WO2024126196A1

WO2024126196A1 - Branched fatty acyl isethionates

Info

Publication number: WO2024126196A1
Application number: PCT/EP2023/084501
Authority: WO
Inventors: Valentina ABET; Selvanathan Arumugam; Jenna Christine DOUTHIT; Agustina GENTILE; Adrian John JERVIS; Thomas Alan KWAN; Teanoosh Moaddel; Paul Damien Price; Jose Guillermo Rosa
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2022-12-16
Filing date: 2023-12-06
Publication date: 2024-06-20

Abstract

An anionic surfactant comprises a compound or mixture of compounds having the formula wherein R1 comprises hydrogen or methyl or hydroxy, R2 comprises methyl, hydroxy, or hydrogen, R'2 comprises methyl, hydroxy, or hydrogen, and R3 comprises a hydrocarbon group having 1 to 18 carbon atoms, including straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof; and wherein M+ is a monovalent cation; wherein if both R2 and R'2 comprise hydrogen, then R1 does not comprise hydrogen if R3 is a linear hydrocarbon group and wherein if R3 is a branched hydrocarbon, then all of R2, R2, and R1 comprise hydrogen.

Description

BRANCHED FATTY ACYL ISETHIONATES

Field of the invention

Disclosed herein is an anionic surfactant. The anionic surfactant comprises a compound or a mixture of compounds having the formula

wherein Ri comprises hydrogen or methyl or hydroxy, R2 comprises methyl, hydroxy, or hydrogen, R’2 comprises methyl, hydroxy, or hydrogen, and R3 comprises a hydrocarbon group having 1 to 18 carbon atoms, including straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof; and wherein M⁺ is a monovalent cation; wherein if both R2and R’2 comprise hydrogen, then R1 does not comprise hydrogen if Rs is a linear hydrocarbon group and wherein if R3 is a branched hydrocarbon, then all of R2, R2, and R1 comprise hydrogen.

Background of the invention

Fatty acid esters such as isethionate esters are anionic surfactants that can be used in a variety of applications including cleansers, such as soaps, cosmetic compositions, and cleansing formulations. For example, sodium cocoyl isethionate (SCI) is widely used in syndet bars because of its low solubility in water and mildness to the skin (e.g., non-skin irritating) as compared with less mild fatty acid soap bars. However, because of its low water solubility, SCI is generally not suitable for use in liquid cleansers. One way to improve the water solubility of SCI is to combine it with other surfactants such as taurates, amphoacetates, betaines, or a combination thereof. However, this combination of surfactants can produce a hazy solution that tends to separate during storage. Additionally, isethionates are not generally stable longterm outside of a pH range of 6 to 8.

Isethionates can be branched or linear.

U.S. Patent No. 8,008,239 B2 discloses acylalkylisethionate esters useful in consumer products. The acylalkylisethionate esters are produced by reacting one or more carboxylic acids with one or more alkyl-substituted hydroxyalkyl sulfonates under esterification reaction conditions. The alkyl-substituted hydroxyalkyl sulfonates used as a raw material in producing the esters are prepared by reacting bisulfite with one or more alkylene oxides.

It is continually desired to provide mild surfactants that are stable across a range of pH values, that are transparent in various cleansing compositions, structure in water to build viscosity, and that are water soluble without the need for additional surfactants, all while retaining excellent in- use properties, such as lather.

Summary of the invention

Disclosed in various aspects are surfactants.

An anionic surfactant comprises: a compound or mixture of compounds having the formula:

wherein Ri comprises hydrogen or methyl or hydroxy, R2 comprises methyl, hydroxy, or hydrogen, R’2 comprises methyl, hydroxy, or hydrogen, and R3 comprises a hydrocarbon group having 1 to 18 carbon atoms, including straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof; and wherein M⁺ is a monovalent cation; wherein if both R2 and R’2 comprise hydrogen, then R1 does not comprise hydrogen if R3 is a linear hydrocarbon group and wherein if R3 is a branched hydrocarbon, then all of R2, R2, and R1 comprise hydrogen.

These and other features and characteristics are more particularly described below.

Detailed description of the invention

Disclosed herein is an anionic surfactant. The anionic surfactant is branched. For example, the anionic surfactant can be branched isethionate, more specifically, isethionate branched on the fatty acyl tail. It was unexpectedly found that isethionates branched on the tail (i.e. , the fatty acyl tail) have more hydrolytic stability in an aqueous formulation as compared to linear isethionates. Since linear isethionates are prone to hydrolysis, which causes a drop in formulation viscosity, improved hydrolytic stability helps to enable better formulation viscosity stability over the lifetime of products produced using the anionic surfactant. Additionally, hydrolysis of linear isethionate in a low pH formulation (e.g., less than 6) leads to loss of optical clarity and transition to the lamellar phase from the isotropic phase because of the generation of fatty acids. Furthermore, since linear isethionates are not stable, they require the use of other co-primary surfactants such as taurates or are used mostly in amphoteric rich formulations. Branched isethionates can enable anionic rich formulations without the need for other co-primary surfactants. It was also unexpectedly found that branched isethionates exhibit lower Krafft points that are well below room temperature (about 20°C). With the lower Krafft points, the branched isethionate can enable optical clarity for formulations made therefrom at lower temperatures (e.g., 4 to 25°C). The lower Krafft points of the branched isethionates disclosed herein can also limit any unwanted crystallization at the lower temperatures thereby enabling improved formulation stability when storage temperature is lower such as in winter. The tail branched isethionates were further found to demonstrate superior lathering capabilities as compared to linear isethionates meaning that the branched isethionates can be an ideal choice of surfactant in personal care products in which lathering is desired. The branched isethionates additionally can assist in reducing the amount of salt needed in formulations made therefrom to achieve a desired viscosity. For example, no salt may be required in formulations made using branched isethionates.

An anionic surfactant can comprise a compound or mixture of compounds having the formula:

The compound comprises at least one branched functional group at the R position. R can comprise a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group can include straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof.

M⁺ can be a monovalent cation. For example, M⁺ can comprise sodium, potassium, ammonium, lithium, caesium, rubidium, francium, alkylammonium, triethanolammonium, or a combination thereof.

The branched functional groups can comprise alkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxy groups, or a combination thereof. Any of these functional branching groups can be saturated, unsaturated, or a combination thereof. The alkyl groups can comprise a linear alkane. The linear alkane can have 1 to 20 carbons. The alkyl groups can comprise a branched alkane. The branched alkane can have 1 to 20 carbons. The alkyl groups can comprise acyclic alkane. The alkyl groups can comprise cyclic alkane. The alkyl groups can comprise the linear alkane, the branched alkane, the acyclic alkane, the cyclic alkane, or a combination thereof. Any of these linear, branched, acyclic, or cyclic alkanes can be saturated, unsaturated, or a combination thereof.

For example, the alkyl groups can comprise methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, or a combination thereof. Any of these alkyl groups can be saturated, unsaturated, or a combination thereof.

The aryl groups can comprise a substituted group having 1 to 20 carbons. The aryl groups can comprise an unsubstituted aryl group having 1 to 20 carbons. The aryl groups can comprise a substituted groups having 1 to 20 atoms, an unsubstituted group having 1 to 20 carbons, or a combination thereof.

For example, the aryl groups can comprise phenyl, benzyl, or a combination thereof.

The alkoxy groups can comprise linear oxy-alkane, branched oxy-alkane, or a combination thereof.

For example, the alkoxy groups can comprise methoxy, ethoxy, propoxy, iso-propoxy, butoxy, sec-butoxy, tert-butoxy, or a combination thereof.

The aryloxy groups can comprise a substituted aryloxy group having 1 to 20 carbons. The aryloxy groups can comprise an unsubstituted aryloxy group having 1 to 20 carbons. The aryloxy groups can comprise an oxy-methyl group having 1 to 20 carbons. The aryloxy groups can comprise a substituted aryloxy group having 1 to 20 carbons, an unsubstituted aryloxy group having 1 to 20 carbons, an oxy-methyl aryl group having 1 to 20 carbons, or a combination thereof.

For example, the aryloxy groups can comprise phenoxy, benzyloxy, or a combination thereof.

The hydroxy groups can be further chemically derivatized into other functional groups. For example, the hydroxy groups can be derivatized into ethers (e.g., methoxy, ethoxy, t-butoxy), polyoxy ethers (e.g., ethoxylation), carboxylic acids, esters, ketones, acetals, hemiacetal, amines, amides, urethanes, or a combination thereof.

In an embodiment, the compound or mixture of compounds can have the formula:

In this formula, the compound or mixture of compounds is branched at Ri, R2, R’2, R3, or a combination thereof.

R1 can comprise branched functional groups. R1 can also comprise hydroxy or methyl or hydrogen. The branched functional groups can comprise alkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxy groups, or a combination thereof. Any of these functional branching groups can be saturated, unsaturated, or a combination thereof.

The alkyl groups can comprise a linear alkane. The linear alkane can have 1 to 20 carbons. The alkyl groups can comprise a branched alkane. The branched alkane can have 1 to 20 carbons.

The alkyl groups can comprise acyclic alkane. The alkyl groups can comprise cyclic alkane. The alkyl groups can comprise the linear alkane, the branched alkane, the acyclic alkane, the cyclic alkane, or a combination thereof. Any of these linear, branched, acyclic, or cyclic alkanes can be saturated, unsaturated, or a combination thereof.

For example, the aryl groups can comprise phenyl, benzyl, or a combination thereof. The alkoxy groups can comprise linear oxy-alkane, branched oxy-alkane, or a combination thereof.

In an embodiment, Ri comprises hydrogen or hydroxy or methyl. In an embodiment, Ri is hydrogen or hydroxy or methyl.

R2 and R’2 can comprise branched functional groups. R2 and R’2 can comprise methyl or hydrogen or hydroxy. The branched functional groups can comprise alkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxy groups, or a combination thereof. Any of these functional branching groups can be saturated, unsaturated, or a combination thereof. In an embodiment, if R2 comprises a hydroxy group, then R’2 does not comprise a hydroxy group. In another embodiment, if R’2 comprises a hydroxy group, then R2 does not comprise a hydroxy group. If both R2 and R’2 comprise hydrogen, then Ri does not comprise hydrogen if R3 is a linear hydrocarbon group. If R3 is a branched hydrocarbon, then all of R2, R2, and Ri can comprise hydrogen.

The alkyl groups can comprise a linear alkane. The linear alkane can have 1 to 20 carbons. The alkyl groups can comprise a branched alkane. The branched alkane can have 1 to 20 carbons. The alkyl groups can comprise acyclic alkane. The alkyl groups can comprise cyclic alkane. The alkyl groups can comprise the linear alkane, the branched alkane, the acyclic alkane, the cyclic alkane, or a combination thereof. Any of these linear, branched, acyclic, or cyclic alkanes can be saturated, unsaturated, or a combination thereof.

The hydroxy groups can be further chemically derivatized into other functional groups. For example, the hydroxy groups can be derivatized into ethers (e.g., methoxy, ethoxy, t-butoxy), polyoxy ethers (e.g., ethoxylation), carboxylic acids, esters, ketones, acetals, hemiacetal, amines, amides, urethanes, or a combination thereof. In an embodiment, R2 or R’2 comprises methyl, hydrogen, or hydroxy. In an embodiment, R2 or R’2 is methyl, or hydrogen, or hydroxy.

R3 can comprise a hydrocarbon. The hydrocarbon can have 1 to 18 carbons. The hydrocarbon group can include straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof.

M⁺ in the formula can be monovalent cation. For example, M⁺ can comprise sodium, potassium, ammonium, lithium, caesium, rubidium, francium, alkylammonium, triethanolammonium, or a combination thereof.

In an embodiment, the compound or mixture of compounds can have the formula:

In this formula, the compound or mixture of compounds is branched at R1, R’1, R2, R’2, R3, or a combination thereof.

R1 or R’1 can comprise branched functional groups. R1 or R’1 can comprise hydrogen or methyl or hydroxy. The branched functional groups can comprise alkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxy groups, or a combination thereof. Any of these functional branching groups can be saturated, unsaturated, or a combination thereof. In an embodiment, if R2 comprises a hydroxy group, then R’2 does not comprise a hydroxy group. In another embodiment, if R’2 comprises a hydroxy group, then R2 does not comprise a hydroxy group.

The alkyl groups can comprise acyclic alkane. The alkyl groups can comprise cyclic alkane. The alkyl groups can comprise the linear alkane, the branched alkane, the acyclic alkane, the cyclic alkane, or a combination thereof. Any of these linear, branched, acyclic, or cyclic alkanes can be saturated, unsaturated, or a combination thereof. For example, the alkyl groups can comprise methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, or a combination thereof. Any of these alkyl groups can be saturated, unsaturated, or a combination thereof.

In an embodiment, Ri or R’i comprises hydrogen or methyl or hydroxy. In an embodiment, Ri or R’i is hydrogen or methyl or hydroxy.

R2 and R’2 can comprise branched functional groups. R2 and R’2 can comprise methyl, or hydroxy, or hydrogen. The branched functional groups can comprise alkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxy groups, or a combination thereof. Any of these functional branching groups can be saturated, unsaturated, or a combination thereof. In an embodiment, if R2 comprises a hydroxy group, then R’2 does not comprise a hydroxy group. In another embodiment, if R’2 comprises a hydroxy group, then R2 does not comprise a hydroxy group.

In an embodiment, R2 or R’2 comprises methyl, hydroxy, or hydrogen. In an embodiment, R2 or R’2 is methyl, hydroxy, or hydrogen. If both R2 and R’2 comprise hydrogen, then R1 does not comprise hydrogen. If Rs is a linear hydrocarbon group. If Rs is a branched hydrocarbon, then all of R2, R2, and R1 can comprise hydrogen.

In an embodiment, the anionic surfactant is a branched isethionate. The branched isethionate can comprise 2-methyl lauroyl isethionate, 3-methyl lauroyl isethionate, or 2,2-dimethyl isethionate. In an embodiment, the branched isethionate is 2-methyl lauroyl isethionate, 3-methyl lauroyl isethionate, or 2,2-dimethyl isethionate. In an embodiment, the branched isethionate can comprise sodium 2-methyl lauroyl isethionate, sodium 3-methyl lauroyl isethionate, or sodium 2,2-dimethyl lauroyl isethionate. In an embodiment, the branched isethionate is sodium 2-methyl lauroyl isethionate, sodium 3-methyl lauroyl isethionate, or sodium 2,2-dimethyl lauroyl isethionate.

A cleansing composition can be formulated from the anionic surfactant disclosed herein. The cleansing composition can be a liquid cleansing composition or a cleansing bar. The cleansing composition can be a wash composition (liquid or bar) for the hands, body, face, etc., a shampoo, or a conditioner. The branched isethionate disclosed herein can be present in such compositions in an amount of 1 to 15% by weight, based on the weight of the cleansing composition, for example, 2 to 12% by weight, based on the weight of the cleansing composition, for example, 2 to 10% by weight, based on the weight of the cleansing composition, for example, 3 to 8% by weight, based on the weight of the cleansing composition, for example, 3 to 7% by weight, based on the weight of the cleansing composition, for example, 3 to 6% by weight, based on the weight of the cleansing composition, including any and all ranges and values subsumed therein.

Cleansing compositions made using the anionic surfactant can include additional ingredients. For example, the cleansing compositions can include additional surfactants, including anionic, amphoteric, zwitterionic, nonionic, cationic, or a combination thereof,

An additional surfactant can contain Cs-C alkyl groups, for example, C12-C16 alkyl groups, for example, C10-C14 alkyl groups, or mixtures thereof. For example, the surfactant and/or cosurfactant can contain C10 alkyl groups, C12 alkyl groups, C14 alkyl groups, or any combination thereof.

An additional anionic surfactant used can include aliphatic sulfonates, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate. The anionic surfactant may also be an alkyl sulfate (e.g., C12-C18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:

RO(CH₂CH₂O)_nSO3M wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of at least 1 .0, preferably less than 5, and most preferably 1 to 4, and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium.

The additional anionic surfactant may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C6-C22 sulfosuccinates); alkyl and acyl taurates (often methyl taurates), alkyl and acyl sarcosinates, sulfoacetates, C8-C22 alkyl phosphates and phosphonates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, sulphoacetates, alkyl glucosides and acyl isethionates, and the like. Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:

R¹OC(O)CH₂CH(SO₃M)CO₂M; and amide-MEA sulfosuccinates of the formula:

R¹CONHCH₂CH₂OC(O)CH₂CH(SO₃M)CO₂M wherein R¹ ranges from Cs-C₂₂ alkyl.

Sarcosinates are generally indicated by the formula:

R²CON(CH₃)CH₂CO₂M, wherein R² ranges from Cs-C₂o alkyl.

Taurates are generally identified by formula:

R³CONR⁴CH₂CH₂SO₃M wherein R³ is a Cs-C₂o alkyl, R⁴ is a C1-C4 alkyl.

M is a solubilizing cation as previously described.

The additional surfactant can contain Cs-C acyl isethionates. These esters are prepared by a reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.

The acyl isethionate may be an alkoxylated isethionate such as is described in llardi et al., U.S. Pat. No. 5,393,466, entitled "Fatty Acid Esters of Polyalkoxylated isethonic acid; issued Feb. 28, 1995; hereby incorporated by reference. This compound has the general formula:

R⁵C— (0)0— C(X)H— C(Y)H— (OCH₂— CH₂)_m— SO₃M wherein R⁵ is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are each independently hydrogen or an alkyl group having 1 to 4 carbons and M is a solubilizing cation as previously described. In the cleansing compositions, the additional anionic surfactant used can be 2-acrylamido-2- methylpropane sulfonic acid, ammonium lauryl sulfate, ammonium perfluorononanoate, potassium lauryl sulfate, sodium alkyl sulfate, sodium dodecyl sulfate, sodium laurate, sodium laureth sulfate, sodium lauroyl sarcosinate, sodium stearate, sodium sulfosuccinate esters, sodium lauroyl isethionate, or a combination thereof. Such anionic surfactants are commercially available from suppliers like Galaxy Surfactants, Clariant, Sino Lion, Stepan Company, and Innospec.

An additional anionic surfactant used can be sodium lauroyl glycinate, sodium cocoyl glycinate, sodium lauroyl glutamate, sodium cocoyl glutamate, sodium lauroyl isethionate, sodium cocoyl isethionate, sodium methyl lauroyl taurate, sodium methyl cocoyl taurate, sodium laureth sulfate, sodium pareth sulfate, alpha olefin sulfonate (AOS), or a combination thereof. Such anionic surfactants are commercially available from suppliers like Galaxy Surfactants, Clariant, Sino Lion and Innospec. Sodium cocoyl isethionate, sodium methyl lauroyl taurate, sodium lauroyl glyconate, sodium methyl lauroyl isethionate, sodium laureth sulfate, sodium pareth sulfate, alpha olefin sulfonate (AOS), or a combination thereof can be the preferred anionics suitable for use when used in the cleansing composition.

The additional anionic surfactant can be present in an amount of 0.01% by weight to 35% by weight, for example, 0.5% by weight to 30% by weight, for example, 1% by weight to 25% by weight, for example, 1 % by weight to 20% by weight, for example, 1 % by weight to 17% by weight, for example, 1% by weight to 15% by weight, for example, 1% by weight to 12.5% by weight of the overall cleansing composition, including any all ranges and values subsumed therein.

Amphoteric surfactants can be included in the cleansing compositions disclosed herein. Amphoteric surfactants (which depending on pH can be zwitterionic) include sodium acyl amphoacetates, sodium acyl amphopropionates, disodium acyl amphodiacetates and disodium acyl amphodipropionates where the acyl (i.e. , alkanoyl group) can comprise a C7-C18 alkyl portion. Illustrative examples of amphoteric surfactants include sodium lauroamphoacetate, sodium cocoamphoacetate, sodium lauroamphoacetate, or a combination thereof.

The amphoteric surfactant can be present in an amount of 0.01% by weight to 35% by weight, for example, 0.5% by weight to 30% by weight, for example, 1 % by weight to 25% by weight, for example, 1% by weight to 20% by weight, for example, 1 % by weight to 17% by weight, for example, 1 % by weight to 15% by weight, for example, 1 % by weight to 12.5% by weight, for example, 1% by weight to 10% by weight, for example, 1% by weight to 6% by weight, for example, 1 % by weight to 4% by weight, of the overall cleansing composition, including any all ranges and values subsumed therein.

As to the zwitterionic surfactants employed in the cleansing composition, such surfactants include at least one acid group. Such an acid group may be a carboxylic or a sulphonic acid group. They often include quaternary nitrogen, and therefore, can be quaternary amino acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms and generally comply with an overall structural formula:

R⁶— [— C(O)— NH(CH₂)q— ],— N⁺(R⁷)(R⁸)-A— B where R⁶ is alkyl or alkenyl of 7 to 18 carbon atoms; R⁷ and R⁸ are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; q is 2 to 4; r is 0 to 1 ; A is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and B is — CO₂ — or — SO₃ — .

Desirable zwitterionic surfactants for use in the cleansing composition disclosed herein and within the above general formula include simple betaines of formula:

R⁶— N⁺(R⁷)(R⁸)-CH₂CO₂- and amido betaines of formula:

R⁶— CONH(CH₂)_t— N⁺ (R⁷)(R⁸)-CH₂CO₂- where t is 2 or 3.

In both formulae R⁶, R⁷ and R⁸ are as defined previously. R⁶ may, in particular, be a mixture of Ci₂ and C14 alkyl groups derived from coconut oil so that at least half, preferably at least three quarters of the groups R⁶ have 10 to 14 carbon atoms. R⁷ and R⁸ are preferably methyl.

A further possibility is that the zwitterionic surfactant is a sulphobetaine of formula:

R⁶ — N⁺(R⁷)(R⁸)-(CH₂)3SO₃- or R⁶— CONH(CH₂)_U— N⁺(R⁷)(R⁸)-(CH₂)₃SO₃- where u is 2 or 3, or variants of these in which — (CH₂)₃SO₃‘ is replaced by — CH₂C(OH)(H)CH₂SO₃-.

In these formulae, R⁶, R⁷ and R⁸ are as previously defined.

Illustrative examples of the zwitterionic surfactants desirable for use include betaines such as lauryl betaine, betaine citrate, cocodimethyl carboxymethyl betaine, cocoamidopropyl betaine (CAPB), coco alkyldimethyl betaine, and laurylamidopropyl betaine. An additional zwitterionic surfactant suitable for use includes cocoamidopropyl sultaine, for example, cocamidopropyl hydroxysultaine. Preferred zwitterionic surfactants include lauryl betaine, betaine citrate, sodium hydroxymethylglycinate, (carboxymethyl) dimethyl-3-[(1 -oxododecyl) amino] propylammonium hydroxide, coco alkyldimethyl betaine, (carboxymethyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxy methyl) dimethyloleylammonium hydroxide, cocoamidopropyl betaine, (carboxylatomethyl) dimethyl(octadecyl)ammonium, cocamidopropyl hydroxysultaine, or a combination thereof. Such surfactants are made commercially available from suppliers like Stepan Company, Solvay, Evonik and the like and it is within the scope of the cleansing compositions disclosed herein to employ mixtures of the aforementioned surfactants.

The zwitterionic surfactant can be present in an amount of 0.01 % by weight to 35% by weight, for example, 0.5% by weight to 30% by weight, for example, 1 % by weight to 25% by weight, for example, 1% by weight to 20% by weight, for example, 1 % by weight to 17% by weight, for example, 1 % by weight to 15% by weight, for example, 1 % by weight to 12.5% by weight, for example, 1% by weight to 10% by weight, for example, 1% by weight to 6% by weight, for example, 1 % by weight to 4% by weight, of the overall cleansing composition, including any all ranges and values subsumed therein.

Nonionic surfactants can be used in the cleansing composition. When used, nonionic surfactants are typically used at levels as low as 0.5, 1 , 1.5, or 2% by weight and at levels as high as 6, 8, 10 or 12% by weight of the overall cleansing composition, including any all ranges and values subsumed therein. The nonionic surfactants which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic surfactant compounds are alkyl (C6-C₂₂) phenols, ethylene oxide condensates, the condensation products of aliphatic (Cs-C ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other nonionic surfactants include long chain tertiary amine oxides, long chain tertiary phosphine oxides, dialkyl sulphoxides, and the like.

In an aspect, nonionic surfactants can include fatty acid/alcohol ethoxylates having the following structures a) HOCH2(CH2)_s(CH2CH2O)_c H or b) HOOC(CH2)_v(CH2CH2O)d H; where s and v are each independently an integer up to 18; and c and d are each independently an integer from 1 or greater. In an aspect, s and v can be each independently 6 to 18; and c and d can be each independently 1 to 30. Other options for nonionic surfactants include those having the formula HOOC(CH2)i — CH=CH — (CH2)k(CH2CH2O)_z H, where i, k are each independently 5 to 15; and z is 5 to 50. In another aspect, i and k are each independently 6 to 12; and z is 15 to 35.

The nonionic surfactant may also include a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al., entitled "Compositions Comprising Nonionic Glycolipid Surfactants issued Feb. 14, 1995; which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, titled "Use of N-Poly Hydroxyalkyl Fatty Acid Amides as Thickening Agents for Liquid Aqueous Surfactant Systems" issued Apr. 23, 1991 ; hereby incorporated into the subject application by reference.

Illustrative examples of nonionic surfactants that can optionally be used in the cleansing compositions disclosed herein include, but are not limited to, polyglycoside, cetyl alcohol, decyl glucoside, lauryl glucoside, octaethylene glycol monododecyl ether, n-octyl beta-d- thioglucopyranoside, octyl glucoside, oleyl alcohol, polysorbate, sorbitan, stearyl alcohol, or a combination thereof.

In an aspect, cationic surfactants can be used in the cleansing composition of the present application.

One class of cationic surfactants includes heterocyclic ammonium salts such as cetyl or stearyl pyridinium chloride, alkyl amidoethyl pyrrylinodium methyl sulfate, and lapyrium chloride. Tetra alkyl ammonium salts are another useful class of cationic surfactants for use. Examples include cetyl or stearyl trimethyl ammonium chloride or bromide; hydrogenated palm or tallow trimethylammonium halides; behenyl trimethyl ammonium halides or methyl sulfates; decyl isononyl dimethyl ammonium halides; ditallow (or distearyl) dimethyl ammonium halides, and behenyl dimethyl ammonium chloride.

Still other types of cationic surfactants that may be used are the various ethoxylated quaternary amines and ester quats. Examples include PEG-5 stearyl ammonium lactate (e.g., Genamin KSL manufactured by Clariant), PEG-2 coco ammonium chloride, PEG-15 hydrogenated tallow ammonium chloride, PEG 15 stearyl ammonium chloride, dipalmitoyl ethyl methyl ammonium chloride, dipalmitoyl hydroxyethyl methyl sulfate, and stearyl amidopropyl dimethylamine lactate.

Still other useful cationic surfactants include quaternized hydrolysates of silk, wheat, and keratin proteins, and it is within the scope of the cleansing composition to use mixtures of the aforementioned cationic surfactants.

If used, cationic surfactants will make up no more than 1.0% by weight of the cleansing composition. When present, cationic surfactants typically make up from 0.01 to 0.7%, and more typically, from 0.1 to 0.5% by weight of the cleansing composition, including all ranges subsumed therein.

Cationic polymers can be included in cleansing compositions made with the anionic surfactants disclosed herein, for example, in shampoo or conditioner formulations. Desirable cationic polymers include homopolymers which are cationically substituted or can be formed from two or more types of monomers. The weight average (M_w) molecular weight of the polymers will generally be between 100,000 and 3 million Daltons. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof. If the molecular weight of the polymer is too low, then the cleansing effect is poor. If too high, then there can be problems of high extensional viscosity leading to stringiness of the composition when it is poured.

The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus, when the polymer is not a homopolymer it can contain spacer non-cationic monomer units. The ratio of the cationic to non-cationic monomer units is selected to give polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm (milli-equivalents per gram). The cationic charge density of the polymer is determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.

Desirable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.

The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary, are preferred.

Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.

The cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.

Suitable (non-limiting examples of) cationic polymers include: cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Patent No. 4,009,256); cationic polyacrylamides (as described in International Publication No. WO 1995/22311).

Other cationic polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. Cationic polysaccharide polymers desirable for use include monomers of the formula:

A-O-[R-N⁺(R¹)(R²)(R³)X-], wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹, R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e. , the sum of carbon atoms in R¹, R² and R³) is preferably about 20 or less, and X is an anionic counterion.

Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from the Amerchol Corporation, for instance under the tradename Polymer LM-200.

Other cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g., as described in U.S. No. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g., as described in U.S. No. Patent 3,958,581). Examples of such materials include the polymer LR and JR series from Dow, generally referred to in the industry (CTFA) as Polyquaternium 10.

A particularly desirable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in their JAGUAR™ trademark series). Examples of such materials are JAGUAR™ C13S, JAGUAR™ C14, JAGUAR™ C17, and JAGUAR™ S.

Mixtures of any of the above cationic polymers can be used.

Other desirable cationic polymers include cationic polysaccharide polymers, cationic diallyl quaternary ammonium-containing polymers, mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, cationic polyacrylamines, or a combination thereof. For example, the cationic polymer can comprise cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, or a combination thereof. Cationic polymers will generally be present at levels of 0.01 to 5%, preferably from 0.02 to 1%, more preferably from 0.05 to 0.8% by total weight of cationic polymer based on the total weight of the composition, including any and all ranges and values subsumed therein.

Cleansing compositions made using the anionic surfactant disclosed herein can contain 1.0 to 10.0% by weight of a conditioning agent based on the total weight of the cleansing composition.

The conditioning agent can comprise behentrimonium chloride, stearamidopropyl dimethylamine, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, hydrogenated tallow alkyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl propyleneglycol phosphate dimethyl ammonium chloride, stearoyl amidopropyl dimethyl benzyl ammonium chloride, stearoyl amidopropyl dimethyl (myristylacetate) ammonium chloride, N- (stearoyl colamino formyl methy) pyridinium chloride, or a combination thereof.

One class of conditioning agent includes heterocyclic ammonium salts such as cetyl or stearyl pyridinium chloride, alkyl amidoethyl pyrrylinodium methyl sulfate, lapyrium chloride, or a combination thereof.

Tetra alkyl ammonium salts are another useful class of conditioning agents. Examples include cetyl or stearyl trimethyl ammonium chloride or bromide, hydrogenated palm or tallow trimethylammonium halides, behenyl trimethyl ammonium halides or methyl sulfates, decyl isononyl dimethyl ammonium halides, ditallow (or distearyl) dimethyl ammonium halides, behenyl dimethyl ammonium chloride, or a combination thereof.

Still other types of cationic surfactant conditioning agents that can be used are the various ethoxylated quaternary amines and ester quats. Examples include PEG-5 stearyl ammonium lactate (e.g., Genamin KSL manufactured by Clariant), PEG-2 coco ammonium chloride, PEG- 15 hydrogenated tallow ammonium chloride, PEG 15 stearyl ammonium chloride, dipalmitoyl ethyl methyl ammonium chloride, dipalmitoyl hydroxyethyl methyl sulfate, stearyl amidopropyl dimethylamine lactate, or a combination thereof.

Even other conditioning agents include quaternized hydrolysates of silk, wheat, and keratin proteins, or a combination thereof. Oat peptide is another useful additive in the cleansing compositions. Other desirable conditioning agents comprise copolymers of 1-vinyl-2-pyrrolidone and 1 -vinyl-3- methylimidazolium salt; copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate; cationic diallyl quaternary ammonium-containing polymers, or a combination thereof.

The cationic diallyl quaternary ammonium-containing polymers can comprise dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride.

The conditioning agent can additionally optionally comprise a silicone. When present, the silicone conditioning agent can comprise dimethicone, amodimethicone, cyclomethicone, dimethiconol and dimethiconol/silsesquioxane copolymer, isohexadecane, or a combination thereof.

The conditioning agent can be present in an amount of 0.1 to 5% by weight, for example, 0.25 to 4% by weight, for example, 0.5 to 3% by weight, for example, 1.0 to 2.5% by weight, for example, 0.1 to 1.0% by weight, based on the total weight of the cleansing composition, including any and all ranges and values subsumed therein.

Cleansing compositions as disclosed herein can comprise less than 3.0% by weight sulfate, preferably less than 1.0% by weight, and most preferably, no (0.0% by weight) sulfate such that the cleansing compositions are essentially sulfate free or entirely sulfate free.

Preservatives can desirably be incorporated into the cleansing composition to protect against the growth of potentially harmful microorganisms. Preservatives are antimicrobial ingredients added to maintain the microbiological safety of products. They act to inhibit the growth of microbes and so reduce the level of microbial contamination. As personal cleansing formulations such as those disclosed herein contain biodegradable ingredients, they can become unpleasant and unsafe if microbial breakdowns is not controlled. Microbial growth is water dependent, so preservatives must partition to some extent into the aqueous phase of a formulation. Commonly used preservatives can be categorized into the following five classes:

1) Parabens such as Methyl-, Propyl-, and Butylparaben and Germaben II are derived from parahydroxy benzoic acid. These materials are economical and effective against fungals and some Gram negative bacteria but need a second ingredient to control Gram positives. They also tend to partition more towards the oil phase in emulsion-containing formulations. They are widely employed at levels of 0.01-0.3% by weight of the cleansing composition and are generally considered safe - though there have been concerns over possible estrogenic activity and links to cancer.

2) Formaldehyde Releasers such as Germall Plus, DMDM Hydantoin, and Imadozolidinyl or Diazolidinyl Urea. This class of materials is effective against bacteria but offers only weak antifungal activity. They are used at levels of 0.1 -0.5% by weight in the pH range 3-8. The low levels of free formaldehyde released ensure microbial inhibition, but cause concerns as potential carcinogens.

3) Isothiazolinones such as methylcholoroisothiazolinone (MCI), methylisothiazolinone (Ml), and Kathon. Isothiazolinones offer broad spectrum effectiveness over a broad pH range, but they may cause skin irritation for some consumers. This class of materials is employed at low levels, on the order of 10’s of ppms.

4) Phenoxyethanol, marketed as Optiphen or Optiphen Plus and NeoIone PH 100. Phenoxyethanol is often considered as a milder alternative to parabens or formaldehyde-donors but has a narrow spectrum of applicability to Gram negative bacteria. It is generally combined with caprylyl glycol, sorbic acid/potassium sorbate, or EDTA to create broad spectrum efficacy. It is applicable over a wide range of pH, with a typical usage level of 1% or less. However, there are some concerns over possible carcinogenic activity.

5) Organic Acids such as Benzoic Acid/Sodium Benzoate, Sorbic Acid/Potassium Sorbate, Salicylic Acid/Sodium Salicylate, and Levulinic or Anisic Acids. The use of these acids is confined to aqueous applications in the pH range of 2-6. They typically are used at higher levels than some of the above alternatives and have somewhat weaker efficiency against bacteria (which can be augmented by combination with diazolidinyl urea), though they are very good against fungi. This class of preservatives are generally considered as natural.

Preservatives for use in the cleansing compositions disclosed herein can include organic acid based preservatives, preferably sodium benzoate, caprylyl glycol, or a combination thereof. Traditional preservatives for use include hydantoin derivatives and propionate salts.

Other preservatives for use are iodopropynyl butyl carbamate (IPBC), phenoxyethanol, 1 ,2- octanediol, hydroxyacetophenone, ethylhexylglycerine, hexylene glycol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate, dimethyl-dimethyl (DMDM) hydantoin and benzyl alcohol and mixtures thereof. Other preservatives include sodium benzoate, sodium dehydroacetate, chlorophenesin, decylene glycol, methylchloroisothiazolinone, methylisothiazolinone, or a combination thereof. The preservatives should be selected having regard for the use of the composition and possible incompatibilities between the preservatives and other ingredients in the cleansing composition. Also preferred is a preservative system with hydroxyacetophenone alone or in a mixture with other preservatives. Particularly preferred is sodium benzoate, iodopropynyl butyl carbamate, phenoxyethanol, or a combination thereof.

As noted herein preservative that includes phenoxyethanol (with or without capryloyl glycine and/or undecylenoyl glycine), iodopropynyl butylcarbamate, benzoic acid (and/or a derivative of benzoic acid natural or synthetic) as well as mixtures thereof are very suitable and often desired for use in the cleansing comoposition.

Preservatives can be used in an amount 0.001 to 1.5% by weight, for example, 0.002 to 1.5% by weight, for example, 0.003 to 1.5% by weight, for example, 0.004 to 1.5% by weight, for example, 0.005 to 1.5% by weight, for example, 0.006 to 1.5% by weight, for example, 0.007 to 1.5% by weight, for example, 0.008 to 1.5% by weight, for example, 0.1 to 1.5% by weight, for example, 0.5 to 1.5% by weight, of the overall cleansing composition, including an all ranges and values subsumed therein.

Again, it is preferred that the compositions are free of or substantially free of isothiazolinones, hydantoins and parabens. Substantially free of or essentially free of as disclosed herein means less than 0.5% by weight, and preferably, less than 0.3% by weight, and most preferably, less than 0.15% by weight (or less than 0.1% or 0.05% or 0.04 to 0.01% or 0.0% (none) by weight) based on total weight of the cleansing composition.

As to heterocyclic impurities, like 1,4-dioxane, the same can be removed with biofilters (nitrogen removal biofilters), and processes that employ ozone and ozone with peroxide where the impurities may be removed from solutions comprising them including those with sulfated surfactants. The cleansing compositions can be formulated to comprise less than 25 ppm heterocyclic impurities. Preferably, the cleansing compositions have less than 10 ppm, and preferably, less than 5 ppm, and most preferably, less than 2 ppm, and less than 1 ppm or even less than 0.05 ppm or no heterocyclic impurities like 1,4-dioxane.

The cleansing compositions disclosed herein typically contain water in an amount of 20 to 95% by weight, more particularly 50 to 90% by weight, based on the total weight of the cleansing composition, for example, 75 to 90% by weight, based on the total weight of the cleansing composition, including any and all ranges and values subsumed therein. Such water contents are representative of a relatively broad range of compositions, including both concentrated and non-concentrates products, with formulations having water contents of 20 to less than 50% by weight of water being typical of concentrated products.

The cleansing composition can additionally include various additives including, but not limited to, colorants, anti-dandruff agents, skin feel agents, hair dyes, styling polymer, silicon oil, cationic polymers, or a combination thereof. Each of these substances can be present in an amount of 0.03 to 5% by weight, preferably between 0.1 and 3% by weight of the total weight of the cleansing composition, including any and all ranges and values subsumed therein. For example, when present, colorants can be present in an amount of 5 parts per million (ppm) to 15 ppm, for example, about 15 ppm.

Additional optional ingredients which may be present in the cleansing compositions are, for example: fragrances; coloring agents; opacifiers and pearlizers such as zinc stearate, magnesium stearate, titanium dioxidie (TiC>2), ethylene glycol monostearate (EGMS), ethylene glycol distearate (EGDS) or LYTRON 621 (Styrene/Acrylate copolymer) and the like; antioxidants, for example, butylated hydroxytoluene (BHT) and the like; stabilizers; suds boosters, such as for example, coconut acyl mono- or diethanol amides; ionizing salts, such as, for example, sodium chloride and sodium sulfate, and other ingredients such as are conventionally used in liquid soap formulations. The total amount of such additional optional ingredients is typically 0 to 10% by weight, more particularly from 0.1 to 5% by weight, based on the total weight of the cleansing composition.

The compositions typically include one or more skin benefit agents. The term “skin benefit agent” is defined as a substance which softens or improves the elasticity, appearance, and youthfulness of the skin (stratum corneum) by either increasing its water content, adding, or replacing lipids and other skin nutrients, or both, and keeps it soft by retarding the decrease of its water content. Included among the skin benefit agents are emollients, including, for example, hydrophobic emollients, hydrophilic emollients, or blends thereof.

The cleansing composition can further comprise an emollient. The emollient can be present in an amount of 0.01 to 5.0% by weight, based on the total weight of the cleansing composition including any and all ranges and values subsumed therein. In an embodiment, the emollient comprises an oil, a butter, a wax, or a combination thereof. The oil can be Baobab seed oil, Argan kernel oil, behenyl neopentanoate, Borage seed oil, Rapeseed seed oil, Tamanu seed oil, False Flax seed oil, Camellia seed oil, caprylic/capric triglyceride, Safflower seed oil, coco-caprylate/caprate, Coconut oil, Hazel seed oil, Crambe seed oil, Cotton seed oil, Sunflower seed oil, Sea Buckthorn oil, isopropyl myristate, isononyl isonanonoate, isopropyl palmitate, jojoba esters, lanolin oil and lanolin derivatives, Limnanthes Alba (Meadowfoam) seed oil, Linseed seed oil, Macadamia seed oil, Moringa seed oil, Evening Primrose oil, Olive fruit oil, Babassu seed oil, Rice germ oil, Avocado oil, Sacha inchi seed oil, Sweet Almond oil, Castor seed oil, Rosehip seed oil, Chia seed oil, Sage oil, Mongongo kernel oil, Marula seed oil, Sesame seed oil, Sal seed oil, silicone, Jojoba seed oil, squalane, Thyme oil, algae oil, Wheat germ oil, Grapeseed oil, Corn oil, or a combination thereof.

The butter can be aloe butter, avocado butter, bacuri butter, cocoa butter, coconut butter, coffee bean butter, cupuagu butter, hemp seed butter, illipe butter, kokum butter, macadamia nut butter, mango butter, mochacchino butter, murumuru butter, olive butter, pistachio nut butter, refined butter, shea butter, sweet almond butter, tucuma butter, ucuuba butter, or a combination thereof.

The wax can be carnauba, spermaceti, beeswax, lanolin, and derivatives thereof.

Other useful skin benefit agents include the following:

(a) silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; amino, alkyl, alkylaryl, and aryl silicone oils;

(b) fats and oils including natural fats and oils such as soybean, rice bran, persic, and mink oils; cacao fat; beef tallow and lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono, di and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride;

(c) hydrophobic and hydrophilic plant extracts;

(d) hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil;

(e) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PLIFA);

(f) higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol;

(g) esters such as cetyl octanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol monolaurate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate;

(h) essential oils and extracts thereof such as mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, sugar cane, chamomile, yarrow, liquorice, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, Citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene and terpenoid oils;

(i) polyhydric alcohols, for example, glycerine, sorbitol, propylene glycol, and the like; and polyols such as the polyethylene glycols, examples of which are: Polyox WSR-205 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750, and PEG 7M;

(j) lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957;

(k) vitamins, minerals, and skin nutrients such as milk, vitamins A, E, and K; vitamin alkyl esters, including vitamin C alkyl esters; magnesium, calcium, copper, zinc and other metallic components;

(l) sunscreens such as octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789);

(m) phospholipids; and

(n) anti-aging compounds such as alpha-hydroxy acids and beta-hydroxy acids.

Skin benefit agents commonly account for up to 30% by weight of the cleansing composition, with levels of 0 to 25% by weight preferred, more particularly 0 to 20% by weight, being typical of the levels at which those skin benefit agents are employed in many of the subject formulations. Preferred skin benefit agents include fatty acids, hydrocarbons, polyhydric alcohols, polyols and mixtures thereof, with emollients that include at least one C12 to C fatty acid, petrolatum, glycerol, sorbitol and/or propylene glycol being of particular interest in one or more embodiments.

Other optional ingredients include water soluble/dispersible polymers. These polymers can be cationic, anionic, amphoteric or nonionic types with molecular weights higher than 100,000 Dalton. They are known to increase the viscosity and stability of liquid personal cleansing formulation, to enhance in-use and after-use skin sensory properties, and to enhance lather creaminess and lather stability. When present, the total amount of such polymers commonly present in the cleansing compositions is 0.1 to 10% by weight, based on the total weight of the cleansing composition.

Examples of water soluble or dispersible polymers include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof; modified and nonmodified starch granules and pregelatinized cold water soluble starch; emulsion polymers such as ACLIYLN® 28, ACULYLN® 22 or CARBAPOL® Aqua SF1 ; cationic polymer such as modified polysaccharides including cationic guar available from Rhone Poulenc under the trade name JAGUAR™ C13S, JAGUAR™ C14S, JAGUAR™ C17, or JAGUAR™ C16; cationic modified cellulose such as UCARE™ Polymer JR 30 or JR 40 from Amerchol; N- HANCE® 3000, N-HANCE® 3196, N-HANCE® GPX 215 or N-HANCE® GPX 196 from Hercules; synthetic cationic polymer such as MERQUAT® 100, MERQUAT® 280, MERQUAT® 281 and MERQUAT® 550 sold by Nalco; cationic starches such as STALOK® 100, 200, 300 and 400 sold by Staley Inc.; cationic galactomannans such as GALACTASOL® 800 series by Henkel, Inc.; QUADROSOFT® LM-200; and Polyquaternium-24. Also suitable are high molecular weight polyethylene glycols such as POLYOX® WSR-205 (PEG 14M), POLUOX® WSR-N-60K (PEG 45), and POLYOX® WSR-301 (PEG 90M).

An opacifier may be optionally present in the cleansing composition. When opacifiers are present, the composition is generally opaque. Examples of opacifiers include titanium dioxide, zinc oxide, and the like. A particularly preferred opacifier that can be employed when an opaque soap composition is desired is ethylene glycol mono- or di-stearate, for example in the form of a 20% solution in sodium lauryl ether sulphate. An alternative opacifying agent is zinc stearate.

The product can take the form of a water-clear, i.e., transparent composition, in which case it will not contain an opacifier.

Desirably the optional skin benefit agents used in the antimicrobial composition disclosed herein include niacinamide (vitamin B3), tocopherol (Vitamin E), aloe vera, alpha-hydroxy acids and esters, beta-hydroxy acids and esters, hydroxyethyl urea, polyhydroxy acids and esters, creatine, hydroquinone, t-butyl hydroquinone, mulberry, hyaluronic acid and salts thereof (including, but not limited to, Na+ and K+ salts of the same), extract, liquorice extract, resorcinol derivatives, or a combination thereof. For example, the skin benefit agent can be sodium hyaluronate. Such benefit agents, including sodium hyaluronate can be present in an amount of 0.0001 to 10%, for example, 0.001 to 6.5%, for example, 0.01 to 3.5%, and for example, 0.01% by weight, based on total weight of the cleansing composition including any and all values and ranges subsumed therein.

Further optional water-soluble skin benefit agents include acids, such as amino acids like arginine, valine or histidine. Other vitamins can be used such as vitamin B2, picolinamide, panthenol (vitamin B5), vitamin Be, vitamin C, a combination thereof or the like. Derivatives (generally meaning something that has developed or been obtained from something else), and especially, water soluble derivatives of such vitamins can also be employed. For instance, vitamin C derivatives such as ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate, and ascorbyl glycoside may be used alone or in combination with each other. Niacinamide derivatives such as nicotinamide adenine dinucleotide (NADH) and nicotinamide adenine dinucleotide phosphate (NADPH) may be used alone or in combination with each other. Electrolytes such as NaCI and/or KCI, MgCh may also be used. The total amount of optional water-soluble benefit agents (including mixtures) when present in the composition disclosed herein can be 0.0001 to 10%, preferably, 0.001 to 6.5%, and most preferably, 0.01 to 3.5% by weight, based on total weight of the cleansing composition, including any and all values and ranges subsumed therein.

It is also within the scope of the cleansing composition to optionally include oil soluble benefit agents. Illustrative examples of the types of oil soluble benefit agents that can optionally be used in the cleansing composition disclosed herein include components such as vitamins like vitamin A, D, E (tocopherol) and K (and their oil soluble derivatives).

Other optional oil soluble benefit agents for use include resorcinols and resorcinol derivatives like 4-hexyl resorcinol, 4-phenylethyl resorcinol, 4-cyclopentyl resorcinol, 4-cyclohexyl resorcinol

4-isopropyl resorcinol or a combination thereof. Also, 5-substituted resorcinols like 4-cyclohexyl-

5-methylbenzene-1 ,3-diol, 4-isopropyl-5-methylbenzene-1 ,3-diol, combination thereof or the like may be used. The 5-substituted resorcinols and their synthesis are described in commonly assigned U.S. Patent No. 10,470,986 B2.

Even other oil soluble benefit agents that can be used include omega-3 fatty acids, omega-6 fatty acids, climbazole, magnolol, honokiol, farnesol, ursolic acid, myristic acid, geranyl geraniol, oleyl betaine, cocoyl hydroxyethyl imidazoline, hexanoyl sphingosine, 10-hydroxystearic acid, 12-hydroxystearic acid (12HSA), petroselinic acid, conjugated linoleic acid, stearic acid, palmitic acid, lauric acid, terpineol, thymol essential components, the dissolution auxiliary selected from limonene, pinene, camphene, cymene, citronellol, citronellal, geraniol, nerol, linalool, rhodinol, borneol, isoborneol, menthone, camphor, safrole, isosafrole, eugenol, isoeugenol, tea tree oil, eucalyptus oil, peppermint oil, neem oil, lemon grass oil, orange oil, bergamot oil, or a combination thereof of any of the oil soluble benefit agents.

Another optional oil soluble benefit agent that may be used is a retinoic acid precursor. The retinoic acid precursor can be retinol, retinal, retinyl ester, retinyl propionate, retinyl palmitate, retinyl acetate or a combination thereof. Retinyl propionate, retinyl palmitate and combinations thereof are typically preferred. Still another retinoic acid precursor for use is hydroxyanasatil retinoate made commercially available under the name RETEXTRA® as supplied by Molecular Design International. The same may be used in a combination with any of the oil soluble benefit agents described herein.

When an optional (i.e., 0.0 to 1 .5% by weight based on the total weight of the cleansing composition) oil soluble benefit agent is used, it typically is present in an amount of 0.001 to 1.5% by weight of the overall cleansing composition including any and all values and ranges subsumed therein, and for example, 0.05 to 1.2% by weight, for example, 0.05 to 0.5% by weight of the total weight of the cleansing composition. . In an embodiment, palmitic acid and/or 12-hydroxystearic acid and glycerol are present in the cleansing compositions, with or without niacinamide.

In another embodiment, 0.001 to 1.5% or from 0.01 to 1% by weight hyaluronic acid and/or dihydroxyacetone is used in the cleansing compositions if desired.

Preferred skin benefit agents include fatty acids, hydrocarbons, polyhydric alcohols, polyols, and mixtures thereof, with emollients that include at least one C12 to C fatty acid, petrolatum, glycerol, sorbitol, and/or propylene glycol being of particular interest in one or more embodiments. The agents may be added at an appropriate step during the process of making the cleansing composition. Some benefit agents may be introduced as macro domains.

Other optional ingredients like antioxidants, perfumes, polymers, colorants, deodorants, dyes, enzymes, foam boosters, germicides, anti-microbials, lathering agents, pearlescers, skin conditioners, stabilizers, or superfatting agents, may be added in suitable amounts in the process of making the cleansing composition. Sodium metabisulphite, ethylene diamine tetra acetic acid (EDTA), borax, or ethylene hydroxy diphosphonic acid (EHDP) can be added to the formulation. Such ingredients can be added in amounts of 0.01 to 2.5% by weight, for example, 0.01 to 2.0% by weight, for example, 0.02 to 2.0% by weight, for example, 0.04 to 2.0% by weight, for example, 0.04 to 1.5% by weight, for example, 0.05 to 1.5% by weight, including any and all ranges and values subsumed therein.

The cleansing composition disclosed herein can optionally be used to deliver antimicrobial benefits. Antimicrobial agents that can be included to deliver these benefits include oligodynamic metals or compounds thereof. Preferred metals are silver, copper, zinc, gold, or aluminum. In the ionic form it may exist as a salt or any compound in any applicable oxidation state. Preferred silver compounds are silver oxide, silver nitrate, silver acetate, silver sulfate, silver benzoate, silver salicylate, silver carbonate, silver citrate, silver phosphate, or a combination thereof, with silver oxide, silver sulfate and silver citrate being of particular interest in one or more embodiments. In at least one aspect, the silver compound is silver oxide. Oligodynamic metal or a compound thereof can be included in an amount of 0.0001 to 2%, preferably 0.001 to 1% by weight of the cleansing composition. Alternately an essential oil antimicrobial active may be included in the cleansing composition. Essential oil actives which can be included are terpineol, thymol, carvacol, (E) -2(prop-1-enyl) phenol, 2- propylphenol, 4- pentylphenol, 4-sec-butylphenol, 2-benzyl phenol, eugenol, or a combination thereof. Furthermore, preferred essential oil actives are terpineol, thymol, carvacrol, thymol, or a combination thereof, with the most preferred being terpineol or thymol, or a combination thereof. When present, essential oil actives can be included in an amount of 0.001 to 1 %, preferably 0.01 to 0.5% by weight of the composition.

Even other ingredients which may be used include octopirox (piroctone), zinc pyrithione, chloroxylenol, triclosan, cetylpyridinium chloride, as well as silver compounds including silver oxide, nitrate, sulfate, phosphate, carbonate, acetate, benzoate, a combination thereof or the like. If used, these other components typically make up from 0.001 to 1 .6% by weight of the overall cleansing composition including any and all values and ranges subsumed therein, and preferably, from 0.01 to 1.2% by weight.

The cleansing composition can further comprise a humectant. The humectant can be present in an amount of 0.5to 15% by weight, preferably 1 to 10% by weight, more preferably 1 to 8% by weight of the antibacterial composition. The humectant can be employed to assist in moisturization effects of the cleansing composition. Humectants are generally known as moisturizers that attract water from the air or deeper in the skin. Stated another way, humectants draw water into the skin, hair, or nails. The humectants can generally be polyhydric alcohol type materials. Typical polyhydric alcohols include glycerol (i.e., glycerine or glycerin), propylene glycol, dipropylene glycol, polypropylene glycol (e.g., PPG-9), polyethylene glycol, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1 ,3-butylene glycol, isoprene glycol, 1 ,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol, or a combination thereof. Most preferred is glycerin, propylene glycol, dipropylene glycol, or a combination thereof. In an embodiment, the humectant can be propylene glycol, butylene glycol, dipropylene glycol, glycerin, triethylene glycol, erythritol, capryl glycol, hyaluronic acid, polypropylene glycol-7 proypyl heptyl ether, or a combination thereof.

Adjusters suitable to modify the pH of the cleansing compositions can be used. Such pH adjusters include triethylamine, NaOH, KOH, H2SO4, HCI, CeHsO? (i.e. , citric acid) or mixtures thereof. The pH adjusters are added at amounts such that the final pH of the composition is as defined herein.

The pH of the composition is assessed by using conventional instrumentation such as a pH meter made commercially available from Thermo Scientific®. A pH of the cleansing composition can be 3 to 9, preferably, 4 to 8, more preferably, 5 to 7.

Thickening agents are optionally suitable for use in the cleansing composition. Particularly useful are the polysaccharides. Examples include fibers, starches, natural/synthetic gums and cellulosics. Representative of the starches are chemically modified starches such as sodium hydroxypropyl starch phosphate and aluminum starch octenylsuccinate. Tapioca starch is often preferred, as is maltodextrin. Suitable gums include xanthan, sclerotium, pectin, karaya, arabic, agar, guar (including Acacia Senegal guar), carrageenan, alginate and combinations thereof. Suitable cellulosics include hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethylcellulose, sodium carboxy methylcellulose (cellulose gum/carboxymethyl cellulose) and cellulose (e.g., cellulose microfibrils, cellulose nanocrystals or microcrystalline cellulose). Sources of cellulose microfibrils include secondary cell wall materials (e.g., wood pulp, cotton), bacterial cellulose, and primary cell wall materials. Preferably the source of primary cell wall material is selected from parenchymal tissue from fruits, roots, bulbs, tubers, seeds, leaves and combination thereof; more preferably is selected from citrus fruit, tomato fruit, peach fruit, pumpkin fruit, kiwi fruit, apple fruit, mango fruit, sugar beet, beet root, turnip, parsnip, maize, oat, wheat, peas and combinations thereof; and even more preferably is selected from citrus fruit, tomato fruit and combinations thereof. A most preferred source of primary cell wall material is parenchymal tissue from citrus fruit. Citrus fibers, such as those made available by Herbacel® as AQ Plus can also be used as source for cellulose microfibrils. The cellulose sources can be surface modified by any of the known methods including those described in Colloidal Polymer Science, Kalia et al., “Nanofibrillated cellulose: surface modification and potential applications” (2014), Vol 292, Pages 5-31.

Synthetic polymers are yet another class of effective thickening agent. This category includes crosslinked polyacrylates such as the Carbomers, acrylate copolymers, acrylates/ acrylate (C - C30) alkyl acrylate crosspolymers, polyacrylamides such as Sepigel® 305 and taurate copolymers such as Simulgel® EG and Aristoflex® AVC, the copolymers being identified by respective INCI nomenclature as Sodium Acrylate/Sodium Acryloyldimethyl Taurate and Acryloyl Dimethyltaurate/Vinyl Pyrrolidone Copolymer. Another preferred synthetic polymer suitable for thickening is an acrylate-based polymer made commercially available by Seppic and sold under the name Simulgel INS100. Calcium carbonate, salts like sodium chloride, fumed silica, and magnesium-aluminum-silicate may also be used.

The amounts of the thickening agent, when used, can be 0.001 to 5%, by weight of the composition. Often, thickeners are present at from 0.8 to 3.5% by weight, and preferably, from 1.0 to 3.0% by weight of the cleansing composition when petrolatum (0.01 to 1% by weight) is included. In an embodiment, cationic thickeners can be present in an amount of 0.01 to 2.5% and preferably 0.05 to 1.8%, and most preferably, from 0.2 to 1 .2% by weight of the wash composition.

The self-foaming cleansing composition can further include a chelator. The chelator can be present in an amount of 0.01 to 1.0% by weight, based on the total weight of the self-foaming cleansing composition, for example, 0.05 to 0.75% by weight, based on the total weight of the self-foaming cleansing composition including any and all ranges and values subsumed therein.

In an embodiment, the chelator comprises ethylyene diaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), pentasodium diethylenetriaminepentaacetate, trisodium N-(hydroxyethyl)-ethylenediaminetracetate, an acid form of ethylyene diaminetetraacetic acid (EDTA), phytic acid, or a combination thereof.

In an embodiment, the chelator comprises sodium gluconate, nitrilotriacetic acid (NTA), ethylene diamine disuccinic acid (EDDS), iminodisuccinic acid (IDS), salts of methylglycinediacetic acid, methylglycinediacetic acid (MGDA), L-glutamic acid N,N-diacetic acid (GLDA), ethylenediamine- N,N'-diglutaric acid (EDDG), ethylenediamine-N,N'-dimalonic acid (EDDM), 3-hydroxy-2,2- iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA), sodium citrate, or a combination thereof. The aforementioned chelators are biodegradable.

The cleansing composition can additionally contain an emulsifier. The emulsifier can be selected from a C10-C20 fatty alcohol or acid hydrophobe condensed with about 2 to about 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C2-C10 alkyl phenols condensed with 2 to 20 moles of alkylene oxide; mono- and di-fatty acid esters of ethylene glycol; sorbitan, mono- and di- C8-C20 fatty acids; and polyoxyethylene sorbitan, or a combinations thereof. Alkyl polyglycosides and saccharide fatty amides (e.g., methyl gluconamides) can also be used as nonionic emulsifiers.

When used, emulsifiers typically have an HLB (hydrophilic-lipophilic balance) of 7.5 to 28, and preferably, 8 to 25, and most preferably, 9 to 20, including any and all ranges and values subsumed therein, e.g., nonionic emulsifier can include polysorbate 20 (Tween 20), polyoxyethylene (20) sorbitan monooleate (Tween 80). Other emulsifiers that can be used include emulsifying wax, cetearyl glucoside and combinations with cetearyl alcohol also known as Montanov 68, or a combination thereof. When present, the emulsifier can be present in an amount of 0 to 3% by weight, for example, 1 % by weight of the cleansing composition.

Optionally, the emulsifier can comprise a phospholipid such as hydrogenated phosphatidylcholine (i.e. , lecithin) in the emulsifier amounts previously described.

Preferably, the emulsifier is selected from polysorbate 20 (Tween 20), polyoxyethylene (20) sorbitan monooleate (Tween 80), emulsifying wax, cetearyl glucoside, cetearyl alcohol, glyceryl stearate, cetyl alcohol, or a combination thereof.

Without wishing to be bound by theory it is believed that branching near the head group of the surfactant disclosed herein sterically protects the ester bond slowing hydrolysis and also disrupts packing thereby resulting in enhancement in performance benefits such as lowering of the Krafft temperature and better foamability. Such branching also favors more cylindrical geometries when combined with zwitterionic surfactants providing the observed viscosity build without salt as compared to its linear counterpart.

Furthermore, the branching on the tail of the surfactants disclosed herein in addition to improving the hydrolytic stability and lowering Krafft point thereby improving solubility, would also have unique way of packing at the interface to improve foam stability and provide a unique of way of structuring to build viscosity with low salt or no salt (e.g., no potassium chloride or ther salts used). The improvement in hydrolytic stability and Krafft points can also be achieved by having a branching on the head group as disclosed in U.S. Patent No. 8,008,239 B2). But having a branching at the head functionality (other side of the carbonyl) makes it a bulkier head group and has disadvantages such as poor structuring for viscosity build, poor salt response for thickening, can form lamellar phase only at very narrow conditions. This often requires more cosurfactant to compensate for the larger head to balance out the packing parameter to get more worm-like structures (favorable structuring for viscosity build) or form more lamellar (useful in new formats).

Except where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word “about.” All amounts are by weight of the final composition, unless otherwise specified.

Skin, as used herein, is meant to include skin on the arms (including underarms), face, feet, neck, chest, hands, legs, buttocks and scalp (including hair). Such end use composition is one suitable to be wiped or washed off, and preferably, washed off with water. The cleansing composition can be a home care cleaning composition but is preferably a shampoo, make-up wash, facial wash, hand wash or personal care liquid body wash, or a cleansing bar. Viscosity, as used herein, is taken with a Discovery HR-2 Rheometer using sand blasted plates (40 millimeters) having a 1000 micron gap and a first shear rate SA of 0.4 s^-1 for a first viscosity A and a second shear rate SB of 10 s^-1 for a second viscosity B, both at 25°C and 20 second intervals. The cleansing composition may, optionally, comprise medicinal or therapeutic agents, but preferably, is a wash which is cosmetic and non-therapeutic.

It should be noted that in specifying any range of concentration or amount, any particular upper concentration can be associated with any particular lower concentration or amount as well as any subranges consumed therein. In that regard, it is noted that all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25% by weight, or, more specifically, 5% by weight to 20% by weight, in inclusive of the endpoints and all intermediate values of the ranges of 5% by weight to 25% by weight, etc.). “Combination is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms “first”, “second”, and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” herein do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term it modifies, thereby including one or more of the term (e.g., the film(s) includes one or more films). Reference throughout the specification to “one embodiment”, “one aspect”, “another embodiment”, “another aspect”, “an embodiment”, “an aspect” and so forth means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment or aspect is included in at least one embodiment or aspect described herein and may or may not be present in other embodiments or aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments or aspects.

All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference. While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

For the avoidance of doubt the word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of.” In other words, the listed steps, options, or alternatives need not be exhaustive.

The disclosure of the invention as found herein is to be considered to cover all aspects as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy. Unless otherwise specified, numerical ranges expressed in the format "from x to y" are understood to include x and y. In specifying any range of values or amounts, any particular upper value or amount can be associated with any particular lower value or amount. All percentages and ratios contained herein are calculated by weight unless otherwise indicated. The various features of the present invention referred to in individual sections above apply, as appropriate, to other sections mutatis mutandis. Consequently, features specified in one section may be combined with features specified in other sections as appropriate. Any section headings are added for convenience only and are not intended to limit the disclosure in any way.

Examples

The following examples are merely illustrative of the cleansing compositions disclosed herein and are not intended to limit the scope hereof.

In the following examples, branched isethionates as disclosed herein, were made and tested for various properties versus linear isethionates.

Representative procedure for the synthesis of sodium fatty acyl isethionates: Trifluoroacetic anhydride (1 .5 mole equivalents, Solvent) was added to a solution of the fatty acid (1.0 mole equivalent) in trifluoroacetic acid (9 mole equivalents, Solvent/Catalyst), followed by sodium isethionate (1.0 molar equivalent) and the mixture was stirred at room temperature (~22 °C) for 2.5 hours. At this time, thin layer chromatography [silica gel plate eluted with ethyl acetate: isopropanol: water (6:3:1)] showed the clean formation of a single product and no starting materials remaining. The solvents were then removed in vacuum at 40 °C to give a white foam which was diluted with cold deionized water (90 milliliters) and freeze dried to give product as a white solid ( 95-99% yield).

The specific fatty acids needed to synthesize the branched isethionate can be obtained either through chemical synthesis route or through biosynthetic route e.g., fermentation using specific organisms.

Example 1 : Hydrolytic Stability of Isethionates - Linear vs. Branched

In this example, several branched isethionates that were branched on the fatty acyl tail were made and tested for hydrolytic stability by measuring the pH of a 10% surfactant solution at 50°C with calibration at the same temperature. The pH drift was measured over time. Generally, over time isethionates undergo hydrolysis such that they break down into fatty acid and isethionate, leading to an overall lower pH value for the surfactant solution. A smaller change in pH over time indicated a more hydrolytically stable material.

The linear isethionates were C12 (Comparative Sample 1 (CS1)) and C14 (Comparative Sample 2 (CS2)) isethionate as shown below.

C14 Linear Isethionate o o

The tail branched isethionates tested included 2-methyl lauroyl isethionate (Sample 1), 3-methyl lauroyl isethionate (Sample 2), and 2,2-dimethyl lauroyl isethionate (Sample 3) as shown below.

2,2-dimethyl lauroyl isethionate (C14)

2-methyl lauroyl isethionate (C13)

3-methyl lauroyl isethionate (C13)

The results for the hydrolytic stability are demonstrated in Table 1.

Table 1: Hydrolytic Stability of Isethionates - Linear vs. Branched

As can be seen from the results in Table 1 , all three tail branched isethionates demonstrated superior hydrolytic stability as compared to either linear isethionate as the pH delta change after 30 days for all three branched isethionates was under 0.30, while for the linear isethionates was over 1.0. Example 2: Krafft Point of Isethionates - Linear vs. Branched

Krafft point is a measure of the temperature above which the solubility of a surfactant rises sharply. At this temperature, the solubility of the surfactant becomes equal to the critical micelle concentration (CMC).

Table 2 lists the materials that were tested for Krafft point and the measured Krafft point. Comparative Sample 3 (CS3) was a linear isethionate, while Samples 4 to 6 were all branched isethionates. The samples were a 1 weight % aqueous solution.

Table 2: Krafft Point of Isethionates - Linear vs. Branched

As can be seen from Table 2, the tail branched isethionates have lower Krafft points compared to linear. With the lower Krafft points, the tail branched isethionate can enable optical clarity for formulations made therefrom at lower temperatures (e.g., 4 to 25°C). The lower Krafft points of branched isethionates can also limit any unwanted crystallization at the lower temperatures thereby enabling improved formulation stability when storage temperature is lower such as in winter.

Example 3: Lathering in Anionic Rich Bodywash - Linear vs. Branched

In this example, the surfactants from Example 1 were used to create anionic rich cleansing formulations with the base formula as listed in Table 3. Lathering was measured with a Kruss foam analyzer using cold tap water at 400 seconds (s). The pH of the cleansing compositions made was 6.9. Results of the foaming tests are shown in Table 4. Table 3: Base Formulation for Cleansing Compositions

*ethylenediaminetetraacetic acid

“phenoxyethanol

‘“iodopropynyl butylcarbamate ““potassium chloride

Table 4: Lathering in Anionic Rich Bodywash - Linear vs. Branched

As can be seen from the data in Table 4, cleansing formulations using the tail branched isethionates demonstrate superior lathering as compared to cleansing formulations using linear isethionates. This is shown by the higher foam heights in Samples 1 to 3 as compared to the foam heights in CS1 and CS2. The foam heights for Samples 1 to 3 are nearly double those found in CS2. It was also observed that cleansing formulations using the tail branched isethionates had creamier and volumizing foams as compared to cleansing compositions made using linear isethionates.

Example 4: Viscosity in Anionic Rich Bodywash - Linear vs. Branched

In this example, the surfactants from Example 2 were used to create anionic rich isotropic cleansing compositions with the base formulation as shown in Table 3. The pH was 7.0. Viscosity was measured with a Discovery HR-2 Rheometer using 40mm sand blasted plates with a 100 micron gap and a shear rate of 4 s’¹. Viscosity was measured at 25 °C. Results are listed in Table 5. Table 5: Viscosity in Anionic Rich Bodywash - Linear vs. Branched

As can be seen from the data in Table 5, the branched isethionates disclosed herein where the branching is on the fatty acyl tail can build a higher viscosity in anionic rich cleansing formulations without requiring any added salt as compared to cleansing compositions formulated with linear isethionates. It was unexpected to find that the branched isethionates were capable of building viscosity such that a salt was not required. As noted in Table 3, there was 0% potassium chloride present in the inventive compositions.

Claims

Claims:

1. An anionic surfactant comprising a compound or mixture of compounds having the formula:

wherein the compound is branched at R1, R2, R’2, R3, or a combination thereof; wherein R1 comprises hydrogen or methyl or hydroxy, R2 comprises methyl, hydroxy, or hydrogen, R’2 comprises methyl, hydroxy, or hydrogen, and R3 comprises a hydrocarbon group having 1 to 18 carbon atoms, including straight-chain hydrocarbon groups, branched hydrocarbon groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, or a combination thereof; and wherein M⁺ is a monovalent cation; wherein if both R2and R’2 comprise hydrogen, then R1 does not comprise hydrogen if Rs is a linear hydrocarbon group and wherein if R3 is a branched hydrocarbon, then all of R2, R2, and R1 comprise hydrogen.

2. The anionic surfactant of Claim 1 , wherein the branching is saturated, wherein the branching is unsaturated, or a combination thereof.

3. The anionic surfactant of Claim 1 or Claim 2, wherein M⁺ comprises sodium, potassium, ammonium, lithium, caesium, rubidium, francium, alkylammonium, triethanolammonium, or a combination thereof.

4. The anionic surfactant of any of the preceding claims, wherein the hydroxy group branching is further chemically derivatized into other functional groups.

5. The anionic surfactant of Claim 4, wherein the hydroxy groups can be derivatized into ethers, polyoxy ethers, carboxylic acids, esters, ketones, acetals, hemiacetal, amines, amides, urethanes, or a combination thereof.

6. The anionic surfactant of Claim 5, wherein the ethers comprise methoxy, ethoxy, t-butoxy, or a combination thereof.

7. The anionic surfactant of any of the preceding claims, wherein the anionic surfactant is a branched isethionate.

8. The anionic surfactant of Claim 7, wherein the branched isethionate comprises 2-methyl lauroyl isethionate, 3-methyl lauroyl isethionate, or 2,2-dimethyl isethionate.

9. The anionic surfactant of Claim 8, wherein the branched isethionate comprises sodium 2- methyl lauroyl isethionate, sodium 3-methyl lauroyl isethionate, or sodium 2,2-dimethyl lauroyl isethionate.

10. A cleansing composition comprising the compound or mixture of compounds of any of the preceding claims, wherein the cleansing composition is a liquid cleansing composition, preferably wherein the cleansing composition is a wash composition, shampoo, or conditioner.