CA2131174C

CA2131174C - Cleansing compositions

Info

Publication number: CA2131174C
Application number: CA002131174A
Authority: CA
Inventors: Michel Joseph Giret; Anne Langlois; Roland Philip Duke
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-03-25
Filing date: 1993-03-18
Publication date: 1999-01-12
Anticipated expiration: 2013-03-18
Also published as: EG20556A; EP0636166A1; WO1993019149A1; EP0636166A4; MY109164A; MA22840A1; CN1078746A; MX9301658A; AU3811193A; CN1047620C; CA2131174A1

Abstract

A personal cleansing product comprising (a) from about 5% to about 50% by weight mixed surfactant system which comprises (i) from about 1 % to about 20 % by weight of composition of anionic surfactant, and (ii) from about 1 % to aobut 20 %
by weight of composition of amphoteric surfactant, (b) from about 3 ~ to about 40 ~ by weight of an insoluble nonionic oil or wax, and (c) water, wherein the anionic surfactant and amphoteric surfactant together comprises from about 5 ~ to about 30 ~ by weight of the composition, the weight ratio of anionic surfactant amphoteric surfactant is in the range from about 1:5 to about 20:1,the weigth ratio of total surfactant:nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water emulsion having a viscosity in the range from 10,000 to 40,000 cps and a yield point of at least 50 dyne/cm 2. The cleaning products demonstrate excellent lathering, mildness, stability, risibility and conditioning benefits.

Description

2~3~L7~ PCI/US93/02411 CLEANSING COMPOSITIONS
TECHNICAL FIELD

The present invention relates to cle~nsinP compositions. In particular it relates to foam-producing personal cle~ncing compositions suitable for simlllt~nPously cle~ncin~: 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.

BACKGROUND OF THE INVENTION
Fo~min~: cosmetic compositions must satisfy a number of criteria including cle~n~inP power, fo~ming properties and mil~lnes~/low irritancy with respect to the skin, hair and the ocular mucosae. Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure. The outermost of these layers, referred to as the stratum col..c~m, is known to be composed of 250 A protein bundles su-lol-nded by 80 A thick layers.
Hair simil~rly has a protective outer coating enclosing the hair fibre which is called the cuticle. Anionic surf~ct~nt~ can penetrate the stratum corneum membrane and the cuticle and, by delipidization destroy membrane integrity. This intelrere.lce with skin and hair protective membranes can lead to a rough skin feel and eye irritation and may eventll~lly permit the surf~c~nt to interact with the keratin and hair proteins creating irritation and loss of barrier and water retention functions.

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.

49 213'1174 PCI/US93/0241 1 Certain synthetic surfactants are known to be mild. However, a major drawback of most mild synthetic surfactant systems when form~ te~l for shampooing or personal cle~nsing is poor lather perrolll.ance compared to the highest shampoo and bar soap standards.
Thus, surfactants that are among the mildest, such as sodium lauryl glyceryl ether sulfonate, (AGS), are marginal in lather. The use of known high s~dsing anionic surfact~nts with lather boosters, on the other hand, can yield acceptable lather volume and quality but at the e~pense of clinical skin mil~lness. These two facts make the surf~ct~nt 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 cle~n~ing, the broad mass of consumers remain tliss~isfie~l by the mil~ness of present day cle~ncin~ compositions, fintlinp, 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 m~int~in skin suppleness and hydration and to co,lllteract the delipidi7ing effect of the cleanser.

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

SUMMARY OF THE INVENTION
The subject of the present invention is a foam-producing cleansing product suitable for personal cle~nsin~ of the skin or hair and which may be used as foam bath and shower products, skin cleansers and shampoos etc. According to one aspect of the invention, there is provided a personal cle~n~inP composition comprising:

wo 93/19149 Z131174 Pcr/usg3/o24l 1 (a) from about 5 % to about 50% by weight of a mi~ced surfachnt system which comprises:
(i) from about 1% to about 20% by weight of composition of anionic surf~ct~nt, and (ii) from about 1% to about 20~o by weight of composition of amphoteric surfachnt, (b) from about 3 % to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes, and (c) water, wherein the anionic surfachnt and amphoteric surf~ct~nt together comprise from about 5% to about 30% by weight of the composition, the weight ratio of anionic surf~ct~nt-amphoteric surf~Gt~nt is in the range from about 1:5 to about 20:1, the weight ratio of total surf~ct~nt: nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water eml~lsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25~C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~C).

All concentrations and ratios herein are by weight of the cle~ncing composition, unless otherwise specified. Surf~ct~nt chain lengths are also on a weight average chain length basis, unless other~,vise specified.

The invention relates to a foam-producing cle~l-cin~ composition with superior lathering characteristics (cre~miness, abl)n~1~nce, stability) combined with excellent mil~lness to the skin and hair, together with good stability, cle-~ncinP ability and conditioning ~el~l~ance. The invention also relates to a wash and rinse-off personal cle~nsing product having the above lathering, mil~ness, rinsibility, stability and conditioning benefits.

The cle~ncin~ compositions herein are based on a combination of mild surf~ct~nts which in general terms can be selected from anionic, amphoteric, nonionic and behine surf~ct~nts and mi~ctures thereof. The compositions preferably comprise a mi~ture of anionic and amphoteric surf~ct~ntc and highly preferred systems also incorporate a nonionic or 2~3117~; PCI/US93/02411 betaine surf~ct~nt Other suitable compositions within the scope of the invention comprise mixtures of anionic with one or more nonionic or betaine surfactants or mix~lre thereof; and mixtures of amphoteric with one or more nonionic or betaine surf~ct~nts or mixture thereof. The level of each of the anionic and amphoteric surfact~nts is generally in the range from about 1% to about 20%, preferably from about 2% to about 15~, and especially from about 3% to about 12% by weight of the composition.
The weight ratio of anionic surfactant:amphoteric 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 anionic and amphoteric surf~ct~nts is generally about 5% to about 30%, preferably from about 8% to about 25~ and especially from about 10% to about 20% by weight of the cle~n.cing composition. The nonionic or betaine surf~ct~nt, on the other hand, preferably constitlltes from about 0.1% to about 20%, more preferably from about 0.1 ~i to about 10% and especially from about 1 % to about 8 % by weight of the composition. The total level of surfactant, inclusive of anionic, amphoteric, nonionic, betaine and other surfactant components, is prefe~ably from about 5 % to about 50%, more ~refelably from about 10~o to about 30% by weight of composition.

Anionic surfact~ntc suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include ethoxylated alkyl s~llf~tes, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl gll~t~m~tes, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarCosin~tes and fatty acid/l~rotehl con~en~tes, and mi~ctures thereof. Alkyl and/or acyl chain lengths for these surf~ct~nts are Cg-C22, preferably C10-C18 rreferred for use herein from the viewpoint of optim-lm 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 so~lil)m and m~nesium being the preferred countelions. Particularly yiefe~led are the alkyl sulf~tes cont~ininP from about 2 to 6, preferably 2 to 4 moles of ethylene oxide, l49 213'~ Pcr/US93/024l 1 such as so~ m laureth-2 sulfate, sodium laureth-3 sulfate and m~npsium sodium laureth-3.6 sulfate. In preferred embo~limP~ts, the anionic surf~ct~nt contains at least about 50%, especially at least about 75% by weight of ethoxylated alkyl sulfate. Again, in preferred embo~ime~ts, the anionic surf~ct~nt counterions are selected from m~nesium and mixtures of m~nesium with one or more counterions selected from alkali metal, ammonium and alkanol3mmonium, this being preferred from the viewpoint of providing optiml~m lathering, mil-lness, emolliency, viscosity and stability. Thus, according to another aspect of the invention there is provided a personal cle~ncin~ composition comprising:

(a) from about 5% to about 50% by weight of a mixed surfactant system which comprises:
(i) from about 1% to about 20% by weight of composition of anionic surfactant, and (ii) from about 1% to about 20% by weight of composition of amphoteric surf~ct~nt, (b) from about 3 % to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or wa~es, and (c) water, wherein the anionic surf~chnt and amphoteric surfactant together comprise from about 5% to about 30% by weight of the composition, the weight ratio of anionic surf~ct~nt ~mphoteric surf~Gt~nt is in the range from about 1:5 to about 20:1, the weight ratio of total surf~ct~nt- nonionic oil or wa~ is in the range from about 10:1 to about 1:3, and wherein the anionic surf~ct~nt coul-telions are selected from m~nesium and mixtures of m~nesium with one or more counterions selected from alkali metal, ammonium and ~lk~nolammonium. In prefelled embo~lim~nts, m~nesium is preferably present in an amount equivalent to at least 10 mole %, ~refelably at least 20 mole % of the anionic surf3ct~nt. It will be understood that m~neSillm can be introduced into the compositions of the invention either as the preformed m~pnesium or partial m~nesium salt of the anionic surfactant, or in the form of a water-soluble, non-surface active m~nesium salt, for e~ample m~nesium chloride, m~nesium sulfate or hydrate thereof.

WO 93/19149 Z~3'~ 4 PCr/US93/02411 Preferred compositions for use herein also contain an amphoteric surfactant. Amphoteric surfactants suitable for use in the compositions of the invention include:

(a) imi(l~701inium surf~ct~nts of formula (II) C2H4~R2 1 ~ + ~

wherein R1 is C7-C22 alkyl or alkenyl, R2 is hydrogen or CH2Z, each Z is independently C02M or CH2C02M, and M is H, alkali metal, ~lk~line earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula RlCONH ( CH2 ) 2N CH2 Z

wherein R1, R2 and Z are as defined above;

(b) aminoalkanoates of formula (IV) Rl NH(CH2)nC02M

and imino~i~lk~noates of formula (V) RlN[(CH2)mc02M]2 wherein n and m are numbers from 1 to 4, and Rl and M are independently selected from the groups specified above; and 149 2131~L74 PCr/US93/0241 1 (c) mi~lres thereof.

Suitable amphoteric surf~ct~nts of type (a) are marketed under the trade name Miranol and Empigen and are understood to coml,lise a complex mixt~lFe of species. Traditionally, the Miranols have been described as having the general formula II, although the CTFA Cosmetic Ingredient Dictionary, 4th Edition indicates the non-cyclic structure m.
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.

F-~mples of suitable amphoteric surf~ct~nts of type (a) include compounds of formula II and/or III in which R1 is CgH17 (especially iso-capryl), CgH19 and Cl 1H23 alkyl. Especially prefel.ed are the compounds in which R1 is CgH1g, Z is C02M and R2 is H; the compounds in which R1 is Cl1H23, Z is C02M and R2 is CH2C02M;
and the compounds in which R1 is C11H23, Z is C02M and R2 is H.

In CTFA nomenclature, materials preferred for use in the present invention include cocoamphocarbo~cypropionate, coco~mphocarboxy propionic acid, and especially coco~mpho~cet~te and coco~mphodiacetate (otherwise referred to as cocoamphocarboxyglycinate). Specific commercial products include those sold under the trade names of Empigen CDL60 and CDR 60 (Albright & Wilson) Miranol H2M conc., Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol C2M SF, Miranol CM Special (Rhone-Poulenc); Al~ateric 2CIB (Alkaril Ch~mic~l~); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona ~n.1ustries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Che_icals).

It will be understood that a number of commercially-available amphoteric surfactants of this type are m~mlf~ct~red and sold in the form of electroneutral complexes with, for e~ample, hydro~cide counterions or witb anionic sulfate or sulfonate surf~ct~n~s, especially those of the slllf~teA Cg-C1g alcohol, Cg-Clg ethoxylated alcohol or Cg-C1g acyl WO 93/19149 2~3~ t~ PCI'/US93/02411 glyceride types. Preferred from the viewpoint of mil~lness and product stability, however, are compositions which are esse~ti~lly free of (non-ethoxylated) s-llf~t~ alcohol surf~ct~nts. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomple~ced forms of the surf~ct~nt~, any anionic surf~ct~nt counterions being considered as part of the overall anionic surf~ct~nt component content.

F~mples of suitable amphoteric surf~ct~ntc of type (b) include salts, especially the triçth~nol~mmonium 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 Henkel and Mirataine by Rhone-Poulenc. Amphoterics preferred for use herein, however, are those of formula II and/or III.

The compositions of the invention also contain from about 3 % to about 40%, preferably from about 5% to about 20%, and more preferably from about 8% to about 15% by weight of an insoluble nonionic oil or wax or mixture thereof, the oil or wax being insoluble in the sense that it is insoluble in the cle~nsinP composition liquid matrix at a temperature of 25~C. In addition, the oil or wax is present in composition in a level such that the weight ratio of total surf~ct~nt-oil or wax is in the range from about 10:1 to about 1:3" preferably from about 5:1 to about 1:2, and especially from about 2:1 to about 1:1, this being preferred from the viewpoint of providing personal cle~n.~inp compositions having optimum lathering, mil~lne~s, emolliency, rinsibility and stability characteristics.

Suitable oils and waxes for use herein can be selected from 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 Cg-C30 fatty acids such as isopropyl myristate and cetyl ricinoleate, beeswax, sahurated and lln~hlrated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolah m and squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil like lanolin derivatives, ~nim~l and W O 93/19149 ~ ~ 3 ~ ~ 7 4 PC~r/US93/02411 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, corn 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, diisostearylm~l~te, diisostearyldimerate and triisostearyltrimerate. Of the above, highly preferred from the viewpoint of optimum lathering and mildness are the vegetable triglyceride oils.

Preferred from the viewpoint of conditioning effectiveness in a rinse-off application are compositions in the form of oil-in-water emulsions wherein the average size of the emulsion droplets is in the range from about 1 to about 150 microns, preferably from about 2 to a~out 50 microns, and more preferably from about 3 to about 10 rnicrons (droplet size being measured by, for example, laser diffraction using, e.g.
a Malvern Series 2600).

The oil or wa~ is preferably used herein in combination with a rnild surfactant system. Suitable mild surfactants include those having a Relative Skin }~arrier Penetration Value of less than about 75, preferably less th~n a~out 50 and more preferably less than about 40, Relative Skin Barrier Penetration Value being measured according to the test method set out in EP-A-0203750. Surfactants which have Relative Barrier Penetration Values of greater than 75 can be used along with the mild surfactant at low levels in the compositions of this invention, as long as their use does not significantly change the clinical skin mildness of the total cleansing composition.

Thus according to another aspect of the invention, there is provided a personal clea~sing composition comprising:

(a) from about 5% to about 50% by weight of a mi~ed surfactant system having a Relative Skin Barrier Penetration Value of less than about 75, ~', D.

WO 93/19149 , t21~ 4 PCI'/US93/02411 (b) from about 3% to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes, and (c) water, wherein the weight ratio of total surfactant: nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, S rmp, 25~C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~C).

The compositions herein preferably also contain from about 0.1 to about 20%, more prefe~dbly from about 0.1 % to about 10%, and especially from about 1 % to about 8 % of a nonionic or betaine surfactant.
Preferred herein from the viewpoint of optimllm lathering and mildness are nonionic surf~ct~nts selected from C12-C14 fatty acid mono- and diethanolamides; alkylpolysaccharides having the general formula (VI) RO(CnH2nO)tzx where Z is a moiety derived from glucose, fructose or ~ ctose~ R is Cg-Clg 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; polyhydroxy fatty acid amide surf~ct~ntc having the general formula (VII) e R~g where Rg is H, Cl-C4 hydrocarbyl, 2-hydro~cyethyl, 2-hydroxypropyl or a mixture thereof, R8 is Cs-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; and polyethyleneglycol glyceryl fatty ester surf~ct~ntc having the formula (IX) WO 93/19149 2~ Pcr/uss3/0241 l RcocH2cH (OH) CH2 (OCH2CH2 ) nOH

wberein n is from about S 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 S to 19 carbon atoms, ~referably 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; and mixtures of said alkyl polys~cch~ride, amide or glyceryl fatty ester surf~ct~ntc.

The l,referred alkyl polysaccharides herein are alkylpolyglucosides having the formula VI wherein Z is a glucose residue, R is Cg-C1g alkyl or alkenyl, t is from 0 to 10, preferably 0, n is 2 or 3, ~refelably 2, and is from about 1.5 to 4. In the above, x and t are understood to be weight average values and saccharide s~1bsl;L.~ion is preferably at the 1- position of the s~cch~ide. In general terms, C12-C14 alkyl polys~cch~rides are ~refel~ from the viewpoint of lathering and Cg-C1o 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 alkylpolyglllcosi~les can be prepared by a two step procedure in which a short chain alcobol (C1 6) is reacted with glucose or a polyglucoside (x = 2 to 4) to yield a short chain alkyl pll)coside (~c = 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 S%, most prefeldbly 0% of the alkylpolyglucoside.

The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkylpolysaccharide surf~c~nt is prefe~bly 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 WO 93/19149 Z~3~174 PCI'/US93/02411 al'kylmonosaccharide is about 20% to about 70%, preferably 30% to 60%, more ~refelably 30% to 50% by weight of the total of the alkylpolysaccharide .

The prefelled polyhydroxy fatty acid amide surf~c~nts are those in which Rg is Cl 4 alkyl, preferably methyl, and R8 is C7-Clg alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, or mixture thereof; and Z2 is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connecte~ to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z2 preferably will be derived from a reducing sugar in a reductive ~min~tion reaction; more preferably Z2 is a glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose, ctose, mannose, and xylose. As raw materials, high de~ctrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be ili7e~ 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 inte~e~l to exclude other suitable raw materials.
Z2 preferably will be selected from the group conci~tin~ of-CH2(CHOH)n-CH20H,-CH(CH20H)-(CHOH)nl-CH20H,-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 Rg(CO)N(CH3)CH2(CHOH)4CH2OH wherein R8 is a C11-C17 straight chain alkyl or alkenyl group.

Suitable glyceryl fatty ester surfact~nts include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl p~lm~te, 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.

2~31~7~
WO 93/19149 ' : ~ PCr/US93/02411 Suitable surf~ct~nts of this class are commercially available from Sherex Chemical Co. (Dublin, Ohio, USA) under their Varonic LI line of surf~t~ntc. 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~0 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M-40 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK 40 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG
45 palm kernel glyceride). Especially preferred are monotallowate and cocoate fatty ester derivatives of polyethylene glycol, or mixtures thereof, particularly materials such as PEG 82 glyceryl monotallowate and PEG
30 glyceryl cocoate, and mixtures thereof. Also especially preferred herein is PEG (6) capric/caprylic glyceride (Softigen 767).

Betaine surf~ct~nts suitable for inclusion in the composition of the invention include alkyl bet~ines of the formula RsR6R7N+(CH2)nM
(VII) and amido bet~ines of the formula (VIII) Rsco(cH2)mN(cH2) nM
R~

wherein Rs is C12-C22 alkyl or alkenyl, R6 and R7 are independently Cl-C3 alkyl, M is H, alkali me~al, ~lk~line earth metal, ammonium or ~lk~nQl~mmQnium, and n, m are each numbers from 1 to 4. Preferred bet~ines include coco~mi-lopropyl-limethylcarboxymethyl betaine and lauryl~mi~lopropyl-limethylcarboxymethyl betaine.

Of the above nonionic and betaine surfactants, highly preferred for use herein are the alkylpolysaccharides having the general formula VI, this being preÇerled from the viewpoint of providing optim-lm lathering, mil~ness, emolliency, rinsibility and stability characteristics. Thus, WO 93/19149 2~31174 PCI'/US93/02411 according to another aspect of the invention, there is provided a personal cle~ncing composition comprising:

(a) from about 5 % to about 50% by weight of a mi~ced surfactant system which comprises (i) from about 1% to about 20% by weight of anionic surfact~ntS
(ii) from about 1% to about 20% by weight of amphoteric surf~ct~nt, and (iii) from about 0. 1% to about 20% by weight of alkylpolys~cch~ride having the general formula (VI) RO(CnH2nO)tZx where Z is a moiety derived from ~hlcose, fructose or ctose~ R is Cg-C1g alkyl or alkenyl, n is 2 or 3, t is from O to 10 and x is from about 1 to 10, preferably from about 1.5 to 4 (b) from about 3~ to about 40~o of an insoluble, nonionic oil or wax or mixture of insoluble nonionic oils or wa~es, and (c) water, wherein the anionic surf~ct~nt and amphoteric surf~ct~nt together comprise from about 5~ to about 30~o by weight of the composition, the weight ratio of anionic surf~ct~nt amphoteric surf~ct~nt is in the range from about 1:5 to about 20:1, the weight ratio of total surfactant: nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water eml.llsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, S rmp, 25~C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~C).

The compositions of the invention l~refe~ably also contain from about 0.5% to about 6%, preferably from about 1.5~ to about 5~o by weight of saturated or llns~tllrated acyl fatty acids having a weight average chain length of from 10 to 18, prererably from 12 to 16 carbon 2~31~7~
WO 93/t9149 PCI/US93/02411 atoms. Highly preferred are myristic saturated fatty acid and palm kernel nc~rated fatty acid. The fatty acid is valuable both from the viewpoint of providing emolliency benefits and also for controlling the viscosity and stability of the final composition. Highly prefelred from the viewpoint of providing optimum viscosity and low temperature stability characteristics are compositions comprising the on~ rated fatty acids.

According to a further aspect of the invention therefore, there is provided a personal cle-~n~in~ composition comprising:

(a) from about 5% to about 50% by weight of a mixed surf~ct~n~
system which comprises:
(i) from about 1% to about 20~ by weight of composition of anionic surf~c~nt, and (ii)from about 1% to about 20% by weight of composition of amphoteric surfactant, (b) from about 3 % to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes;

(c) from about 0.5% to about 8% by weight of llns~t~lrated fatty acid, with weight average carbon chain length of from 10 to 18 carbon atoms; and (d) water, wherein the anionic surfactant and amphoteric surfactant together comprise from about 5% to about 30% by weight of the composition, the weight ratio of anionic surf~ct~nt: amphoteric surfacPnt is in the range from about 1:5 to about 20:1, the wight ratio of total surf~ct~n~: nonionic oil or wa~ is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, Srmp, 25~C, 1 min) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~C).

WO 93/19149 Z~3 Ll'74 The compositions of the invention preferably also contain a cationic or nonionic polymeric skin or hair conditioning agent at a level from about 0.01% to about 5~i, 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 enh~ncing the cre~minçss 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 inct~nce, by light scattering, being generally from about 2,000 to about 3,000,000, prefeldbly from about 5,000 to about 1,000,000).

Useful polymers are the cationic, nonionic, amphoteric, and anior~ic 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 meth~cr~ylic acid; cationic and nonionic cellulose resins; cationic copolymers of dimethyldiallylammonium chloride and acrylic acid; cationic homopolymers of rlimethyldiallyl~mmonium chloride; cationic polyalkylene and etho~ypolyalkylene jmines; 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-l~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 tlimçthyldiallyl~mmonium chloride available commercially under the trade name Merquat 100, copolymers of ~1imçtlly aminoethylmçth~crylate and acryl~mi~e, copolymers of ~limethyldiallyl~mmonium chloride and acryl~mi~e, available commercially under the trade names Merquat 550 and Merquat S, WO 93/19149 ~31:~ 7~ PCI'/US93/02411 quaternized vinyl pyrrolidone acrylate or meth~crylate copolymers of amino alcohol available commercially under the trade name Gafquat, and polyalkyleneimin~s such as polyethylenimine and ethoxylated polyethylerliminç.

Anionic polymers suitable herein include hydrophobically-modified cross-linked polymers of acrylic acid having amphip~thic 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 e~cample, 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 ~refefably from about 2000 to about 10,000 cps, especially from about 5,000 to about 7,000 cps. Prefefled 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 (shear stress at zero shear rate) of at least 50 dynes/cm2, preferably at least 100 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~C). In highly l)refe.red embo~liments, the composition of the invention also display a shear stress versus te~ ,erature profile such that (S4s-Ss)/Ss is less than about 0.4, preferably less than about 0.2, and more preferably less than about 0.1, where St is the shear stress in dynes/cm2 at tell.pe~ature t(~C) and at a shear rate of 500 sec~
(Brookfield RVT, Spindle CP52, Plate Code A).

It is a feature of the compositions of the invention that the particular surf~c~nt mixtures employed therein display excellent lathering characteristics even in the presence of high levels of dispersed oil phase.
Although the reasons for this are not fully understood, it is believed to reflect at least in part, the rheological pro~ellies of the compositions of the invention and in particular the rheological behaviour of the compositions as they are admixed with water during use.

WO 93/19149 2~C3~4 PCI'/US93/0241 1 The cle~ncin~ compositions can optionally include a hair or skin moisturi_er which is soluble in the cle~ncin~ composition matrix. The prefelred level of moisturizer is from about 0.5% to about 20% by weight. In prefe~led embo~im~nts, the moisturizer is selected from:

1. water-soluble liquid polyols;
2. essenti~l 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 moisturi_ers are glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and propylene glycol ethers of methyl glucose (e.g. methyl glucam-20), sodium pyrrolidone carboxylic acid, lactic acid, urea, L-proline, gll~nilline, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel and ~cet~mi~e MEA and mi~ctures thereof. Of the above, glycerine is highly preferred.

A number of additional optional materials can be added to the cle~ncin~ compositions. Such materials include yroteills 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, Eu~yl (RTM) K400, Bronopol (2-bromo-2-nilro~lopane-1,3-diol), sodium ben7o~te and 2-phenoxyethanol;
other moisturizing agents such as hyaluronic acid, chitin, and starch-grafted sor~ m polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, p~ l., VA, USA and described in US-A-4,076,663; solvents such as hexylene glycol and propylene glycol; low te~ e~ature phase modifiers such as ammonium ion sources (e.g. NH4 Cl); viscosity control agents such as m~pnesium sulfate and other electrolytes; colouring agents;
pearlescers and opacifiers such as ethylene glycol ~licte~rate, TiO2 and TiO2-coate~l mica; perfumes and perfume solubilizers etc. Water is also present at a level preferably of from about 459~Z~ to about 92% preferably at least about 60% by weight of the compositions herein.

WO 93/19149 2~3i~ ~4 ~ PCI'/US93/02411 . 19 The pH of the compositions is l,refeldbly from about 4 to about 8, more preferably from about 4.5 to about 6.5.

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 desi~n~tion:

Amphoteric 1 Empigen CDL 60 - an aqueous mixture of 23.5 %
cocoampho~ce~te(the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is H, and Z is C02Na) and 1.35% cocoamphoAi~ce~te (the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is CH2C02Na and Z is C02Na).

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

Anionic 1 Sodium laureth-2 sulfate Anionic 2 M~Pnesium sodium laureth 3.6 s~llf~ç

APG Alkylpolys~cch~ride of formula VI in which R is Cg-C1o alkyl, t is 0, Z is a glucose residue and x is about 1.5.

GA Polyhydroxy fatty acid amide of formula VII in which R8 is C11-C17 alkyl, Rg is methyl, and Z2 is CH2(CHOH)4CH20H

DEA Coconut diethanol~mi~le MEA Coconut monoethanol~mi~le Betaine Cocoamidopropyl~imethylcarboxymethyl betaine WO 93/19149 2~3~ ~t74 PCr/US93/0241 1 Polymer 1 Merquat 550 - Copolymer of acryl~mi~le and dimethyldiallyl ammonium chloride, m.wt. 2.5 x 106 (8% solution) Polymer 2 Polymer JR 400 - hydroxyethylcellulose reacted with epichlorohydrin and quaternized with trimethyl~min~, m.wt. 4 x 106 MA Myristic Acid PKA Palm Kernel Acid Preservative DMDM Hydantoin Pearlescer Ethyleneglycoldistearate/emlllsifier mixture Oil Soyabean oil Softigen 767 PEG(6) caprylic/capryl glycerate Mg M~gnesium sulfate heptahydrate 2~ 4 WO 93/19149 PCI'/US93~02411 _ 21 Examples I to VII
The following are personal cleansing cs~m~ositions in the form of shower foam products and which are represen~tive of the present invention:

II III IV V VI VII VIII

Amphoteric 1 7.5 3.0 S.0 5.0 2.5 5.0 S.0 S.0 Amphoteric 2 - 5.0 3.0 - 5.0 hnionic 1 2.5 - 6.0 4.0 7.5 10.0 10.0 10.0 ~Llionic 2 5.0 9.0 4.0 6.0 A P G 2.5 1.0 2.0 - - 2.5 G A - 1.0 - 2.0 2.0 - 2.5 2.5 D E A 3.0 1.0 - 2.0 1.0 3.0 - 3.0 M E A - - - - - - 3.0 Be~aine - 2.0 2.0 1.0 2.5 2.5 - 2.5 Polymer 1 - 0.1 0.2 - 0.1 0.2 - 0.2 Polymer 2 0.2 0.1 - 0.2 0.1 - 0.2 SoRigen 767 - - - - - 2.0 1.0 2.0 M A 4.0 2.0 1.5 1.0 2.0 2.0 2.0 P K A - - - - - - - 2.0 Oil 8.0 12.0 9.0 12.0 8.0 10.0 1 1 .0 10.0 Preservative 0.15 0.15 0.15 0.15 0.15 0.2 0.2 0.2 WO 93119149 213~1~4 PCI'/US93/02411 II III IV V VI VII VIII

Pearlescer 0.5 - - 1.0 1.0 2.0 1.0 2.0 Perfume 1.0 l.0 l.0 1.0 1.0 1.0 l.0 1.0 Glycerine - - - - 3.0 3.0 Mg 1.0 - - - 2.0 - - 0.5 Water to 100 WO 93/19149 PCI'/US93/02411 2~3'~ 79~ 23 Compositions I to VII are prepared by forming a surf~ct~nt phase A
cont~inin~ a portion of the water, the anionic and amphoteric surf~ct~nts and the rem~inin~ watèr-soluble, oil-insoluble ingredients, forming an oil phase B
cont~inin~ the MA, DEA, Softigen and oil, admixing B with A at about 40~-70~C, cooling to ambient temperature then adding the rem~inin~ water, preservative and water. The average particle size of the emulsion droplets is about 5 micron. (Malvern Series 2600 laser diffraction). The compositions have a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25~C, lmin) in the range from lO,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25~).

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

Claims

What is claimed is:-

1. A personal cleansing composition comprising:

(a) from about 5% to about 50% by weight of a mixed surfactant system which comprises:

(i) from about 1% to about 20% by weight of composition of anionic surfactant selected from ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates and fatty acid/protein condensates, and mixtures thereof, and (ii) from about 1% to about 20% by weight of composition of amphoteric surfactant, (b) from about 3% to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes, and (c) water, wherein the anionic surfactant and amphoteric surfactant together comprise from about 5% to about 30% by weight of the composition, the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:5 to about20:1, the weight ratio of total surfactant:nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25°C, 1 min) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm 2 (Brookfield RVT, Spindle CP52, Plate Code A, 25°C), and wherein are excluded personal cleansing compositions which comprise an adduct prepared from vegetable oils containing non-conjugated polyunsaturated fatty acid esters which are conjugated and elaidinized and then modified via Diels - Alder addition with a member of the group consisting of acrylic acid, fumaric acid and maleic anhydride.

2. A composition according to Claim 1 comprising from about 2% to about 15% by weight of each of the anionic surfactant and the amphoteric surfactant.

3. A composition according to Claim 1 wherein the anionic surfactant comprises an ethoxylated C8-C22 alkyl sulfate.

4. A composition according to Claim 1 wherein the amphoteric surfactant is 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 (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 in (a) above; and (c) mixtures thereof.

5. A composition according to Claim 4 wherein the amphoteric is selected from the imidazolinium derivatives of formula II, or ammonium derivatives of formula III, or a mixture thereof.

6. A composition according to Claim 5 wherein the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:2 to about 5:1.

7. A composition according to Claim 6 wherever the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:1 to about 2:1.

8. A composition according to Claim 6 wherein the anionic surfactant and amphoteric surfactant together comprise from about 8% to about 25% by weight of the composition.

9. A composition according to Claim 8 additionally comprising from about 0.1 % to about 20% by weight of nonionic or betaine surfactant or mixture thereof.

10. A composition according to Claim 9 wherein the nonionic surfactant is selected from alkyl polysaccharides having the general formula RO(CnH2O)tZx where Z is a moiety derived from glucose, fructose or galactose, R is C8-18 alkyl or alkenyl, n is 2 or 3, t is from 0 to 10 and x is from 1.5 to 4; 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; polyethyleneglycol glyceryl fatty ester surfactants having the formula (IX) wherein n is from about 5 to about 200 and wherein R comprises an aliphatic radical having from about 5 to 19 carbon atoms; and mixtures of said amide or glyceryl fatty ester surfactants.

11. A composition according to Claim 1 comprising from about 5 %
to about 20% by weight of the nonionic oil or wax or mixture thereof.

12. A composition according to Claim 11 additionally comprising from about 0.5% to about 6% by weight of a saturated or unsaturated fatty acid having a weight-average chain length of from 10 to 18 carbon atoms.

13. A composition according to Claim 1 additionally comprising from 0.01% to 5% 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.

14. A composition according to Claim 1 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.

15. A composition according to Claim 1 wherein the anionic surfactant comprises at least 50% thereof of ethoxylated C8-C22 alkyl sulfate and wherein the surfactant counterions are selected from magnesium and mixtures of magnesium with one or more counterions selected from alkalimetal, ammonium and alkanolammonium.

16. A composition according to Claim 1 wherein the weight ratio of total surfactant:nonionic oil or wax is in the range from about 5:1 to about 1:2.

17. A personal cleansing composition comprising:

(a) from about 5% to about 50% by weight of a mixed surfactant system which comprises:

(i) from about 1% to about 20% by weight of composition of anionic surfactant, and (ii) from about 1% to about 20% by weight of composition of amphoteric surfactant, (b) from about 3% to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes;

(c) from about 0.5% to about 8% by weight of unsaturated fatty acid with weight average carbon chain length of from 10 to 18 carbon atoms; and (d) water, wherein the anionic surfactant and amphoteric surfactant together comprise from about 5% to about 30% by weight of the composition, the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:5 to about 20:1, the weight ratio of total surfactant:nonionic oil or wax is in the range from about 10:1 to about 1:3, and wherein the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rpm, 25°C, 1 min) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm 2 (Brookfield RVT, Spindle CP52, Plate Code A, 25°C).