Personal care rinse-off formulation

Abstract

There is provided an aqueous personal care rinse-off formulation, the aqueous personal care rinse-off formulation comprising: a dermatologically acceptable vehicle; a dermatologically acceptable cleansing surfactant; and a gradient polymer comprising: 5%-35% by weight of structural units of (meth) acrylic acid; 35 wt% to 65 wt% of a structural unit of C1-8 alkyl (meth) acrylate; gt; 10% to 30% by weight of structural units of a dedicated associative monomer having structure I wherein R1 is a linear saturated C12-26 alkyl group; wherein R2 is hydrogen or a methyl group, and wherein n is from 10 to 30; 0.01 wt% to 2 wt% of a structural unit of a polyethylenically unsaturated monomer; wherein the gradient polymer comprises lt; 0.05% by weight of structural units of sulfonated monomers; wherein the polymer comprises lt; 0.02% by weight of structural units of a monomer having structure II wherein R3 is-H or-CH3; r4 is-H or a-C1-4 alkyl group; r5 is a-C1-4 alkyl group; a is 0 to 50; b is 0 to 20; c is 0 to 50; a + c is 1 to 100 and d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

Description

[0001] The present invention relates to an aqueous personal care rinse-off formulation. Specifically, the present invention relates to an aqueous personal care rinse-off formulation comprising: a dermatologically acceptable vehicle; a dermatologically acceptable cleansing surfactant; and a gradient polymer comprising: (a) 5 wt% to 35 wt% of structural units of (meth)acrylic acid based on the dry weight of the gradient polymer; (b) 35 wt% to 65 wt% of structural units of (meth)acrylic acid C 1-8 alkyl ester; (c) >10 wt% to 30 wt% of structural units of a dedicated associative monomer of Structure I

[0002]

[0003] wherein each R 1 is independently selected from the group consisting of linear saturated C 12-26 alkyl groups; wherein each R 2 is independently selected from the group consisting of hydrogen and methyl groups, and wherein n is 10 to 30; and (d) 0.01 wt% to 2 wt% of structural units of a multi-ethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises <0.05 wt% of structural units of a sulfonated monomer based on the dry weight of the gradient polymer; wherein the polymer comprises <0.02 wt% of structural units of a monomer of Structure II based on the dry weight of the gradient polymer

[0004]

[0005] wherein each R 3 is independently selected from the group consisting of -H and -CH3; wherein each R 4 is independently selected from the group consisting of -H and -C 1-4 alkyl groups; wherein each R 5 is independently selected from the group consisting of -C 1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

[0006] Amino acid based surfactants have a range of desirable properties for personal care rinse-off formulations, such as shampoos, body washes. Such surfactants are typically of natural origin and are readily biodegradable. They are very mild and cause less irritation to the skin and hair compared to more traditional sulfate and sulfonate based surfactants such as sodium lauryl sulfate and sodium lauryl ether sulfate. They tend to exhibit lower toxicity and reduced negative impact on the environment compared to more traditional sulfate and sulfonate based surfactants. They have good cleansing and foaming performance.

[0007] Nevertheless, formulations containing amino acid-based surfactants present challenges for effective thickening. Some conventional thickeners achieve their target viscosity at high usage levels, which can adversely affect foaming properties. In other cases, conventional thickeners provide sufficient thickening, but the formulation viscosity is sensitive to temperature changes; it becomes watery at high temperatures and gel-like at low temperatures. Some conventional thickeners, such as xanthan gum or cellulose esters, exhibit potential compatibility issues, leading to phase separation.

[0008] Therefore, viscosity modifiers remain in demand for aqueous personal care wash-off formulations that can achieve increased viscosity at low shear rates while maintaining the required flowability at higher shear rates, particularly for aqueous personal care wash-off formulations containing amino acid surfactants (e.g., shampoos, shower gels).

[0009] This invention provides an aqueous personal care wash-off formulation comprising: a dermatologically acceptable carrier; a dermatologically acceptable cleansing surfactant; and a gradient polymer comprising: (a) 5% to 35% by weight (meth)acrylic acid structural units based on the dry weight of the gradient polymer; and (b) 35% to 65% by weight (meth)acrylic acid C based on the dry weight of the gradient polymer. 1-8 (c) Structural units of alkyl esters; (d) Structural units of dedicated associative monomers having structure I, ranging from >10% to 30% by weight.

[0010]

[0011] Each R 1 Independently selected from straight-chain saturated C 12-26 alkyl groups; wherein each R 2 The components are independently selected from hydrogen and methyl groups, and where n is 10 to 30; and (d) 0.01 wt% to 2 wt% of the structural units of the polyene-bonded unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer contains <0.05 wt% of the structural units of the sulfonated monomer based on the dry weight of the gradient polymer; wherein the polymer contains <0.02 wt% of the structural units of the monomer having structure II based on the dry weight of the gradient polymer.

[0012]

[0013] Each R 3 Independently selected from -H and -CH3; where each R 4 Independently selected from -H and -C 1-4 alkyl groups; wherein each R 5 Independently selected from -C1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

[0014] The present application provides an aqueous personal care rinse-off formulation comprising: a dermatologically acceptable vehicle; a dermatologically acceptable cleansing surfactant; and a gradient polymer comprising: (a) 5 wt% to 35 wt% of structural units of (meth)acrylic acid based on the dry weight of the gradient polymer; (b) 35 wt% to 65 wt% of structural units of (meth)acrylic acid C 1-8 alkyl ester; (c) >10 wt% to 30 wt% of structural units of a dedicated associative monomer having Structure I, wherein the structural monomer units of the dedicated associative monomer having Structure I are a blend of: a first dedicated associative monomer having Structure la

[0015]

[0016] wherein each R 1a is independently selected from the group consisting of linear saturated C 12-19 alkyl groups; wherein each R 2a is independently selected from the group consisting of hydrogen and methyl groups, and wherein na is 10 to 30; and a second dedicated associative monomer having Structure lb

[0017]

[0018] wherein each R 1b is independently selected from the group consisting of linear saturated C 20-26 alkyl groups; wherein each R 2b is independently selected from the group consisting of linear saturated hydrogen and methyl groups, and wherein nb is 10 to 30; and (d) 0.01 wt% to 2 wt% of structural units of a multiethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises <0.05 wt% of structural units of a sulfonated monomer based on the dry weight of the gradient polymer; wherein the polymer comprises <0.02 wt% of structural units of a monomer having Structure II based on the dry weight of the gradient polymer

[0019]

[0020] wherein each R 3 is independently selected from the group consisting of -H and -CH3; wherein each R 4 is independently selected from the group consisting of -H and -C 1-4 alkyl groups; wherein each R 5 is independently selected from the group consisting of -1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

[0021] The present invention provides a method of cleansing at least one of mammalian skin and hair, the method comprising: applying to the skin or hair of a mammal an aqueous personal care rinse-off formulation of the present invention; and rinsing the aqueous personal care rinse-off formulation from the skin or hair with a rinse water. DETAILED DESCRIPTION

[0022] We have surprisingly found that gradient polymers as described herein are beneficial for the formulation of aqueous personal care rinse-off cleansing products, particularly aqueous personal care rinse-off cleansing products containing amino acid surfactants (e.g., shampoos, body washes), to increase viscosity at low shear rates while maintaining the flow properties of the product at higher shear rates.

[0023] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

[0024] The percentage of monomer units in a polymer is the percentage of the weight of the solid or pure monomer, i.e., excluding any water present in the polymer emulsion.

[0025] As used herein and in the appended claims, the term "structural monomer unit" refers to the residue of the indicated monomer; thus showing the structural monomer unit of ethyl acrylate:

[0026]

[0027] wherein the dotted line indicates the point of attachment to the polymer backbone.

[0028] As used herein and in the appended claims, the term "(meth)acrylic acid" is intended to be used as a general expression covering both acrylic acid and methacrylic acid.

[0029] As used herein and in the appended claims, the term "(meth)acrylate" is intended to be used as a general expression covering both acrylate and methacrylate.

[0030] As used herein and in the appended claims, the term "gradient polymer morphology" refers to a polymer having a continuously varying monomer composition content. The preparation of gradient polymers having a gradient polymer morphology is well known in the art. U.S. Patent 3,804,881, hereby incorporated by reference in its entirety, discloses a process for preparing a gradient polymer having a gradient polymer morphology, wherein the process comprises polymerizing at least one primary polymerizable monomer feed having a varying composition by continuously adding at least one different secondary polymerizable monomer feed to the at least one primary polymerizable monomer feed.

[0031] The term "dermatologically acceptable" as used herein and in the appended claims refers to ingredients that are generally used for topical application to the skin and is intended to emphasize that toxic substances are not contemplated as part of the present application when present in the amounts typically found in skin care compositions.

[0032] Preferably, the aqueous personal care rinse-off formulation of the present application is selected from the group consisting of shampoo, conditioning shampoo, body wash, exfoliating body wash, facial cleanser, exfoliating facial cleanser, and liquid hand soap. More preferably, the aqueous personal care rinse-off formulation of the present application is selected from the group consisting of shampoo, conditioning shampoo, body wash, facial cleanser, and liquid hand soap. Most preferably, the aqueous personal care rinse-off formulation of the present application is selected from the group consisting of shampoo and conditioning shampoo.

[0033] Preferably, the aqueous personal care rinse-off formulations of the present application comprise: a dermatologically acceptable vehicle (preferably, wherein the aqueous personal care rinse-off formulation comprises 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of the dermatologically acceptable vehicle based on the weight of the aqueous personal care rinse-off formulation); a dermatologically acceptable cleansing surfactant (preferably, wherein the aqueous personal care rinse-off formulation comprises 1% to 60% by weight (preferably, 5% to 57.5% by weight; more preferably, 25% to 55% by weight; most preferably, 30% to 52.5% by weight) of the dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation) (preferably, wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant); and a gradient polymer (preferably, wherein the aqueous personal care rinse-off formulation comprises 0.1% to 15% by weight (preferably, 0.5% to 10% by weight; more preferably, 0.75% to 5% by weight; most preferably, 1% to 2.5% by weight) of the gradient polymer based on the weight of the aqueous personal care rinse-off formulation), the gradient polymer comprising: (a) 5% to 35% by weight (preferably, 10% to 35% by weight; more preferably, 20% to 34% by weight; most preferably, 26% to 32% by weight) of structural monomer units of (meth)acrylic acid monomers based on the dry weight of the gradient polymer; (b) 35% to 65% by weight (preferably, 40% to 60% by weight; more preferably, 45% to 55% by weight; most preferably, 48% to 54% by weight) of structural monomer units of (meth)acrylic acid C 1-8 alkyl ester monomers based on the dry weight of the gradient polymer; (c) >10% to 30% by weight (preferably, 12% to 30% by weight; more preferably, 15% to 25% by weight; most preferably, 16% to 20% by weight) of structural monomer units of special-purpose associative monomers having Structure I

[0034]

[0035] wherein each R 1 is independently selected from linear saturated C 12-26 alkyl groups (preferably, C 12-24 alkyl groups; more preferably, C 14-24 alkyl groups; most preferably, C 16-22 alkyl groups); wherein each R 2 is independently selected from hydrogen and methyl groups (preferably, wherein R 2is a methyl group), and wherein n is 10 to 30 (preferably, 12 to 30; more preferably, 15 to 28; most preferably, 18 to 26); and (d) 0.01 wt% to 2 wt% (preferably, 0.05 wt% to 1 wt%; more preferably, 0.08 wt% to 0.5 wt%; most preferably, 0.1 wt% to 0.2 wt%) of structural monomer units of a multiethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.05 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a sulfonated monomer (e.g., AMPS) based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.02 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a monomer having structure II based on the dry weight of the gradient polymer

[0036]

[0037] wherein each R 3 is independently selected from the group consisting of -H and -CH3; wherein each R 4 is independently selected from the group consisting of -H and -C 1-4 alkyl group; wherein each R 5 is independently selected from the group consisting of -C 1-4alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100, and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology. More preferably, the aqueous personal care rinse-off formulation of the present application comprises: a dermatologically acceptable vehicle (preferably, wherein the aqueous personal care rinse-off formulation comprises 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of the dermatologically acceptable vehicle based on the weight of the aqueous personal care rinse-off formulation); a dermatologically acceptable cleansing surfactant (preferably, wherein the aqueous personal care rinse-off formulation comprises 1% to 60% by weight (preferably, 5% to 57.5% by weight; more preferably, 25% to 55% by weight; most preferably, 30% to 52.5% by weight) of the dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation) (preferably, wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant); and a gradient polymer (preferably, wherein the aqueous personal care rinse-off formulation comprises 0.1% to 15% by weight (preferably, 0.5% to 10% by weight; more preferably, 0.75% to 5% by weight; most preferably, 1% to 2.5% by weight) of the gradient polymer based on the weight of the aqueous personal care rinse-off formulation), the gradient polymer comprising: (a) 5% to 35% by weight (preferably, 10% to 35% by weight; more preferably, 20% to 34% by weight; most preferably, 26% to 32% by weight) of structural monomer units of (meth)acrylic monomers based on the dry weight of the gradient polymer; (b) 35% to 65% by weight (preferably, 40% to 60% by weight; more preferably, 45% to 55% by weight; most preferably, 48% to 54% by weight) of structural monomer units of (meth)acrylic C 1-8 alkyl ester monomers based on the dry weight of the gradient polymer; (c) >10% to 30% by weight (preferably, 12% to 30% by weight; more preferably, 15% to 25% by weight; most preferably, 16% to 20% by weight) of structural monomer units of a dedicated associative monomer having Structure I; wherein the dedicated associative monomer having Structure I is a blend of: a first dedicated associative monomer having Structure la (preferably, 51% to 99% by weight; more preferably, 75% to 97% by weight; most preferably, 85% to 95% by weight of the first dedicated associative monomer having Structure la based on the weight of the dedicated associative monomer having Structure I)

[0038]

[0039] Each R 1a Independently selected from straight-chain saturated C 12-19 Alkyl groups (preferably, straight-chain saturated C4 groups) 12-18 Alkyl groups; more preferably, straight-chain saturated C 14-18 Alkyl groups; most preferably, straight-chain saturated C 16-18 alkyl groups); wherein each R 2a Independently selected from hydrogen and methyl groups (preferably, wherein R 2 (is a methyl group), and wherein na is 10 to 30 (preferably 12 to 30; more preferably 15 to 28; most preferably 18 to 26); and a second dedicated associating monomer having structure Ib (preferably 1% to 49% by weight; more preferably 3% to 25% by weight; most preferably 6% to 15% by weight of the first dedicated associating monomer having structure Ib, based on the weight of the dedicated associating monomer having structure I).

[0040]

[0041] Each R 1b Independently selected from straight-chain saturated C 20-26 Alkyl groups (preferably, straight-chain saturated C4 groups) 20-24 Alkyl groups; more preferably, straight-chain saturated C 21-23 Alkyl groups; most preferably, straight-chain saturated C 22 alkyl groups); wherein each R 2b The structural monomer unit of the polyene-bonded unsaturated monomer is independently selected from straight-chain saturated hydrogen and methyl groups (preferably methyl groups), and wherein nb is 10 to 30 (preferably 15 to 30; more preferably 18 to 28; most preferably 20 to 28) based on the dry weight of the gradient polymer; and (d) 0.01 wt% to 2 wt% (preferably 0.05 wt% to 1 wt%; more preferably 0.08 wt% to 0.5 wt%; most preferably 0.1 wt% to 0.2 wt%) of the gradient polymer; wherein the gradient polymer comprises <0 wt% of the polyene-bonded unsaturated monomer based on the dry weight of the gradient polymer. 0.05 wt% (preferably, <0.01 wt%; more preferably, <0.001 wt%; still more preferably, <0.0001 wt%; most preferably, less than the detectable limit) of sulfonated monomers (e.g., AMPS) structural monomer units; wherein the gradient polymer comprises <0.02 wt% (preferably, <0.01 wt%; more preferably, <0.001 wt%; still more preferably, <0.0001 wt%; most preferably, less than the detectable limit) of structural monomer units of a monomer having structure II based on the dry weight of the gradient polymer, wherein each R 3 Independently selected from -H and -CH3; where each R 4independently selected from -H and -C 1-4 alkyl groups; wherein each R 5 independently selected from -C 1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100, and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

[0042] Preferably, the aqueous personal care wash-off formulation of the present application comprises 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of a dermatologically acceptable vehicle based on the weight of the aqueous personal care wash-off formulation. More preferably, the aqueous personal care wash-off formulation of the present application comprises: 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of a dermatologically acceptable vehicle based on the weight of the aqueous personal care wash-off formulation; wherein the dermatologically acceptable vehicle comprises water. Still more preferably, the aqueous personal care wash-off formulation of the present application comprises: 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of a dermatologically acceptable vehicle based on the weight of the aqueous personal care wash-off formulation; wherein the dermatologically acceptable vehicle is selected from the group consisting of: water and an aqueous C 1-4 alcohol mixture. Most preferably, the aqueous personal care wash-off formulation of the present application comprises: 25% to 98.9% by weight (preferably, 30% to 94.5% by weight; more preferably, 40% to 74.5% by weight; most preferably, 45% to 69% by weight) of a dermatologically acceptable vehicle based on the weight of the aqueous personal care wash-off formulation; wherein the dermatologically acceptable vehicle is water.

[0043] Preferably, the water used in the aqueous personal care wash-off formulation of the present application is at least one of distilled water and deionized water. More preferably, the water used in the aqueous personal care wash-off formulation of the present application is both distilled and deionized.

[0044] Preferably, the aqueous personal care rinse-off formulation of the present application comprises from 1% to 60% by weight (preferably, from 5% to 57.5%; more preferably, from 25% to 55%; most preferably, from 30% to 52.5%) of a dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation. More preferably, the aqueous personal care rinse-off formulation of the present application comprises from 1% to 60% by weight (preferably, from 5% to 57.5%; more preferably, from 25% to 55%; most preferably, from 30% to 52.5%) of a dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation; wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant. Still more preferably, the aqueous personal care rinse-off formulation of the present application comprises from 1% to 60% by weight (preferably, from 5% to 57.5%; more preferably, from 25% to 55%; most preferably, from 30% to 52.5%) of a dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation; wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant selected from the group consisting of salts of alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, valine, sarcosine, and mixtures thereof.Yet more preferably, the aqueous personal care rinse-off formulation of the present application comprises from 1% to 60% by weight (preferably, from 5% to 57.5% by weight; more preferably, from 25% to 55% by weight; most preferably, from 30% to 52.5% by weight) of a dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation; wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant selected from the group consisting of dipotassium capryloyl glutamate, dipotassium undecylenoyl glutamate, disodium capryloyl glutamate, disodium cocoyl glutamate, disodium lauroyl glutamate, disodium stearoyl glutamate, disodium undecylenoyl glutamate, potassium capryloyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, potassium myristoyl glutamate, potassium stearoyl glutamate, potassium undecylenoyl glutamate, sodium capryloyl glutamate, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium olivoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, sodium undecylenoyl glutamate, cocoyl methyl beta-alaninate, lauroyl beta-alaninate, lauroyl methyl beta-alaninate, myristoyl beta-alaninate, potassium lauroyl methyl beta-alaninate, sodium cocoyl alaninate, sodium cocoyl methyl beta-alaninate, and sodium myristoyl methyl beta-alaninate, palmitoyl glycinate, sodium lauroyl glycinate, sodium cocoyl glycinate, sodium myristoyl glycinate, potassium lauroyl glycinate, potassium cocoyl glycinate, potassium lauroyl sarcosinate, potassium cocoyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, sodium palmitoyl sarcosinate, lauroyl ammonium sarcosinate, sodium lauroyl aspartate, sodium myristoyl aspartate, sodium cocoyl aspartate, sodium caproyl aspartate, disodium lauroyl aspartate, disodium myristoyl aspartate, disodium cocoyl aspartate, disodium caproyl aspartate, potassium lauroyl aspartate, potassium myristoyl aspartate, potassium cocoyl aspartate, potassium caproyl aspartate, dipotassium lauroyl aspartate, dipotassium myristoyl aspartate, dipotassium cocoyl aspartate, dipotassium caproyl aspartate, and mixtures thereof. Most preferably, the aqueous personal care rinse-off formulation of the present application comprises from 1% to 60% by weight (preferably, from 5% to 57.5% by weight; more preferably, from 25% to 55% by weight; most preferably, from 30% to 52.5% by weight) of a dermatologically acceptable cleansing surfactant based on the weight of the aqueous personal care rinse-off formulation; wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant selected from the group consisting of sodium cocoyl glutamate, sodium cocoyl alaninate, sodium cocoyl glycinate, sodium lauroyl sarcosinate, and mixtures thereof.

[0045] Preferably, the dermatologically acceptable cleansing surfactant comprises a mixture of an amino acid surfactant and a non-amino acid surfactant. More preferably, the dermatologically acceptable cleansing surfactant comprises a mixture of an amino acid surfactant and a non-amino acid surfactant; wherein the amino acid surfactant is selected from the group consisting of salts of alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, valine, sarcosine, and mixtures thereof; and wherein the non-amino acid surfactant is selected from the group consisting of alkyl polyglycosides (e.g., coco-glucoside, alkyl xyloside); amine-based surfactants (e.g., stearamidopropyl dimethylamine); amphoacetates (e.g., sodium cocoamphoacetate); betaines (e.g., alkyl betaines such as cetyl betaine and amido betaines such as cocamidopropyl betaine); carboxylates (e.g., sodium lauryl glucose carboxylate); fatty alcohols (e.g., cetearyl alcohol, stearyl alcohol, cetyl alcohol, lauryl alcohol); fatty alkylolamides (e.g., cocamide monoethanolamide, cocamide diethanolamide, soya amide diethanolamide, lauramide diethanolamide, oleamide monoiso-propanolamide, stearamide monoethanolamide, myristamide monoethanolamide, lauramide monoethanolamide, capricamide diethanolamide, ricinoleamide diethanolamide, myristamide diethanolamide, stearamide diethanolamide, oleamide diethanolamide, tallowamide diethanolamide, lauramide monoiso-propanolamide, tallowamide monoethanolamide, isostearamide diethanolamide, isostearamide monoethanolamide); isethionates (e.g., sodium coco- isethionate, sodium lauroyl methyl isethionate); quaternary ammonium compounds (e.g., behentrimonium chloride, cetyltrimethylammonium chloride); succinates (e.g., disodium lauryl sulfosuccinate); sulfates (e.g., sodium lauryl ether sulfate (SLES)); sulfoacetates (e.g., sodium lauryl sulfoacetate); sulfonates (e.g., C 14-16sodium methyl cocoyl taurate, and mixtures thereof. Yet more preferably, the dermatologically acceptable cleansing surfactant comprises a mixture of an amino acid surfactant and a non-amino acid surfactant; wherein the amino acid surfactant is selected from the group consisting of dipotassium capryloyl glutamate, dipotassium undecylenoyl glutamate, disodium capryloyl glutamate, disodium cocoyl glutamate, disodium lauroyl glutamate, disodium stearoyl glutamate, disodium undecylenoyl glutamate, potassium capryloyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, potassium myristoyl glutamate, potassium stearoyl glutamate, potassium undecylenoyl glutamate, sodium capryloyl glutamate, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium olivoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, sodium undecylenoyl glutamate, cocoyl methyl beta-alanine, lauroyl beta-alanine, lauroyl methyl beta-alanine, myristoyl beta-alanine, lauroyl methyl beta-alanine potassium, cocoyl alanine sodium, cocoyl methyl beta-alanine sodium, and myristoyl methyl beta-alanine sodium palmitoyl glycinate, lauryl glycinate sodium, cocoyl glycinate sodium, myristoyl glycinate sodium, lauryl glycinate potassium, cocoyl glycinate potassium, lauroyl sarcosinate potassium, cocoyl sarcosinate potassium, cocoyl sarcosinate sodium, lauroyl sarcosinate sodium, myristoyl sarcosinate sodium, oleyl sarcosinate sodium, palmitoyl sarcosinate sodium, lauroyl sarcosinate ammonium, lauroyl aspartate sodium, myristoyl aspartate sodium, cocoyl aspartate sodium, caproyl aspartate sodium, lauroyl aspartate disodium, myristoyl aspartate disodium, cocoyl aspartate disodium, caproyl aspartate disodium, lauroyl aspartate potassium, myristoyl aspartate potassium, cocoyl aspartate potassium, caproyl aspartate potassium, lauroyl aspartate dipotassium, myristoyl aspartate dipotassium, cocoyl aspartate dipotassium, caproyl aspartate dipotassium, and mixtures thereof; and wherein the non-amino acid surfactant is selected from the group consisting of alkyl polyglycosides (e.g., coco-glucoside, alkyl xyloside); betaines (e.g., alkyl betaines such as cetyl betaine and amido betaines such as cocamidopropyl betaine), and mixtures thereof. Most preferably, the dermatologically acceptable cleansing surfactant comprises a mixture of an amino acid surfactant and a non-amino acid surfactant; wherein the amino acid surfactant is selected from the group consisting of sodium cocoyl glutamate, sodium cocoyl alaninate, sodium cocoyl glycinate, sodium lauroyl sarcosinate, and mixtures thereof; and wherein the non-amino acid surfactant is selected from the group consisting of coco-glucoside, cocamidopropyl betaine, and mixtures thereof.

[0046] Preferably, the aqueous personal care rinse-off formulations of the present application comprise from 0.1 wt% to 15 wt% (preferably, from 0.5 wt% to 10 wt%; more preferably, from 0.75 wt% to 5 wt%; most preferably, from 1 wt% to 2.5 wt%) of a gradient polymer based on the weight of the aqueous personal care rinse-off formulation; wherein the gradient polymer comprises: (a) from 5 wt% to 35 wt% (preferably, from 10 wt% to 35 wt%; more preferably, from 20 wt% to 34 wt%; most preferably, from 26 wt% to 32 wt%) of structural monomer units of (meth)acrylic monomers based on the dry weight of the gradient polymer; (b) from 35 wt% to 65 wt% (preferably, from 40 wt% to 60 wt%; more preferably, from 45 wt% to 55 wt%; most preferably, from 48 wt% to 54 wt%) of structural monomer units of (meth)acrylic C 1-8 alkyl ester monomers based on the dry weight of the gradient polymer; (c) >10 wt% to 30 wt% (preferably, from 12 wt% to 30 wt%; more preferably, from 15 wt% to 25 wt%; most preferably, from 16 wt% to 20 wt%) of structural monomer units of a dedicated associative monomer having Structure I

[0047]

[0048] wherein each R 1 is independently selected from linear saturated C 12-26 alkyl groups (preferably, C 12-24 alkyl groups; more preferably, C 14-24 alkyl groups; most preferably, C 16-22 alkyl groups); wherein each R 2 is independently selected from hydrogen and methyl groups (preferably, wherein R 2is a methyl group), and wherein n is 10 to 30 (preferably, 12 to 30; more preferably, 15 to 28; most preferably, 18 to 26); and (d) 0.01 wt% to 2 wt% (preferably, 0.05 wt% to 1 wt%; more preferably, 0.08 wt% to 0.5 wt%; most preferably, 0.1 wt% to 0.2 wt%) of structural monomer units of a multiethylenically unsaturated monomer, based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.05 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a sulfonated monomer (e.g., AMPS), based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.02 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a monomer having Structure II

[0049]

[0050] wherein each R 3 is independently selected from the group consisting of -H and -CH3; wherein each R 4 is independently selected from the group consisting of -H and -C 1-4 alkyl groups; wherein each R 5 is independently selected from the group consisting of -C 1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100, and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology. More preferably, the aqueous personal care rinse-off formulation of the present application comprises 0.1 wt% to 15 wt% (preferably, 0.5 wt% to 10 wt%; more preferably, 0.75 wt% to 5 wt%; most preferably, 1 wt% to 2.5 wt%) of a gradient polymer, based on the weight of the aqueous personal care rinse-off formulation; wherein the gradient polymer comprises: (a) 5 wt% to 35 wt% (preferably, 10 wt% to 35 wt%; more preferably, 20 wt% to 34 wt%; most preferably, 26 wt% to 32 wt%) of structural monomer units of a (meth)acrylic acid monomer, based on the dry weight of the gradient polymer; (b) 35 wt% to 65 wt% (preferably, 40 wt% to 60 wt%; more preferably, 45 wt% to 55 wt%; most preferably, 48 wt% to 54 wt%) of structural monomer units of a (meth)acrylic acid C 1-8alkyl ester monomer; (c) from >10 wt% to 30 wt% (preferably, from 12 wt% to 30 wt%; more preferably, from 15 wt% to 25 wt%; most preferably, from 16 wt% to 20 wt%) of structural monomer units of a dedicated associative monomer having structure I based on the dry weight of the gradient polymer; wherein the dedicated associative monomer having structure I is a blend of: a first dedicated associative monomer having structure la (preferably, from 51 wt% to 99 wt%; more preferably, from 75 wt% to 97 wt%; most preferably, from 85 wt% to 95 wt% of the first dedicated associative monomer having structure la based on the weight of the dedicated associative monomer having structure I)

[0051]

[0052] wherein each R 1a is independently selected from linear saturated C 12-19 alkyl groups (preferably, linear saturated C 12-18 alkyl groups; more preferably, linear saturated C 14-18 alkyl groups; most preferably, linear saturated C 16-18 alkyl groups); wherein each R 2a is independently selected from hydrogen and methyl groups (preferably, wherein R 2 is a methyl group), and wherein na is from 10 to 30 (preferably, from 12 to 30; more preferably, from 15 to 28; most preferably, from 18 to 26); and a second dedicated associative monomer having structure lb (preferably, from 1 wt% to 49 wt%; more preferably, from 3 wt% to 25 wt%; most preferably, from 6 wt% to 15 wt% of the first dedicated associative monomer having structure lb based on the weight of the dedicated associative monomer having structure I)

[0053]

[0054] wherein each R 1b is independently selected from linear saturated C 20-26 alkyl groups (preferably, linear saturated C 20-24 alkyl groups; more preferably, linear saturated C 21-23 alkyl groups; most preferably, linear saturated C 22 alkyl groups); wherein each R 2bindependently selected from the group consisting of a linear saturated hydrogen and a methyl group (preferably, a methyl group), and wherein nb is 10 to 30 (preferably, 15 to 30; more preferably, 18 to 28; most preferably, 20 to 28); and (d) 0.01 wt% to 2 wt% (preferably, 0.05 wt% to 1 wt%; more preferably, 0.08 wt% to 0.5 wt%; most preferably, 0.1 wt% to 0.2 wt%) of structural monomer units of a multiethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.05 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a sulfonated monomer (e.g., AMPS) based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.02 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than a detectable limit) of structural monomer units of a monomer having structure II, wherein each R 3 independently selected from the group consisting of -H and -CH3; wherein each R 4 independently selected from the group consisting of -H and -C 1-4 alkyl groups; wherein each R 5 independently selected from the group consisting of -C 1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100, and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

[0055] Preferably, the gradient polymer comprises 90 wt% to 100 wt% (preferably, 95 wt% to 100 wt%; more preferably, 98 wt% to 100 wt%; still more preferably, 99 wt% to 100 wt%; yet more preferably, 99.9 wt% to 100 wt%; most preferably, 100 wt%) of structural monomer units present in the gradient polymer that are structural monomer units of (a)-(d). The structural monomer units of the gradient polymer do not include end groups on the gradient polymer derived from a chain transfer agent or an initiator (e.g., a residue of a chain transfer agent).

[0056] Preferably, the gradient polymer comprises 5 to 35 wt.-% (preferably, 10 to 35 wt.-%; more preferably, 20 to 34 wt.-%; most preferably, 26 to 32 wt.-%) of structural monomeric units of a (meth)acrylic acid monomer; wherein the (meth)acrylic acid monomer is selected from the group consisting of methacrylic acid, acrylic acid and mixtures thereof, based on the dry weight of the gradient polymer. More preferably, the gradient polymer comprises 5 to 35 wt.-% (preferably, 10 to 35 wt.-%; more preferably, 20 to 34 wt.-%; most preferably, 26 to 32 wt.-%) of structural monomeric units of a (meth)acrylic acid monomer; wherein the (meth)acrylic acid monomer is a mixture of methacrylic acid and acrylic acid, based on the dry weight of the gradient polymer. Most preferably, the gradient polymer comprises 5 to 35 wt.-% (preferably, 10 to 35 wt.-%; more preferably, 20 to 34 wt.-%; most preferably, 26 to 32 wt.-%) of structural monomeric units of a (meth)acrylic acid monomer; wherein the (meth)acrylic acid monomer is a mixture of 30 to 60 wt.-% (preferably, 32 to 58 wt.-%; more preferably, 33 to 55 wt.-%) of methacrylic acid and 40 to 70 wt.-% (preferably, 32 to 58 wt.-%; more preferably, 33 to 55 wt.-%) of acrylic acid, based on the weight of the mixture.

[0057] Preferably, the gradient polymer comprises 35 to 65 wt.-% (preferably, 40 to 60 wt.-%; more preferably, 45 to 55 wt.-%; most preferably, 48 to 54 wt.-%) of structural monomeric units of a (meth)acrylic acid C 1-8 alkyl ester monomer (preferably, a (meth)acrylic acid C 1-6 alkyl ester monomer; more preferably, a (meth)acrylic acid C 2-3 alkyl ester monomer; most preferably, an acrylic acid C2alkyl ester monomer), based on the dry weight of the gradient polymer. More preferably, the gradient polymer comprises 35 to 65 wt.-% (preferably, 40 to 60 wt.-%; more preferably, 45 to 55 wt.-%; most preferably, 48 to 54 wt.-%) of structural monomeric units of a (meth)acrylic acid C 1-8 alkyl ester monomer; wherein the (meth)acrylic acid C 1-8The alkyl ester monomer is selected from the group consisting of ethyl (meth)acrylate, propyl (meth)acrylate, and mixtures thereof (preferably, ethyl acrylate, propyl acrylate, and mixtures thereof). Most preferably, the gradient polymer comprises 35 to 65 weight % (preferably, 40 to 60 weight %; more preferably, 45 to 55 weight %; most preferably, 48 to 54 weight %) of (meth)acrylic acid C 1-8 alkyl ester monomer; wherein the (meth)acrylic acid C 1-8 The alkyl ester monomer is ethyl acrylate.

[0058] Preferably, the gradient polymer comprises > 10 to 30 weight % (preferably, 12 to 30 weight %; more preferably, 15 to 25 weight %; most preferably, 16 to 20 weight %) of structural monomer units of the dedicated associative monomer having Structure I

[0059]

[0060] wherein each R 1 is independently selected from a linear saturated C 12-26 alkyl group (preferably, a linear saturated C 12-24 alkyl group; more preferably, a linear saturated C 14-24 alkyl group; most preferably, a linear saturated C 16-22 alkyl group); wherein each R 2 is independently selected from hydrogen and a methyl group (preferably, wherein R 2 is a methyl group), and wherein n is 10 to 30 (preferably, 12 to 30; more preferably, 15 to 28; most preferably, 18 to 26). More preferably, the gradient polymer comprises > 10 to 30 weight % (preferably, 12 to 30 weight %; more preferably, 15 to 25 weight %; most preferably, 16 to 20 weight %) of structural monomer units of the dedicated associative monomer having Structure I; wherein the dedicated associative monomer having Structure I is a blend of a first dedicated associative monomer having Structure la (preferably, 51 to 99 weight %; more preferably, 75 to 97 weight %; most preferably, 85 to 95 weight % of the first dedicated associative monomer having Structure la based on the weight of the dedicated associative monomer having Structure I)

[0061]

[0062] wherein each R 1a is independently selected from a linear saturated C 12-19 alkyl group (preferably, a linear saturated C 12-18alkyl groups; more preferably, straight chain saturated C 14-18 alkyl groups; most preferably, straight chain saturated C 16-18 alkyl groups); wherein each R 2a is independently selected from hydrogen and methyl groups (preferably, wherein R 2 is a methyl group), and wherein na is 10 to 30 (preferably, 12 to 30; more preferably, 15 to 28; most preferably, 18 to 26); and a second specialized associative monomer having Structure Ib (preferably, 1 wt% to 49 wt%; more preferably, 3 wt% to 25 wt%; most preferably, 6 wt% to 15 wt% of the first specialized associative monomer having Structure Ib based on the weight of the specialized associative monomer having Structure I)

[0063]

[0064] wherein each R 1b is independently selected from straight chain saturated C 20-26 alkyl groups (preferably, straight chain saturated C 20-24 alkyl groups; more preferably, straight chain saturated C 21-23 alkyl groups; most preferably, straight chain saturated C 22 alkyl groups); wherein each R 2b is independently selected from straight chain saturated hydrogen and methyl groups (preferably, methyl groups); and wherein nb is 10 to 30 (preferably, 15 to 30; more preferably, 18 to 28; most preferably, 20 to 28) (preferably, wherein R 1a and R 1b differ by less than 8 carbon atoms (more preferably, less than 7 carbon atoms).

[0065] Preferably, the gradient polymer comprises 0.01 to 2 wt.-% (preferably 0.05 to 1 wt.-%; more preferably 0.08 to 0.5 wt.-%; most preferably 0.1 to 0.2 wt.-%) of structural monomer units of a multiethylenically unsaturated monomer, based on the dry weight of the gradient polymer. More preferably, the gradient polymer comprises 0.01 to 2 wt.-% (preferably 0.05 to 1 wt.-%; more preferably 0.08 to 0.5 wt.-%; most preferably 0.1 to 0.2 wt.-%) of structural monomer units of a multiethylenically unsaturated monomer; wherein the multiethylenically unsaturated monomer is selected from the group consisting of multiunsaturated aromatic monomers (e.g. divinylbenzene, divinyl naphthalene, trivinylbenzene); multiunsaturated alicyclic monomers (e.g. 1,2,4-trivinylcyclohexane); difunctional esters of phthalic acid (e.g. diallyl phthalate); multiunsaturated aliphatic monomers (e.g. isoprene, butadiene, 1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene); polyalkenyl ethers (e.g. triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylolpropane diallyl ether); multiunsaturated esters of polyols or polyacids (e.g. 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, polyethylene glycol di(meth)acrylate); alkylene bisacrylamides (e.g. methylene bisacrylamide, propylene bisacrylamide); hydroxyl and carboxyl derivatives of methylene bisacrylamide (e.g. N,N'-bishydroxymethyl methylene bisacrylamide); polyethylene glycol di(meth)acrylates (e.g. ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate); multiunsaturated silanes (e.g. dimethyl divinyl silane, methyl trivinyl silane, allyl dimethyl vinyl silane, diallyl dimethyl silane, tetravinyl silane); multiunsaturated stannanes (e.g. tetraallyl tin, diallyl dimethyl tin) and mixtures thereof. Still more preferably, the gradient polymer comprises 0.01 to 2 wt.-% (preferably 0.05 to 1 wt.-%; more preferably 0.08 to 0.5 wt.-%; most preferably 0.1 to 0.2 wt.-%) of structural monomer units of a multiethylenically unsaturated monomer, based on the dry weight of the gradient polymer; wherein the multiethylenically unsaturated monomer is a polyalkenyl ether.Most preferably, the gradient polymer comprises 0.01 to 2 wt% (preferably, 0.05 to 1 wt%; more preferably, 0.08 to 0.5 wt%; most preferably, 0.1 to 0.2 wt%) of structural monomer units of a multi-ethylenically unsaturated monomer; wherein the multi-ethylenically unsaturated monomer is trimethylolpropane diallyl ether, based on the dry weight of the gradient polymer. Most preferably, the gradient polymer comprises 0.01 to 2 wt% (preferably, 0.05 to 1 wt%; more preferably, 0.08 to 0.5 wt%; most preferably, 0.1 to 0.2 wt%) of structural monomer units of a multi-ethylenically unsaturated monomer; wherein the multi-ethylenically unsaturated monomer is trimethylolpropane diallyl ether, based on the dry weight of the gradient polymer.

[0066] Preferably, the gradient polymer further comprises 0.01 to 2 wt% (preferably, 0.02 to 1 wt%; more preferably, 0.04 to 0.5 wt%; most preferably, 0.06 to 0.1 wt%) of residues of a chain transfer agent, based on the dry weight of the gradient polymer. More preferably, the gradient polymer further comprises 0.01 to 2 wt% (preferably, 0.02 to 1 wt%; more preferably, 0.04 to 0.5 wt%; most preferably, 0.06 to 0.1 wt%) of residues of a chain transfer agent; wherein the chain transfer agent is selected from the group consisting of sulfur- and disulfide-containing compounds (e.g., C 1-18 alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, thioesters, C 1-18 alkyl disulfides, aryl disulfides, polyfunctional mercaptans); phosphite and hypophosphite esters; halogenated alkyl compounds (e.g., carbon tetrachloride, bromo-trichloromethane); unsaturated chain transfer agents (e.g., a-methylstyrene) and mixtures thereof. Still more preferably, the gradient polymer further comprises 0.01 to 2 wt% (preferably, 0.02 to 1 wt%; more preferably, 0.04 to 0.5 wt%; most preferably, 0.06 to 0.1 wt%) of residues of a chain transfer agent; wherein the chain transfer agent is C 1-18 alkyl mercaptans. Most preferably, the gradient polymer further comprises 0.01 to 2 wt% (preferably, 0.02 to 1 wt%; more preferably, 0.04 to 0.5 wt%; most preferably, 0.06 to 0.1 wt%) of residues of a chain transfer agent; wherein the chain transfer agent is n-dodecyl mercaptan, based on the dry weight of the gradient polymer.

[0067] Preferably, the gradient polymer comprises a structural monomer unit of a sulfonated monomer based on a dry weight of <0.05% by weight (preferably, <0.01% by weight; more preferably, <0.001% by weight; still more preferably, <0.0001% by weight; most preferably, less than the detectable limit) of the gradient polymer; wherein the sulfonated monomer is selected from the group consisting of: 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxysulfonic acid, 2-hydroxy-1-propanesulfonic acid (HAPS), 2-sulfoethyl(meth)acrylic acid, 2-sulfopropyl(meth)acrylic acid, 3-sulfopropyl(meth)acrylic acid, 4-sulfobutyl(meth)acrylic acid, salts thereof, and mixtures thereof.

[0068] Preferably, the gradient polymer comprises structural monomer units of a monomer having structure II, in an amount of <0.02 wt% (preferably <0.01 wt%; more preferably <0.001 wt%; still more preferably <0.0001 wt%; most preferably, less than the detectable limit) based on the dry weight of the gradient polymer.

[0069]

[0070] Each R 3 Independently selected from -H and -CH3; where each R 4 Independently selected from -H and -C 1-4 alkyl groups; wherein each R 5 Independently selected from -C 1-4 Alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100; and wherein d is 1 to 4.

[0071] Preferably, the gradient polymer comprises, based on a dry weight of <0.01% (preferably <0.005% by weight; more preferably <0.001% by weight; still more preferably <0.0001% by weight; most preferably, less than the detectable limit) of structural monomer units of monomers selected from the group consisting of: styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, and mixtures thereof.

[0072] Preferably, the gradient polymer comprises <2% by weight (preferably <1% by weight; more preferably <0.5% by weight; still more preferably <0.1% by weight; even more preferably <0.01% by weight; still even more preferably <0.001% by weight; most preferably, less than the detectable limit) of a monomer unit selected from the group consisting of: (meth)acrylic acid C 6-18alkyl ester monomers, vinyl esters of alkanecarboxylic acids having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl(meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof.

[0073] Preferably, the gradient polymer comprises: (a) 5 to 35 weight percent (preferably, 10 to 35 weight percent; more preferably, 20 to 34 weight percent; most preferably, 26 to 32 weight percent) of structural monomer units of (meth)acrylic monomers, based on the dry weight of the gradient polymer; (b) 35 to 65 weight percent (preferably, 40 to 60 weight percent; more preferably, 45 to 55 weight percent; most preferably, 48 to 54 weight percent) of structural monomer units of (meth)acrylic Ci to C4 alkyl ester monomers, based on the dry weight of the gradient polymer; (c) >10 to 30 weight percent (preferably, 12 to 30 weight percent; more preferably, 15 to 25 weight percent; most preferably, 16 to 20 weight percent) of structural monomer units of specialized associative monomers having Structure I, based on the dry weight of the gradient polymer; wherein the specialized associative monomers having Structure I are a blend of: a first specialized associative monomer having Structure la (preferably, 51 to 99 weight percent; more preferably, 75 to 97 weight percent; most preferably, 85 to 95 weight percent of the first specialized associative monomer having Structure la, based on the weight of the specialized associative monomers having Structure I), wherein each R 1-8 alkyl ester monomers, vinyl esters of alkanecarboxylic acids having 6 to 18 carbon atoms, N-vinylalkylamides having 6 to 18 carbon atoms, N-alkyl(meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof. 1a independently selected from linear saturated C 12-19 alkyl groups (preferably, linear saturated C 12-18 alkyl groups; more preferably, linear saturated C 14-18 alkyl groups; most preferably, linear saturated C 16-18 alkyl groups); wherein each R 2a is independently selected from hydrogen and methyl groups (preferably, wherein R 2 is a methyl group), and wherein na is 10 to 30 (preferably, 12 to 30; more preferably, 15 to 28; most preferably, 18 to 26); and a second specialized associative monomer having Structure Ib (preferably, 1 to 49 weight percent; more preferably, 3 to 25 weight percent; most preferably, 6 to 15 weight percent of the first specialized associative monomer having Structure Ib, based on the weight of the specialized associative monomers having Structure I), wherein each R 1b independently selected from linear saturated C 20-26 alkyl groups (preferably, linear saturated C 20-24 alkyl groups; more preferably, linear saturated C 21-23 alkyl groups; most preferably, linear saturated C 22alkyl groups); wherein each R 2b is independently selected from the group consisting of linear saturated hydrogen and methyl groups (preferably, methyl groups), and wherein nb is 10 to 30 (preferably, 15 to 30; more preferably, 18 to 28; most preferably, 20 to 28); and (d) 0.01 wt% to 2 wt% (preferably, 0.05 wt% to 1 wt%; more preferably, 0.08 wt% to 0.5 wt%; most preferably, 0.1 wt% to 0.2 wt%) of structural monomer units of a multiethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.05 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than the detectable limit) of structural monomer units of a sulfonated monomer (e.g., AMPS) based on the dry weight of the gradient polymer; wherein the gradient polymer comprises < 0.02 wt% (preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than the detectable limit) of structural monomer units of a monomer having structure II, wherein each R 3 is independently selected from the group consisting of -H and -CH3; wherein each R 4 is independently selected from the group consisting of -H and -C 1-4 alkyl groups; wherein each R 5 is independently selected from the group consisting of -C 1-4 alkyl groups; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100, and wherein d is 1 to 4; wherein the gradient polymer has a gradient polymer morphology; and has any one or more of the following conditions (i)-(v): (i) wherein R 1a and R 1b(i) wherein the structural monomer units of the (meth)acrylic monomer include structural monomer units of both methacrylic acid and acrylic acid; (ii) wherein the gradient polymer contains < 0.01 wt% (preferably, < 0.005 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%; most preferably, less than the detectable limit) of structural monomer units of monomers selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl methacrylate, and mixtures thereof, based on the dry weight of the gradient polymer; (iii) wherein the gradient polymer contains < 2 wt% (preferably, < 1 wt%; more preferably, < 0.5 wt%; still more preferably, < 0.1 wt%; yet more preferably, < 0.01 wt%; still yet more preferably, < 0.001 wt%; most preferably, less than the detectable limit) of structural monomer units of monomers selected from the group consisting of alkyl (meth)acrylate having 6 to 18 carbons, vinyl alkanoate having 6 to 18 carbon atoms, N-vinyl alkyl amide having 6 to 18 carbon atoms, N-alkyl (meth)acrylamide having 6 to 18 carbon atoms, and mixtures thereof, based on the dry weight of the gradient polymer; and / or (iv) wherein the gradient polymer contains 90 to 100 wt% (preferably, 95 to 100 wt%; more preferably, 98 to 100 wt%; still more preferably, 99 to 100 wt%; yet more preferably, 99.9 to 100 wt%; most preferably, 100 wt%) of structural monomer units present in the gradient polymer, which structural monomer units are the structural monomer units of (a)-(d).

[0074] Preferably, the aqueous personal care rinse-off formulation of the present application further comprises at least one ingredient selected from the group consisting of: absorbents; aesthetic enhancing agents (e.g., starch); alpha hydroxy acids; anti-aging agents; anti-dandruff agents; anti-fungal agents; anti-microbial agents; anti-oxidants (e.g., butylated hydroxytoluene); anti-bacterial agents; anti-static agents; bioactive agents; bleaching agents; chelating agents; coloring agents; conditioning agents (e.g., silicones, polyquatemiums, cationic guar); dyes; emollients; emulsifiers; film formers (e.g., water resistant agents); fixative polymers; foaming agents; fragrances; hard particles; humectants (e.g., glycerin, sorbitol, monoglycerides, lecithin, glycolipids, fatty alcohols, fatty acids, polysaccharides, sorbitan esters, polysorbate esters (e.g., polysorbate 20, polysorbate 40, polysorbate 60, and polysorbate 80), glycols (e.g., propylene glycol), glycol analogs, triol, triol analogs, cationic polymeric polyols); lubricants; opacifying agents; pearlescent agents; penetrating agents; pH adjusting agents; pigments; plant extracts; preservatives (e.g., benzoic acid, sorbic acid, phenoxyethanol); proteins / amino acids; rheology modifiers; salts (e.g., NaCl); sensory modifying agents; slip agents; soaps; soft particles; sunscreen additives; suspending agents; ultraviolet inhibitors; vitamins; and mixtures thereof.

[0075] Preferably, the aqueous personal care rinse-off formulation of the present application further comprises from 0 wt% to 10 wt% (preferably, from 0 wt% to 3 wt%) of a salt (e.g., NaCl) based on the weight of the aqueous personal care rinse-off formulation.

[0076] Preferably, the aqueous personal care rinse-off formulation of the present application further comprises an anti-microbial agent. More preferably, the aqueous personal care rinse-off formulation of the present application further comprises an anti-microbial agent; wherein the anti-microbial agent is selected from the group consisting of: phenoxyethanol, benzoic acid, benzyl alcohol, sodium benzoate, DMDM hydantoin, 2-ethylhexylglycerin ether, and an isothiazolinone (e.g., methylchloroisothiazolinone, methylisothiazolinone). Still more preferably, the aqueous personal care rinse-off formulation of the present application further comprises an anti-microbial agent; wherein the anti-microbial agent is an isothiazolinone (more preferably, wherein the anti-microbial agent is selected from the group consisting of: methylisothiazolinone, methylchloroisothiazolinone, and mixtures thereof; most preferably, wherein the biocide is methylisothiazolinone).

[0077] Preferably, the aqueous personal care rinse-off formulation of the present application further comprises a pH adjusting agent. More preferably, the aqueous personal care rinse-off formulation of the present application further comprises a pH adjusting agent. Most preferably, the aqueous personal care rinse-off formulation of the present application further comprises a pH adjusting agent; wherein the pH of the aqueous personal care rinse-off formulation is from 4.5 to 9 (preferably, from 5 to 8; most preferably, from 5 to 7).

[0078] Preferably, the pH adjuster is selected from the group consisting of at least one of the following: citric acid, lactic acid, hydrochloric acid, aminoethylpropylene glycol, triethanolamine, monoethanolamine, sodium hydroxide, potassium hydroxide, and amino-2-methyl-1-propanol. More preferably, the pH adjuster is selected from the group consisting of at least one of the following: citric acid, lactic acid, sodium hydroxide, potassium hydroxide, triethanolamine, and amino-2-methyl-1-propanol. Still more preferably, the pH adjuster includes triethanolamine. Most preferably, the pH adjuster is triethanolamine.

[0079] Preferably, the method of cleaning at least one of mammalian skin and hair (preferably, at least one of human skin and hair) according to the present invention comprises: applying the aqueous personal care wash-off formulation of the present invention to mammalian skin or hair (preferably, human skin or hair); and rinsing the aqueous personal care wash-off formulation off the skin or hair with rinsing water.

[0080] Some embodiments of the present invention will now be described in detail in the following examples.

[0081] Synthesis S1 : Gradient polymer

[0082] Add deionized water (350 g) and sodium lauryl sulfate (9.1 g) to a 3 L, 4-necked round-bottom reactor equipped with a mechanical stirrer, thermocouple, condenser, and nitrogen injector. Purge the reactor with nitrogen and heat to 85 °C. Prepare the following separately: (1) Prepare monomeric emulsion A from the following: deionized water (450 g); sodium lauryl sulfate (16.4 g); ethyl acrylate (EA) (262 g); lipophilic modified monomer (Lipo 1) having the following structure (82.1 g).

[0083]

[0084] Where R 1 It is a straight-chain saturated C 16-18 Alkyl groups and n is an average of 18 to 26; lipophilic modified monomer (Lipo 2) with the following structure (9.6 g)

[0085]

[0086] Where R 1 It is a straight-chain saturated C 22 Alkyl groups and n is an average of 20 to 28; methacrylic acid (MAA) A) (101.1 g) and n-dodecyl mercaptan (n-DDM) (0.4 g); (2) monomer emulsion additive B was prepared by mixing: deionized water (70 g); sodium lauryl sulfate (9.1 g); trimethylolpropane diallyl ether (x-link) (0.81 g) and methacrylic acid (MAA B ) (4.82 g); (3) initiator solution (C1) was prepared by dissolving ammonium persulfate (0.35 g) in deionized water (15 g), and (4) initiator solution (C2) was prepared by dissolving ammonium persulfate (0.55 g) in deionized water (84 g). At a reactor temperature of about 85 °C, the reactor was charged with initiator solution (C1). Monomer emulsion (A) was then charged to the reactor while monomer emulsion additive (B) was charged to monomer emulsion (A). The rate was controlled such that the feed of monomer emulsion (A) started at ½ rate for the first 10 minutes and at 1 rate until the end at 120 min, and where the feed of monomer emulsion additive (B) ended over 100 min. Simultaneously, initiator solution (C2) was fed to the reactor over 125 min. After these additions were complete, the monomer emulsion and initiator feed lines were flushed with deionized water, followed by monomer chasing with free radical catalyst and activator.

[0087] Synthesis S2-S4: Gradient polymers

[0088] The gradient polymers in Synthesis S2-S4 were prepared according to the procedure described in Synthesis S1, with the exception that the composition was varied as described in Table 1.

[0089] Table 1

[0090]

[0091] Synthesis S5: Non-gradient polymer

[0092] To a 3 L, 4 necked round bottom reactor, equipped with a mechanical stirrer, a thermocouple, a condenser and a nitrogen sparge, was added deionized water (275 g) and sodium lauryl sulfate (9.1 g). The reactor was purged with nitrogen and warmed to 85 °C. Separately, the following were prepared, namely: (1) monomer emulsion A was prepared from: deionized water (570 g); sodium lauryl sulfate (25.5 g); ethyl acrylate (EA) (262 g); lipophilic modifying monomer (Lipo 1) having the structure

[0093]

[0094] where R 1 is a linear saturated C16-18 Lipophilic modifying monomer (Lipo 2) having the following structure (9.6 g)

[0095]

[0096] where R 1 is a linear saturated C 22 alkyl group and n is an average value of 20 to 28; methacrylic acid (MAA) (50.5 g); acrylic acid (AA) (101.1 g); n-dodecyl mercaptan (n-DDM) (0.4 g) and trimethylolpropane diallyl ether (x-link) (0.81 g); (2) an initiator solution (C1) was prepared by dissolving ammonium persulfate (0.35 g) in deionized water (15 g), and (3) an initiator solution (C2) was prepared by dissolving ammonium persulfate (0.55 g) in deionized water (84 g). At a reactor temperature of about 85 °C, the reactor was charged with the initiator solution (C1). The monomer emulsion (A) was then charged to the reactor. The rate was controlled such that the feed of monomer emulsion (A) started at ½ rate for the first 10 minutes and at 1 rate until the end at 120 min. Separately, the initiator solution (C1) started simultaneously with the feed of monomer emulsion (A) and was fed to the reactor over 125 min. After these additions were complete, the monomer and initiator feed lines were flushed with deionized water followed by a monomer purge with free radical catalyst and activator.

[0097] Synthesis S6-S8: Non-gradient polymers

[0098] The non-gradient polymers in Synthesis S6-S8 were prepared according to the procedure described in Synthesis S5, except for the composition as described in Table 2.

[0099] Table 2

[0100]

[0101] Viscosity and haze measurements

[0102] For each of the polymers prepared according to Synthesis S1-S8 as reported in Table 3, the following procedure was used to determine the solution viscosity and haze of a solution containing 0.75% polymer active:

[0103] 1. Weigh out enough polymer to provide 0.75% of polymer in the final formulation.

[0104] 2. Pre-dilute with deionized water to make 169 g solution.

[0105] 3. Add 11.0 g of 20% w / w sodium hydroxide aqueous solution and stir effectively with a top stirrer until homogeneous.

[0106] 4. Equilibrate in a warm water bath for 10-15 minutes. Therefore, the internal temperature of the solution is 20℃.

[0107] 5. The measured pH should be between 7.8 and 10. Adjust with 20% sodium hydroxide if necessary.

[0108] 6. Use a Brinell viscometer with a corresponding spindle to measure viscosity at 20°C and at 0.3 rpm, 3 rpm, 6 rpm, 12 rpm, 20 rpm, 30 rpm and 60 rpm to obtain measurement results with a scale of at least 10%.

[0109] 7. Transfer the sample to a 1oz vial for turbidity measurement.

[0110] 8. Centrifuge the 1oz vial at 3,500 rpm for 20 minutes.

[0111] 9. Measure the turbidity in turbidity units (NTU) using a turbidimeter at 20°C.

[0112] The results of viscosity and turbidity measurements are reported in Table 3.

[0113] Table 3

[0114]

[0115] Comparative examples CF1 -CF6 and examples F1 -F6: cleaning formulations

[0116] Aqueous personal care cleaning formulations were prepared in each of Comparative Examples CF1-CF6 and Examples F1-F6 having the formulations shown in Table 4.

[0117] The phase A components (if any) of each of Comparative Examples CF1-CF6 and Examples F1-F6 were mixed with gentle stirring until dissolved. The phase B components were mixed together in a separate container. The mixed phase B components were then slowly added to the mixed phase A components (if any). The phase C components were then added to the mixed phase A components (if any) and phase B components. The appropriate amount of phase D components was then mixed as needed to adjust to the pH shown in Table 4. The viscosity of the resulting aqueous personal care cleaning formulation was then measured at 20°C using a Brookfield viscometer with the corresponding principal axis, as listed in Table 5.

[0118]

[0119] Table 5

[0120]

[0121] Comparative examples CF7-CF10 and examples F7-F10: cleaning formulations

[0122] An aqueous personal care cleansing formulation was prepared in each of Comparative Examples CF7-CF10 and Examples F7-F10 having the formulations shown in Table 6. The A-phase components were mixed together. The mixed B-phase components were then slowly added to the mixed A-phase components. As needed, the appropriate C-phase components were mixed into the mixed A-phase and B-phase components to adjust the pH. The viscosity of the resulting aqueous personal care cleansing formulation was then measured using a Brookfield viscometer with the corresponding spindle at 20 °C at 20 rpm, as listed in Table 7. The turbidity of each formulation was measured using a Micro 100 Turbidimeter (HF Scientific, Inc.), as listed in Table 7.

[0123]

[0124] Table 7

[0125]

[0126] Rheology data

[0127] The aqueous personal care cleansing formulations prepared according to Comparative Examples CF7-CF10 and Examples F7-F10 were characterized for rheology using a Discovery HR-3 hybrid rheometer (TA Instruments) with a 40 mm parallel plate geometry. All tests were conducted at 25 °C. The tests included an amplitude sweep from 0.0002 rad to 0.15 rad at an oscillatory displacement of 1 rad / s, and a flow sweep from 0.01 s -1 to 500 s -1 The G’, G”, and tan delta values were obtained from the amplitude in the linear viscoelastic region, and the viscosity values were obtained from the shear rate sweep, as listed in Table 8.

[0128] Table 8

[0129]

Claims

1. An aqueous personal care rinse-off formulation comprising: a dermatologically acceptable vehicle; a dermatologically acceptable cleansing surfactant; and a gradient polymer comprising: (a) from 5 wt% to 35 wt% of structural units of (meth)acrylic acid based on the dry weight of the gradient polymer; (b) 35 to 65% by weight, based on the dry weight of the gradient polymer, of structural units of a C 1-8 alkyl ester of a C1-8alkyl (meth)acrylate; (c) from >10 wt% to 30 wt% of structural units of a dedicated associative monomer having structure I wherein each R is independently selected from the group consisting of linear saturated C 1 C1-C4alkyl group; and each R is independently selected from the group consisting of linear saturated C 12-26 alkyl group; and each R is independently selected from the group consisting of linear saturated wherein each R 2 is independently selected from hydrogen and methyl groups, and wherein n is 10 to 30; and (d) from 0.01 wt% to 2 wt% of structural units of a multi-ethylenically unsaturated monomer based on the dry weight of the gradient polymer; wherein the gradient polymer comprises <0.05 wt% of structural units of a sulfonated monomer based on the dry weight of the gradient polymer; wherein the polymer comprises <0.02 wt% of structural units of a monomer having structure II based on the dry weight of the gradient polymer Each R 3 Independently selected from -H and -CH3; where each R 4 Independently selected from -H and -C 1-4 alkyl groups; wherein each R 5 Independently selected from -C 1-4 Alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50; wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymer morphology.

2. The aqueous personal care rinse-off formulation of claim 1, wherein the structural monomer units of a dedicated associative monomer having structure I is a blend of a first dedicated associative monomer having structure la wherein each R is independently selected from a linear saturated C 1a 12-19 alkyl group; wherein each R is independently selected from a linear saturated C 2a is independently selected from hydrogen and a methyl group, and wherein na is 10 to 30; and​ a second dedicated associative monomer having structure lb wherein each R is independently selected from a linear saturated C 1b independently selected from a linear saturated C 20-26 alkyl group; wherein each R is independently selected from a linear saturated C 2b independently selected from a linear saturated C independently selected from a linear saturated C 3. The aqueous personal care rinse-off formulation of claim 1, wherein the structural units of (meth)acrylic acid includes structural units of both methacrylic acid and acrylic acid.

4. The aqueous personal care rinse-off formulation of claim 1, wherein a single stage gradient polymer comprises <0.01 wt% of structural units of a monomer selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate, and mixtures thereof based on the dry weight of the gradient polymer.

5. The aqueous personal care rinse-off formulation of claim 1, wherein the polymer comprises <2 wt% of a monomer selected from the group consisting of (meth)acrylic alkyl esters having 6 to 18 carbons, vinyl alkanoates having 6 to 18 carbon atoms, N-vinyl alkyl amides having 6 to 18 carbon atoms, N-alkyl (meth)acrylamides having 6 to 18 carbon atoms, and mixtures thereof based on the dry weight of the gradient polymer.

6. The aqueous personal care rinse-off formulation of claim 1, wherein the dermatologically acceptable vehicle comprises water.

7. The aqueous personal care rinse-off formulation of claim 1, wherein the dermatologically acceptable cleansing surfactant comprises an amino acid surfactant.

8. The aqueous personal care rinse-off formulation of claim 1, wherein the amino acid surfactant is selected from the group consisting of sodium cocoyl glutamate, sodium cocoyl alaninate, sodium cocoyl glycinate, sodium lauroyl sarcosinate, and mixtures thereof.

9. The aqueous personal care rinse-off formulation of claim 1, wherein the aqueous personal care rinse-off formulation further comprises a thickening salt.

10. A method of cleansing at least one of mammalian skin and hair, the method comprising: (a) applying to the skin or hair an aqueous personal care wash-off formulation according to claim 1 ; and (b) rinsing the aqueous personal care wash-off formulation from the skin or hair with rinsing water.

Images