WO2026002781A1

WO2026002781A1 - Cleansing composition

Info

Publication number: WO2026002781A1
Application number: PCT/EP2025/067241
Authority: WO
Inventors: Kierstyn HARRIS; Douglas John Hiban; Teanoosh Moaddel; Laurie POINTS; Paul Damien Price
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2024-06-24
Filing date: 2025-06-19
Publication date: 2026-01-02
Anticipated expiration: 2026-12-24

Abstract

A lamellar cleansing composition comprising: a) a furan-based anionic sulphate free surfactant; b) a co-surfactant selected from a zwitterionic surfactant, an amphoteric surfactant and mixtures thereof; c) water; d) an oil; e) a starch; f) from 0.5 wt% to 6 wt %, preferably 1.5 wt % to 5 wt %, most preferable from 2 wt % to 4wt % of a fatty material comprising from 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms more preferably 12 to 22 carbon atoms, selected from a free fatty acid, a free fatty alcohol and mixtures thereof; wherein the furan-based anionic sulphate free surfactant comprises: A) a head group comprising i) a furan ring ii) a sulphonate group directly attached to the furan ring; wherein the furan-based anionic sulphate free surfactant has the structure of Formula (I): Formula (I) where R is a hydrophobic alkyl tail group having a carbon chain length of 8 to 18, 18:1 and 18:2 where R groups of different chain lengths can be used in combination as a blend, preferably a blend of chain lengths of C12 and C14 and X is a counterion, selected from organic and inorganic counterions; B) an amide containing linker group; and C) a hydrophobic alkyl tail group having a carbon chain length of 8 to 18; wherein where the co-surfactant contains an amido propyl linker, and where one of the free fatty material or the starch is present in an amount of greater than 2 wt %, then the other must be present in an amount of less than 2 wt %; P0000842WO CPL 38 wherein the pH of the composition is from less than 5.5; and wherein the composition has a viscosity of 150,000 to 2000000, preferably 175,000 to 1000000, more preferably 200,000 to 750000 mPa.s, at 0.1 s-1, and 3000 to 12000 at 10 s-1 when measured at 25 degrees Centigrade (C), using sandblasted 40mm parallel plates, on a Wingspan rheometer.

Description

CLEANSING COMPOSITION

Field of the Invention

The present invention relates to cleansers having a lamellar structure that comprise a furan based surfactant.

Background of the Invention

Consumers desire home and personal cleaning formulations that have an acceptable, and stable viscosity so that the product can, for example, be applied in a controlled manner and readily spread in use.

Alternatives to traditional sulphate-based surfactants are increasingly in demand for use in home and personal cleansing formulations. “Sulphate free” cleaning surfactants have provided one such alternative and can be used with traditional co-surfactants. However, such surfactant systems have either proven difficulty to thicken and have limited solubility or limited pH window for use. Use of higher levels of salt and of polymeric thickeners result in cost and processing issues and do not always overcome the issues faced. It has thus been necessary to employ narrow ratios of anionic surfactant to co-surfactant, with higher proportions of the co-surfactant in order to boost viscosity. Such restrictions on formulation space are clearly limiting to product development and choice.

WO 2015/084813 discloses a furan-based chemical comprising a furan group, hydrophilic group and hydrophobic group, wherein the hydrophilic group can be ionic, zwitterionic, or non-ionic, and further, and wherein said hydrophobic group can be alkyl or alkenyl, linear or branched moieties.

WO 2015/094970 discloses Linear mono- and dialkyl ethers of furan-2,5-dimethanol (FDM) and/or 2, 5-bis(hydroxymethyl)tetrahydrofuran (bHMTHF), methods for their preparation, and derivative chemical compounds thereof are described.

George Kraus et al. “A Direct Synthesis of Renewable Sulfonate-Based Surfactants” Journal of Surfactants and Detergents vol. 16, no. 3, 1 May 2013 (2013-05-01), pages 317-320 discloses ester and ether linked furan-based surfactants with beta-hydroxy sulfonate headgroups. The compositions are described as being unstable at basic pH ranges.

WO2020229158 A1 discloses a furan-based surfactant comprising a beta sulphonate head group, a furan and a C10-20 hydrophobic group which is either attached directly to the furan or by way of a linker.

LIS2021045987 A1 discloses a lamellar personal cleansing composition comprising: acyl isethionate; acyl glycinate; acyl glutamate; and 4) optionally an amphoteric surfactant; and a lamellar structurant, preferably lauric acid or lauryl alcohol, a thickener, at a pH of 6 to 8. The compositions display a viscosity in the range of 20,000-30,000 cps.

US2022192934 A1 discloses a lamellar composition comprising: acyl isethionate; methyl acyl taurate comprising lauroyl methyl taurate, cocoyl methyl taurate in combination with a structurant comprising caprylic acid, lauric acid, myristic acid or a mixture thereof; a zwitterionic surfactant comprising cocam idopropyl betaine; and a surfactant. A ratio of methyl acyl taurate to acyl isethionate surfactant of between 1.25:1 to 1 :1.25 is emplyedand the composition may comprise glycerol.

US20080153729 A1 discloses a liquid cleanser comprising: (a) fatty acyl isethionates; (b) a cosurfactant preferably zwitterionic synthetic surfactant; (c) of alkanolamide and/or alkylamineoxide; (d) straight chain fatty acids &/or mixture of straight chain fatty acids with straight chain fatty alcohols and/or aliphatic hydrocarbon oils; said liquid cleansing composition contains liquid crystalline (lamellar) phase.

Despite the prior art there remains a need for new non-sulphate based cleansing surfactants that are suitable for use in a wide range of commercially useful cleansing formulations.

The rheological behavior of all surfactant solutions, including liquid cleansing solutions, is strongly dependent on the microstructure, i.e., the shape and concentration of micelles or other selfassembled structures in solution.

When there is sufficient surfactant to form micelles (concentrations above the critical micelle concentration or CMC), for example, spherical, cylindrical (rod-like or discoidal), spherocylindrical, or ellipsoidal micelles may form. As surfactant concentration increases, ordered liquid crystalline phases such as lamellar phase, hexagonal phase, cubic phase or L3 sponge phase may form. In general, the microstructure of most personal care products consist of either an isotropic dispersion including spherical micelles; and rod micelles; or an ordered liquid crystalline phase such as a lamellar or hexagonal phases or mixtures thereof. As noted above, micelles may be spherical or rod-like. Hexagonal phases consist of long cylindrical micelles arranged in a hexagonal lattice. Lamellar phases as used herein, means having bilayers of surfactant in arrangement where polar head groups align with water to shield fatty acid acyl chains from the water arranged as surfactant bilayers alternating with layers of water and/or solvent.

It is of increasing interest to develop a mild cleansing composition that lathers well, and that results in consumer desirable moisturizing and/or lubrication sensory attributes without leaving skin or hair feeling tacky or draggy. It is also of increasing interest to develop such cleansing products which can incorporate oils, especially at high levels, while still yielding a consumer desirable product.

We have now found that a new furan-based anionic surfactant behaves like a traditional anionic surfactant. Unlike other sulphate free technologies, which are difficult to thicken, viscosity can be built across a wide range of surfactant ratios, when used in conjunction with co-surfactant(s). The compositions are stable across an unusually wide pH range. Advantageously, the furan- based anionic surfactant is naturally derived thus avoiding petrochemical based syntheses.

A mild cleansing composition comprising the furan-based anionic surfactant surprisingly delivers consumer desirable moisturizing sensory attributes, the cleansing composition having an anionic surfactant comprising a furan sulfonate. Such a composition also comprises zwitterionic and/or amphoteric surfactant. The cleansing composition is not only mild on skin, scalp or hair but also, and surprisingly, lathers well, and unexpectedly, delivers consumer desirable moisturizing and/or lubrication sensory attributes after use. Such a cleansing composition does not leave the skin, hair or scalp feeling tacky or draggy, and is stable.

Furthermore, we have found that the new furan-based anionic surfactant does not require a typical lamellar structurant to enable the formation of a lamellar structured cleanser. This is unlike other sulphate free technologies, which do require lamellar structurants to form a lamellar phase. The compositions are stable across a pH range of less than 5.5, preferably from 4 to 5.25, more preferably from 4.2 to 5. Definition of the Invention

Accordingly, in a first aspect there is provided a lamellar cleansing composition comprising: a) a furan-based anionic sulphate free surfactant; b) a co-surfactant selected from a zwitterionic surfactant, an amphoteric surfactant and mixtures thereof; c) water; d) an oil; e) a starch; f) from 0.5 wt% to 6 wt %, preferably 1.5 wt % to 5 wt %, most preferable from 2 wt % to 4wt % of a fatty material comprising from 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms more preferably 12 to 22 carbon atoms, selected from a free fatty acid, a free fatty alcohol and mixtures thereof; wherein the furan-based anionic sulphate free surfactant comprises:

A) a head group comprising i) a furan ring ii) a sulphonate group directly attached to the furan ring;

B) an amide containing linker group; and

C) a hydrophobic alkyl tail group having a carbon chain length of 8 to 18; wherein the furan-based anionic sulphate free surfactant has the structure of Formula (I):

Formula (I) where R is a hydrophobic alkyl tail group having a carbon chain length of 8 to 18, 18:1 and 18:2 where R groups of different chain lengths can be used in combination as a blend, preferably a blend of chain lengths of C12 and C14 and X is a counterion, selected from organic and inorganic counterions; wherein where the co-surfactant contains an amido propyl linker, and where one of the free fatty material or the starch is present in an amount of greater than 2 wt %, then the other must be present in an amount of less than 2 wt %; wherein the pH of the composition is from less than 5.5; and wherein the composition has a viscosity of 150,000 to 2000000, preferably 175,000 to 1000000, more preferably 200,000 to 750000 mPa.s, at 0.1 s^-1, and 3000 to 12000 at 10 s^-1 when measured at 25 degrees Centigrade (C), using sandblasted 40mm parallel plates, on a Wingspan rheometer.

A second aspect of the invention provides a method of cleaning a surface comprising applying to the surface a composition of the first aspect.

One way to determine the presence of a lamellar phase the inventive composition is to view the composition in a microscope fitted with cross-polarizers. The lamellar phase will have a distinct optical pattern known to those skilled in the art.

Detailed Description of the Invention

Many raw materials contain, what are known in the industry as, carry-over ingredients. These are often used for example as processing aids, preservatives, emulsifiers, etc. These carry-over ingredients are present in very small quantities (for example less than 0.05 wt % of the total composition) and perform a function for the raw material (for example as an emulsifier for a silicone). Carry-over ingredients are present in the full compositions at levels that are too low to have a material effect on the properties of the composition. They are not intended to be part of the invention.

The furan-based anionic sulphate free surfactant

The head group

The head group comprises: i) a furan ring; and ii) a sulphonate group directly attached to the furan ring; wherein the furan-based anionic sulphate free surfactant has the structure of Formula (I):

Formula (I) where R is a hydrophobic alkyl tail group having a carbon chain length of 8 to 18, 18:1 and 18:2 where R groups of different chain lengths can be used in combination as a blend, preferably a blend of chain lengths of C12 and C14 and X is a counterion, selected from organic and inorganic counterions.

The sulphonate group is directly attached to the furan ring.

There is no chemical unit (group or moiety), for example a methylene group (CH₂), between the sulphonate group and the furan ring.

The furan-based anionic sulphate free surfactant can be readily derived from bio-mass.

The amide linker group

The linker group comprises an amide and a saturated hydrocarbon chain. The saturated hydrocarbon chain is preferably selected from an ethylene group and a methylene group, most preferably a methylene group (CH₂).

The hydrophobic alkyl tail

The hydrophobic alkyl tail is an alkyl chain comprising a carbon chain length of 6 to 18, preferably from 8 to 16 carbon chains, most preferably from 10 to 14.

The hydrophobic alkyl chain can be linear or branched, preferably linear.

The hydrophobic alkyl chain can be saturated or unsaturated, preferably saturated. Preferred unsaturated chain include C18: 1 , C18:2 and C18:3, most preferred C18:1.

Blends of chain lengths may also be used, for example a blend of C12 and C14, preferably in a wt:wt ratio of 2:1.

The anionic sulphate free surfactant has a structure as defined in Formula (I):

Formula (I) where R is a hydrophobic alkyl tail group having a carbon chain length of from 8 to 18, preferably from 8 to 16 carbon chains, most preferably from 10 to 14; and where X is a counterion, suitably selected from organic and inorganic counterions. The counterion may be a proton.

Preferred counterions include alkali metals, especially sodium and potassium, and ammonium and triethanolammonium cations.

The

The lamellar cleansing composition comprises: a) the furan-based anionic sulphate free surfactant as described above; b) a co-surfactant selected from a zwitterionic surfactant, an amphoteric surfactant and mixtures thereof; c) water; d) an oil; e) a starch; f) from 0.5 wt% to 6 wt %, preferably 1.5 wt % to 5 wt %, most preferable from 2 wt % to 4wt % of a fatty material comprising from 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms more preferably 12 to 22 carbon atoms, selected from a free fatty acid, a free fatty alcohol and mixtures thereof; and wherein the pH of the composition is from 5.5 to 7.5; and wherein the composition has a viscosity of 150,000 to 2000000, preferably 175,000 to 1000000, more preferably 200,000 to 750000mPa.s, at 0.1 s^-1, and 3000 to 12000 at 10 s^-1 when measured at 25 degrees C, using sandblasted 40mm parallel plates, on a Wingspan rheometer.

The cleansing composition comprises a furan-based sulphate free anionic surfactant as described above.

Preferably, the cleansing composition is selected from a shampoo, body wash, face cleanser and a hand wash.

Most preferably, the cleansing composition is a shampoo or a body wash.

Preferably, the cleansing composition comprises an amount of furan-based anionic sulphate free surfactant of from 0.5 to 20 wt %, preferably from 1 to 15 wt %, more preferably from 2 to 12, even more preferably from 3 to 10, most preferably 3 to 9 wt %, by weight of total composition.

Preferably, the cleansing composition comprises a total amount of furan-based anionic sulphate free surfactant and co-surfactant of from 0.5 to 25 wt %, preferably from 1 to 20 wt %, more preferably from 8 to 12 wt % by weight of total composition.

Preferably the cleansing composition has a weight ratio of furan-based anionic sulphate free surfactant to co-surfactant in the range of from 4:1 to 1 :4, preferably from 7:3 to 3:7.

Method of making furan-based sulphate free anionic surfactant

The furan-based sulphate free anionic surfactant of the present invention may be made by any suitable process. An example of a suitable process is as follows.

Amidation reaction: Furfurylamine (1 eq) and triethylamine (1.1 eq) were mixed in ethyl acetate (6 g/100 ml) at 0 °C. The acyl chloride (1.05 eq) was then added dropwise. After complete addition, the mixture was heated to 70 °C and stirred for 16h. TLC (EtOAc:PE 2:1 , PMDA stain) showed a new spot with Rf = 0.5 and consumption of starting furfurylamine. Water was added to quench, the crude was filtered hot and the solid precipitate was washed with further hot ethyl acetate. The filtrate was evaporated to dryness, affording the corresponding furfurylamide as an off-white solid (82-99%).

N-(furan-2-ylmethyl)dodecanamide. Using furfurylamine (15 g), dodecanoyl chloride (38.5 ml) and triethylamine (4.0 ml). Pale yellow solid, 99% yield. ¹H NMR (MeOD), 5 (ppm): 7.40, dd, 1 H, J = 0.8 and 1.8 Hz; 6.33-6.32, m, 1 H; 6.22, dd, 1 H, J = 0.8 and 3.1 Hz; 4.33, s, 2 H; 2.19, t, 2 H, J = 7.0 Hz; 1.61-1.58, m, 2 H; 1.31-1.28, m, 16 H; 0.90, t, 1 H, J = 6.7 Hz.

Sulfonation reaction: Furfurylamide (1 eq) was dissolved in acetonitrile (20 g/100 ml) at 0 °C. Chlorosulfonic acid (3 eq) was then added dropwise. After complete addition, the reaction was warmed up to RT and stirred for 3h. ¹H NMR (MeOD) showed disappearance of the proton at 7.4 ppm, corresponding to C4-H in the furan ring, confirming substitution at this position. Water was carefully added, followed by NaOH (50% in water) until pH 8. Most of the solvent was removed in vacuo and the residue was resuspended in acetone. The solid precipitate was collected, washed with hot acetone, dried and subjected to soxhlet extraction in methanol for 48h. This solution was then treated with activated carbon at reflux for 3h. The filtrate was evaporated to dryness, affording the corresponding sulphonated product as a pale-yellow solid (62-76%).

5-(dodecanamidomethyl)furan-2-sulfonate. Using /V-(furan-2-ylmethyl)dodecanamide (40 g) and chlorosulfonic acid (24 ml). Off-white solid, 65% yield. ¹H NMR (DMSO-de), 5 (ppm): 8.28, t, 1 H, J = 5.6 Hz; 6.28, d, 1 H, J = 3.2 Hz; 6.08, d, 1 H, J = 3.2 Hz; 4.20, d, 2 H, J = 5.6 Hz; 2.09, t, 2 H, J = 7.2 Hz; 1.52-1.45, m, 2 H; 1.27-1.24, m, 16 H; 0.85, t, 1 H, J = 6.7 Hz.

The co-surfactant

Preferably, the co-surfactant is selected from a zwitterionic surfactant, an amphoteric surfactant and mixtures thereof.

Examples of suitable amphoteric and zwitterionic co-surfactants include alkyl amine oxides (for example lauryl amine oxide); alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines; alkyl amphoacetates (for example sodium cocoamphoacetate); alkyl amphopropionates, alkylamphoglycinates; alkyl amidopropyl hydroxysultaines; and mixtures thereof.

Preferably, the amphoteric or zwitterionic co-surfactant is selected from alkyl betaines, alkyl amidopropyl betaines, alkyl hydroxysultaines, alkyl amidopropyl hydroxy sultaines, and mixtures thereof.

Most preferred examples of amphoteric and zwitterionic surfactants for use in the compositions of the invention include lauryl betaine, cocam idopropyl betaine, lauryl hydroxysultaine, cocamidopropyl hydroxysultaine and mixtures thereof.

A particularly preferred amphoteric or zwitterionic co-surfactant is selected from cocamidopropyl betaine and lauryl hydroxysultaine.

The zwitterionic or amphoteric co-surfactant is preferably present in an amount of from 1 to 10 wt %, preferably 1.5 to 9 wt %, more preferably 2 to 9 wt %, based on the weight of the total composition. Where the co-surfactant contains an amido propyl linker, and where one of the free fatty material or the starch is present in an amount of greater than 2 wt %, then the other must be present in an amount of less than 2 wt %.

Preferably the fatty material will be present at a level of from 1 to 6 wt%, preferably from 1.5 to 5 wt %, most preferably from 2 to 4 wt %.

The compositions of the invention preferably comprise from 50 to 98, preferably 60 to 95 wt %, most preferably 70 to 90 wt % water by weight of the total composition.

Concentrated compositions may comprise less water.

The pH range of the cleansing composition is from less than 5.5, preferably from 4 to 5.25, more preferably from 4.2 to 5.

The oil

Oils are suitable and often desired for use in the wash compositions of this invention, the same include any oils allowed for topical application via a wash composition, and preferably, an oil suitable to contact skin, scalp and hair that is natural and sustainable.

The oil is preferably selected from silicone oil and non-silicone oils selected from mineral oil and triglyceride oil (also referred to herein as fatty ester oils).

Suitable non-silicone oils are selected from hydrocarbon oils, fatty ester oils and mixtures thereof.

The hydrocarbon oils can be natural or synthetic.

Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms. Also suitable are branched chain hydrocarbon oils, which preferably contain from about 12 to about 42 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2 to C6 alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, polyalphaolefin, squalane, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Another suitable material is polyisobutylene.

A preferred polyalphaolefin is commercially available as Silkflo 366 ™ (dec-1-ene) ex Ineos. Suitable fatty esters are characterised by having at least 6 carbon atoms and include esters with hydrocarbyl chains derived from fatty acids or alcohols. Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.

Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C1-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soyabean oil and coconut oil.

The hydrophobic non-silicone oil is preferably selected from hydrocarbon oils selected from paraffin oil, mineral oil, polyalphaolefin oil, esters with hydrocarbyl chains derived from fatty acids or alcohols and mixtures thereof.

Preferably oils are naturally sourced and sustainable for example, arachis oil, castor oil, coconut oil, corn oil, cotton seed oil, olive oil, rapeseed oil, safflower seed oil, sesame seed oil, soybean oil, hydrogenated soybean oil, avocado oil, macadamia nut oil, argan oil, pomegranate oil, argan Moroccan oil, moringa oil, blueberry oil, raspberry oil, walnut oil, pecan oil, peanut oil, bayberry oil, mango seed oil, jojoba oil, hydrolyzed jojoba oil, mixtures thereof or the like.

Illustrative examples of other natural oils suitable for use in this invention include squalane, canola oil, avocado seed oil, pumpkin seed oil, rapeseed oil, coconut oil, com oil, cottonseed oil, olive oil, palm oil, peanut oil, walnut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, camelina oil, penny cress oil, hemp oil, algal oil, jojoba oil, rice bran, almond, persic and cacao fat.

In some embodiments, hardened oils obtained by hydrogenating the aforementioned oils.

Further oils include synthetic mono, di and triglycerides such as myristic acid glyceride and 2- ethylhexanoic acid glyceride; still other essential oils and extracts can include mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, 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, jojoba, 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, or a mixture thereof.

A preferred group of triglyceride oils are selected from coconut oil, moringa oil, argan oil and sunflower oil, and soya bean oil. A highly preferred oil is coconut oil.

Short chain linear and branched alkanes having a chain length of C9 to C13 are also suitable.

In an embodiment of the invention, the oil selected for use comprises a mixture of soybean oil (liquid at 25°C) and hydrogenated soybean oil (solid at 59°C, melting point 61-66°C) where the soybean oil and hydrogenated soybean oil are present at a weight ratio of 1:4 to 4:1, and preferably, from 1 :3 to 3:1, and most preferably, from 1:2 to 2:1.

The oil is homogenously dispersed in the lamellar wash composition (using conventional apparatus and moderate shear with temperature varying from 30 to 85°C, often 45 to 75°C) forming oil droplets or particles having a size from 1 to 250 microns, and preferably, from 1 to 100 microns, and most preferably, from 1 to 50 microns in size (or from 2 to 40 microns or from 2 to 35 microns or from 2 to 10 microns or from 2.5 to 8 microns in size). Another suitable size range is a droplet size that is less than 1 micron or from 25 to 950 nm, and preferably, from 40 to 800 nm, and most preferably, from 50 to 750 nm (or from 65 to 700 nm, or from 70 to 650 nm, or from 80 to 650 nm, or from 120 to 625 nm).

Another oil suitable for use in skin wash compositions of the present invention is petroleum jelly, CAS No. 8009-03-08, whereby such occlusive is a combination of hydrocarbons mainly having carbon chains longer than 25. Therefore, petroleum jelly is characterized as a composition made predominately of the paraffin series that can be obtained by, for example, dewaxing lubricating oil stock (or crude oil refining) whereby the same melts at temperatures from 35 to 72°C (more often 40 to 70°C) and boils at a temperature of 285°C or higher and often at a temperature between 295 and 325°C. The petroleum jelly is characterized as a semi-solid at room temperature (22°C) and spreads well topically at skin’s natural temperature of 33 to 37°C. Free of polycyclic aromatics, the most well-known and best produced petroleum jelly is sold under the brand name Vaseline®. As used herein, petroleum jelly and petrolatum are meant to be the same. Semi-solid, as used herein, means soft like Vaseline®, not pourable at room temperature but spreadable on skin at room temperature.

Other suitable materials are those which are made to mimic petroleum jelly (“petroleum jelly substitute” or “substitute”) but are not derived from petroleum or any biproduct or residue recovered from the processing of the same such as processing for gas production. They are, therefore, preferably plant-based, sustainable, soft solids that melt at temperatures similar to those described for petroleum jelly (more often from 29 to 65°C). In an embodiment of the invention, the petroleum jelly substitute used has a melting point from 30 to 62°C or from 30 to 60°C or from 30 to 55°C or from 30 to 50°C or from 30 to 45°C.

Other suitable non-Petrolatum hydrophobic emollients in the inventive composition include but are not limited to the following:

(a) waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof;

(b) hydrophobic and hydrophillic plant extracts;

(c) non-Petrolatum hydrocarbons such as polybutene, liquid paraffins, microcrystalline wax, ceresin, squalene, pristan and mineral oil;

(d) 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 distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate;

(e) mixtures of any of the foregoing components, and the like.

Starch

Starches that may be selected for use include nonmodified starch granules, in general, like potato starch, waxy maize starch as well as simple corn starch, i.e., a starch that gelatinizes at around 75°C. Pure-Gel® starches from Grain Processing Corporation are chemically modified corn starch granules having a gelatinization temperature at about 53°C and are often considered for use. Modified and/or nonmodified starch granules with gelatinization temperatures from 30° to 85°C, and preferably, from 30° to 80°C, and most preferably, from 35 to 75°C are suitable for inclusion in the lamellar wash compositions of the invention. The gelatinization of starch can be measured by Differential Scanning Calorimetry (DSC). In general, and notwithstanding the starch selected for use, it is typically preferred that the granules of the starch selected, upon use in the final lamellar wash composition, swell at least 200%, and preferably at least 400%, and more preferably, at least 600%, and most preferably, at least 800% by volume in the lamellar wash composition to form swollen starch gel particles with a size in the range of 2 to 300 micrometers, or preferably, from 3 to 275 microns, and most preferably, from 4 to 245 microns. Examples of thickeners suitable to select are Pure Gel B990, Pure Gel B992, Pure Gel B980 and Pure Dent starches made commercially available from Grain Processing Corporation. Additional polymeric carbohydrates suitable for use (i.e., starch granules) are National™ 1545, Amioca corn starch, Clearjel, National 1333, Colflo 67, Novation 1600, Novation 2700 or Purity 420 made available from Ingredion. Chemically modified starch granules are also suitable for use. Starch granules modified with nonionic hydrophilic groups such as hydroxyethyl or hydroxypropyl and/or ionic groups such as phosphate, carboxylate, sulfate or sulfonate and dialkyl/trialkyl amino groups can also be suitable for use.

Even other polymeric carbohydrates suitable for use are water soluble starches like Ultra-Sperse®, tapioca and waxy maize starch, and National 1215 pregelatinized unmodified corn starch or mixtures thereof. Still others include Structure® ZEA and Structure® (2143 or 6892), hydroxypropyl modified corn starch, or Structure® XL, a cross-linked pregelatinized hydroxypropyl starch phosphate or mixtures thereof, whereby the same are also available commercially from Nouryon. Others like BASF and Cargill provide Cosmedia® HP Starch and StarDesign™ Care, respectively. Such hydroxypropyl starch phosphate has a molecular weight of 238 (C27H48O10), Cas No. 53124- 00-8.

Optional further thickeners

Optional other useful thickeners that can be used include carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl or carboxymethyl cellulose, 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 often with gelatinization temperatures between 30 to 85°C.

Additional thickeners that also may be selected for use include Versathix™ (PEG- 150 Pentaerythrityl

Tetrastearate (and) PPG-2 Hydroxyethyl cocamide and water), Aristoflex AVC (ammonium acryloyldimethyltaurate/VP copolymer), Carbomer such as Carbopol 980 (crosslinked polyacrylic acid), Carbopol® llltrez 10 and 20 (hydrophobically modified crosslinked polyacrylic acid); alkaline soluble emulsion polymers such as Aculyn 28, Acuyln 22 or Carbopol Aqua SF1

Still other thickeners can include carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl carboxymethyl cellulose, carrageenan, hydroxymethyl carboxypropyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof.

Still other preferred thickeners can include acrylate containing homo and copolymers such as the crosslinked poly acrylates available 2.5 under the CARBOPOL trade name, the hydrophobically modified cross linked polyacrylates available under the AQUA trade name, and the PEMULEN trade name (all sold by Lubrizol Company, Wickliffe, Ohio) and the alkali swellable acrylic latex polymers sold by Rohm and Haas (Philadelphia, Pa.) under the ARYSOL or ACULYN trade names Preferred acrylates are the Aqua SF-1® and Carbopol Ultrez 21® polymers.

Preferred thickeners are Hydroxypropyl Methocellulose such as Methocel® 40-100 and Methocel 40-202 (Dow Chemicals, Midland, Mich.), Sodium Hydroxypropyl starch phosphate such as Pure- Gel B990 (Grain Processing Corp., Muscatine, Iowa), and Xanthan Gum such as Keltrol CG (CPKelco, Atlanta, Ga.).

The total amount of thickener used often makes up from 0.75% to 6%, and preferably, from 1 to 5.5%, and most preferably, from 2.25 to 5.5% (or from 2.50 to 5% or from 2.50 to 4.75% or from 2.5 to 4.5) by weight of the lamellar wash composition.

The fatty material

The compositions of the invention comprise from 0.5 wt% to 6 wt %, preferably 1.5 wt % to 5 wt %, most preferable from 2 wt % to 4wt % of a fatty material comprising from 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms more preferably 12 to 22 carbon atoms, selected from a free fatty acid, a free fatty alcohol and mixtures thereof.

Where the co-surfactant contains an amido propyl linker, and where one of the free fatty material or the starch is present in an amount of greater than 2 wt %, then the other must be present in an amount of less than 2 wt %. Preferably the "fatty material" is a fatty alcohol, an alkoxylated fatty alcohol, a fatty acid or a mixture thereof. More preferably the linear fatty material is selected from a fatty alcohol and a fatty acid, most preferably a fatty alcohol.

Preferably, the alkyl chain of the fatty material is fully saturated but can also optionally include branched or unsaturated chains. Representative fatty materials comprise from 8 to 22 carbon atoms, preferably 10 to 22 more preferably 12 to 22.

Suitable fatty alcohols comprise from 8 to 22 carbon atoms, preferably 10 to 22, most preferably C12 to C16. Fatty alcohols are typically compounds containing straight chain alkyl groups. Preferably, the alkyl groups are saturated but can also optionally include branched or unsaturated chains. Examples of preferred fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol and mixtures thereof. Still other preferred fatty alcohols can include oleyl, behenyl, cholesterol and 2-hexydecanol alcohol;

The use of these materials is advantageous in that they contribute to the formation of the lamellar structure.

Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols having from about 12 to about 18 carbon atoms in the alkyl chain can be used in place of, or in addition to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof.

Suitable fatty acids comprise from 8 to 22 carbon atoms, preferably 10 to 22, most preferably C12 to C16. Desired fatty acids are typically compounds containing straight chain alkyl groups but can also optionally include branched or unsaturated chains. Preferably, the alkyl groups are saturated. Examples of preferred fatty acids include decanoic acid, lauric acid, palmitic acid, stearic acid and mixtures thereof. Still other suitable fatty acids can include behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PLIFA) or mixtures thereof. The use of these materials is advantageous in that they contribute to the formation of the lamellar structure.

The level of fatty material in the cleansing composition of the invention is suitably from 0.01 to 10, preferably from 0.1 to 10, and more preferably from 0.1 to 5 percent by weight of the total composition. The

The compositions of the invention preferably comprise an inorganic electrolyte. Suitable inorganic electrolytes for use in the invention include metal chlorides (such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, ferric chloride and aluminum chloride) and metal sulphates (such as sodium sulphate and magnesium sulphate). The inorganic electrolyte is used to provide viscosity to the composition.

Examples of preferred inorganic electrolytes for use in the invention include sodium chloride, potassium chloride, magnesium sulphate and mixtures thereof, most preferably sodium chloride.

Mixtures of any of the above described materials may also be suitable.

Where present, the level of inorganic electrolyte in compositions of the invention ranges from 0.1 to 3%, preferably from 0.25 to 2.5% (by total weight of the composition).

It is intended that the inorganic electrolyte is distinct from any inorganic electrolytes that may be present in the raw materials of the invention, as “carry over”.

The viscosity of the compositions of the invention typically range from 150,000 to 2000000, preferably 175,000 to 1000000, more preferably 200,000 to 750000 mPa.s, at 0.1 s^-1, and 3000 to 12000 at 10 s'¹ when measured at 25 degrees C, using sandblasted 40mm parallel plates, on a Wingspan rheometer.

At these ranges the composition is pourable yet thick enough to satisfy the consumer desire for thick compositions.

Further Ingredients

The compositions may comprise additional anionic surfactants. Suitable examples include nonsulphate containing surfactants such as fatty acyl derivatives, preferably lauroyl or cocoyl, of glycinates, taurates, isethionates and sarcosinates; and alpha olefin sulphonates and mixtures thereof. Other examples include sulphate containing surfactants for example sulphated surfactants such as alkyl sulphates and alkyl ethoxy sulphates for example sodium lauryl ether sulphate (SLES) and trideceth sulphate.

Where present, the total level of furan-based anionic sulphate free surfactant and additional anionic surfactant will be from 0.5 to 20 wt %, preferably from 1 to 15 wt %, more preferably from 2 to 12, even more preferably from 3 to 10 wt %, by weight of total composition.

A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include, for example, fragrance, dyes and pigments, pH adjusting agents (for examples organic acids, sodium hydroxide), pearlescers, opacifiers, preservatives, antimicrobials, structurants, solvents, feel modifying polymers. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the composition).

The compositions for use in the invention preferably comprise a preservative. Preferred preservatives include sodium benzoate and caprylyl glycol.

Where present, the preservative is preferably present in an amount of from 0.01 to 2 wt %, more preferably 0.01 to 1 wt %, most preferably 0.1 to 1 wt %, by total weight of the composition.

Method of making furan-based sulphate free anionic surfactant

The furan-based sulphate free anionic surfactant of the present invention may be made by any suitable process. Examples of a suitable process is as follows.

Amidation reaction: Furfurylamine (1 eq) and triethylamine (1.1 eq) were mixed in ethyl acetate (6 g/100 ml) at 0 °C. The acyl chloride (1.05 eq) was then added dropwise. After complete addition, the mixture was heated to 70 °C and stirred for 16h. TLC (EtOAc:PE 2:1 , PMDA stain) showed a new spot with Rf = 0.5 and consumption of starting furfurylamine. Water was added to quench, the crude was filtered hot and the solid precipitate was washed with further hot ethyl acetate. The filtrate was evaporated to dryness, affording the corresponding furfurylamide as an off-white solid (82-99%). N-(furan-2-ylmethyl)dodecanamide. Using furfurylamine (15 g), dodecanoyl chloride (38.5 ml) and triethylamine (4.0 ml). Pale yellow solid, 99% yield. ¹H NMR (MeOD), 5 (ppm): 7.40, dd, 1 H, J = 0.8 and 1.8 Hz; 6.33-6.32, m, 1 H; 6.22, dd, 1 H, J = 0.8 and 3.1 Hz; 4.33, s, 2 H; 2.19, t, 2 H, J = 7.0 Hz; 1.61-1.58, m, 2 H; 1.31-1.28, m, 16 H; 0.90, t, 1 H, J = 6.7 Hz.

5-(dodecanamidomethyl)furan-2-sulfonate. Using /\/-(furan-2-ylmethyl)dodecanamide (40 g) and chlorosulfonic acid (24 ml). Off-white solid, 65% yield. ¹H NMR (DMSO-de), 5 (ppm): 8.28, t, 1 H, J = 5.6 Hz; 6.28, d, 1 H, J = 3.2 Hz; 6.08, d, 1 H, J = 3.2 Hz; 4.20, d, 2 H, J = 5.6 Hz; 2.09, t, 2 H, J = 7.2 Hz; 1.52-1.45, m, 2 H; 1.27-1.24, m, 16 H; 0.85, t, 1 H, J = 6.7 Hz.

Optionally, the cleansing composition in accordance the invention may contain further ingredients, (non-limiting examples of which are described below) to enhance performance and/or consumer acceptability.

Suitable cationic polymers may be homopolymers which are cationically substituted or may 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 conditioning effect is poor. If too high, then there may 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. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. 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 6 meq/g, preferably 0.2 to 3.0 meq/g. The cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.

Suitable 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 polymerised 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 (PDADMAC) 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 4,009,256); cationic polyacrylamides(as described in WO95/22311). 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 suitable for use in compositions for use in the invention 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. Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in U.S. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. 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. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, 15 referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.

A particularly suitable 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 and JAGUAR C17.

Also, preferred cationic polymers are quaternary nitrogen-containing polysaccharides, preferably quaternary nitrogen-containing cellulose ethers, such as those described in U.S. Pat. Nos. 3,472,840; 3,962,418; 4,663,159, and U.S. Pat. No. 5,407,919. Particularly preferred are quaternary nitrogen-containing hydroxyethyl celluloses. Examples of such cationic polymers are salts of hydroxyethyl cellulose reacted with a trimethyl ammonium substituted epoxide such as Polyquaternium-10, made commercially available by Dow® as UCARE™ Polymer JR-125, UCARE Polymer JR-400, UCARE Polymer KF, UCARE Polymer J R-30M, UCARE Polymer LR- 400, UCARE Polymer LR-30M, UCARE Polymer LK mixtures thereof or the like.

Other preferred cationic polymers include those known as hydrophobically-modified cationic conditioning polymers such as those made commercially available also by Dow® under the names SoftCATTM SL 5, SoftCAT SL 30, SoftCAT SL 60, SoftCAT SL 100, SoftCAT SK-L, SoftCAT SK-M, and SoftCAT SK-H. Included for suitable use in the invention are those cationic polymers referred to as Polyquaternium-7, Polyquaternium-44, Polyquaternium 24 or mixtures thereof.

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (Commercially available from Rhone-Poulenc in their JAGUAR trademark series). Examples are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity, JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity), JAGUAR C16, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution. Particularly preferred cationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C16 and JAGUAR C162, especially JAGUAR C13S, and JAGUAR C-14/BFG. The JAGUAR C14/BFG material is the same molecule as JAGUAR C13, except that a glyoxal cross linker has replaced the boron. Other cationic thickeners known in the art may be used provided that they are compatible with the inventive formulation.

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

Cationic polymer will generally be present in the cleansing composition for use in the invention at levels of from 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.

If a silicone oil is optionally used, the same can include, for example linear and cyclic polydimethylsiloxane; amino, alkyl, alkylaryl, and aryl silicone oils. Still other examples include PEG-3 Dimethicone, PEG-8 Dimethicone, PEG-9 Dimethicone, PEG-10 Dimethicone, PEG-11 Methyl ether dimethicone, PEG-12 Dimethicone, PEG-14 Dimethicone, PEG-17 Dimethicone, PEG-32 Dimethicone mixtures thereof or the like.

Still further suitable silicones include polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Preferably, the silicone is selected from the group consisting of dimethicone, dimethiconol, amodimethicone and mixtures thereof. Also preferred are blends of amino-functionalised silicones with dimethicones.

The internal phase viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 cst at 25 °C the viscosity of the silicone itself is preferably at least 60,000 cst, most preferably at least 500,000 cst, ideally at least 1,000,000 cst. Preferably the viscosity does not exceed 10⁹ cst for ease of formulation.

Emulsified silicones for use in the compositions of the invention will typically have a D90 silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 micron, ideally from 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size (D50) of 0.15 micron are generally termed microemulsions.

Silicone particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments.

Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are emulsions /microemulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation.

A further preferred class of silicones for inclusion in compositions of the invention are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include: polysiloxanes having the CTFA designation "amodimethicone". A preferred amodimethicone is available from Dow Corning as DC 7134.

Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning). Suitable quaternary silicone polymers are described in EP-A-0 530 974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt.

Also suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant.

Pre-formed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2-7224, DC2-8467, DC2-8177 and DC2-8154 (all ex Dow Corning).

The total amount of silicone is preferably from 0.1 wt % to 10 wt % of the total composition more preferably from 0.1 wt % to 5 wt %, most preferably 0.25 wt % to 3 wt % is a suitable level.

The compositions of the present invention may include an appearance modifier to improve visual appearance and/or consumer appeal of the product. Most preferably the appearance modifier is a pearlescer selected from mica, titanium dioxide, titanium dioxide coated mica, ethylene glycol distearate (INCI glycol distearate) and mixtures thereof.

Nonionic Surfactants

One or more nonionic surfactants may be used in the cleansing composition of the present invention.

Nonionic surfactants are preferably used at levels as low as 0.5, 1 , 1.5 or 2% by wt. and at levels as high as 6, 8, 10 or 12% by wt. The nonionics 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 detergent compounds are alkyl (C6 C22) phenols ethylene oxide condensates, the condensation products of aliphatic (C8- C18) 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 so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxide, and the like. Preferred nonionic surfactants include fatty acid/alcohol ethoxylates having the following structures a) HOCH₂(CH₂)_n(CH₂CH₂O)xH or b) HOOC(CH₂)_m(CH₂CH₂O)yH; where m, n are independently <18; and x, y are independently >1. preferably m, n are independently 6 to 18; x, y are independently 1 to 30; c) HOOC(CH₂)j-CH=CH (CH₂)k(CH₂CH₂O)_zH; where i, k are independently 5 to 15; and z is independently 5 to 50. Preferably i, k are independently 6 to 12; and z is independently 15 to 35.

The nonionic 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. titled "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.

Skin Benefit Agent

The composition of the invention may comprise a skin benefit agent. The skin benefit agent is preferably selected from optical and sensory modifiers (e.g. exfoliants), emollients, anti-acne actives, antimicrobial and antifungal actives, antiwrinkle and anti-skin atrophy actives, skin barrier repair actives, artificial tanning actives, skin lightening actives, sunscreen actives, anti-itch ingredients, fragrance, moisturizers (e.g. occlusive like petroleum jelly; or non-occlusive like glycerin) optical modifiers and mixtures thereof.

Other suitable examples of surfactants described above which may be used are described in "Surface Active Agents and Detergents" (Vol. I & II) by Schwartz, Perry & Berch, incorporated into the subject application by reference in its entirety. In addition, the inventive cleansing composition of the invention may include 0 to 15% by wt. optional ingredients as follows: perfumes; sequestering agents, such as tetrasodium ethylenediaminetetraacetate (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and soluble coloring agents, and the like; all of which are useful in so enhancing the appearance or cosmetic properties of the product. The compositions may further comprise antimicrobials such as 2-hydroxy-4,2',4' trichlorodiphenylether (DP300); preservatives such as dimethyloldimethylhydantoin (Glydant 55 XL1000), parabens, sorbic acid etc., and the like. The compositions may also comprise coconut acyl monoor 2.5 diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may also be used to advantage. Preferably strongly ionizing salts, otherwise known as electrolytes, will be present at less than 3, 2 or 1% by wt. Antioxidants such as, for example, butylated hydroxytoluene (BHT) and the like may be used advantageously in amounts of about 0.01 % or higher if appropriate.

The term "emollient" 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. Moisturizers that also are Humectants such as polyhydric alcohols, e.g. glycerin and propylene glycol, and the like; and polyols such as the polyethylene glycols and the like may be used as hydrophilic emollients. Humectants are preferably used at levels as low as 1 , 3 or 5% by wt. and at levels as high as 6, 8 or 10% by wt.

Clay, silica and other particle based comparative structuring agent(s) may be present at less than 1.5, 1 or 0.5% by wt. and preferably are not present in the inventive composition. These agents include but are not limited to dispersed amorphous silica selected from the group consisting of fumed silica and precipitated silica and mixtures thereof. As used herein the term "dispersed amorphous silica" refers to small, finely divided non-crystalline silica having a mean agglomerate particle size of less than about 100 microns.

Other examples of comparative structurants include but are not limited to dispersed smectite clay including bentonite and hectorite and mixtures thereof. Bentonite is a colloidal aluminum clay sulfate. Hectorite is a clay containing sodium, magnesium, lithium, silicon, oxygen, hydrogen and fluorine.

Advantageously, active agents other than conditioning agents such as emollients or moisturizers defined above may be added to the cleansing composition in a safe and effective amount during formulation to treat the skin during the use of the product provided that they do not exceed solubility limits whereby the reflectance increases beyond 80% in the cleansing composition. Suitable active ingredients include those that are soluble in the aqueous phase, in the Petrolatum phase or in both phases. Suitable active agents may be advantageously selected from antimicrobial and antifungal actives, vitamins, anti-acne actives; anti-wrinkle, anti-skin atrophy and skin repair actives; skin barrier repair actives; non-steroidal cosmetic soothing actives; artificial tanning agents and accelerators; skin lightening actives; sunscreen actives; sebum stimulators; sebum inhibitors; anti-oxidants; protease inhibitors; skin tightening agents; anti-itch ingredients; hair growth inhibitors; 5-alpha reductase inhibitors; desquamating enzyme enhancers; anti-glycation agents; topical anesthetics, or mixtures thereof; and the like. These active agents may be selected from water soluble active agents, oil soluble active agents, pharmaceutically acceptable salts and mixtures thereof.

Also useful in the compositions of the invention are ingredients selected from organic solvents (ethanol), other thickeners, sequestrants (EDTA), coloring agents, opacifiers, pearlisers (zinc stearate, TiC>2), preservatives (for example Glydant, parabens, sodium benzoate, caprylyl glycol), antioxidants (BHT) and mixtures thereof).

The term "active agent" as used herein, means personal care actives which can be used to deliver a benefit to the skin and/or hair and which generally are not used to confer a conditioning benefit, as is conferred by humectants and emollients previously described herein. The term "safe and effective amount" as used herein, means an amount of active agent high enough to modify the condition to be treated or to deliver the desired skin care benefit, but low enough to avoid serious side effects. The term "benefit," as used herein, means the therapeutic, prophylactic, and/or chronic benefits associated with treating a particular condition with one or more of the active agents described herein. What is a safe and effective amount of the active agent ingredient will vary with the specific active agent, the ability of the active to penetrate through the skin, the age, health condition, and skin condition of the user, and other like factors.

Preferably the composition of the present invention comprise from about 0.01 % to about 50%, more preferably from about 0.05% to about 25%, even more preferably 0.1 % to about 10%, and most preferably 0.1% % to about 5%, by weight of the active agent component.

Anti-acne actives can be effective in treating acne vulgaris, a chronic disorder of the pilosebaceous follicles. Nonlimiting examples of useful anti-acne actives include the keratolytics such as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylic acid such as 5-octanoyl salicylic acid and 4 methoxysalicylic acid, and resorcinol; retinoids such as retinoic acid and its derivatives (e.g., cis and trans); sulfur-containing D and L amino acids and their derivatives and salts, particularly their N-acetyl derivatives, mixtures thereof and the like. Antimicrobial and antifungal actives can be effective to prevent the proliferation and growth of bacteria and fungi. Nonlimiting examples of antimicrobial and antifungal actives include b-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, 2,4,4'- trichloro-2'-hydroxy diphenyl ether, 3,4,4 -trichlorobanilide, phenoxyethanol, triclosan; triclocarban; and mixtures thereof and the like. Anti-wrinkle, anti-skin atrophy and skin repair actives can be effective in replenishing or rejuvenating the epidermal layer. These actives generally provide these desirable skin care benefits by promoting or maintaining the natural process of desquamation.

Nonlimiting examples of antiwrinkle and anti-skin atrophy actives include 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; retinoic acid and its derivatives (e.g., cis and trans); retinal; retinol; retinyl esters such as retinyl acetate, retinyl palmitate, and retinyl propionate; vitamin B3 compounds (such as niacinamide and nicotinic acid), alpha hydroxy acids, beta hydroxy acids, e.g. salicylic acid and derivatives thereof (such as 5- octanoyl salicylic acid, heptyloxy 4 salicylic acid, and 4-methoxy salicylic acid); mixtures thereof and the like.

Skin barrier repair actives are those skin care actives which can help repair and replenish the natural moisture barrier function of the epidermis. Nonlimiting examples of skin barrier repair actives include lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957; ascorbic acid; biotin; biotin esters; phospholipids, mixtures thereof, and the like. Non-steroidal cosmetic soothing actives can be effective in preventing or treating inflammation of the skin. The soothing active enhances the skin appearance benefits of the present invention, e.g., such agents contribute to a more uniform and acceptable skin tone or color. Nonlimiting examples of cosmetic soothing agents include the following categories: propionic acid derivatives; acetic acid derivatives; fenamic acid derivatives; mixtures thereof and the like. Many of these cosmetic soothing actives are described in U.S. Pat. No. 4,985,459 to Sunshine et al., issued Jan. 15, 1991 , incorporated by reference herein in its entirety.

In another embodiment of the invention, the composition comprises 12 hydroxystearic acid.

Artificial tanning actives can help in simulating a natural suntan by increasing melanin in the skin or by producing the appearance of increased melanin in the skin. Nonlimiting examples of artificial tanning agents and accelerators include dihydroxyacetone; tyrosine; tyrosine esters such as ethyl tyrosinate and glucose tyrosinate; mixtures thereof, and the like.

Skin lightening actives can actually decrease the amount of melanin in the skin or provide such an effect by other mechanisms. Nonlimiting examples of skin lightening actives useful herein include aloe extract, alpha-glyceryl-L-ascorbic acid, aminotyroxine, ammonium lactate, glycolic acid, hydroquinone, 4 hydroxyanisole, mixtures thereof, and the like.

Also useful herein are sunscreen actives. A wide variety of sunscreen agents are described in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11 , 1992; U.S. Pat. No. 5,073,372, to Turner et al., issued 2.5 Dec. 17, 1991 ; U.S. Pat. No. 5,073, 371 , to Turner et al. issued Dec. 17, 1991 ; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology, all of which are incorporated herein by reference in their entirety.

Nonlimiting examples of sunscreens which are useful in the compositions of the present invention are those selected from the group consisting of octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789), 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N- dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, oxybenzone, mixtures thereof, and the like. Sebum stimulators can increase the production of sebum by the sebaceous glands. Nonlimiting examples of sebum stimulating actives include bryonolic acid, dehydroetiandro sterone (DHEA), orizanol, mixtures thereof, and the like.

Sebum inhibitors can decrease the production of sebum by the sebaceous glands. Nonlimiting examples of useful sebum inhibiting actives include aluminum hydroxy chloride, corticosteroids, dehydroacetic acid and its salts, dichlorophenyl imidazoldioxolan (available from Elubiol), mixtures thereof, and the like.

Also useful as actives in the present invention are protease inhibitors. Protease inhibitors can be divided into two general classes: the proteinases and the peptidases. Proteinases act on specific interior peptide bonds of proteins and peptidases act on peptide bonds adjacent to a free amino or carboxyl group on the end of a protein and thus cleave the protein from the outside. The protease inhibitors suitable for use in the present invention include, but are not limited to, proteinases such as serine proteases, metalloproteases, cysteine proteases, and aspartyl protease, and peptidases, such as carboxypepidases, dipeptidases and aminopepidases, mixtures thereof and the like. Other useful as active ingredients in the present invention are skin tightening agents. Nonlimiting examples of skin tightening agents which are useful in the compositions of the present invention include monomers which can bind a polymer to the skin such as terpolymers of vinylpyrrolidone, (meth)acrylic acid and a hydrophobic monomer comprised of long chain alkyl (meth)acrylates, mixtures thereof, and the like. Active ingredients in the present invention may also so include antiitch ingredients. Suitable examples of anti-itch ingredients which are useful in the compositions of the present invention include hydrocortisone, methdilizine and trimeprazineare, mixtures thereof, and the like.

Nonlimiting examples of hair growth inhibitors which are useful in the compositions of the present invention include beta estradiol, anti angiogenic steroids, curcuma extract, cycloxygenase inhibitors, evening primrose oil, linoleic acid and the like. Suitable 5-alpha reductase inhibitors such as ethynylestradiol and genistine mixtures thereof, and the like.

Nonlimiting examples of desquamating enzyme enhancers which are useful in the compositions of the present invention include alanine, aspartic acid, N methyl serine, serine, trimethyl glycine, mixtures thereof, and the like.

A nonlimiting example of an anti-glycation agent which is useful in the compositions of the present invention would be Amadorine (available from Barnet Products Distributor), and the like.

The compositions of the present invention preferably include a pearlescer to improve visual appearance and/or consumer appeal of the product. Most preferably the pearlescer is selected from mica, titanium dioxide, titanium dioxide coated mica ethylene glycol distearate (INCI glycol distearate) and mixtures thereof.

Unless otherwise indicated, ratios, percentages, parts, and the like, referred to herein, are by weight.

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. 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 compositions disclosed herein and are not intended to limit the scope hereof.

In these examples, the “furan sulfonate” was made according to the method given herein above, under the heading “Method of making furan-based sulphate free anionic surfactant”. The resulting furan sulfonate surfactant had a 2:1 blend of C12 and C14 tails.

Example 1 : Inventive Compositions 1 - 3 and comparative 4 - 5, with viscosities

The inventive compositions in Table 1 were prepared. The compositions were lamellar.

Table 1 : Compositions of Inventive Examples 1-3 and comparative examples 4-5 comprising a 2:1 blend of C12 and C14 tails

Claims

1. A lamellar cleansing composition comprising: a) a furan-based anionic sulphate free surfactant ; b) a co-surfactant selected from a zwitterionic surfactant, an amphoteric surfactant and mixtures thereof; c) water; d) an oil; e) a starch; f) from 0.5 wt% to 6 wt %, of a fatty material comprising from 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms more preferably 12 to 22 carbon atoms, selected from a free fatty acid, a free fatty alcohol and mixtures thereof; wherein the furan-based anionic sulphate free surfactant comprises:

A) a head group comprising i) a furan ring ii) a sulphonate group directly attached to the furan ring; wherein the furan-based anionic sulphate free surfactant has the structure of Formula (I):

Formula (I) where R is a hydrophobic alkyl tail group having a carbon chain length of 8 to 18, 18:1 and 18:2 where R groups of different chain lengths can be used in combination as a blend, preferably a blend of chain lengths of C12 and C14 and X is a counterion, selected from organic and inorganic counterions;

B) an amide containing linker group; and

C) a hydrophobic alkyl tail group having a carbon chain length of 8 to 18; wherein where the co-surfactant contains an amido propyl linker, and where one of the free fatty material or the starch is present in an amount of greater than 2 wt %, then the other must be present in an amount of less than 2 wt %; wherein the pH of the composition is from less than 5.5; and wherein the composition has a viscosity of 150,000 to 2000000, preferably 175,000 to 1000000, more preferably 200,000 to 750000 mPa.s, at 0.1 s^-1, and 3000 to 12000 at 10 s'¹ when measured at 25 degrees Centigrade (C), using sandblasted 40mm parallel plates, on a Wingspan rheometer.

2. A lamellar cleansing composition as clamed in claim 1 , wherein the fatty material is in an amount of 1 to 6 wt%, preferably from 1.5 to 5 wt %, most preferably from 2 to 4 wt %.

3. A lamellar cleansing composition as claimed in claim 1 or claim 2, wherein the starch is selected from modified and nonmodified starch granules, with gelatinization temperatures from 30° to 85°C as measured by Differential Scanning Calorimetry.

4. A lamellar cleansing composition as claimed in any preceding claim, wherein the oil is selected from silicone oil and non-silicone oils selected from mineral oil and triglyceride oil.

5. A lamellar cleansing composition as claimed in any preceding claim, which comprises an inorganic electrolyte.

6. A lamellar cleansing composition as claimed in any preceding claim, wherein the amount of furan-based anionic sulphate free surfactant is from 0.5 to 20 wt %, preferably from 1 to 15 wt %, more preferably from 2 to 10, even more preferably from 3 to 8 wt %, by weight of total composition.

7. A lamellar cleansing composition as claimed in any preceding claim, wherein the total amount of furan-based anionic sulphate free surfactant and co-surfactant is from 0.5 to 25 wt %, preferably from 1 to 20 wt %, by weight of total composition.

8. A lamellar cleansing composition as claimed in any preceding claim, wherein the weight ratio of furan-based anionic sulphate free surfactant to co-surfactant is in the range of from 8:2 to 2:8, preferably from 7:3 to 3:7.

9. A lamellar cleansing composition as claimed in any preceding claim, wherein the zwitterionic surfactant or amphoteric surfactant is selected from alkyl betaines, alkyl amidopropyl betaines, alkyl hydroxysultaines, alkyl amidopropyl hydroxy sultaines, and mixtures thereof.

10. A lamellar cleansing composition as claimed in any preceding claim, which is selected from a shampoo, a body wash, a face cleanser and a hand wash, preferably a shampoo or body wash.

11. A lamellar cleansing composition as claimed in any preceding claim, wherein the furan- based anionic sulphate free surfactant as claimed in claim 1, wherein the amide linker group comprises an amide and a saturated hydrocarbon chain.

12. A lamellar cleansing composition as claimed in any preceding claim wherein the furan- based anionic sulphate free surfactant has a saturated hydrocarbon chain that is a methylene group.

13. A lamellar cleansing composition as claimed in any preceding claim wherein the furan- based anionic sulphate free surfactant has an alkyl chain comprising a carbon chain length of 8 to 18, preferably from 8 to 16 carbon chains, most preferably from 10 to 14.

14. A lamellar cleansing composition as claimed in claim 13 wherein the alkyl chain is linear.

15. A method of cleaning a surface comprising applying to the surface a lamellar cleansing composition as defined in any one of claims 1 to 14.