EP4780408A1

EP4780408A1 - Silicone depositing shampoo for damaged hair

Info

Publication number: EP4780408A1
Application number: EP24782419.6A
Authority: EP
Inventors: Janet MCMILLAN; Michaeleen L. PACHOLSKI; Tanner MCDANIEL; Timothy J. Young; Wanglin Yu; Sung-Yu Ku; Daniel S. Miller; Bethany K. Johnson; Lyndsay M. LEAL; Isabelle Van Reeth
Original assignee: Dow Global Technologies LLC; Rohm and Haas Co; Dow Silicones Corp
Current assignee: Dow Global Technologies LLC; Rohm and Haas Co; Dow Silicones Corp
Priority date: 2023-09-18
Filing date: 2024-09-13
Publication date: 2026-07-29
Also published as: WO2025064309A1; CN121793943A; KR20260074964A

Abstract

A shampoo formulation is provided comprising: water; an alcohol ethoxysulfate surfactant of formula I (I) wherein each R1 and R2 is independently a C1‑16 alkyl group; wherein the sum of the carbon atoms in R1 and R2 is 7-17; wherein M+ is a cation balancing the negative charge of the -SO3- anion of formula I; and wherein x is 1 in 95-100 mol% of the alcohol ethoxysulfate surfactant of formula I; a dermatologically acceptable silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5-5 wt%; and wherein the deposition aid polymer comprises <0.1 % of the linkages between individual glucose units in the deposition aid polymer are β-1,3 linkages.

Description

SILICONE DEPOSITING SHAMPOO FOR DAMAGED HAIR

[0001] The present invention relates to shampoo formulations. In particular, the present invention relates to a shampoo formulation for damaged hair (preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair) comprising: water; an alcohol ethoxysulfate surfactant of formula I wherein each R¹ and R² is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R¹ and R² is 7 to 17; wherein M⁺ is a cation balancing the negative charge of the -SO3" anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a dermatologically acceptable silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5 to 5 wt%; and wherein the deposition aid polymer comprises < 0.1 % of the linkages between individual glucose units in the deposition aid polymer are P-1,3 linkages.

[0002] Shampoo formulations typically include an anionic surfactant, which is the principal suds producer, along with a secondary surfactant. Alkyl ethoxy sulfate anionic surfactants (e.g., alcohol ethoxysulfate surfactants (AES)) have established use in a variety of shampoo formulations. Conventional AES anionic surfactants; however, have been associated with undesirable 1 ,4 dioxane content. Regulators are increasingly restricting the amount of 1 ,4 dioxane that may be present in consumer products. For example, New York State has banned all but trace amounts of 1 ,4 dioxane in cleaning products. Typically, a consumer product must contain less than 10 parts per million by weight (ppm) of 1,4 dioxane to be compliant with the regulations. One contributor of the unintended incorporation of 1,4 dioxane in consumer products can be the inclusion of alkyl ethoxy sulfate anionic surfactants.

[0003] Inclusion of 1 ,4 dioxane in conventional AES surfactants is believed to occur at multiple points in time. A first point of 1 ,4 dioxane generation in conventional AES surfactants is believed to occur during the sulfation process of alcohol ethoxylates to make alcohol ethoxy sulfates. The alcohol ethoxylate intermediates for the production of conventional alcohol ethoxy sulfate surfactants are made via ethoxylation (i.e., the reaction of an alcohol with ethylene oxide) that typically results in a distribution of alcohol ethoxylate oligomers. It is believed that under the sulfation process conditions during the manufacture of conventional AES surfactants, 1,4 dioxane can form. A second point of 1,4 dioxane generation in association with conventional AES surfactants is believed to occur during handling and processing of the conventional AES surfactants. Handling and processing of conventional AES surfactants often involves acidic conditions at ambient, or elevated, temperature. Prolonged exposure to acidic environments for conventional AES surfactants and their alcohol ethoxylate precursors may result in the formation of 1 ,4 dioxane. Further, exposure to elevated temperatures (e.g., up to 280 °C) during processing, storage and/or handling may result in the decomposition of conventional AES surfactants resulting in the formation of dioxane.

[0004] Traditionally, 1,4 dioxane content in conventional AES surfactants and products incorporating such surfactants has been addressed by the use of stripping techniques. For example, where 1,4 dioxane concentrations are above a target threshold, a stripping process is employed to remove excess 1 ,4 dioxane from the conventional AES surfactants or product incorporating same. The stripping process is not only expensive and time consuming, but also is not a guarantee to meet the increasingly stringent regulatory requirements. Further, as 1 ,4 dioxane may form over time as a response to how the conventional AES surfactant or product is handled and further processed, any previously applied stripping techniques may be nullified by the generation of new 1 ,4 dioxane. As such, ensuring that a product comprising an AES surfactant is compliant with the appropriate regulations by the time it is sold to an end consumer is a difficult challenge.

[0005] Accordingly, there remains a need for shampoo formulations having an anionic alcohol ethoxysulfate surfactant that resists forming 1,4-dioxane both during the sulfation process to form the surfactant and subsequently when the alcohol ethoxysulfate surfactant is exposed to elevated temperatures of up to 280 °C; particularly shampoo formulations for damaged hair that deposits silicone to the hair.

[0006] The present invention provides a shampoo formulation for damaged hair, comprising: water; an alcohol ethoxysulfate surfactant of formula I wherein each R¹ and R² is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R¹ and R² is 7 to 17; wherein M⁺ is a cation balancing the negative charge of the -SO anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a dermatologically acceptable silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5 to 5 wt%; and wherein the deposition aid polymer comprises <0. 1 % of the linkages between individual glucose units in the deposition aid polymer are P-1,3 linkages.

[0007] The present invention provides a method of depositing silicone on damaged hair, comprising: providing a damaged hair; selecting a shampoo formulation of the present invention having a synergistic silicone depositing combination of the alcohol ethoxysulfate surfactant of formula I, the deposition aid polymer and the dermatologically acceptable silicone; wetting the damaged hair with water; and applying the shampoo formulation to the wetted damaged hair to provide clean hair; wherein the dermatologically acceptable silicone is associated with the clean hair.

DETAILED DESCRIPTION

[0008] In addition to resisting the formation of 1 ,4 dioxane both during the sulfation process to form the alcohol ethoxysulfate surfactant of formula I and subsequently when the alcohol ethoxysulfate surfactant of formula I is exposed to elevated temperatures of up to 280 °C during processing, storage and/or handling; we have surprisingly found that a combination of such alcohol ethoxysulfate surfactant of formula I (as described herein) and a deposition aid polymer (as described herein) significantly improves deposition of silicone from shampoo to damaged hair (preferably bleached hair).

[0009] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight (e.g., “ppm” means parts per million by weight).

[0010] The term “solids weight” as used herein and in the appended claims in reference to the shampoo formulation and the alcohol ethoxysulfate surfactant of formula I means dry weight, i.e., excluding any water that may be present.

[0011] 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 Liquid Chromatography - Practice of Gel Permeation and Gel Filtration Chromatography, Second Edition, A.M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported herein in units of Daltons, or equivalently, g/mol.

[0012] Preferably, the shampoo formulation of the present invention, comprises: water (preferably, 43 to 98 wt% (more preferably, 52.5 to 97 wt%; still more preferably, 68.25 to 93 wt%; most preferably, 82.3 to 88 wt%), based on weight of the shampoo formulation, of water); an alcohol ethoxysulfate surfactant of formula I (preferably, 0.5 to 35 wt% (more preferably, 1 to 20 wt%; still more preferably, 5 to 15 wt%; most preferably, 8 to 10 wt%), based on weight of the shampoo formulation, of the alcohol ethoxysulfate surfactant of formula I) wherein each R¹ and R² is independently a Ci-16 alkyl group (preferably, a C1-15 alkyl group; more preferably, a C 1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R¹ and R² is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R¹ and R² are linear alkyl groups; more preferably, wherein R¹ is a methyl group and R² is a linear C10-12 alkyl group; most preferably, wherein R¹ is a methyl group and R² is a linear C10 alkyl group); wherein M⁺ is a cation balancing the negative charge of the -SOs’ anion in formula I (preferably, wherein M⁺ is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation); and wherein is 1 in 95 to 100 mol% (preferably, 96 to 100 mol%; more preferably, 97 to 100 mol%; most preferably, 97.5 to 100 mol%) of the alcohol ethoxy sulfate surfactant of formula I (preferably, as determined using ¹³C nuclear magnetic resonance characterization); a dermatologically acceptable silicone (preferably, 0.05 to 12 wt% (more preferably, 0.1 to 10 wt%; still more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 wt%), based on weight of the shampoo formulation, of the dermatologically acceptable silicone); and a deposition aid polymer (preferably, 0.01 to 2 wt% (more preferably, 0.05 to 1.5 wt% still more preferably, 0.1 to 1 wt%; most preferably, 0.2 to 0.4 wt%), based on the weight of the shampoo formulation, of the deposition aid polymer), wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties (preferably, wherein the quaternary ammonium moieties are of formula II wherein pendant oxygen on the dextran base polymer; wherein X is a divalent linking group bonding the quaternary nitrogen to the pendent oxygen on the dextran base polymer (preferably, wherein X is selected from divalent hydrocarbon groups, which may optionally be substituted (e.g., with a hydroxy group, an alkoxy group, an ether group); more preferably, wherein X is a -CH2CH(OR⁵)CH2- group; wherein R⁵ is selected from the group consisting of a hydrogen and a Ci-4 alkyl group (preferably, a hydrogen); most preferably, X is a -CH2CH(OH)CH2- group); wherein R³ is selected from the group consisting of a C1-7 alkyl group (preferably, a C1-3 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); and wherein R⁴ is independently selected from the group consisting of a C1-22 alkyl group (preferably, selected from the group consisting of a C1-3 alkyl group and a C6-22 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); (preferably, wherein the dextran base polymer has a weight average molecular weight of 50,000 to 2,000,000 Daltons (preferably, 75,000 to 1,000,000 Daltons; more preferably, 80,000 to 750,000 Daltons; most preferably, 100,000 to 700,000 Daltons); wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5 to 5 wt% (preferably, 0.75 to 2.5 wt%; more preferably, 0.8 to 2.25 wt%; most preferably, 1 to 2 wt%); and wherein the deposition aid polymer comprises < 0.1 % of the linkages between individual glucose units in the deposition aid polymer are P-1,3 linkages.

[0013] Preferably, the shampoo formulation of the present invention, comprises: 43 to 98 wt% (preferably, 52.5 to 97 wt%; more preferably, 68.25 to 93 wt%; most preferably, 82.3 to 88 wt%), based on the weight of the shampoo formulation, of water. More preferable, the shampoo formulation of the present invention, comprises: 43 to 98 wt% (preferably, 52.5 to 97 wt%; more preferably, 68.25 to 93 wt%; most preferably, 82.3 to 88 wt%), based on the weight of the shampoo formulation, of water; wherein the water is at least one of distilled water, deionized water and industrial soft water. Still more preferably, the shampoo formulation of the present invention, comprises: 43 to 98 wt% (preferably, 52.5 to 97 wt%; more preferably, 68.25 to 93 wt%; most preferably, 82.3 to 88 wt%), based on the weight of the shampoo formulation, of water, wherein the water is distilled and deionized. Most preferably, the shampoo formulation of the present invention, comprises: 43 to 98 wt% (preferably, 52.5 to 97 wt%; more preferably, 68.25 to 93 wt%; most preferably, 82.3 to 88 wt%), based on the weight of the shampoo formulation, of a water, wherein the water is distilled, deionized and industrial soft to avoid introduction of undesirable metal ions to the shampoo formulation.

[0014] Preferably, the shampoo formulation of the present invention, comprises 0.5 to 35 wt% (preferably, 1 to 20 wt%; more preferably, 5 to 15 wt%; most preferably, 8 to 10 wt%), based on weight of the shampoo formulation, of an alcohol ethoxysulfate surfactant of formula I; wherein each R¹ and R² is independently a Ci-i6 alkyl group (preferably, a C1-15 alkyl group; more preferably, a C1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R¹ and R² is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R¹ and R² are linear alkyl groups; more preferably, wherein R¹ is a methyl group and R² is a linear C10-12 alkyl group; most preferably, wherein R¹ is a methyl group and R² is a linear C10 alkyl group); wherein M⁺ is a cation balancing the negative charge of the -SOf anion in formula I (preferably, wherein M⁺ is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation); and wherein x is 1 in 95 to 100 mol% (preferably, 96 to 100 mol%; more preferably, 97 to 100 mol%; most preferably, 97.5 to 100 mol%) of the alcohol ethoxy sulfate surfactant of formula I (preferably, as determined using ¹³C nuclear magnetic resonance characterization).

[0015] Preferably, the alcohol ethoxysulfate surfactant of formula I contains < 9 ppm (preferably, < 8 ppm; more preferably, < 7 ppm; still more preferably, < 6 ppm; yet more preferably, < 5 ppm; still yet more preferably, < 4 ppm; yet still more preferably, < 3 ppm; still even more preferably, < 2 ppm; yet even more preferably, < 1 ppm; still yet even more preferably, < 0.25 ppm; most preferably, less than the detectable limit), based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of 1 ,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection low temperature gas chromatography-mass spectrometry method for organic layer and liquid chromatographymass spectrometry method for aqueous layer).

[0016] Preferably, the alcohol ethoxysulfate surfactant of formula I contains < 2 wt% (preferably, < 1.75 wt%; more preferably, < 1.5 wt%; still more preferably, < 1.25 wt%; yet more preferably, < 1.1 wt%; most preferably, < 1 wt%), based on solids weight of the alcohol ethoxysulfate surfactant of formula T, of an alcohol sulfate surfactant of formula IV wherein each R⁶ and R⁷ is independently a Cni6 alkyl group (preferably, a Cni5 alkyl group; more preferably, a C1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R⁶ and R⁷ is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; still more preferably, 11 to 13; most preferably, 11 or 13)(preferably, wherein R⁶ and R⁷ are linear alkyl groups; more preferably, wherein R⁶ is a methyl group and R⁷ is a linear C10-12 alkyl group; most preferably, wherein R⁶ is a methyl group and R⁷ is a linear C10 alkyl group); and wherein A⁺ is a cation balancing the negative charge of the -SO3" anion in formula IV (preferably, wherein A⁺ is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation).

[0017] Preferably, the shampoo formulation of the present invention comprises an alcohol ethoxysulfate surfactant of formula I as described above, wherein the alcohol ethoxysulfate surfactant of formula I has elevated thermal stability. More preferably, the shampoo formulation of the present invention comprises an alcohol ethoxysulfate surfactant of formula I as described above, wherein the alcohol ethoxysulfate surfactant of formula I has enhanced thermal stability. The term “elevated thermal stability” as used herein and in the appended claims means that the alcohol ethoxy sulf ate surfactant of formula I when heated to 110 °C contains < 9 ppm (preferably, < 8 ppm; more preferably, < 7 ppm; still more preferably, < 6 ppm; yet more preferably, < 5 ppm; still yet more preferably, < 4 ppm; even more preferably, < 3 ppm; still even more preferably, < 2 ppm; yet even more preferably, < 1 ppm; most preferably, < 0.5 ppm), based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of 1 ,4-dioxane (preferably, wherein the 1 ,4-dioxane content is measured by liquid injection low temperature gas chromatography-mass spectrometry method for organic layer and liquid chromatography-mass spectrometry method for aqueous layer). The term “enhanced thermal stability” as used herein and in the appended claims means that the alcohol ethoxy sulfate surfactant of formula I when heated to 280 °C contains < 10 ppm, based on solids weight of the alcohol ethoxysulfate surfactant of formula I, of 1 ,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection gas chromatography-mass spectrometry method for organic layer and liquid chromatographymass spectrometry method for aqueous layer).

[0018] Preferably, the shampoo formulation of the present invention, comprises 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone.

More preferably, the shampoo formulation of the present invention, comprises 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 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 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., DOWSIL™ 979 emulsion) and mixtures thereof. Still more preferably, the shampoo formulation of the present invention, comprises 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 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. Yet more preferably, the shampoo formulation of the present invention, comprises 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 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 yet more preferably, the shampoo formulation of the present invention, comprises 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 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 0.05 to 12 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.5 to 5 wt%; most preferably, 1 to 3 wt%), based on weight of the shampoo formulation, of a dermatologically acceptable silicone; wherein the dermatologically acceptable silicone comprises a dimethiconol (e.g., DOWSIL™ 1785 POE Emulsion — INCI Name: Dimethiconol (and) TEA-Dodecylbenzenesulfonate).

[0019] Preferably, the shampoo formulation of the present invention comprises 0.01 to 2 wt% (preferably, 0.05 to 1.5 wt% more preferably, 0.1 to 1 wt%; preferably, 0.2 to 0.4 wt%), based on the weight of the shampoo formulation, of a deposition aid polymer; wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties. More preferably, the shampoo formulation of the present invention comprises 0.01 to 2 wt% (preferably, 0.05 to 1.5 wt% more preferably, 0.1 to 1 wt%; preferably, 0.2 to 0.4 wt%), based on the weight of the shampoo formulation, of a deposition aid polymer; wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer enhances deposition of silicone from the shampoo formulation onto damaged hair (preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair). Most preferably, the shampoo formulation of the present invention comprises 0.01 to 2 wt% (preferably, 0.05 to 1.5 wt% more preferably, 0.1 to 1 wt%; preferably, 0.2 to 0.4 wt%) (0.3 wt%) , based on the weight of the shampoo formulation, of a deposition aid polymer; wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer enhances deposition of silicone from the shampoo formulation onto a damaged hair (preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair); wherein the deposition aid polymer has a Kjeldahl nitrogen content corrected for ash and volatiles, TKN, of 0.5 to 5 wt% (preferably, 0.75 to 2.5 wt%; more preferably, 0.8 to 2.25 wt%; most preferably, 1 to 2 wt%)(measured according to ASTM method D-2364); and wherein the deposition aid polymer enhances deposition of silicone from the shampoo formulation onto damaged hair (preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair). [0020] Preferably, the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the dextran base polymer is a branched chain dextran polymer. More preferably, the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the dextran base polymer comprises a branched chain dextran polymer; wherein the branched chain dextran polymer comprises 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 hy 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 deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the dextran base polymer is a branched chain dextran polymer; wherein the branched chain dextran polymer comprises 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 V wherein R 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 contain less than 0.01 wt%, based on weight of the dextran base polymer, of alternan. More preferably, the dextran base polymer contain less than 0.001 wt%, based on weight of the dextran base polymer, of alternan. Most preferably, the dextran base polymer contain less than the detectable limit of alternan.

[0022] Preferably, the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the quaternary ammonium moieties are of formula II bound to a pendant oxygen on the dextran base polymer wherein pendant oxygen on the dextran base polymer; wherein X is a divalent linking group bonding the quaternary ammonium moiety to the pendent oxygen on the dextran base polymer (preferably, wherein X is selected from divalent hydrocarbon groups, which may optionally be substituted (e.g., with a hydroxy group, an alkoxy group, an ether group); more preferably, wherein X is a -CH2CH(OR⁵)CH2- group; wherein R⁵ is selected from the group consisting of a hydrogen and a C1-4 alkyl group (preferably, a hydrogen); most preferably, X is a -CH2CH(OH)CH2- group); wherein R³ is selected from the group consisting of a C1-7 alkyl group (preferably, a C1-3 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); and wherein R⁴ is selected from the group consisting of a C 1-22 alkyl group (preferably, selected from the group consisting of a C1-3 alkyl group and a C6-22 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group). More preferably, the deposition aid polymer is a cationic dextran polymer; wherein the cationic dextran polymer, comprises a dextran base polymer functionalized with quaternary ammonium groups; wherein the quaternary ammonium groups are of formula III bound to a pendent oxygen on the dextran base polymer wherein R³ is selected from the group consisting of a C1-7 alkyl group (preferably, a C1-3 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); wherein R⁴ is selected from the group consisting of a C 1-22 alkyl group (preferably, selected from the group consisting of a C1-3 alkyl group and a C6-22 alkyl group; more preferably, a methyl group and an ethyl group; most preferably, a methyl group); and wherein R⁵ is selected from the group consisting of a hydrogen and a C1-4 alkyl group (preferably, a hydrogen). Most preferably, the deposition aid polymer is a cationic dextran polymer; wherein the cationic dextran polymer, comprises a dextran base polymer functionalized with quaternary ammonium groups; wherein the quaternary ammonium groups are of formula III bound to a pendent oxygen on the dextran base polymer; wherein R^s is a hydrogen; and wherein each R³ and R⁴ is a methyl group.

[0023] Preferably, the deposition aid polymer comprises < 0.001 meg/gram (preferably, < 0.0001 meq/gram; more preferably, < 0.00001 meq/gram; most preferably, < detectable limit) of aldehyde functionality.

[0024] 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 P-1,4 linkages.

[0025] 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 [3-1,3 linkages.

[0026] 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.

[0027] Preferably, the shampoo formulation of the present invention, further comprises an additional cleaning surfactant. More preferably, the shampoo formulation of the present invention further comprises 0.01 to 20 wt% (preferably, 0.1 to 15 wt%; more preferably, 1 to 10 wt%; most preferably, 2 to 4 wt%), based on weight of the shampoo formulation, of an additional cleaning surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof. Still more preferably, the shampoo formulation of the present invention further comprises 0.01 to 20 wt% (preferably, 0. 1 to 15 wt%; more preferably, 1 to 10 wt%; most preferably, 2 to 4 wt%), based on weight of the shampoo formulation, of an additional cleaning surfactant; wherein the additional cleaning surfactant is selected from the group consisting of an ethanolamine of a fatty acid (e.g., cocamide monoethanolamine), a betaine (e.g., cocamidopropyl betaine) and a mixture thereof. Most preferably, the shampoo formulation of the present invention further comprises 0.01 to 20 wt% (preferably, 0. 1 to 15 wt%; more preferably, 1 to 10 wt%; most preferably, 2 to 4 wt%), based on weight of the shampoo formulation, of an additional cleaning surfactant; wherein the additional cleaning surfactant comprises a mixture of cocamide monoethanolamine and cocamidopropyl betaine.

[0028] Preferably, the shampoo formulation of the present invention, further comprises a chelating agent. More preferably, the shampoo formulation of the present invention, further comprises 0.01 to 2 wt% (preferably, 0.05 to 1 wt%; more preferably, 0.075 to 0.75 wt%; most preferably, 0.1 to 0.3 wt%), based on weight of the shampoo formulation, of the chelating agent. Most preferably, the shampoo formulation of the present invention, further comprises 0.01 to 2 wt% (preferably, 0.05 to 1 wt%; more preferably, 0.075 to 0.75 wt%; most preferably, 0.1 to 0.3 wt%), based on weight of the shampoo formulation, of the chelating agent; wherein the chelating agent comprises tetrasodium ethylenediaminetetraacetic acid.

[0029] Preferably, the shampoo formulation of the present invention, further comprises an additive selected from the group consisting of an absorbent; an acid; an antidandruff agent; an antifrizz agent; an antimicrobial agent/preservative (e.g., benzoic acid, sorbic acid, phenoxyethanol, methylisothiazolinone, ethylhexyl glycerin); an antioxidant (e.g., butylated hydroxytoluene); an antistatic agent; a bleaching agent; a bioactive agent; a colorant; a conditioning agent (e.g., guar hydroxypropyltrimonium chloride, PQ-10, PQ-7); an emulsifying agent; a foaming agent; a fragrance; a hair styling agent; a hair waving/straightening agent; 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 lubricating agent; a natural ingredient (e.g., natural oil); an opacifier; a pearlizing agent; a pH adjusting agent; a pigment; a plant extract; a preservative (e.g., benzoic acid, sorbic acid, phenoxyethanol, methylisothiazolinone); a protein/amino acid; a salt; a sensory modifier; a slip agent; a soap; a sunscreen additive; a thickener (e.g., PEG- 150 pentaerythrityl tetrastearate, carbomer); a vitamin and a wax. More preferably, the shampoo formulation of the present invention, further comprises an additive selected from the group consisting of an antimicrobial agent/preservative (e.g., benzoic acid, sorbic acid, phenoxyethanol, methylisothiazolinone, ethylhexyl glycerin); a thickener (e.g., PEG-150 pentaerythrityl tetrastearate); and a pH adjusting agent (e.g., citric acid). Most preferably, the shampoo formulation of the present invention, further comprises an additive selected from the group consisting of a mixture of phenoxyethanol and methylisothiazolinone; PEG- 150 pentaerythrityl tetrastearate and citric acid.

[0030] Preferably, the shampoo formulation of the present invention contains < 10 ppm (preferably, < 5 ppm; more preferably, < 4 ppm; yet more preferably, < 3 ppm; still more preferably, < 2 ppm; yet still more preferably, < 1 ppm; still yet more preferably, < 0.5 ppm; even more preferably, < 0.25 ppm; still even more preferably, < 0.15 ppm; most preferably, less than the detectable limit), based on solids weight of the shampoo formulation, of 1,4 dioxane (preferably, wherein the 1,4 dioxane content is measured by chromatograph-mass spectrometry; more preferably wherein the 1,4 dioxane content is measured by liquid injection low temperature gas chromatography-mass spectrometry method for organic layer and liquid chromatography-mass spectrometry method for aqueous layer).

[0031] Preferably, the shampoo formulation of the present invention, comprises < 1 wt% (preferably, < 0.1 ; more preferably, < 0.01 wt%; still more preferably, < 0.0015 wt%; yet more preferably^ 0.001 wt%; most preferably, less than detectable limit), based on solids weight of the shampoo formulation, of an alcohol sulfate surfactant of formula IV wherein each R⁶ and R⁷ is independently a Ci-i6 alkyl group (preferably, a Ci-15 alkyl group; more preferably, a C1-14 alkyl group; most preferably, a linear C1-13); wherein the sum of the carbon atoms in R⁶ and R⁷ is 7 to 17 (preferably, 10 to 16; more preferably, 11 to 15; most preferably, 12 or 14)(preferably, wherein R⁶ and R⁷ are linear alkyl groups; more preferably, wherein R⁶ is a methyl group and R⁷ is a linear C10-12 alkyl group; most preferably, wherein R⁶ is a methyl group and R⁷ is a linear C10 alkyl group); and wherein A⁺ is a cation balancing the negative charge of the -SOf anion in formula IV (preferably, wherein A⁺ is a cation selected from the group consisting of a nitrogen containing cation (e.g., an ammonium cation), a metal cation (e.g., an alkali metal cation, an alkaline earth metal cation), a boron containing cation and a phosphorous containing cation; more preferably, an ammonium cation, an alkali metal cation and an alkaline earth metal cation; still more preferably, an ammonium cation, a sodium cation and a calcium cation; most preferably, a sodium cation). [0032] Preferably, the method of depositing silicone on damaged hair (preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair) of the present invention, comprises: providing a damaged hair ((preferably, chemically treated hair; more preferably, colored or bleached hair; most preferably, bleached hair) mammalian hair (preferably, human hair); selecting a shampoo formulation of the present invention having a synergistic silicone depositing combination of an alcohol ethoxysulfate surfactant of formula I, a deposition aid polymer, as described above, and a dermatologically acceptable silicone; wetting the damaged hair with water; applying the shampoo formulation to the wetted damaged hair to provide clean hair, wherein the dermatologically acceptable silicone is associated with the clean hair. Preferably, the method of depositing silicone on damaged hair of the present invention, further comprises rinsing the shampoo formulation from the clean hair with a rinse water.

[0033] Some embodiments of the present invention will now be described in detail in the following Examples.

Experimental Materials

Synthesis SI: C12EO

[0034] A 3 liter (L) 3-neck glass round bottom flask, equipped with an overhead stirred through the center neck, reflux condenser and-a heating jacket was used for the etherification of 1 -dodecene and monoethylene glycol with the catalyst. To ensure good mixing, a pitch blade impeller was used for agitation. A reaction mixture of 551.7 grams (g) ethylene glycol and 505.8 g 1 -dodecene was prepared and loaded in the reactor together with 61-g catalyst in powdered form at 23 °C. The impeller stirring rate was set to be at 400 revolutions per minute (“rpm”). The reactor was heated to 135 °C in over the course of 30 minutes, held at 135 °C for 18 hours and then the reactor was cooled down to 23 °C by shutting off the heater. The reaction mixture was separated into a monoethylene glycol and catalyst phase and an olefin phase using a separation funnel.

[0035] A distillation apparatus was constructed using a 1 -liter round bottom flask connected to a short path distillation head with a thermometer adapter and a condenser with a vacuum adapter at the outlet. The distillation flask was heated in an aluminum block by an IKA heated stir-plate. The distillation pot was charged with the combined olefin phase and then stirring and vacuum were applied. Significant boiling was observed but no condensate was observed or collected. The temperature of the heating block was raised to 75 °C and unreacted dodecane was collected at a distillation head temperature of 25 °C to 50 °C and a pressure of 13.3-40 pascals (Pa). The heating block temperature was raised gradually to 140 °C and an intermediate fraction containing both monoether alcohol ethoxylates and dodecenes was recovered while the head temperature increased from 50 °C to 75 °C at a pressure of 13 Pa. The C12EO was collected at a head temperature of 70 °C to 115 °C and a pressure of 6 Pa to 33 Pa. The heating block temperature was raised gradually to 200 °C and an intermediate fraction containing both monoether alcohol ethoxylates and diether was collected while the head temperature increased from 115 °C to 130 °C at a pressure of 6 Pa. The distillation was discontinued and the diether, which remained in the pot, was collected. The C12EO was carried to the next sulfation process to make sulfate anionic surfactant. Synthesis S2: C12EO Sulfate

[0036] All chemical manipulations were conducted under a dry nitrogen atmosphere. Prior to the experiment all glassware was heated in a laboratory oven to remove residual water. A 2-L three-neck round bottom flask was loaded with dichloromethane (500 mL) and C12EO prepared according to Synthesis SI (48.4 g, 0.21 mol, 1.0 equivalents). The reaction flask was equipped with an overhead mechanical stirrer, additional funnel, and thermocouple.

Next, chlorosulfonic acid (14.5 mL, 0.221 mol, 1.1 equivalents) was carefully loaded into the additional funnel. The reaction flask was then submerged into an ice-bath and allowed to cool for 20 minutes, down to 0 °C. Once the reaction was cooled, chlorosulfonic acid was added to the reaction flask dropwise, at a rate of approx. 1.0 mL per minute, over approximately 20 minutes. During the addition of chlorosulfonic acid the reaction temperature did not exceed 5 °C. After the addition, the reaction was allowed to react, and the temperature was kept between 0 and 5 °C, for 3 hours. At this time, the reaction was neutralized by slow dropwise addition of an aqueous NaOH solution (18.0 g NaOH in 500 mL of water, 0.9 molar). The rate of addition was slow enough to not exceed 5 °C over the course of addition. The addition of the aqueous NaOH solution continued until the reaction became basic. The crude biphasic product was analyzed for dioxane content.

Dichloromethane was then carefully removed from the crude biphasic product in vacuo. During the removal of the dichloromethane, a large amount of foam was observed. Upon removal of the dichloromethane, the remaining aqueous solution was placed in a freeze drier/lyophilizer to yield a purified secondary alcohol ethoxylate sulfate product, C12EO Sulfate, as a whiteish solid (47.7 grams). The purified product was used for the perfomance and property testing.

Synthesis S3: ALEO1 Sulfate

[0037] ALEO1 sulfate was prepared from ALEO1 in the same manner as described in Synthesis S2.

Synthesis S4; SA3EO Sulfate

[0038] SA3EO sulfate was prepared from SA3EO in the same manner as described in Synthesis S2.

Synthesis S5: Branched Chain Cationic Dextran Polymer

[0039] A 500 ml, four-necked, round-bottomed flask was charged with a 30% aqueous solution of dextran (129.83 g; Ultradex 530) and a 70% aqueous solution of glycidyl trimethylammonium chloride (20.88 g; Quab 151). The flask was fitted with a stirring paddle and electric motor, a nitrogen inlet, a rubber serum cap, and a Claisen adaptor connected to a subsurface thermocouple connected to a J-KEM controller, and a Friedrich condenser connected to a mineral oil bubbler. The flask contents were then stirred under nitrogen for one hour to remove any entrained oxygen in the system. After the one hour nitrogen purge was completed a 25% aqueous sodium hydroxide solution (6.35 g) was added and heat was applied to the flask contents using a J-KEM controller and heating mantle. The heating set-point was adjusted to 70 °C. When the flask contents reached 70 °C, the timer was started, and the flask contents were allowed to react for 4 hours under nitrogen.

[0040] The flask contents were then cooled in a water bath while maintaining a positive nitrogen pressure in the flask. The reaction mixture was neutralized by adding glacial acetic acid (2.5 g) using a syringe and allowing the mixture to stir for 10 minutes at which point a 1 % EUXYL PE 9010 preservative was added to teh flask contents. A portion of the product polymer was isolated by nonsolvent precipitation in methanol; the isolated polymer product was obtained as a white solid (26.68 g), with a volatiles content of 3.89%, an ash content (as sodium chloride) of 0.09%, and a Kjeldahl nitrogen content (corrected for ash and volatiles) of 1.61 %, corresponding to a DS_qUat of 0.225. The remainer of The product polymer was used without purification (30% active polymer).

Active Sulfate (EO=Q) Content of Surfactants

[0041] The active sulfate concentration in the surfactants noted in TABLE 1 was determined using a procedure modification of Tumey, M.E., Cannell, D.W. Alkaline methylene blue method for determination of anionic surfactants and for amine oxides in detergents. J. Am. Oil Chem. Soc., 42, 544-46 (1965) and Epton, S.R. A new method for the rapid titrimetric analysis of sodium alkyl sulphates and related compounds. Trans. Faraday Soc., 44, 226-30 (1948).

Determination of Moles of Hyamine

[0042] Sodium Dioctyl Sulfosuccinate (SDQSS), Control Solution: A 20 mL scintillation vial was loaded with 0.8 g (± 0.1 mg) of sodium dioctyl sulfosuccinate of known purity (>99%). The vial was filled with 10 mL of deionized water and was transferred to a 250 mL volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. Once the transfer was complete, the sample was diluted to 250 mL with deionized water. The flask was then stoppered, and the solution was thoroughly mixed by repeatedly inverting the flask.

[0043] Methylene Blue Chloride Solution: A 20 mL scintillation vial was loaded with 0.050 g (± 0.005) of methylene blue chloride. The vial was filled with 10 mL of deionized water and was transferred to a 1 L graduated cylinder. This process was repeated 3-5 times to ensure the sample was transferred. The methylene blue solution was then diluted to 1 L with deionized water. This solution was then transferred to a 2 L glass jug. Once transfer was complete, 10 mL of concentrated sulfuric acid and 50 g of anhydrous sodium sulfate was carefully added to the methylene blue solution and mixed thoroughly.

[0044] Hyamine 1622 Solution: A 20 mL scintillation vial was loaded with 1.1 grams of Hyamine 1622. The vial was filled with 10 mL of deionized water and was transferred to a 1 L volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. The sample was then diluted to 1 L with deionized water. The solution was thoroughly mixed by repeatedly inverting the flask and was then filtered into a 1 L glass bottle.

[0045] Standardization of Hyamine Solution: A 100 mL glass bottle was loaded with 5 mL of the sodium dioctyl sulfosuccinate solution via pipette. Next, 20 mL of methylene blue chloride solution and 25 mL of chloroform was added via pipette. The 100 mL bottle was capped and shaken thoroughly for several seconds. Hyamine 1622 solution was then titrated into the methylene blue/chloroform biphasic mixture at 0.5 mL increments. After each addition the bottle was capped and shaken vigorously. The additions of Hyamine 1622, in 0.5 mL increments, were continued until the blue color in the chloroform layer (or lower layer) began to migrate to the upper layer. At this point, the incremental additions of Hyamine 1622 were decreased to 0. 1 mL and continued until the endpoint is reached. The endpoint was reached when the blue color intensity of both layers was matched. This standardization was completed in triplicate. The moles of the Hyamine 1622 was then calculated using the following formula wherein MOIH is the moles of hyamine; CSvoi is the volume of control solution tested (i.e., 5 mL); CSmass is the total grams of control (SDOSS) added to the control solution (g); Hcsvoi is the amount of hyamine solution required to reach the endpoint (mL); CSMW is the molecular weight of the control solution, SDOSS (i.e., 444.56 g/mol).

Determination of active sulfate in surfactants

[0046] A 20 mL scintillation vial was loaded with 0.9 to 1.1 grams of surfactant sample, weighed to the nearest 0.1 mg. The vial was then filled with 10 mL of deionized water and transferred to a 250 mL volumetric flask. This process was repeated 3-5 times to ensure the sample was transferred. Once the transfer was complete, the sample was diluted with deionized water to 250 mL. The flask was then stoppered, and the solution was thoroughly mixed by repeatedly inverting the flask. Next, a 100 mL glass bottle was loaded with 5 mL of the test sample solution via pipette. The 100 mL glass bottle was then loaded with 20 mL of the methylene blue solution and 25 mL of chloroform via pipette. The glass bottle was capped and shaken vigorously for several seconds. Hyamine 1622 solution was then titrated into the methylene blue/chloroform biphasic mixture at 0.5 mL increments. After each addition the bottle was capped and shaken vigorously. The additions of Hyamine 1622, in 0.5 mL increments, was continued until the blue color in the chloroform layer (or lower layer) began to migrate to the upper layer. At this point, incremental additions of Hyamine 1622 were reduced to 0.1 mL and continued until the endpoint was reached. The endpoint being the point at which the color intensity of both layers was matched. Each sample was repeated in triplicate. The percent active sulfate content (wt%) was calculated using by the following formula: 100 wherein Hsvoi is the amount of Hyamine solution required to reach the endpoint (mL); MOIH is the moles of Hyamine (determined from standard solution described above); SMV/ is the weight average molecular weight of surfactant (g/mol); Svoi is the volume of surfactant tested (i.e., 5 mL); S_mass is the total grams of surfactant added to 250 mL solution (g). The results are provided in TABLE 1.

EQ Distribution of Surfactants

[0047] The distribution of EO adducts in the surfactants listed in TABLE 1 was determined by NMR or UHPLC-MS as noted using the methodology set forth below with the results provided in TABLE 1.

Nuclear Magnetic Resonance EQ Distribution Characterization (NMR) [0048] Samples of surfactant to be analyzed were prepared by dissolving the surfactant in deuterated dimethyl sulfoxide containing 0.025 M chromium (III) acetylacetonate. Nuclear magnetic resonance (¹³C NMR) spectra of the samples were then collected on a Bruker AVANCE 400 MHz spectrometer equipped with a 10 mm cryo-probe set to 25 °C, with the following parameters: a 90°-pulse, inverse-gated decoupling, a 1.38 second acquisition time, and a 6.4 second recycle delay. 2048 scans were collected. The data was processed in MNOVA, and the chemical shifts were referenced to the solvent peak at 39.52 ppm. A DEPT- 135 experiment was also acquired with the same parameters, but with a 2.0 second recycle delay, and 2048 scans. The ratios of different EO adducts are calculated by integrating and comparing the intensity of the ethylene oxide alcohol end groups from about 60-61 ppm, the ethylene oxide backbone groups from about 69-70 ppm, the ethylene oxide end group ether peak from about 71-72 ppm, the unreacted primary alcohol peaks from about 60-61 ppm, and the unreacted secondary alcohol peaks from about 65-66 ppm.

Sodium lauryl ether sulfate analysis by UHPLC-MS

[0049] Ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) conditions: [0050] Procedure: The compositions containing commercial surfactants were analyzed by ultra-high performance liquid chromatography mass spectrometry (UHPLC-MS) with electrospray ionization (ESI). For the analysis, stock solutions were prepared at concentrations of 25 ppm in a 50/50 mixture of methanol/water. The alcohol ethoxylate samples were diluted 1:100 in 50/50 methanol/water in duplicate and vortexed for a few seconds. Then they were diluted 1:10 in 50/50 methanol/water to give a final dilution of 1 : 1 ,000. Ethal® LA-4 was the standard used for the commercial 1 -mole sodium laureth sulfate and Ethal® LA-7 was the standard used for the commercial 3-mole sodium laureth sulfate. Calibration standards were prepared at 10 ppm, 5 ppm, 2 ppm and 1 ppm in 50/50 methanol/water.

[0051] Alkyl sulfates were diluted from the 1 :1,000 preparation in 50/50 methanol/water to give a final solution of 1 :20,000. POLYSTEP® B-N-5 was used as the standard for the alkyl sulfate analysis. Standards were prepared in 50/50 methanol/water at concentrations of 5 ppm, 2 ppm, 1 ppm and 0.5 ppm.

[0052] The samples were analyzed using a Waters ACQUITY® UPLC system equipped with a Waters BEH Cl 8 1.7 pm 1 x 50 mm column. Mass spectrometry was conducted using a Waters LCT Premier TOF Mass Spectrometer with ESI. Measurements were conducted in both positive and negative ion mode. Each sample preparation was injected three times for analysis. The ratios of the different EO adducts were calculated by the peak area and are reported in TABLE 1.

TABLE 1

[0053] At least 95 mol% of the oligomers of the product of Synthesis S2 had an n of 1 and no more than 5 mol% the oligomers have an n of > 2. Specifically, > 98 mol% of the oligomers of the product of Synthesis S2 had an n of 1 and < 2 mol% of the oligomers had an n of > 2. 1,4-Dioxane Content of Surfactants

[0054] The 1,4-dioxane content in the surfactants listed in TABLE 2 was determined by liquid injection low temperature gas chromatography-mass spectrometry (GC-MS) method for organic layer and liquid chromatography-mass spectrometry (LC-MS) method for aqueous layer as noted using the methodology set forth below with the results provided in TABLE 2. [0055] Gas chromatography-Mass spectrometry (GC-MS) conditions for organic layer 1 ,4-dioxane measurement:

[0056] Standards were prepared by adding dioxane in tetrahydrofuran (“THF”) and diluting down to 0.1-100 ppm.

[0057] Samples were prepared by mixing 3.3 g from the organic (DCM) layer of the crude process mixture and 6.7 g of THF, the solution was then allowed to shake for about 20 minutes. The solids were then centrifuged to the bottom and the supernatant was vialed in an autosampler vial. Spiked samples were prepared by spiking dioxane standard in THF into separate samples at 5-10 ppm. [0058] Liquid chromatography-mass spectrometry (LC-MS) conditions for aqueous layer 1 ,4-dioxane content measurement:

[0059] Samples were injected neat or diluted with water 1 :4. Standards were prepared by preparing a dioxane in THF stock solution and the diluting down with water to 0.1-100 ppm.

Calculation of Dioxane Content Relative to Solids

[0060] The ppm of dioxane content relative to solids content in the sample is calculated according to the following equation.

Concentration of Dioxane in Solution (-r^or ppM ) * Total Reaction Volume (L)

- — - - - x 10

Theoretical Yield of product (mg) ⁶

TABLE 2

[0061] The gas chromatography results for the SA3EO sulfate surfactant indicate the secondary alcohol with an average of 3 moles of ethylene oxide per molecule contained 2 ppm of 1,4-dioxane in the organic phase at 110 °C and indicates the potential for structures having n > 2 to produce 1,4-dioxane. Interestingly, when the inlet temperature was increased to 280 °C, the dioxane content of SA3EO sulfate increased from 2 ppm to 1,471 ppm 1 ,4-dioxane in the organic phase. This result indicates that sulfated surfactants having n > 2 may develop observable 1,4-dioxane at 110 °C, but also that such surfactants may be unstable at elevated temperatures of 280 °C which could result in significant 1,4-dioxane formation. Similarly to SA3EO sulfate, gas chromatography results for the ALEO1 sulfate surfactant indicate the formation of > 9 ppm of 1,4-dioxane relative to the solids at 110 °C. Further, the ALEO1 sulfate surfactant also exhibited a large generation of 1,4-dioxane (259 ppm) at 280 °C, suggesting that the ALEO1 sulfate surfactant lacks stability at high temperatures. The inventive C12EO sulfate surfactant with > 95 mol% having n of 1 and < 5 mol% having n > 2 demonstrates a low 1 ,4-dioxane content. Surprisingly, the inventive C12EO sulfate surfactant also demonstrates an extremely low 1,4-dioxane content and falls below the limit of detection (LOD) of the GC and LC methods. Using the LOD as a basis, this indicates that the dioxane content for the C12EO sulfate is < 1.6 ppm relative to solids, at 110 °C.

Interestingly, the inventive C12EO sulfate, when the inlet temperature is increased to 280 °C, the 1,4-dioxane content of the material is still less than 1 ppm (i.e., 0.58 ppm), which indicates that the inventive C12EO sulfate has increased thermal stability relative to the comparative materials. Comparative Examples CF1-CF5 and Example Fl: Shampoo Formulation

[0062] The rinse off formulation of each of Comparative Examples CF1-CF5 and

Example Fl was prepared by mixing together the components in the weight proportions noted in TABLE 3 adjusted to pH 5 to 5.5 (as necessary) with citric acid.

TABLE 3

Silicone Deposition

[0063] The silicone deposition on hair from the rinse off formulations prepared according to Comparative Examples CF1-CF5 and Example Fl 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.

[0064] Silicone deposition from the rinse off formulations of Comparative Examples CF1-CF5 and Example Fl onto two types of hair tresses (2 g, 4 hour bleached hair & 8 hour bleached hair from International Hair Importers) was evaluated. Each hair tress was initially washed in a 9 wt% sodium lauryl sulfate (SLS) solution for 30 seconds and then rinsed with water flowing at 0.4 L/min for 60 seconds. Following the initial wash step, the hair tresses were then treated with a rinse off formulation of one of Comparative Examples CF1-CF5 and Example Fl by applying 0.8 g of the rinse off formulation to the hair tress and massaging in for 60 seconds on each side and then rinsing with water flowing at 0.4 L/min for 30 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 by 3 mm section of hair. The instrument parameters used are provided in T BLE 4. The mol% of the silicon from the shampoo formulation deposited on the hair is reported in TABLE 5.

TABLE 4

TABLE 5

Claims

We claim:

1. A shampoo formulation for damaged hair, comprising: water; an alcohol ethoxysulfate surfactant of formula I wherein each R¹ and R² is independently a Ci-16 alkyl group; wherein the sum of the carbon atoms in R¹ and R² is 7 to 17; wherein M⁺ is a cation balancing the negative charge of the -SCty anion of formula I; and wherein x is 1 in 95 to 100 mol% of the alcohol ethoxy sulfate surfactant of formula I; a dermatologically acceptable silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties; wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 0.5 to 5 wt%; and wherein the deposition aid polymer comprises < 0.1 % of the linkages between individual glucose units in the deposition aid polymer are P-1,3 linkages.

2. The shampoo formulation of claim 1 , wherein the shampoo formulation contains <10 ppm, based on solids weight of the shampoo formulation, of 1,4 dioxane measured by chromatography mass spectrometry.

3. The shampoo formulation of claim 1, wherein R¹ is a methyl group and R² is a linear C10-12 alkyl group.

4. The shampoo formulation of claim 3, wherein R² is a linear C10 alkyl group; and wherein the dextran base polymer is a branched chain dextran polymer comprising a plurality of glucose structural units; wherein 90 to 98 mol% of the glucose structural units are connected by a-D-1,6 linkages and 2 to 10 mol% of the glucose structural units are connected by a- 1,3 linkages; wherein the dextran base polymer has a weight average molecular weight of 100,000 to 700,000 Daltons.

5. The shampoo formulation of claim 4, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties of formula II wherein pendant oxygen on the dextran base polymer; wherein X is a divalent linking group bonding the quaternary nitrogen to the pendent oxygen on the dextran base polymer; wherein R³ is selected from the group consisting of a C1-7 alkyl group; and wherein R⁴ is selected from the group consisting of a C1-22 alkyl group; wherein the deposition aid polymer has a Kjeldahl nitrogen content, TKN, of 1 to 2 wt%.

6. The shampoo formulation of claim 5, wherein the deposition aid polymer is a dextran base polymer functionalized with quaternary ammonium moieties having formula III wherein pendant oxygen on the dextran base polymer; wherein each R³ and R⁴ is a methyl group; wherein R⁵ is a hydrogen.

7. The shampoo formulation of claim 6, further comprising an additional cleaning surfactant, wherein the additional cleaning surfactant comprises cocamide monoethanolamine and cocamidopropyl betaine; and a chelating agent, wherein the chelating agent comprises tetrasodium ethylenediaminetetraacetic acid.

8. The shampoo formulation of claim 7, wherein the shampoo formulation comprises:

68.25 to 93 wt%, based on weight of the shampoo formulation, of water;

5 to 15 wt%, based on weight of the shampoo formulation, of the alcohol ethoxy sulfate surfactant of formula I;

0.5 to 5 wt%, based on weight of the shampoo formulation, of the dermatologically acceptable silicone;

0. 1 to 1 wt%, based on weight of the shampoo formulation, of the deposition aid polymer;

1 to 10 wt%, based on weight of the shampoo formulation, of the additional cleaning surfactant; and

0.075 to 0.75 wt%, based on weight of the shampoo formulation, of the chelating agent.

9. The shampoo formulation of claim 8, wherein the shampoo formulation contains <10 ppm, based on solids weight of the shampoo formulation, of 1,4 dioxane measured by chromatography mass spectrometry.

10. A method of depositing silicone on damaged hair, comprising: providing a damaged hair; selecting a shampoo formulation of claim 1 having a synergistic silicone depositing combination of the alcohol ethoxysulfate surfactant of formula I, the deposition aid polymer and the dermatologically acceptable silicone; wetting the damaged hair with water; and applying the shampoo formulation to the wetted damaged hair to provide clean hair; wherein the dermatologically acceptable silicone is associated with the clean hair.