The total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%. Inorganic builders that may be present include sodium carbonate, crystalline and amorphous aluminosilicates, for example, zeolites, and layered silicates.

Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate, may also be present. Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates,

carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and

alkenylmalonates and succinates; and sulphonated fatty acid salts. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

[0092] The detergent composition may also contain a peroxy bleach compound, for example, an inorganic persalt or an organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor), for example a peroxycarboxylic acid precursor, more especially a peracetic acid precursor such as tetraacetyl ethylenediamine, or a peroxybenzoic acid or peroxycarbonic acid precursor.

[0093] Detergent compositions intended for personal care use such as shampoo compositions can contain other ingredients selected for example from conditioners to facilitate combing and/or styling of the hair and/or to improve the shine and/or softness of the hair, perfumes, fragrances, colorants such as dyes, essential oils, vitamins, buffering agents, stabilizers and preservatives.

[0094] Detergent powders can, for example, be prepared by spray-drying a slurry of compatible heat insensitive ingredients, or by mixing and granulation of raw materials, preferably using a high-speed mixer/granulator. Less robust or more heat sensitive ingredients can be

subsequently incorporated into the detergent powder; the foam- inhibiting composition of the invention is preferably subsequently incorporated in this way.

[0095] The granulated foam control composition is present in the detergent composition in an amount of from 0.1 to 15%wt based on the weight of the detergent composition, alternatively of from 0.5 to 10%wt, alternatively of from 1 to 8%wt.

[0096] The present detergent comprising the granulated foam control composition is suitable for use at temperatures ranging of from 5 to 50°C, alternatively of from 5 to 40°C, alternatively of from 10 to 40°C, and at water hardness ranging of from 0 to 500 mg/L.

[0097] The present invention provides for a use of a polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in a granulated foam control composition.

[0098] The present invention provides for the use of a granulated foam control composition as described above to reduce foam during the rinsing stage of a laundry washing procedure.

[0099] Also provided is a method to reduce foam during the rinsing stage of a laundry washing procedure by providing for a granulated foam control composition as described above in a laundry detergent composition.

[0100] Other benefits imparted form the granulated foam control composition may include ease of ironing, softness, fragrance delivery.

EXAMPLES

Water uptake test - Figure 1

[0101] A water uptake test was designed to verify suitability of the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 to improve cohesion of the granulated foam control composition. The test requires provision of a compressed disk and measurements of water uptake in specific conditions.

[0102] In a first step, a mixture of the polyethylene glycol of MW ranging of from 100,000 to 10,000,000, the binder and the carrier is prepared in aqueous solution, in a plastic vessel under shear in a Hauschild speedmixer DAC 150. The second step is to transfer the mixture in an aluminum cup to be dried in an oven for 4 hours at 60°C. The dried powder is then crunched in a mortar and pestle agate for 2min. 0.27g of the crunched powder is used to make a compressed disk using an equipment for IR disk preparation, applying 2 bar of pressure for 2min.

[0103] The water update of the compressed disk is then evaluated as follows. The compressed disk is initially weighted in an aluminum cup. The disk is put on a spatula which is damped into crystallizer containing 700 imL of wash liquor for 15 seconds. The disk is then gently put down on a paper towel to remove excess and surface water. The weight of the disk is then measured again. The disk is put back on the spatula and damped again into the wash liquor for 1 minute. These steps are repeated until the disk starts to break or falls apart.

[0104] The wash liquor is made of 2L of soft water, 10g of Viva powder and a water hardness at 10°f ([Mg solution] = 72 g/L and [Ca solution] = 262 g/L).

[0105] The percentage of weight uptake is the (disk weight at t - disk weight at t0)x100 / disk weight at tO; to being the initial time, t is damping time. The water uptake profile is provided in Figure 1 , where the X axis represents the time in minutes and the Y axis represents the water uptake in percent. The dotted line A represents the water uptake of a compressed disk comprising polyethylene glycol of MW ranging of from 100,000 to 10,000,000, while the full line B represents a compressed disk free of polyethylene glycol as claimed. The compressed disk free of polyethylene glycol is falling apart after 8 minutes, while the compressed disk comprising polyethylene glycol of MW ranging of from 100,000 to 10,000,000 takes up water regularly for at least 22 minutes.

[0106] The compressed disk should take up to 30% of water in less than 10min, should continue to take up water continuously without breaking or dissolving. In some instances, this test may be used to indicate suitable polyethylene glycol types.

[0107] Without wishing to be bound by theory, it is conceived that the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 will impart water resistance to the granule so that the foam control agent is ultimately released during the rinsing step of the laundry washing procedure and not during the washing step of the washing procedure. Granulated foam control compositions and their assessment

Materials

1 ) Antifoam compound AFC1 : based on a mixture of branched polymethylsiloxane polymer and MQ resin, with 3% of a hydrophobic silica, prepared according to the teaching of EP217501

2) Antifoam compound AFC2: based on a mixture of branched polymethylsiloxane polymer and MQ resin, having 3% of silica rendered hydrophobic according to the teaching of EP0163541

3) Antifoam compound AFC3: based on a mixture of dimethylmethylarylsiloxane polymer and MQ resin, having 6% of a hydrophobic silica

Polyvinyl alcohols

1 ) PVA 4-88 (PVA with a viscosity of 4mPa.s at 4% in water (20°C) and 88% of hydrolyzed functions): 20% solution in water

2) PVA 8-88 (PVA with a viscosity of 8mPa.s at 4% in water (20°C) and 88% of hydrolyzed functions): 20% solution in water

3) PVA 18-88 (PVA with a viscosity of 18mPa.s at 4% in water (20°C) and 88% of

hydrolyzed functions): 20% solution in water

4) PVA 30-88 (PVA with a viscosity of 30mPa.s at 4% in water (20°C) and 88% of

hydrolyzed functions): 10% solution in water

[0108] PAA: Polyacrylic acid: 50% solution of polyacrylic acid, Na-salt, partly neutralized with a molecular weight of approximately 4000 g/mol, solution having a viscosity of 600 mPa.s (Brookfield, 23 ^S C) (used in Comparative example 4)

[0109] Zeolite: Doucil 4A from INEOS, having an average particle size of 2-5 microns

[0110] Sodium sulfate: from Crimidesa, having a particle size characterized by a D50 of 15 microns

Polyethylene oxide

1 ) PEO 1 : Polyoxyethylene glycol of Molecular weight of 4,000,000 (used in Comparative example 3, in Examples 1 to 10, 14 to 18)

2) PEO 2: Polyoxyethylene glycol of Molecular weight of 100,000 (used in Example 1 1 ) 3) PEO 3: Polyoxyethylene glycol of Molecular weight of 600,000 (used in Examples 12 and 20 in solid form and in Example 19 in solution form of 5% active in water)

4) PEO 4: Polyoxyethylene glycol of Molecular weight of 8,000,000 (used in Example 13)

[0111] Commercial VIVA detergent powder purchased in Mexico, intended for hand laundry washing procedures.

[0112] Preparation of granulated foam control compositions: the ingredients of the granulated foam control compositions and their respective amounts are indicated in "wet" conditions, indicating weight percentages of the respective ingredients based on the total weight of the "wet" composition; and in dry conditions, where compositions are estimated as if 100% of the water is removed, although a maximum of 2% wt of residual water may be tolerated. The granulated foam control compositions prepared herein typically were prepared with 180 to 250g of carrier.

Method 1

[0113] Preparation according to the first method of the present invention is as follows, where the steps are sequential steps:

1 ) providing for a liquid foam control composition (i), in the form of an emulsion, comprising blending the binder aqueous solution with alkylbenzenesulfonic acid ABSA anionic surfactant, silicone antifoam compound and water, mechanically mixing the ingredients using a lab blender equipped with a shaft;

2) providing for a carrier (ii), free of polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form;

3) depositing the liquid foam control composition (i) by pouring it very slowly into a drum mixer on the carrier (ii) to produce temporary wet granules;

4) depositing the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form on the temporary wet granules of step 3) by addition into the drum mixer;

5) drying the temporary wet granules of step 4) in a fluidized bed to produce the granulated foam control composition.

Method 2

[01 141 Preparation according to the second method of the present invention is as follows, where the steps are sequential steps:

1 ) providing for a liquid foam control composition (i), in the form of an emulsion, comprising blending the binder aqueous solution with alkylbenzenesulfonic acid ABSA anionic surfactant, silicone antifoam compound and water, mechanically mixing the ingredients using a lab blender equipped with a shaft;

2) providing for a carrier composition (ii) comprising the carrier and the polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form;

3) depositing the liquid foam control composition (i) by pouring it very slowly into a drum mixer on the carrier composition (ii) of step 2) to produce temporary wet granules;

4) drying the temporary wet granules of step 3) in a fluidized bed to produce the granulated foam control composition. Method 3

[0115] Preparation according to the third method of the present invention is as follows, where the steps are sequential steps:

1 ) providing for a liquid foam control composition (i), in the form of an emulsion, comprising blending the aqueous solution of polyethylene glycol of MW ranging of from 100,000 to

10,000,000, with alkylbenzenesulfonic acid ABSA anionic surfactant, silicone antifoam compound and water, mechanically mixing the ingredients using a lab blender equipped with a shaft;

2) providing for a carrier (ii), free of polyethylene glycol of MW ranging of from 100,000 to 10,000,000 in solid form;

3) depositing the liquid foam control composition (i) by pouring it very slowly into a drum mixer on the carrier (ii) of step 2) to produce temporary wet granules;

4) drying the temporary wet granules of step 3) in a fluidized bed to produce the granulated foam control composition.

[0116] The hand laundry washing procedure: a washing phase, a shearing phase and a rinsing phase were carried out in basins with each of the granulated foam control agent prepared as described herein. Basin for the wash 1 and rinse phase 3 and 4 contain 2L of water with a hardness of 100 mg/L CaC03 at 30 ^S C. Three knitted cotton fabrics (weight, 150 g) were used in the hand washing cycle. The shear basin number 2 does not contain water but a plate to rub the fabric to mimic the actual washing phase occurring in real life situation. (26x26cm at the bottom, 30x30cm on top)

[0117] Step 1 : In the washing phase, in basin 1 , 10g of detergent powder and 0.3g of the granulated foam control agent are dispersed in the 2L of water until foam reaches 10cm from the bottom of the basin. Fabrics are placed in the basin, returned once to be wet and a soaking time of 2 minutes is applied.

[0118] Step 2: Each fabric is removed from the wash basin one by one, drained from the excess of water and put aside. Each fabric is then folded in four, rubbed 5 times on each side onto a board in the shear basin 2 and then put aside again during the rubbing of the other fabrics.

[0119] Step 3: The total weight of the 3 fabrics is 400 g +/- 10g after shearing and wringing.

[0120] Step 4: In the rinse basin 3, each fabric is rinsed separately, laid out, folded in 2 in the basin, gently squeezed 5 times by hand, reversed and squeezed 5 times inside the water and finally drained. The 3 fabrics should weight 450g +/- 10g in total.

[0121] Step 5: Step 4 is repeated in rinse basin 4. The 3 fabrics should weight 480g +/- 10g in total.

[0122] Figure 2: surfaces of basins: pictures of the surface of basin 1 is taken after step 2; pictures 3 & 4 are taken at the end of step 5, with step 4 and 5 lasting 4 minutes, where the foam is graded from 0 to 5, 0 corresponding to 'no foam' and 5 to 'surface totally covered by foam'.

[0123] Table 1 below displays the parameters for a good candidate in the scope of the present invention:

- In wash basin: must maintain foam grade superior or equal to 4

In basin 3: foam grade can be inferior or equal to 4 but if foam grade equal to 5, foam grade in basin 4 must be 0

In basin 4: foam grade can be inferior or equal to 2, but foam grade must be 0, if equal foam grade equal to 5 in basin 3.

[0124] The commercial VIVA powder, free of foam control agent, sets the standard for an accepted level of foam during the wash, but maintains too much foam during the rinse steps.

TABLE 1

Comparative examples 1 to 4 and Example 1 : impact of components

[0125] Compositions and results are disclosed in Table 2.

[0126] Comparative example 1 is free of polyethylene glycol of MW ranging of from 100,000 to

10,000,000. While the level of foam is maintained in the wash basin, the level of foam in the rinses is still too high, in view of the present criteria for foam control in the rinse.

[0127] Comparative example 2 features sodium sulfate, a water soluble carrier, and is free of polyethylene glycol of MW ranging of from 100,000 to 10,000,000. The foam control agent is already released in the washing stage with a level of foam of 1 , too low for an acceptable hand wash detergent.

[0128] Comparative example 3 features sodium sulfate, a water soluble carrier, and contains polyethylene glycol of MW ranging of from 100,000 to 10,000,000. Although PE01 is present, the granule is too quickly dissolved and confirms the carrier should be water insoluble.

[0129] Comparative example 4 contains polyacrylic acid as binder and is free of polyethylene glycol of MW ranging of from 100,000 to 10,000,000. This binder is too soluble, the dissolution takes place to quickly during the washing stage, and the foam control agent is released too early. [0130] Example 1 is provided according to the present invention, using Method 2. The foam level in the wash is maintained to an acceptable level, and the level of foam in the first rinse is 1 and in the second rinse is zero. This example demonstrates the ability of the current invention to keep the foam in the wash and release only the antifoam performance into the rinse after rubbing and squeezing of the laundry fabrics.

TABLE 2

Examples 2 to 6: impact of amount of polyethylene glycol or preparation method: [0131]

Compositions and results are disclosed in Table 3.

[0132] Examples 2 to 5, prepared using Method 2, exemplify that the granulated composition of the present invention may be achieved by varying the amount of polyethylene glycol of MW ranging of from 100,000 to 10,000,000 as of from 0.4 to 8 %wt of the dry granulated composition.

[0133] Example 6, prepared using Method 1 , confirms that an alternative method of preparation allows to prepare suitable granulated compositions.

TABLE 3

Examples 7 to 10 and 18: impact of binder type and concentration:

[0134] Compositions and results are disclosed in Table 4.

[0135] Examples 7 to 10, prepared using Method 2, feature various binder types and concentrations, which are varied within the scope of the invention.

[0136] Example 18, prepared using Method 2, features a blend of binders.

In all cases, the antifoam is protected during the washing step in basin 1 and released in the rinses achieving a complete rinse in the second rinse (basin 4). TABLE 4

Examples 11 to 13: impact of PEO and antifoam types:

[0137] Compositions and results are disclosed in Table 5.

[0138] Examples 1 1 , 12, 13, prepared using Method 2, indicate that performances are maintained in the wash and in the rinse, although the viscosity of the polyethylene glycol ranging of from 100,000 to 10,000,000 is varied.

TABLE 5

Examples 14 to 17: impact of antifoam type or plasticizer concentration:

[0139] Compositions and results are disclosed in Table 6.

[0140] Examples 14 and 15 featuring alternative antifoam compounds (AFC2 and AFC3) are suitable within the scope of the invention.

[0141] Examples 16 and 17 indicate that 5% of a plasticizer such as glycerin, can be added while keeping an acceptable control of the foam in the wash and having perfect performance in the rinses, indicating that plasticizers or solvents of the binder may also be used without being detrimental to the performances.

[0142] Examples 14 to 17 were prepared using Method 2.

TABLE 6

Examples 19 and 20: impact of preparation method and binder:

[0143] Compositions and results are disclosed in Table 7.

[0144] The granulated composition of Example 19 was prepared using the third method (Method 3). The PE03 was first prepared as an aqueous solution at 5% in water.

The performances in the rinses are lower but still acceptable within the scope of the present invention.

[0145] The granulated foam control composition of Example 20 was prepared using Method 2, working with PE03 in its solid form. [0146] Both the second and third methods are suitable to prepare the present granulated foam control composition, as evidenced by the suitable performances.

TABLE 7