WO1993021293A1

WO1993021293A1 - Aqueous personal or cosmetic detergent compositions comprising vegetable oil adducts

Info

Publication number: WO1993021293A1
Application number: PCT/US1993/002570
Authority: WO
Inventors: Michel Joseph Giret; Anne Langlois; Roland Philip Duke; Emil Jedla
Original assignee: The Procter & Gamble Company
Priority date: 1992-04-09
Filing date: 1993-03-22
Publication date: 1993-10-28
Also published as: GB9207799D0

Abstract

A detergent, personnal cleansing or cosmetic composition comprising: a) one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic, and cationic surfactants and mixtures thereof, and which comprises at least one surfactant having a structure incorporating one or more amido, amino or ammonio moieties (hereinafter N-surfactant), b) an adduct prepared from vegetable oils containing non-conjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Dies-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride; and c) water, and wherein the vegetable oil adduct is in the form of a solution or dispersion having an average particle size of less than about 1000 nm. In a preferred aspect, the vegetable oil adduct is in vesicular form and can be loaded with cosmetically-active or pharmaceutically-active ingredients.

Description

AQUEOUS PERSONAL OR COSMETIC DETERGENT COMPOSITIONS

COMPRISING VEGETABLE OIL ADDUCTS

TECHNICAL FIELD

The present invention relates to aqueous compositions in the form of solutions or dispersions and which comprise a vegetable oil adduct. In one aspect, it relates to detergent, personal cleansing or cosmetic compositions comprising the vegetable oil adduct in solution or dispersion form. In particular, in this aspect, it relates to foam-producing personal cleansing compositions suitable for simultaneously cleansing and conditioning the skin and/or the hair and which may be used, for example, in the form of foam bath preparations, shower products, skin cleansers, hand, face and body cleansers, shampoos, etc. In another aspect, it relates to compositions comprising an aqueous dispersion of the vegetable oil adduct and wherein the vegetable oil adduct is partly or wholly in the form of vesicles. Such compositions are especially valuable for controlled delivery of water-soluble cosmetically-active and pharmaceutically-active ingredients.

BACKGROUND OF THE INVENTION

Foaming cosmetic and detergent compositions must satisfy a number of criteria including cleansing power, foaming properties and mildness/low iπitancy with respect to the skin, hair and the ocular mucosae.

Ideal cosmetic cleansers should cleanse the skin or hair gently, without defatting and/or drying the hair and skin and without irritating the ocular mucosae or leaving skin taut after frequent use. Most lathering soaps, shower and bath products, shampoos and bars fail in this respect.

Certain synthetic surfactants are known to be mild. However, a major drawback of most mild synthetic surfactant systems when formulated for shampooing or personal cleansing is poor lather performance compared to the highest shampoo and bar soap standards. Thus, surfactants that are among the mildest, such as sodium lauryi glyceryl ether sulfonate, (AGS), are marginal in lather. The use of known high sudsing anionic surfactants with lather boosters, on the other hand, can yield acceptable lather volume and quality but at the expense of clinical skin mildness. These two facts make the surfactant selection, the lather and mildness benefit formulation process a delicate balancing act.

Despite the many years of research that have been expended by the toiletries industry on personal cleansing, the broad mass of consumers remain dissatisfied by the mildness of present day cleansing compositions, finding, for example, that they have to apply a separate cosmetic lotion or cream moisturizer to the skin after using a shower or bath preparation in order to maintain skin suppleness and hydration and to counteract the delipidizing effect of the cleanser.

Thus a need exists for personal cleansing products which will produce a foam which is abundant, stable and of high quality, which are effective hair and skin cleansers, which will not dehydrate the skin or result in loss of skin suppleness, which will provide a level of skin conditioning performance in a wash and rinse-off product which previously has only been provided by a separate post-cleansing cosmetic moisturizer, which has good rinsibility characteristics and which at the same time has stable product and viscosity characteristics and remains fiilly stable under long term and stressed temperature storage conditions.

It has now been found that detergent, personal cleansing and cosmetic compositions having improved emolliency and product stability can be formed by the use of certain vegetable oil adducts prepared in the form of solutions or dispersions, and in particular dispersions of vesicle type. Vesicles can be described as water-encapsulating lipid spheres having a diameter usually of 100 nm or less and which comprise multimolecular lipid layers having a thickness generally of about 3 to 10 nm (see for example Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965)).

Vesicular structures having much larger size, for example up to 10,000 nm are also known in the art. Vesicles are known to be obtained from certain lipids which are capable of forming a mesomorphic (liquid crystalline) phase in an aqueous medium. Vesicle systems are valuable in their own right as vehicles for controlled delivery of water-soluble cosmetic or pharmaceutical ingredients to a target organ, for example the skin. The present invention provides compositions comprising the vegetable oil adduct in vesicle form, as well as processes for the preparation thereof.

All concentrations and ratios herein are by weight of the cleansing composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified. SUMMARY OF THE INVENTION

According to one aspect of the invention, there is provided a detergent, personal cleansing or cosmetic composition comprising: a) one or more surfactants selected from anionic, nonionic, amphoteric,

zwitterionic, and cationic surfactants and mixtures thereof, and which comprises at least one surfactant having a structure incorporating one or more amido, amino or ammonio moieties (hereinafter N-surfactant), b) an adduct prepared from vegetable oils containing non-conjugated

polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Dies- Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride; and c) water, and wherein the vegetable oil adduct is in the form of a solution or dispersion having an average particle size of less than 1000 nm.

In a highly preferred embodiment, the invention takes the form of a foam producing cleansing product suitable for personal cleansing of the skin or hair and which may be used as foam bath and shower products, skin cleansers and shampoos etc.

According to this aspect, the invention relates to a foam-producing cleansing composition with superior lathering characteristics (creaminess, abundance, stability) combined with excellent mildness to the skin and hair, together with good stability, cleansing ability and conditioning performance. The invention also relates to a wash and rinse-off personal cleansing product having the above lathering, mildness, rinsibility, stability and conditioning benefits.

The compositions of the invention comprise as an essential ingredient a surfactant having a structure incorporating one or more amido, amino or ammonio moeities, such a surfactant being referred to herein as an N-surfactant. Suitable N-surfactants can be selected generally from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants and mixtures thereof; amphoteric surfactants are preferred however. The level of N-surfactant is generally from about 0.1 % to about 30% preferably from about 1% to about 15%, and more preferably from about 3% to about 12% by weight of composition.

Amphoteric N-surfactants suitable for use in the compositions of the invention include:

(a) imidazolinium surfactants of formula (II)

wherein R₁ is C₇-C₂₂ alkyl or alkenyl, R₂ is hydrogen or CH₂Z, each Z is independently CO₂M or CH₂CO₂M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (III)

wherein R₁, R₂ and Z are as defined above;

(b) aminoalkanoates of formula (IV)

R₁NH(CH₂)_nCO₂M and iminodialkanoates of formula (V)

R₁N[(CH₂)_mCO₂M]₂ wherein n and m are numbers from 1 to 4, and R₁ and M are independently selected from the groups specified above; and

(c) mixtures thereof. Suitable amphoteric surfactants of type (a) are marketed under the trade name Miranol and are understood to comprise a complex mixture of species. Traditionally, the Miranols have been described as having the general formula II, although the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclic structure III. In practice, a complex mixture of cyclic and non-cyclic species is likely to exist and both definitions are given here for sake of completeness. Preferred for use herein, however, are the non-cyclic species.

Examples of suitable amphoteric surfactants of type (a) include compounds of formula II and/or III in which R₁ is C₈H₁₇ (especially iso-capryl), C₉H₁₉ and

C₁₁H₂₃ alkyl. Especially preferred are the compounds in which R₁ is C₉H₁₉, Z is

CO₂M and R₂ is H; the compounds in which R₁ is C _{1 1}H_23, Z is CO₂M and R₂ is

CH₂CO₂M; and the compounds in which R₁ is C _{1 1}H_23, Z is CO₂M and R₂ is H.

In CTFA nomenclature, materials preferred for use in the present invention include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, and especially cocoamphoacetate and cocoamphodiacetate (otherwise referred to as cocoamphocarboxyglycinate). Specific commercial products include those sold under the trade names of Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol C2M Cone. N.P., Miranol C2M Cone. O.P., Miranol C2M SF, Miranol CM Special (Miranol, Inc.); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals).

It will be understood that a number of commercially-available amphoteric surfactants of this type are manufactured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the sulfated C₈-C₁₈ alcohol, C₈-C₁₈ ethoxylated alcohol or C₈-C₁₈ acyl glyceride types. Preferred from the viewpoint of mildness and product stability, however, are compositions which are essentially free of (non-ethoxylated) sulfated alcohol surfactants. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncompiexed forms of the surfactants, any anionic surfactant counterions being considered as part of the overall anionic surfactant component content.

Examples of suitable amphoteric surfactants of type (b) include salts, especially the triethanolammonium salts and salts of N-lauryl-beta-amino propionic acid and N-lauryl-imino-dipropionic acid. Such materials are sold under the trade name Deriphat by General Mills and Mirataine by Miranol Inc. Amphoterics preferred for use herein, however, are those of formula II and/or III.

Anionic N-surfactants suitable for use in the compositions of the invention can be selected from methyl acyl taurates, fatty acyl glycinates, N-acyi glutamates, acyl sarcosinates, fatty acid/protein condensates and mixtures thereof.

Nonionic N-surfactants suitable for use in the composition of the invention can be selected from polyhydroxy fatty acid amide surfactants having the formula

R₈(CO)N(R₉)Z₂ wherein R₉ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R₈ is C₅-C₃₁ hydrocarbyl and Z₂ is a

polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls directly connected to said chain, or an alkoxylated derivative thereof.

The preferred polyhydroxy fatty acid amide surfactants are those in which R₉ is C_1-4 alkyl, preferably methyl, and R₈ is C₇-C₁₉ alkyl or alkenyl, more preferably straight-chain C₉-C₁₇ alkyl or alkenyl, or mixture thereof; and Z₂ is a

polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z₂ preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z₂ is a giycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose com syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z₂. It should be understood that it is by no means intended to exclude other suitable raw materials. Z₂ preferably will be selected from the group consisting of -CH₂(CHOH)_n-CH₂OH,-CH(CH₂OH)- (CHOH)_n-1-CH₂OH, -CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH₂-(CHOH)₄-CH₂OH.

The most preferred polyhydroxy fatty acid amide has the formula

R₈(CO)N(CH₃)CH₂(CHOH)₄CH₂OH wherein R₈ is a C11-C17 straight chain alkyl or alkenyl group. Zwitterionic N-surfactants suitable for use in the compositions of the invention include alkyl betaines of the formula R₅R₆R₇N⁺(CH₂)_nM (VII) and amido betaines of the formula (VIII)

wherein R5 is C₁₂-C₂₂ alkyl or alkenyl, R₆ and R₇ are independently C₁-C₃ alkyl or hydroxy alkyl, M is H, alkali metal, alkaline earth metal, ammonium or

alkanolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine and

laurylamidopropyldimethylcarboxymethyl betaine.

In addition to the N-surfactant, the compositions of the invention can also contain an auxiliary surfactant which is free of surfactant species having a structure incorporating amido, amino or ammonio moietes. Preferred auxiliary surfactants are selected from anionic and nonionic surfactants and mixtures thereof. The level of auxiliary surfactant, on the other hand, is preferably in the range from about 0.1% to about 30%, more preferably from about 1% to about 15%, and especially from about 3% to about 12% by weight in the case of liquid compositions and from about 50% to about 90%, preferably from about 65% to about 85% by weight in the case of solid bar compositions. The weight ratio of N-surfactant:auxiliary surfactant, on the other hand, is generally from about 1:5 to about 20:1, preferably from about 1:2 to about 5:1, and especially from about 1: 1 to about 2: 1. The total level of N-surfactant and auxiliary surfactants is generally about 0.5% to about 50%, preferably from about 5% to about 25% and especially from about 10% to about 20% by weight in the case of liquid compositions and from about 60% to about 95%, preferably from about 70% to about 90% by weight in the case of solid bar compositions.

Anionic auxiliary surfactants suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include ethoxylated alkyl sulfates, alkyl glyceryi ether sulfonates, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, and mixtures thereof. Alkyl and/or acyl chain lengths for these surfactants are C₈-C_22, preferably C₁₀-C₁₈. In the case of solid bar compositions on the other hand, suitable anionic auxiliary surfactants also include soaps of C₈-C₂₂ fatty acids. Preferred for use herein from the viewpoint of optimum mildness and lathering characteristics are the salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol and from about 1 to about 12 moles of ethylene oxide, with sodium and magnesium being the preferred counterions. Particularly preferred are the alkyl sulfates containing from about 2 to 4 moles of ethylene oxide, such as sodium laureth-2 sulfate, sodium laureth-3 sulfate and magnesium sodium laureth-3.6 sulfate. In preferred embodiments, the anionic surfactant contains at least about 50%, especially at least about 75% by weight of ethoxylated alkyl sulfate. Again, in preferred

embodiments, the anionic surfactant counterions are selected from magnesium and mixtures of magnesium with one or more counterions selected from alkali metal, ammonium and alkanolammonium, this being preferred from the viewpoint of providing optimum lathering, mildness, emolliency, viscosity and stability.

Nonionic auxiliary surfactants suitable for inclusion in the compositions of the invention include alkylpolysaccharides having the general formula (VI)

RO(C_nH_2nO)_tZ_x where Z is a moiety derived from glucose, fructose or galactose, R is C₈-C₁₈ alkyl or alkenyl, n is 2 or 3, t is from 0 to 10 and x is from about 1 to 10, preferably from about 1.5 to 4.

The preferred alkyl polysaccharides herein are alkylpolyglucosides having the formula VI wherein Z is a glucose residue, R is C₈-C₁₈ alkyl or alkenyl, t is from 0 to

10, preferably 0, n is 2 or 3, preferably 2, and x is from about 1.5 to 4. In the above, x and t are understood to be weight average values and saccharide substitution is preferably at the 1- position of the saccharide. In general terms, C₁₂-C₁₄ alkyl polysaccharides are preferred from the viewpoint of lathering and C₈-C₁₀ alkyl polysaccharides from the viewpoint of skin conditioning.

To prepare these compounds, a long chain alcohol (ROH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.

Alternatively, the alkylpolyglucosides can be prepared by a two step procedure in which a short chain alcohol (C _{1 -6}) is reacted with glucose or a polyglucoside (x = 2 to 4) to yield a short chain alkyl glucoside (x = 1 to 4) which can in turn be reacted with a longer chain alcohol (ROH) to displace the short chain alcohol and obtain the desired alkylpolyglucoside. If this two step procedure is used, the short chain alkylglucoside content of the final alkylpolyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the

alkylpolyglucoside.

The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is preferably less than about 2%, more preferably less than about 0.5% by weight of the total of the alkyl polysaccharide plus unreacted alcohol. The amount of alkylmonosaccharide is about 20% to about 70%, preferably 30% to 60%, more preferably 30% to 50% by weight of the total of the

alkylpolysaccharide.

Other suitable nonionic auxiliary surfactants herein include polyethyleneglycol glyceryl fatty ester surfactants having the formula (IX)

wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having from about 5 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more preferably from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms.

Suitable glyceryi fatty ester surfactants include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn oil, preferably glyceryl tallowate and glyceryl cocoate.

Suitable surfactants of this class are commercially available from Sherex

Chemical Co. (Dublin, Ohio, USA) under their Varonic LI line of surfactants. These include, for example, Varonic LI 48 (polyethylene glycol (n=80) glyceryl tallowate, alternatively referred to as PEG 80 glyceryl tallowate), Varonic LI 2 (PEG 28 glyceryl tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI 63 and 67 (PEG 30 and PEG 80 glyceryl cocoates), and from Croda Inc. (New York, USA) under their Crovol line of materials, such as Crovol A-40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M-40 (PEG 20 maize giyceride), Crovol M70 (PEG 60 maize glyceride), Crovol PK-40 (PEG 12 palm kernei glyceride), and Crovol PK-70 (PEG 45 palm kernel glyceride). Especially preferred are monotallowate and cocoate fatty ester derivatives of polyethylene giycol, or mixtures thereof, particularly materials such as PEG 82 glyceryl monotallowate and PEG 30 glyceryl cocoate, and mixtures thereof. Also especially preferred herein PEG (6)

caprylic/capryl glycerate (Softigen 767).

Other suitable nonionic auxiliary surfactants herein include Cg-C[3 aliphatic alcohol ethoxylates generally containing an average of from 1.5 to 25, preferably from

2 to 15 and more preferably from 6 to 10 moles of ethylene oxide per mole of alcohol. The preferred alcohol chain length range is C9-C11 as it has been found that lathering performance is optimum for ethoxylates made from such alcohols. It is also desirable for lathering performance reasons that the hydrophilic-lipophilic balance (HLB) of the ethoxylated alcohol is in the range from 8.0 to 17.0, more preferably from 11.0 to 17.0 and most preferably from 11.0 to 15.0.

The compositions of the invention also contain a vegetable oil adduct which preferably has the general formula (I):

wherein x, y are integers of from 3 to 9, R3 and R4 are independently selected from saturated and unsaturated C7-C22 hydrocarbyl, each Zγ being CO2M and wherein

M is H, or a salt-forming cation, preferably alkali metal, ammonium or

alkanolammonium.

Materials of this kind can generally be described as adducts prepared from vegetable oils containing non-conjugated polyunsaturated fatty acid esters which are conjugated and elaidinized then modified by Dies-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride. The adducts and their preparation are described in US-A-4740367, the adducts being marketed under the trade name Ceraphyl GA (Van Dyke). The vegetable oil adduct preferably comprises from about 0.5% to about 25%, preferably from about 0.5% to about 15%, more preferably from about 1% to about 10% by weight of the compositions herein. Preferred vegetable oil adducts are those of Formula I prepared from soybean oil (x + y = 12) and adducts derived by Dies-Alder addition of vegetable oils with fumaric acid. A preferred method of preparing adducts herein is to react two moles of vegetable oil with one mole of the dienophile in the presence of catalytic amounts of iodine, the conjugation and elaidinization agent. This produces a 50:50 blend of adduct together with disproportionated (conjugated) vegetable oil.

The vegetable oil adduct is present in the compositions of the invention in the form of a solution or dispersion having an average particle size of less than about 10,000 nm, preferably less than about 1,500 nm, more preferably less than about 1000 nm (measured for example by Quasi-Elastic Light Scattering (90° angle) using a Helium/Neon Laser, a Malvern goniometer with temperature control (25°C) and a Brookhaven BI2030AT digital correlator. In calculating particle size, the particles are assumed to be spherical and the refractive index and viscosity of the continuous phase are assumed to be the same as for water. Alternatively, particle size can be determined using quasi-elastic (dynamic) light scattering and electron microscopy (see M. S.

McCracken and M. C. Sammons, J. Pharm. Sci. 76, 56-59, 1987)). In preferred embodiments, the average particle size of the disperse phase of vegetable oil adduct is at least about 1 and less than about 1000 nm, preferably from about 50 to about 500 nm. Smaller particles having an average particle size from about 1 nm to about 100 nm, preferably from about 3 nm to about 50 nm, are also suitable however. The weight ratio of N-surfactant to vegetable oil adduct on the other hand is preferably from about 10:1 to about 1:10, more preferably from about 5:1 to about 1:2. Moreover, in highly preferred embodiments, the vegetable oil adduct disperse phase is partly or wholly in the form of unilamellar or multilamellar water-encapsulating vesicles. It is a feature of the invention that the vegetable oil adduct can be prepared in vesicle form following the process described in more detail herein. However, compositions wherein the vegetable oil adduct is at least partly in micellar solution or microemulsion form are also encompassed herein.

Thus, according to another aspect of the invention, there is provided a composition comprising an adduct prepared from vegetable oils containing non- conjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Dies- Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride; and wherein the vegetable oil adduct is partly or wholly in the form of an aqueous dispersion of unilamellar or multilamellar waterencapsulating vesicles. Such vesicular structures preferably display optical activity under polarized light. In general terms, the compositions of the invention can be made by a process of pre-dissolving or pre-dispersing the vegetable oil adduct in the N-surfactant or portion thereof, followed by admixing with the remainder of the composition. In particular, it is important that in compositions additionally comprising an auxiliary surfactant, the vegetable oil adduct is pre-dissolved or pre-dispersed in the N-surfactant or portion thereof prior to admixture with the auxiliary surfactant. In a preferred process for making compositions herein containing the vegetable oil adduct in vesicle form, the vegetable oil adduct is admixed with an N-surfactant, a substoichiometric quantity of water or an aqueous phase is added thereto and thereafter the mixture so prepared is dispersed in a stoichiometric excess of water or an aqueous phase, optionally incorporating one or more auxiliary surfactants.

The aqueous phase which is encapsulated in the vesicles can include a wide variety of active substances. In particular, pharmaceutically active substances or cosmetic substances can be employed. Cosmetic substances can include, for instance, components generally employed for the care of the skin and hair, including polymeric skin conditioning agents, moisturizers, panthenol, humectants such as glycerine, sorbitol, pentaerythritol, inositol, pyrrolidone carboxylic acid and its salts; artificial tanning agents such as dihydoxy acetone, erythrulose, glyceraldehyde and gamma-dialdehydes such as tartaric aldehyde, optionally in the presence of dyes; water-soluble anit-solar agents; antiperspirants; deodorants; astringents; skin refreshing products, tonics; cicatrisive products; keratolytic products; depilatories; perfumed water; extracts of animal or vegetable tissue, such as proteins, polysaccharides and amniotic liquid; water-soluble dyes; antipellicular agents; antiseborrheic agents; oxidizing agents (bleaching agents) such as H2O2; keratin reducing agents such as thioglycolic acid and its salts. Representative active pharmaceutical substances include vitamins; hormones; enzymes, for example, superoxide dismutase; vaccines; anti-inflammatory agents, for example, hydrocortisone; antibiotics; and bactericides. In a preferred aspect of the invention the active substance (eg. panthenol) is incorporated in the substoichiometric quantity of water or aqueous phase which is added to the vegetable oil adduct/N- surfactant mixture in the process described above.

The compositions of the invention for use as personal cleansers preferably also contain from about 0.5% to about 6%, preferably from about 1.5% to about 5% by weight of saturated acyl fatty acids having a weight average chain length of from 10 to 16, preferably from 12 to 14 carbon atoms. Highly preferred is myristic acid. The fatty acid is valuable both from the viewpoint of providing emolliency benefits and also for controlling the viscosity of the final composition.

The compositions of the invention for use as personal cleansers preferably also contain a cationic or nonionic polymeric skin or hair conditioning agent at a level from about 0.01% to about 5%, preferably from about 0.04% to about 2% and especially from about 0.05% to about 1 %. The polymer is found to be valuable for enhancing the creaminess and quality of the foam as well as providing a hair or skin conditioning utility.

Suitable polymers are high molecular weight materials (mass-average molecular weight determined, for instance, by light scattering, being generally from about 2,000 to about 3,000,000, preferably from about 5,000 to about 1,000,000).

Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic and nonionic polymers used in the cosmetic fields as hair or skin conditioning agents.

Representative classes of polymers include cationic and nonionic

polysaccharides; cationic and nonionic homopolymers and copolymers derived from acrylic and/or methacrylic acid; cationic and nonionic cellulose resins; cationic copolymers of dimethyldiallylammonium chloride and acrylic acid; cationic

homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.

By way of exemplification, cationic polymers suitable for use herein include cationic guar gums such as hydroxypropyl trimethyl ammonium guar gum (d.s. of from 0.11 to 0.22) available commercially under the trade names Jaguar C-14-S(RTM) and Jaguar C-17(RTM) and also Jaguar C-16(RTM), which contains hydroxypropyl substituents (d.s. of from 0.8-1.1) in addition to the above-specified cationic groups, and quaternized cellulose ethers available commercially under the trade names Ucare Polymer JR and Celquat. Other suitable cationic polymers are homopolymers of dimethyldiallylammonium chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, available commercially under the trade names Merquat 550 and Merquat S, quaternized vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol available commercially under the trade name Gafquat, and polyaikyleneimines such as

polyethylenimine and ethoxylated polyethylenimine.

Anionic polymers suitable herein include hydrophobically-modified cross-linked polymers of acrylic acid having amphipathic properties as marketed by B F Goodrich under the trade name Pemulen TRI and Pemulen TR2; and the carboxyvinyl polymers sold by B F Goodrich under the trade mark Carbopol and which consist of polymers of acrylic acid cross-linked with polyallyl sucrose or polyallyl pentaeythritol, for example, Carbopol 934, 940 and 950.

The viscosity of the final composition (Brookfield RVT, Spindle 5, 50 rpm, 25°C) is preferably at least about 1,000 cps, more preferably from about 2000 to about 10,000 cps, especially from about 5,000 to about 7,000 cps. Preferred compositions have non-Newtonian viscosity characteristics, however, with a viscosity (Brookfield RVT, Helipath, Spindle T-B, 5 rpm, 25°C, 1 min) in the range of from about 10,000 to about 40,000 cps, more preferably from about 20,000 to about 30,000 cps and a yield point of at least 50 dynes/cm^, preferably at least 100 dynes/cm^ (Brookfield RVT, Spindle CP52, Plate Code A, 25βC).

The compositions of the invention can optionally include a hair or skin moisturizer. The preferred level of moisturizer is from about 3% to about 40% by weight. In preferred embodiments, the moisturizer is nonexclusive and is selected from:

1. water-soluble liquid polyols;

2. essential amino acid compounds found naturally occurring in the stratum corneum of the skin; and

3. water-soluble nonpolyol nonocclusives and mixtures thereof.

Some examples of more preferred nonocclusive moisturizers are glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and propylene glycol ethers of methyl glucose (e.g. methyl glucan-20), polyethylene glycol and propylene glycol ethers of lanolin alcohol (e.g. Solulan-75), sodium pyrrolidone carboxylic acid, lactic acid, urea, L-proline, guanidine, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel, acetamide MEA and mixtures thereof. Of the above, glycerine is highly preferred. A further preferred component of the compositions of the invention is a watersoluble Ca²⁺/Mg²⁺ sequesterant which is preferably added at a level of from about 0.1% to about 5% by weight to provide lather boosting advantages under hard water usage conditions. Suitable sequesterants include polycarboxylates, amino

polycarboxylates, polyphosphates, polyphosphonates and aminopolyphosphonates such as ethylenediaminetetraacetic acid, diethylenetriamine pentaacetic acid, citric acid, gluconic acid, pyrophosphoric acid, etc. and their water-soluble salts.

A number of additional optional materials can be added to the compositions of the invention. Such materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, Bronopol (2-bromo-2-nitropropane-1,3-diol), sodium benzoate and 2- phenoxyethanol; other moisturizing agents such as hylaronic acid, chitin , and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in US-A-4,076,663; solvents such as hexylene glycol and propylene glycol; low temperature phase modifiers such as ammonium ion sources (e.g. NH4 Cl); viscosity control agents such as magnesium sulfate and other electrolytes; colouring agents;

pearlescers and opacifiers such as ethylene glycol distearate, TiO₂ and TiO₂-coated mica; perfumes and perfume solubilizers etc. Conventional nonionic emollient oils and waxes can be included as additional skin and hair conditioning agents at levels from about 0.5% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 6%. Such materials include, for example, water-insoluble silicones inclusive of non-volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, rigid cross-linked and reinforced silicones and mixtures thereof, C₁-C₂₄ esters of C₈-C₃₀ fatty acids such as isopropyl myristate and cetyl ricinoleate, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), lanolin and lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, com oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazlenut oil, olive oil, grapeseed oil, and sunflower seed oil and C₁-C₂₄ esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylmalate, diisostearyldimerate and

triisostearyltrimerate. Of the above highly preferred are the vegetable triglyceride oils. Water is also present at a level preferably of from about 45 % to about 99 % , more preferably at least about 60% by weight in the case of liquid compositions, and from about 5% to about 30% in the case of solid bar form compositions.

The pH of the compositions is preferably from about 4 to about 9, more preferably from about 4.5 to about 8.5, pH being controlled, for example, using a citrate buffer system.

A preferred method for making the compositions herein comprises:

(a) forming a first surfactant phase comprising from about 0.1 % to about 30% by weight of final composition of N-surfactant and wherein the first surfactant phase is essentially free of auxiliary surfactant;

(b) forming a second surfactant phase comprising from about 0.1 % to about 30% by weight of final composition of auxiliary surfactant in the form of an aqueous solution or dispersion;

(c) forming a first oil phase comprising from about 0.5% to about 25% by weight of final composition of the vegetable oil adduct;

(d) forming a second oil phase comprising from about 0.5% to about 20% by

weight of final composition of nonionic emollient oil or wax other than the vegetable oil adduct;

(e) premixing the first oil phase with the first surfactant phase;

(f) admixing the premix of step (e) with a substoichiometric amount of water;

(g) and thereafter admixing the mixture of premix (e) and water with the second surfactant phase and the second oil phase.

The invention is illustrated by the following non-limiting examples.

In the examples, all concentrations are on a 100% active basis and the abbreviations have the following designation: Amphoteric 1 Empigen CDL 60 - an aqueous mixture of 23.5%

cocoamphoacetate (the amphoteric of formula I and/or IV in which R\ is coconut alkyl, R2 is H, and Z is CO₂Na) and 1.35% cocoamphodiacetate (the amphoteric of formula I and/or IV in which R₁ is coconut alkyl, R₂ is CH₂CO₂Na and Z is CC₂Na).

Amphoteric 2 Sodium N-lauryl-beta-amino-propionate.

Anionic Sodium laureth-3 sulfate APG Alkylpolysaccharide of formula VI in which R is C₈-C₁₀ alkyl, t is 0, Z is a glucose residue and x is about 1.5.

DEA Coconut diethanolamide MEA Coconut monoethanolamide Betaine Cocoamidopropyldimethylcarboxymethyl betaine Ceraphyl GA Maleated soybean oil marketed by Van Dyke Polymer 1 Merquat 550 - Copolymer of acrylamide and dimethyldiallyl ammonium chloride, m.wt. 2.5 x 10^ (8% solution)

Polymer 2 Polymer JR-400 - hydroxyethylcellulose reacted with

epichlorohydrin and quaternized with trimethylamine, m.wt. 4 x 10⁶

MA Myristic Acid

Preservative DMDM Hydantoin Pearlescer Ethyleneglycoldistearate/emulsifier mixture Oil Soyabean oil Softigen 767 PEG(6) caprylic/capryl glycerate I Examples I to VII

The following are personal cleansing compositions in the form of shower foam products and which are representative of the present invention. The compositions are made by the process set out hereinabove, the Ceraphyl GA being prepared in the form of a dispersion having an average particle size of less than 500 nm. In the above process, Amphoteric 1 and Amphoteric 2 are incorporated as part of the first surfactant phase and the remaining N-surfactants, if any, are incorporated as part of the second surfactant phase. I II III ιv V VI VII

Amphoteric 1 7.5 3.0 5.0 5.0 2.5 5.0 5.0

Amphoteric 2 - 5.0 3.0 - 5.0 - -

Anionic 2.5 - 6.0 4.0 7.5 10.0 10.0

APG 2.5 - 2.0 2.0 - 2.5 2.5

DEA 3.0 1.0 - 2.0 1.0 3.0 -

MEA - - - - - - 3.0

Betaine - 2.0 2.0 1.0 2.5 2.5 -

Ceraphyl GA 5.0 4.0 6.0 6.0 5.0 5.0 5.0

Polymer 1 - 0.1 0.2 - 0.1 0.2 -

Polymer 2 0.2 0.1 - 0.2 0.1 - 0.2

Softigen 767 - - - - - 2.0 1.0

MA 4.0 2.0 1.5 1.0 2.0 2.0 2.0

Oil - - - - - 5.0 5.0 Preservative 0.15 0.15 0.15 0.15 0.15 0.2 0.2 I II III IV V VI VII

Pearlescer 0.5 - - 1.0 1.0 2.0 1.0

Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Glycerine - - - - - - 3.0

Mg 1.0 - - - 2.0 - -

Water - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - to 100 - - - - - - - - - - - - - - -

The products provide excellent in-use and efficacy benefits including cleansing, lathering, mildness and skin conditioning (hydration, suppleness etc.), rinsibility and stability.

Example VIII

A composition comprising vegetable oil adduct in vesicular form is prepared as follows: 60 parts of Ceraphyl GA are added to 30 parts of Amphoteric 1 and the mixture is stirred at ambient temperature. 5 parts of a 10% aqueous solution of D-panthenol is then added to form a white latex-like mixture. The latex is then admixed with 100 parts of 10% sodium lauryi sulfate solution. The resulting dispersion comprised spherical vesicular structures comprising internal droplets of water and D-panthenol.

Claims

WHAT IS CLAIMED IS :

1. A detergent, personal cleansing or cosmetic composition comprising: a) one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic, and cationic surfactants and mixtures thereof, and which comprises at least one surfactant having a structure incorporating one or more amido, amino or ammonio moieties (hereinafter N-surfactant), b) an adduct prepared from vegetable oils containing non-conjugated

polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Dies-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride; and c) water, and wherein the vegetable oil adduct is in the form of a solution or a dispersion having an average particle size of less than about 1000 nm.

2. A composition according to Claim 1 wherein the N-surfactant comprises an amphoteric surfactant selected from:

(a) imidazolinium derivatives of formula (II)

wherein R₁ is C₇-C₂₂ alkyl or alkenyl, R₂ is hydrogen or CH₂Z, each Z is independently CO₂M or CH₂CO₂M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (HI)

wherein R₁, R₂ and Z are as defined above:

(b) aminoalkanoates of formula (IV)

R₁NH(CH₂)_nCO₂M and iminodialkanoates of formula (V) R₁N[(CH₂)_mCO₂M]₂ wherein n and m are numbers from 1 to 4, and R₁ and M are independently selected from the groups specified in (a) above; and

(c) mixtures thereof.

3. A composition according to Claim 2 wherein the amphoteric surfactant is

selected from the imidazolinium derivatives of formula II and/or ammonium derivatives of formula III.

4. A composition according to any one of Claims 1 to 3 wherein the N-surfactant comprises an anionic surfactant selected from methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl sarcosinates, fatty acid/protein condensates and mixtures thereof.

5. A composition according to any one of Claims 1 to 4 wherein the N-surfactant comprises a nonionic surfactant selected from polyhydroxy fatty acid amide surfactants having the formula R₈(CO)N(R₉)Z₂ wherein R₉ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R₈ is C₅-

C₃₁ hydrocarbyl and Z₂ is a polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls directly connected to said chain, or an alkoxylated derivative thereof.

6. A composition according to any of Claims 1 to 5 wherein the N-surfactant comprises a zwitterionic surfactant selected from alkyl betaines of the formula R₅R₆R₇N⁺(CH₂)_nM (VII) and amido betaines of the formula (Vm)

wherein R₅ is C₁₂-C₂₂ alkyl or alkenyl, R₆ and R₇ are independently C₁-C₃ alkyl, M is H, alkali metal, alkaline earth metal, ammonium or

alkanolammonium, and n, m are each numbers from 1 to 4.

7. A composition according to any of Claims 1 to 6 comprising a mixture of N- surfactant and auxiliary surfactant, the auxiliary surfactant being selected from anionic and nonionic surfactants and mixtures thereof and being free of surfactant species having a structure incorporating amido, amino or ammonio moieties; and wherein the vegetable oil adduct is pre-dissolved in or pre- dispersed with the N-surfactant or portion thereof prior to admixture with the auxiliary surfactant.

8. A composition according to Claim 7 comprising:

(a) from about 0.1 % to about 30 % by weight of N-surfactant, and

(b) from about 0.1 % to about 30 % by weight of auxiliary surfactant, and wherein the N-surfactant and auxiliary surfactant together comprise from about 0.5% to about 50% by weight of the composition, and wherein the weight ratio of N-surfactant:auxiliary surfactant is in the range from about 1:5 to about 20:1.

9. A composition according to Claim 7 or 8 wherein the auxiliary surfactant is selected from ethoxylated alkyl sulfates, alkyl glyceryi ether sulfonates, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, and mixtures thereof.

10. A composition according to any of Claims 7 to 9 comprising from about 1 % to about 15 % , preferably from about 3 % to about 12 % by weight of each of the Nsurfactant and auxiliary surfactant.

1 1. A composition according to any of Claims 7 to 10 wherein the N-surfactant comprises an ethoxylated C₈-C₂₂ alkyl sulfate.

12. A composition according to any of Claims 7 to 11 wherein the auxiliary

surfactant comprises a nonionic surfactant selcted from alkylpolysaccharides having the general formula RO(C_nH_2nO)_tZ_x where Z is a moiety derived from glucose, fructose or galactose, R is C₈-C₁₈ alkyl or alkenyl, n is 2 or 3, t is from 0 to 10 and x is from 1.5 to 4.

13. A composition according to any of Claims 7 to 12 wherein the auxiliary

surfactant comprises a nonionic surfactant selected from polyethyleneglycol glyceryl fatty ester surfactants having the formula (IX)

14. A composition according to any of Claims 8 to 13 wherein the weight ratio of N-surfactant:auxiliary surfactant is in the range from about 1:2 to about 5:1, preferably from about 1:1 to about 2:1.

15. A composition according to any of Claims 8 to 14 wherein the N-surfactant and auxiliary surfactant together comprise from about 5% to about 25%, preferably from about 10% to about 20% by weight of the composition.

16. A composition according to any of Claims 1 to 15 wherein the vegetable oil adduct is in the form of a dispersion having an average particle size of at least about 1 and less than about 1000 nm, preferably from about 50 to about 500 nm.

17. A composition according to any of Claims 1 to 16 wherein the vegetable oil is partly or wholly in the form of a microemulsion or vesicular dispersion.

18. A composition according to any of Claims 1 to 17 wherein the vegetable oil adduct is partly or wholly in the form of an aqueous dispersion of unilamellar or multilamellar, water-encapsulating vesicles.

19. A composition according to Claim 18 wherein the vesicles additionally

encapsulate one or more water-soluble or oil-soluble, cosmetically-active or pharmaceutically-active ingredients.

20. A composition according to any of Claims 1 to 19 comprising from about 0.5% to about 15%, preferably from about 3% to about 10% of the vegetable oil adduct.

21. A composition according to any of Claims 1 to 20 wherein the vegetable oil adduct has the formula Q)

wherein x, y are integers of from 3 to 9, R3 and R4 are independently selected from saturated and unsaturated C7-C22 hydrocarbyl, each Z\ being CO2M and wherein M is H or a salt-forming cation, preferably alkali metal, ammonium or alkanolammonium.

22. A composition according to any of Claims 1 to 21 wherein the weight ratio of N-surfactant component to vegetable oil adduct is from about 10:1 to about 1:10, preferably from about 5:1 to about 1:2.

23. A composition according to any of Claims 1 to 22 additionally comprising from 0.01% to 5%, preferably from about 0.04% to about 2% and more preferably from 0.05% to 1% of a cationic or nonionic polymeric skin or hair conditioning agent, selected from cationic and nonionic polysaccharides; cationic and nonionic homopolymers and copolymers derived from acrylic and/or methacrylic acid, cationic and nonionic cellulose resins; cationic copolymers of dimethyldiallylammonium chloride and acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and

ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.

24. A composition according to any of Claims 1 to 23 additionally comprising

moisturiser selected from glycerin, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and polypropylene glycol ethers of methyl glucose, polyethylene glycol and polypropylene glycol ethers of lanolin alcohol, PEG(6) caprylic/capryl glycerate, sodium pyrrolidone carboxylic acid, lactic acid, L- proline and mixtures thereof.

25. A composition according to any of Claims 1 to 24 comprising from about 0.5% to about 20% of an additional nonionic emollient oil or wax.

26. A composition comprising an adduct prepared from vegetable oils containing non-conjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Dies-Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride; and wherein the vegetable oil adduct is partly or wholly in the form of an aqueous dispersion of unilamellar or multilamellar water-encapsulating vesicles.

27. A composition according to Claim 26 wherein the vesicles additionally

encapsulate one or more water-soluble or oil-soluble cosmetically-active or pharmaceutically-active ingredients.

28. A process of making a composition according to any of Claims 1 to 27, the process comprising admixing the vegetable oil adduct with a surfactant having a structure incorporating one or more amido, amino or ammonio moieties, (hereinafter N-surfactant) adding a substoichiometric quantity of water or an aqueous phase thereto, and thereafter dispersing the mixture thus prepared in a stoichiometric excess of water or an aqueous phase optionally incorporating a surfactant or surfactant mixture free of N-surfactant.