[0001] The present invention relates to a shampoo formulation. In particular, the present invention relates to a shampoo formulation containing: a dermatologically acceptable vehicle; a dermatologically acceptable silicone; a dermatologically acceptable hair cleaning surfactant; a deposition aid polymer, wherein the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein X is a divalent linking group; wherein each R ² is independently selected from the group consisting of a CM alkyl group; and wherein R ³ is a linear or branched C1-16 alkyl group; and (ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein Z is a divalent linking group; wherein a is 0 or 1; and wherein each R ⁵ is a linear or branched ,-22 alkyl group.

[0002] Hair cleansing has become a ubiquitous component of personal hygiene. Cleansing of the hair facilitates the removal of dirt, germs and other things that are perceived as harmful to the hair or the individual. Cleansing formulations typically include a surfactant to promote the removal of materials deposited on the hair. Unfortunately, the cleansing formulations remove both undesirable and desirable materials from hair. For example, cleansing formulations frequently undesirably remove oils from hair; oils operate to protect hair from loss of moisture. Removal of too much oil from hair may leave the hair vulnerable to becoming dry and damaged. One solution to this concern is the selection of mild surfactants. Another approach is to incorporate additives that help replace the oils removed through deposition; however, this approach has proven difficult in implementation, particularly in rinse off applications.

[0003] In U.S. Patent No. 7,067,499, Erazo-Majewicz, et al. disclose personal care and household care product composition comprising at least one cationic polygalactomannan or a derivative of cationic polygalactomannans wherein the derivative moiety on the cationic derivatized polygalactomannan is selected from the group consisting of alkyl, hydroxyalkyl, alkylhydroxyalkyl, and carboxymethyl wherein the alkyl has a carbon chain containing from 1 to 22 carbons and the hydroxyalkyl is selected from the group consisting of hydroxy ethyl, hydroxypropyl, and hydroxybutyl, wherein the at least one cationic polygalactomannan or derivative of cationic polygalactomannans have a mean average molecular weight (Mw) having a lower limit of 5,000 and an upper limit of 200,000 and having a light transmittance in a 10% aqueous solution of greater than 80% at a light wavelength of 600 nm and a protein content of less than 1.0% by weight of polysaccharide, and aldehyde functionality content of at least 0.01 meq/gram.

[0004] While conventionally used deposition aids such as soluble cationic modified celluloses (e.g., polyquaternium-10), guar hydroxypropyltrimonium chloride and other cationic polymers (e.g., polyquatemium-6, polyquatemium-7) provide a certain level of deposition in personal care cleansers; they nevertheless exhibit low efficiency necessitating a relatively high incorporation of the active into the personal care cleanser formulation to facilitate desired results. Such high active (e.g., silicone) levels, however, detrimentally effect the foam/lathery in use consumer feel of the formulation and cost.

[0005] Accordingly, there remains a need for deposition aids that facilitate enhanced efficiency of silicone deposition from shampoo formulations. There is also a continuing need for new deposition aids having an increased natural origin index (IS016128) when compared with conventional deposition aids.

[0006] The present invention provides a shampoo formulation, comprising: a dermatologically acceptable vehicle; a dermatologically acceptable silicone; a dermatologically acceptable hair cleaning surfactant; a deposition aid polymer, wherein the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein X is a divalent linking group; wherein each R ² is independently selected from the group consisting of a CM alkyl group; and wherein R ³ is a linear or branched C1-16 alkyl group; and (ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein Z is a divalent linking group; wherein a is 0 or 1; and wherein each R ⁵ is a linear or branched ,-22 alkyl group.

[0007] The present invention provides a method of depositing silicone on to mammalian hair, comprising: selecting a shampoo formulation of the present invention; and applying the shampoo formulation to mammalian hair; wherein the deposition aid polymer enhances the deposition of the dermatologically acceptable silicone from the shampoo formulation onto the mammalian hair relative to an otherwise identical formulation without the deposition aid polymer.

DETAILED DESCRIPTION

[0008] We have surprisingly found that silicone deposition from shampoo formulations can be enhanced through incorporation of a deposition aid polymer, wherein the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein X is a divalent linking group; wherein each R ² is independently selected from the group consisting of a C _M alkyl group; and wherein R ³ is a linear or branched Ci-i ₆ alkyl group; and (ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein Z is a divalent linking group; wherein a is 0 or 1; and wherein each R ⁵ is a linear or branched Ce-22 alkyl group.

[0009] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. [0010] As used herein, unless otherwise indicated, the phrase "molecular weight" or Mw refers to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as polyethylene glycol standards. GPC techniques are discussed in detail in Modern Size Exclusion Chromatography, W. W. Yau, J. J. Kirkland, D. D. Bly; Wiley-Interscience, 1979, and in A Guide to Materials Characterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p.81- 84. Molecular weights are reported herein in units of Daltons, or equivalently, g/mol. [0011] The term "dermatologically acceptable" as used herein and in the appended claims refers to ingredients that are typically used for topical application to the skin or hair, and is intended to underscore that materials that are toxic when present in the amounts typically found in hair care compositions are not contemplated as part of the present invention.

[0012] Preferably, the shampoo formulation of the present invention is selected from the group consisting of a shampoo and a conditioning shampoo.

[0013] Preferably, the shampoo formulation of the present invention, comprises: a dermatologically acceptable vehicle (preferably, 25 to 99.885 wt% (more preferably, 45 to 98.82 wt%; still more preferably, 79 to 97.15 wt%; most preferably, 84 to 94.4 wt%), based on weight of the shampoo formulation, of the dermatologically acceptable vehicle); a dermatologically acceptable silicone (preferably, 0.1 to 5 wt% (more preferably, 0.15 to 4 wt%; still more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of the dermatologically acceptable silicone); a dermatologically acceptable hair cleaning surfactant (preferably, 0.01 to 74.899 wt% (more preferably, 1 to 54.84 wt%; still more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of the dermatologically acceptable hair cleaning surfactant); and a deposition aid polymer (preferably, 0.005 to 5 wt% (more preferably, 0.03 to 2 wt%; still more preferably, 0.1 to 1 wt%; most preferably, 0.2 to 0.4 wt%), based on weight of the shampoo formulation, of the deposition aid polymer), wherein the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein X is a divalent linking group; wherein each R ² is independently selected from the group consisting of a C _M alkyl group; and wherein R ³ is a linear or branched Ci-i ₆ alkyl group; and (ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein Z is a divalent linking group; wherein a is 0 or 1; and wherein each R ⁵ is a linear or branched Ce-22 alkyl group (preferably, wherein the dextran base polymer has a weight average molecular weight of 1,000 to 3,000,000 Daltons) (preferably; wherein the deposition aid polymer enhances deposition of silicone from the shampoo formulation onto mammalian hair (preferably, human hair)).

[0014] Preferably, the shampoo formulation of the present invention is a liquid formulation. More preferably, the shampoo formulation of the present invention is an aqueous liquid formulation.

[0015] Preferably, the shampoo formulation of the present invention, comprises: 25 to 99.885 wt% (more preferably, 45 to 98.82 wt%; still more preferably, 79 to 97.15 wt%; most preferably, 84 to 94.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable vehicle. Still more preferably, the shampoo formulation of the present invention, comprises: 25 to 99.885 wt% (more preferably, 45 to 98.82 wt%; still more preferably, 79 to 97.15 wt%; most preferably, 84 to 94.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable vehicle; wherein the dermatologically acceptable vehicle comprises water. Yet more preferably, the shampoo formulation of the present invention, comprises: 25 to 99.885 wt% (more preferably, 45 to 98.82 wt%; still more preferably, 79 to 97.15 wt%; most preferably, 84 to 94.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable vehicle; wherein the dermatologically acceptable vehicle is selected from the group consisting of water and an aqueous Ci-4 alcohol mixture. Most preferably, the shampoo formulation of the present invention, comprises: 25 to 99.885 wt% (more preferably, 45 to 98.82 wt%; still more preferably, 79 to 97.15 wt%; most preferably, 84 to 94.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable vehicle; wherein the dermatologically acceptable vehicle is water. [0016] Preferably, the water used in the shampoo formulation of the present invention is at least one of distilled water and deionized water. More preferably, the water used in the shampoo formulation of the present invention is distilled and deionized.

[0017] Preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone (preferably, wherein the dermatologically acceptable silicone conditions hair). More preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone, wherein the dermatologically acceptable silicone is selected from the group consisting of amodimethicone, cyclomethicone, dimethicone, dimethiconol, hexadecyl methicone, hexamethyldisiloxane, bis-diisopropanol amino-PG-propyl disiloxane, methicone, phenyl dimethicone, bis-vinyl dimethicone, stearoxy dimethicone polyalkyl siloxane, polyalkylaryl siloxane, silicone gums (i.e., polydiorganosiloxanes having a weight average molecular weight of 200,000 to 1,000,000 Daltons), polyaminofunctional silicones (e.g., Dow Coming ^® 929) and mixtures thereof. Yet more preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone, wherein the dermatologically acceptable silicone is selected from the group consisting of amodimethicone, cyclomethicone, dimethicone, dimethiconol, hexadecyl methicone, hexamethyldisiloxane, methicone, phenyl dimethicone, stearoxy dimethicone and mixtures thereof. Still yet more preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone, wherein the dermatologically acceptable silicone is selected from the group consisting of amodimethicone, cyclomethicone, dimethicone, dimethiconol, hexadecyl methicone, methicone and mixtures thereof. Still more preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone, wherein the dermatologically acceptable silicone is selected from the group consisting of amodimethicone, dimethicone, dimethiconol and a mixture thereof. Most preferably, the shampoo formulation of the present invention comprises 0.1 to 5 wt% (preferably, 0.15 to 4 wt%; more preferably, 0.25 to 2 wt%; most preferably, 0.4 to 1.5 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone, wherein the dermatologically acceptable silicone comprises a dimethiconol.

[0018] Preferably, the shampoo formulation of the present invention comprises 0.01 to 74.899 wt% (preferably, 1 to 54.84 wt%; more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable hair cleaning surfactant. More preferably, the shampoo formulation of the present invention comprises 0.01 to 74.899 wt% (preferably, 1 to 54.84 wt%; more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable hair cleaning surfactant; wherein the dermatologically acceptable hair cleaning surfactant is selected from the group consisting of alkyl polyglucosides (e.g., lauryl glucoside, coco-glucoside, decyl glucoside), glycinates (e.g., sodium cocoyl glycinate), betaines (e.g., alkyl betaines such as cetyl betaine and ami do betaines such as cocamidopropyl betaine), taurates (e.g., sodium methyl cocoyl taurate), glutamates (e.g., sodium cocoyl glutamate), sarcosinates (e.g., sodium lauroyl sarcosinate), isethionates (e.g., sodium cocoyl isethionate, sodium lauroyl methyl isethionate), sulfoacetates (e.g., sodium lauryl sulfoacetate), alaninates (e.g., sodium cocoyl alaninate), amphoacetates (e.g., sodium cocoamphoacetate), sulfates (e.g., sodium lauryl ether sulfate (SLES)), sulfonates (e.g., sodium C14-16 olefin sulfonate), succinates (e.g., disodium lauryl sulfosuccinate), fatty alkanol amides (e.g., cocamide monoethanolamine, cocamide diethanolamine, soyamide diethanolamine, lauramide diethanolamine, oleamide monoisopropanolamine, stearamide monoethanolamine, myristamide monoethanolamine, lauramide monoethanolamine, capramide diethanolamine, ricinoleamide diethanolamine, myristamide diethanolamine, stearamide diethanolamine, oleylamide diethanolamine, tallowamide diethanolamine, lauramide monoisopropanolamine, tall o warn ide monoethanolamine, isostearamide diethanolamine, isostearamide monoethanolamine) and mixtures thereof. Still more preferably, the shampoo formulation of the present invention comprises 0.01 to 74.899 wt% (preferably, 1 to 54.84 wt%; more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable hair cleaning surfactant; wherein the dermatologically acceptable hair cleaning surfactant includes a sodium lauryl ether sulfate. Yet more preferably, the shampoo formulation of the present invention comprises 0.01 to 74.899 wt% (preferably, 1 to 54.84 wt%; more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable hair cleaning surfactant; wherein the dermatologically acceptable hair cleaning surfactant includes a sodium lauryl ether sulfate; wherein the sodium lauryl ether sulfate is selected from the group consisting of a sodium lauryl ether sulfate having an average of one -(OCH2CH2)- group per molecule, a sodium lauryl ether sulfate having an average of two -(OCH2CH2)- groups per molecule, a sodium lauryl ether sulfate having an average of three -(OCH2CH2)- groups per molecule and mixtures thereof (preferably, wherein the sodium lauryl ether sulfate is selected from the group consisting of a sodium lauryl ether sulfate having an average of two -(OCH2CH2)- groups per molecule, a sodium lauryl ether sulfate having an average of three -(OCH2CH2)- groups per molecule and mixtures thereof; more preferably, wherein the sodium lauryl ether sulfate is a sodium lauryl ether sulfate having an average of two -(OCH2CH2)- groups per molecule). Most preferably, the shampoo formulation of the present invention comprises 0.01 to 74.899 wt% (more preferably, 1 to 54.84 wt%; still more preferably, 2.5 to 20.65 wt%; most preferably, 5 to 15.4 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable hair cleaning surfactant; wherein the dermatologically acceptable hair cleaning surfactant includes a blend of a sodium lauryl ether sulfate, a cocamide monoethanolamine and a cocamidopropyl betaine (preferably, wherein the sodium lauryl ether sulfate is selected from the group consisting of a sodium lauryl ether sulfate having an average of one -(OCH2CH2)- group per molecule, a sodium lauryl ether sulfate having an average of two -(OCH2CH2)- groups per molecule, a sodium lauryl ether sulfate having an average of three -(OCH2CH2)- groups per molecule and mixtures thereof; more preferably, wherein the sodium lauryl ether sulfate is selected from the group consisting of a sodium lauryl ether sulfate having an average of two -(OCH2CH2)- groups per molecule, a sodium lauryl ether sulfate having an average of three -(OCH2CH2)- groups per molecule and mixtures thereof; most preferably, wherein the sodium lauryl ether sulfate has an average of two -(OCH2CH2)- groups per molecule).

[0019] Preferably, the shampoo formulation of the present invention comprises 0.005 to 5 wt% (more preferably, 0.03 to 2 wt%; still more preferably, 0.1 to 1 wt%; most preferably,

0.2 to 0.4 wt%), based on weight of the shampoo formulation, of a deposition aid polymer; wherein the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer; and (ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer; wherein the dextran base polymer has a weight average molecular weight of 1,000 to 3,000,000 Daltons. [0020] Preferably, the dextran base polymer has a weight average molecular weight of 1,000 to 3,000,000 Daltons (preferably, 50,000 to 2,000,000 Daltons; more preferably, 100,000 to 1,000,000 Daltons; still more preferably, 125,000 to 800,000 Daltons; most preferably, 145,000 to 525,000 Daltons). More preferably, the dextran base polymer has a weight average molecular weight of 1,000 to 3,000,000 Daltons (preferably, 50,000 to 2,000,000 Daltons; more preferably, 100,000 to 1,000,000 Daltons; still more preferably, 125,000 to 800,000 Daltons; most preferably, 145,000 to 525,000 Daltons); and the dextran base polymer is a branched chain dextran polymer comprising a plurality of glucose structural units; wherein 90 to 98 mol% (preferably, 92.5 to 97.5 mol%; more preferably, 93 to 97 mol%; most preferably, 94 to 96 mol%) of the glucose structural units are connected by a-D- 1,6 linkages and 2 to 10 mol% (preferably, 2.5 to 7.5 mol%; more preferably, 3 to 7 mol%; most preferably, 4 to 6 mol%) of the glucose structural units are connected by a- 1,3 linkages. Most preferably, the dextran base polymer has a weight average molecular weight of 1 ,000 to 3,000,000 Daltons (preferably, 50,000 to 2,000,000 Daltons; more preferably, 100,000 to 1,000,000 Daltons; still more preferably, 125,000 to 800,000 Daltons; most preferably, 145,000 to 525,000 Daltons); and the dextran base polymer is a branched chain dextran polymer comprising a plurality of glucose structural units; wherein 90 to 98 mol% (preferably, 92.5 to 97.5 mol%; more preferably, 93 to 97 mol%; most preferably, 94 to 96 mol%) of the glucose structural units are connected by a-D-1,6 linkages and 2 to 10 mol% (preferably, 2.5 to 7.5 mol%; more preferably, 3 to 7 mol%; most preferably, 4 to 6 mol%) of the glucose structural units are connected by a- 1,3 linkages according to formula I wherein R ¹ is selected from a hydrogen, a Ci-4 alkyl group and a hydroxy Ci-4 alkyl group; and wherein the average branch off the dextran polymer backbone is < 3 anhydroglucose units. [0021] Preferably, the dextran base polymer contains less than 0.01 wt%, based on weight of the dextran base polymer, of alternan. More preferably, the dextran base polymer contains less than 0.001 wt%, based on weight of the dextran base polymer, of alternan. Most preferably, the dextran base polymer contains less than the detectable limit of alternan.

[0022] Preferably, the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (II) bound to a pendent oxygen on the dextran base polymer

(ii) hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein X is a divalent linking group (preferably, wherein X is selected from divalent alkyl groups, which may optionally be substituted with a hydroxy group, an alkoxy group and/or an ether group; more preferably, wherein X is a -CH ₂ CH(OR ⁴ )CH ₂ - group, where R ⁴ is selected from the group consisting of a hydrogen and a linear or branched Ci- ₄ alkyl group; most preferably, wherein X is a -CH ₂ CH(OH)CH ₂ - group); wherein each R ² is independently selected from a linear or branched Ci- ₄ alkyl group (preferably, a linear or branched C _1-3 alkyl group; more preferably, a Ci - ₂ alkyl group; most preferably, a methyl group); wherein each R ³ is independently selected from a linear or branched C _1-16 alkyl group (preferably, a linear or branched Ci- ₁₂ alkyl group; more preferably, a linear or branched Ci-s alkyl group; still more preferably, a methyl group or a linear or branched Cx alkyl group; most preferably, a methyl group); wherein Z is a divalent linking group (preferably, wherein Z is selected from divalent alkyl groups, which may optionally be substituted with a hydroxy group, an alkoxy group and/or an ether group; more preferably, wherein Z is a -CH ₂ CH(0R ⁶ )CH ₂ 0- group, where R ⁶ is selected from the group consisting of a hydrogen and a linear or branched CM alkyl group; most preferably, wherein Z is a -CH ₂ CH(0H)CH ₂ 0- group); wherein a is a 0 or 1 (preferably, 0); and wherein each R ⁵ is a linear or branched O-22 alkyl group (preferably, a C 10-20 alkyl group; more preferably, a C12-18 alkyl group; most preferably, a C _½ alkyl group). More preferably, the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) quaternary ammonium groups of formula (Ila) bound to a pendent oxygen on the dextran base polymer

(ii) hydrophobic substituents of formula (Ilia), formula (Mb) or both, bound to a pendent oxygen on the dextran base polymer wherein pendent oxygen on the dextran base polymer; wherein R ⁴ is selected from the group consisting of a hydrogen and a linear or branched C1-4 alkyl group (preferably, R ⁴ is a hydrogen); wherein each R ² is independently selected from a linear or branched C alkyl group (preferably, a linear or branched C1-3 alkyl group; more preferably, a C1-2 alkyl group; most preferably, a methyl group); wherein each R ³ is independently selected from a linear or branched C1-16 alkyl group (preferably, a linear or branched Ci-12 alkyl group; more preferably, a linear or branched Ci-8 alkyl group; still more preferably, a methyl group or a linear or branched alkyl group; most preferably, a methyl group); wherein each R ⁵ is a linear or branched 0,-22 alkyl group (preferably, a Cio-20 alkyl group; more preferably, a C12-18 alkyl group; most preferably, a Ci6 alkyl group); and where R ⁶ is selected from the group consisting of a hydrogen and a linear or branched CM alkyl group (preferably, a hydrogen). Most preferably, the deposition aid polymer is a modified carbohydrate polymer, comprising a dextran base polymer functionalized with (i) a quaternary ammonium group of formula (Ila) bound to a pendent oxygen on the dextran base polymer; and (ii) hydrophobic substituents of formula (Ilia) bound to a pendent oxygen on the dextran base polymer; wherein each R ² is a methyl group; wherein each R ³ is a linear or branched Ci- ₁₂ alkyl group (preferably, a linear or branched Ci-8 alkyl group; most preferably, a methyl group or a linear or branched Cx alkyl group); wherein each R ⁴ is a hydrogen; and wherein each R ⁵ is a linear or branched ,- ₂₂ alkyl group (preferably, a Cio- ₂₀ alkyl group; more preferably, a C _12-18 alkyl group; most preferably, a Ci6 alkyl group).

[0023] Preferably, the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5 to 5.0 wt% (preferably, 0.7 to 4 wt%; more preferably, 0.8 to 2.5 wt%; most preferably, 1.4 to 2.0 wt%) measured using a Buchi KjelMaster K-375 automated analyzer, corrected for volatiles and ash measured as described in ASTM method D-2364.

[0024] Preferably, the deposition aid polymer has a hydrophobe degree of substitution, DS, of hydrophobic substituents of formula (III) bound to a pendent oxygen on the dextran base polymer of 0.0025 to 0.05 (preferably, 0.003 to 0.04; more preferably, 0.004 to 0.03).

[0025] Preferably, the deposition aid polymer comprises < 0.001 meq/gram (preferably, < 0.0001 meq/gram; more preferably, < 0.00001 meq/gram; most preferably, < detectable limit) of aldehyde functionality.

[0026] Preferably, the deposition aid polymer comprises < 0.1 % (preferably, < 0.01 %; more preferably, < 0.001 %; most preferably, < detectable limit), of the linkages between individual glucose units in the deposition aid polymer are b-1,4 linkages.

[0027] Preferably, the deposition aid polymer comprises < 0.1 % (preferably, < 0.01 %; more preferably, < 0.001 %; most preferably, < detectable limit), of the linkages between individual glucose units in the deposition aid polymer are b-1,3 linkages.

[0028] Preferably, the deposition aid polymer comprises < 0.001 meq/gram (preferably, < 0.0001 meq/gram; more preferably, < 0.00001 meq/gram; most preferably, < detectable limit) of silicone containing functionality.

[0029] Preferably, the shampoo formulation of the present invention, optionally, further comprises at least one additional ingredient selected from the group consisting of an antimicrobial agent/preservative (e.g., benzoic acid, sorbic acid, phenoxyethanol, methylisothiazolinone); a rheology modifier (e.g., PEG- 150 pentaerythrityl tetrastearate); a soap; a colorant; pH adjusting agent; an antioxidant (e.g., butylated hydroxy toluene); a humectant (e.g., glycerin, sorbitol, monoglycerides, lecithins, glycolipids, fatty alcohols, fatty acids, polysaccharides, sorbitan esters, polysorbates (e.g., Polysorbate 20, Polysorbate 40, Polysorbate 60, and Polysorbate 80), diols (e.g., propylene glycol), diol analogs, triols, triol analogs, cationic polymeric polyols); a wax; a foaming agent; an emulsifying agent; a colorant; a fragrance; a chelating agent (e.g., tetrasodium ethylene diamine tetraacetic acid); a preservative (e.g., benzoic acid, sorbic acid, phenoxy ethanol, methylisothiazolinone); a bleaching agent; a lubricating agent; a sensory modifier; a sunscreen additive; a vitamin; a protein/amino acid; a plant extract; a natural ingredient; a bioactive agent; an anti-aging agent; a pigment; an acid; a penetrant; an anti-static agent; an anti-frizz agent; an antidandruff agent; a hair waving/straightening agent; a hair styling agent; a hair oil; natural oils or ester emollients (e.g., mono-, di- and tri-glycerides such as sunflower seed oil, coconut oil, cottonseed oil, borage oil, borage seed oil, primrose oil, castor and hydrogenated castor oils, rice bran oil, soybean oil, olive oil, safflower oil, shea butter, jojoba oil and combinations thereof); an absorbent; a hard particle; a soft particle; a conditioning agent (e.g., guar hydroxypropyltrimonium chloride, PQ-10, PQ-7, PQ-67); a slip agent; an opacifier; a pearlizing agent and a salt. More preferably, the shampoo formulation of the present invention, optionally, further comprises at least one additional ingredient selected from the group consisting of an antimicrobial agent/preservative (e.g., benzoic acid, sorbic acid, phenoxy ethanol, methylisothiazolinone); a rheology modifier (e.g., PEG-150 pentaerythrityl tetrastearate); and a chelating agent (e.g., tetrasodium ethylene diamine tetraacetic acid).

Most preferably, the shampoo formulation of the present invention, optionally, further comprises at least one additional ingredient selected from the group consisting of an antimicrobial agent/preservative mixture of phenoxyethanol and methylisothiazolinone;

PEG- 150 pentaerythrityl tetrastearate; tetrasodium ethylene diamine tetraacetic acid and a mixture of phenoxyethanol and methylisothiazolinone.

[0030] Preferably, the shampoo formulation of the present invention further comprises a thickener. More preferably, the shampoo formulation further comprises a thickener, wherein the thickener is selected to increase the viscosity of the shampoo formulation, preferably without substantially modifying the other properties of the shampoo formulation. Preferably, the shampoo formulation further comprises a thickener, wherein the thickener is selected to increase the viscosity of the shampoo formulation, preferably without substantially modifying the other properties of the shampoo formulation and wherein the thickener accounts for 0 to 5.0 wt% (preferably, 0.1 to 5.0 wt %; more preferably, 0.2 to 2.5 wt %; most preferably, 0.5 to 2.0 wt%), based on weight of the shampoo formulation. [0031] Preferably, the shampoo formulation of the present invention further comprises an antimicrobial agent/preservative. More preferably, the shampoo formulation of the present invention further comprises an antimicrobial/preservative, wherein the antimicrobial/preservative is selected from the group consisting of phenoxyethanol, benzoic acid, benzyl alcohol, sodium benzoate, DMDM hydantoin, 2-ethylhexyl glyceryl ether, isothiazolinone (e.g., methylchloroisothiazolinone, methylisothiazolinone) and mixtures thereof. Still more preferably, the shampoo formulation of the present invention, further comprises an antimicrobial/preservative, wherein the antimicrobial/preservative is a mixture of phenoxyethanol and an isothiazolinone (more preferably, wherein the antimicrobial/preservative is a mixture of phenoxyethanol and methylisothiazolinone).

[0032] Preferably, the shampoo formulation of the present invention optionally further comprises a pH adjusting agent. More preferably, the shampoo formulation of the present invention, further comprises a pH adjusting agent, wherein the shampoo formulation has a pH of 4 to 9 (preferably, 4.25 to 8; more preferably, 4.5 to 7; most preferably, 4.75 to 6).

[0033] Preferably, the pH adjusting agent is selected from the group consisting of at least one of citric acid, lactic acid, hydrochloric acid, aminoethyl propanediol, triethanolamine, monoethanolamine, sodium hydroxide, potassium hydroxide, amino-2-methyl- 1 -propanol. More preferably, the pH adjusting agent is selected from the group consisting of at least one of citric acid, lactic acid, sodium hydroxide, potassium hydroxide, triethanolamine, amino-2-methyl- 1 -propanol. Still more preferably, the pH adjusting agent includes citric acid. Most preferably, the pH adjusting agent is citric acid.

[0034] Preferably, the method of depositing silicone onto mammalian hair (preferably human hair) of the present invention, comprises: selecting a shampoo formulation of the present invention and applying the shampoo formulation to mammalian hair; wherein the deposition aid polymer enhances the deposition of the dermatologically acceptable silicone from the shampoo formulation onto the mammalian hair relative to an otherwise identical formulation without the deposition aid polymer. More preferably, the method of depositing silicone on to mammalian hair (preferably human hair) of the present invention, comprises: selecting a shampoo formulation of the present invention, wetting the mammalian hair with water; applying the shampoo formulation to the wetted mammalian hair; and rinsing the shampoo formulation from the mammalian hair with water; wherein the deposition aid polymer enhances the deposition of the dermatologically acceptable silicone from the shampoo formulation onto the mammalian hair relative to an otherwise identical formulation without the deposition aid polymer. Most preferably, the method of depositing silicone on to mammalian hair (preferably human hair) of the present invention, comprises: selecting a shampoo formulation of the present invention, wetting the mammalian hair with water; applying the shampoo formulation to the wetted mammalian hair; and rinsing the shampoo formulation from the mammalian hair with water; wherein dermatologically acceptable silicone present in the shampoo formulation is deposited onto the mammalian hair; and wherein the deposition aid polymer enhances the deposition of the dermatologically acceptable silicone from the shampoo formulation onto the mammalian hair relative to an otherwise identical formulation without the deposition aid polymer.

[0035] Some embodiments of the present invention will now be described in detail in the following Examples.

Synthesis SI: Synthesis of Cationic Hexadecyl Modified Dextran Polymer [0036] A 500 mL, four necked, round bottom flask fitted with a rubber serum cap, a nitrogen inlet, a pressure equalizing addition funnel, a stirring paddle and motor, a subsurface thermocouple connected to a J-KEM controller and a Friedrich condenser connected to a mineral oil bubbler was charged with dextran base polymer (20 g; Sigma Aldrich catalog No. D4876) and deionized water (100 g). The contents of the flask were stirred at 70 rpm. While stirring, the head space in the flask was purged with a slow, steady flow of nitrogen (about one bubble per second) for one hour to remove any entrained oxygen in the apparatus. A 50% aqueous sodium hydroxide solution (5.0 g) was then added to the flask contents using a syringe over 2 minutes with continued stirring. After 30 minutes, hexadecyl bromide (15.3 g) was added to the flask contents using a syringe. The addition funnel was charged with 2,3-epoxypropyltrimethylammonium chloride (17.0 g; QUAB ^® 151 available from SKW QUAB Chemicals), which was then added dropwise to the flask contents over 3 minutes with continued stirring. The flask contents were stirred under nitrogen for an additional 10 minutes, and then heat was applied with a set point temperature of 70 °C using a heating mantle. With continued stirring the flask contents were heated at 70 °C for 3 hours.

[0037] The flask contents were then cooled in a water bath while maintaining a positive nitrogen pressure in the flask. A solid polymer product was recovered from the flask contents by non-solvent precipitation in methanol; roughly 1 L of methanol was used for the precipitation of the entire batch. The methanol was decanted off and the polymer recovered was placed in a dish to be dried in vacuo at 50 °C. The dried polymer was manually ground with a mortar and pestle, and screened through a US standard #30 sieve. [0038] The product polymer was obtained as a white solid, with a volatiles content of 4.07%, and ash content (as sodium chloride) of 2.07%, and a Kjeldahl nitrogen content (corrected for ash and volatiles) of 1.507%, corresponding to a cationic substitution, CS, value of 0.217.

Synthesis S2: Synthesis of Cationic Dodecyl Modified Dextran Polymer [0039] In Synthesis S2, cationic dodecyl modified dextran polymer was prepared substantially as described in Synthesis SI but with varying reagent feeds as noted in TABLE 1. The degree of cationic substitution, CS, of the QUAB ^® 151 and the degree of hydrophobic substitution, DS, of dodecyl groups onto the dextran base polymer is reported in TABLE 2. The total Kjeldahl nitrogen, TKN, in the product cationic hexadecyl modified dextran polymers is also reported in TABLE 2.

Synthesis S3: Synthesis of Cationic Dextran Polymer [0040] A 500 mL, four necked, round bottom flask fitted with a rubber serum cap, a nitrogen inlet, a pressure equalizing addition funnel, a stirring paddle and motor, a subsurface thermocouple connected to a J-KEM controller and a Friedrich condenser connected to a mineral oil bubbler was charged with dextran base polymer (28.62 g; Sigma Aldrich catalog No. D4876) and deionized water (103.68 g). The contents of the flask were stirred at 70 rpm. While stirring, the head space in the flask was purged with a slow, steady flow of nitrogen (about one bubble per second) for one hour to remove any entrained oxygen in the apparatus. [0041] The addition funnel was charged with a 70% aqueous solution of 2,3-epoxypropyltrimethylammonium chloride (27.42 g; QUAB ^® 151 available from SKW QUAB Chemicals).

[0042] While stirring the flask contents under nitrogen, a 25% aqueous sodium hydroxide solution (5.36 g) was added to the flask contents over 1 minutes. The flask contents were then continually stirred for thirty minutes before adding the contents of the addition funnel to the flask contents dropwise over 5 minutes. The flask contents were then stirred for 5 minutes before heating the flask contents using a heating mantle with a set point temperature of 55 °C for 1.5 hours.

[0043] The flask contents were then cooled in an ice water bath while maintaining a positive nitrogen pressure in the flask. The flask contents were then neutralized by adding glacial acetic acid (3.80 g) to the flask contents. The flask contents were then stirred for 10 minutes under nitrogen. A polymer product was then recovered from the flask contents by non solvent precipitation in methanol; roughly 700 mL of methanol was used. The methanol was then decanted off and the polymer product was placed in a dish and dried in vacuo at 50 °C overnight.

[0044] The polymer product recovered was sieved through a 30 mesh screen and obtained as a free-flowing white solid (25.89 g) with a volatiles content of 3.42% and an ash content (as sodium acetate) of 0.70%. The total Kjeldahl nitrogen (corrected for ash and volatiles) in the polymer product was determined to be 1.794 wt%, which corresponds to a trimethylammonium degree of substitution of 0.257.

TABLE 1

TABLE 2

Comparative Example CF1 and Examples F1-F2: Shampoo Formulations [0045] A shampoo formulation was prepared in each of Comparative Example CF1 and Examples F1-F2 having the formulation noted in TABLE 3. Specifically, the shampoo formulations were prepared in each of Comparative Examples CF1 and Examples F1-F2 using the following process: In a container, the 30 wt% aqueous solution of sodium lauryl sulfate was dissolved in 20 g of deionized water and heated to 70 °C with constant stirring. The polymer noted in TABLE 3 was then added to the container with stirring (e.g., inventive cationic hydrophobically modified dextran prepared according to Synthesis S1-S2, or comparative cationic dextran prepared according to Synthesis S3). When the polymer was dissolved, the tetrasodium EDTA was then added to the container. Once the container contents reached 70 °C, the 45 wt% aqueous solution a portion of the PEG-150 pentaerythrityl tetrastearate and the 30 wt% aqueous solution of cocamide MEA were added to the container. Then, the 30 wt% solution of cocamidopropyl betaine was added to the container. The contents of the container were then allowed to cool. Once at room temperature, the phenoxyethanol and methylisothiazolinone preservative and the 50 wt% solids aqueous emulsion of dimethiconol and TEA-dodecylbenzenesulfonate were added to the container. The final pH of the product shampoo formulation was then adjusted to a pH of 5 using sodium hydroxide or citric acid as necessary and sufficient water was added to adjust the total formulation weight to 100 g. Additional PEG- 150 pentaerythrityl tetrastearate was added to adjust the final formulation viscosity to 11,000 cP Brookfield viscosity measured using a number 6 spindle at 30 rpm under laboratory conditions.

TABT.F. 3 _

Silicone Deposition Analysis

[0046] The silicone deposition on hair from the shampoo formulations prepared according to Comparative Example CF1 and Examples F1-F2 was quantified using X-ray photoelectron spectroscopy (XPS), which gives a quantitative elemental and chemical state information from the top 10 nm of the hair sample.

[0047] Hair tresses (2 g, European Virgin Brown, VB, or Bleached, B, available from International Hair Importers) were initially washed in a 9 wt% sodium lauryl sulfate solution and rinsed with water flowing at 0.4 L/min for 30 seconds. Following the initial wash step, the hair tresses were then washed with a shampoo formulation of Comparative Example CF1 and Examples F1-F2 by applying 0.8 g of the shampoo formulation to the hair tress and massaging in for 30 seconds on each side and then rinsing with water flowing at 0.4 L/min for 15 seconds on each side. The hair tresses were then evaluated using XPS. The XPS data were acquired from four areas per tress across a 1 cm ² by 3 mm hair bundle. The instrument parameters used are provided in TABLE 4. The mol% of the silicon from the shampoo formulation deposited on the hair is reported in TABLE 5. TABLE 4

TABLE 5