CA2259658A1 - Cleansing compositions - Google Patents

Cleansing compositions Download PDF

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Publication number
CA2259658A1
CA2259658A1 CA 2259658 CA2259658A CA2259658A1 CA 2259658 A1 CA2259658 A1 CA 2259658A1 CA 2259658 CA2259658 CA 2259658 CA 2259658 A CA2259658 A CA 2259658A CA 2259658 A1 CA2259658 A1 CA 2259658A1
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water
composition according
soluble
alkyl
surfactant
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CA 2259658
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French (fr)
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Alan Brooks
Charles Marie Alain Du Reau
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Procter and Gamble Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90Block copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/45Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5422Polymers characterized by specific structures/properties characterized by the charge nonionic

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)

Abstract

A liquid personal cleansing composition comprising from about 0.01 % to about 15 % by weight of a thickening system which consists essentially of associative polymer and polar oil having a required HLB of at least 12, from 0.1 % to about 20 % by weight of a nonionic polyhydroxy fatty acid amide surfactant, from about 1 % to about 60 % by weight of a water-soluble auxiliary surfactant other than the polyhydroxy fatty acid amide surfactant and water. The products provide excellent product thickening and rheological attributes in storage, in dispensing an in-use, in combination with good efficacy benefits including excellent rinsibility, mildness, skin conditioning, skin moisturising, good product stability, cleansing and lathering.

Description

WO ~8/00 l~ PCT/US97/11679 CLEANSING COMPOSITIONS

TECHNICAL FELD

The present invention relates to cle~ncin~ compositions In particular it relates to mild personal cleansing compositions which display improved thickening and rheological properties in combination with good skin feel attributes, rinsing behaviour and fo~rning properties which are suitable for simlllt~neously c}eansing and conditioning the skin and/or the hair and which may be used, for example, in the form of foam bath plep~lions, shower products, skin cleansers, hand, face and body cleansers, sharnpoos, etc.

Back~round Of The Invention Mild cosmetic compositions must satisfy a number of criteria including cleansing power, foaming properties and mildness/low irritancy/good feel 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 forrn the skeleton of its structure. The outermost of these layers, referred to as the stratum corneum, is known to be composed of 250 ~ protein bundles surrounded by 80 ~ thick layers. Hair similarly has a protective outer coating enclosing the hair fibre which is called the cuticle. Anionic surfactants can penetrate the ~ um corneum membrane and the cuticle and, by delipi~ tion destroy membrane integrity. This intelrelellce with skin and hair protective membranes can lead to a rough skin feel and eye irritation and may eventually pennit the surfactant to interact with the keratin and hair proteins creating irritation and loss of balTier 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 hlilat~lg the ocular mucosae or leav~ng 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 rnild synthetic surfactant systems when form~ te~ for shampooing or personal cle~n~ing is poor lather pe.~o,-~ ce compared to the highest shampoo and bar soap standards.
Thus, surf~ct~ntc that are among the mildest are marginal in lather. The use of known high sudsing anionic surfactants such as alkyl sulphates 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 selection of suitable surfactants in the lather and mildness benefit formulation process a delicate balancing act.

In addition to the mildness, cle~ncing and lathering performance attributes desired by consumers it is important that personal cle~n.~ing products fi~rther have good thickening and rheological properties, in product storage, in dispensing and in-use.

It is known that water-soluble polymers can be used to provide desirable product thickening attributes and, furthermore, that hydrophobic modification of water-soluble polymers can improve their thickening efficacy. However, it is also known that the thickening properties of such hydrophobically modified water-soluble polymers can be significantly re~ ee~1 in non-dilute, water-soluble surfactant systems (as discussed in Sau and Landoll 'Polymers in Aqueous Media', Advances in Chemistry Series No. 223, Chapters 8, 17, 18, edited by J.E. Glass). In particular, Applicant has found that in non-dilute, water-soluble surfactant systems, - hydrophobically modified polymers, such as hydrophobically modified hydroxy ethyl cellulose, do not deliver good product thickening. Non-dilute, as ~lefine~l herein, means systems comprising gleatel than about 1% ~y weight of water-soluble surfactant. Water-soluble, as defined herein, means a surfactant having a molecular weight of less than about 20,000 wherein the surf~ct~nt is capable of forming a clear, isotropic solution when dissolved in water at 0.2 % w/w under ambient conditions (25~C).
It is also well known that fatty alcohol ethoxylates and fatty alcohols can thicken systems cont~ining both water-soluble surfactant and electrolyte (as illustrated, for example, in Hoechst Surfactants, WO 98100499 PCT/I~S97/11679 published Trade Literature). However, fatty alcohol ethoxylates and fatty alcohols modify the micellar structure of the water-soluble surfactant system, resulting in undesirable effects on product characteristics such as the lather profile, rinsing behaviour and in-use product feel attributes.
Applicant has also found, that, in order to achieve good product thickening in non-dilute, water-soluble surfactant systems via the exclusive use of a fatty alcohol ethoxylate and/or fatty alcohol thickening agent, the amount of fatty thickener re~uired to deliver acceptable thickening attributes results in re~--ce~ lather and rinsing p-,lrol-llance.

It is known that an additional difficulty associated with the use of fatty alcohol ethoxylate and/or fatty alcohol and electrolyte based thickening systems is that the thickening effect of such materials is highly dependant upon the purity and quality of the raw materials used. This can lead to unpredictability in thickening performance, such as thin products with non-recoverable low viscosity. This unpredictability makes it difficult to efficiently formulate systems using water-soluble surfactants which have predictable viscosity profiles when using these fatty materials.

In addition to the product thinning difficulties faced when attempting to thicken systems cont~ining high levels of surfactant using fatty thickeners, applicant has found that mild, water-soluble nonionic surfactants, such as polyhydroxy fatty acid amides and alkyl polyglycosides are difficult to thicken using fatty thickeners and electrolyte based thiclcening systems.

Thus a need exists for effective thickening systems for mild, non-dilute, water-soluble surfactant systems comprising polyhydroxy fatty acid amide surf~ct~ntc which deliver good product thiG~ening and rheology attributes both in storage, in dispPncing and in-use in combination with the delivery of excellent product characteristics such as lather, cleansing, rinsing, skin mildness and in-use skin feel attributres.

Applicant has found that personal cle~ncin~ compositions having excellent product thickening and rheology attributes, both under product storage and in-use conditions, are provided by the combination of a .

thickening system consisting essentially of associative polymer and polar oil in combination with polyhydroxy fatty acid amide surf~ct~nt and a non-dilute, water-soluble, auxiliary surfactant matrix.

Surnmarv Of The Invention The subject of the present invention is a mild, non-dilute, foam-producing, easily rinsed, cle~n.~ing products suitable for personal cle~n~ing of the skin or hair which have good thickening and rheology properties and which may be used as shower products, skin cleansers and shampoos etc. According to one aspect of the invention, there is provided a liquid personal cleansing composition comprising:

(a) from about 0.01% to about 15% by weight of a thickening system which consists essentially of associative polymer and polar oil having a required HLB of at least 12.

(b) from about 0.1% to about 20% by weight of a nonionic polyhydroxy fatty acid amide surfactant having the general formula (III):

wherein R8 is Cs-C31 hydrocarbyl, Rg is hydrogen, C1-Cg alkyl or hydroxyalkyl and Z2 is a polyhydroxyhydrocarbyl moiety;

- (c) from about 1% to about 60% by weight of water-soluble auxiliary surfactant other than the polyhydroxy fatty acid amide surfactant of (b), selected from anionic surfactant, nonionic, zwitterionic and amphoteric surfactants and mi~lures thereof; and CA 022',96F,8 1998-12-30 (d) water.

wherein the average carbon chain length of the po}ar oil is from about 10 to about 18 carbon atoms and is substantially similar to the average carbon chain length of the combined polyhydroxy fatty acid amide and other surfactants in the water-soluble, non-dilute surf~ct~nt matrix.

In a highly l.,efe~led emborlime~t~ the invention takes the forrn of a non-dilute, foam producing liquid cle~n~ing composition having good product thickening and rheological properties.

All concentrations and ratios herein are by weight of the cle~n~ing composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified.

Detailed Description of the Invention The liquid cle~n.cing compositions herein combine a thickening system con.~ ting essentially of associative polymer and polar oil in combination with polyhydroxy fatty acid amide surfactant and an auxiliary surfactant matrix and, optionally, polymeric skin conditioning agents. Plef~.led embodiments also contain perfume or cosmetic oils.

Thickenin~ SYstem The liquid cle~n.~ing compositions herein are based on a thickening system con.~i~ting essen~i~lly of associative polymer, preferably hydrophobically modified water-soluble, nonionic polymer, and polar oil having a required HLB value of at least about 12, in combination with polyhydroxy fatty acid amide surfactant and an auxiliary water-soluble, non-dilute surfactant system, and optionally polymeric skin conditioning agents.

The total level of associative polymer and polar oil in the thickening system according to the present invention is from about 0.01%

CA 022~96~8 1998-12-30 to about 15%, preferably about 0.01% to about 10%, more preferably from about 0.05% to about 8%, most l.lefel~bly from about 0.1% to about 4%, especially from about 0.1% to about 2%, most especially from about 0.5% to about 1.5% by weight. The ,urefe.led ratio of associative polymer to polar oil is in the range of from about 1:5 to about 5:1, more efe.ably from about 1:3 to about 3:1, most preferably from about 1:2 to about 1:2.

The thickening system of the invention is valuable for the delivery of good product thickening and rheological attributes during product storage, dispen.cing and use.

A further benefit of the thickening systems of the present invention is that the product thickening is not dependant of the presence of electrolyte in the surfactant matrix. Thus, it is now possible to formulate a non-dilute, water-soluble surfactant matrix having desirable product thickening and rheological attributes without the use of an electrolyte.

Applicant has found that this independence from electrolyte is particularly valuable for the delivery of desirable thickening properties when form~ ting mild, non-dilute, water-soluble surfactant systems comprising polyhydroxy fatty acid amide surfactants (as discussed hereina~er).

Associative Polvmers The thicLenin~ systems of the present invention contain, as an essenti~l component, an associative polymer at a level of from about O.Ol~/o to about 12%, ~refelably from about 0.01% to about 10%, more prefe,~bly from about 0.05% to about 8%, most llrefelably ~om about 0.1% to about 4%, especially from about 0.1% to about 2%, most especially from about 0.5% to about 1.5% by weight. Associative polymers are valuable, in the compositions herein, in combination with polar oils having a required HLB of at least 12, for the delivery of good product thickenin~ and rheological attributes in non-dilute, water-soluble surfactant systems comprising polyhydroxy fatty acid amide and auxiliary surfactants.

... ....

In the compositions according to the present invention preferred associative polymers are nonionic associative polymers having an average molecular weight in the range of from about 2,000 to about 2,000,000, preferably from about 10,000 to about 1,000,000, more preferably from about 20,000 to about 800,000.

Associative polymers are a subclass of water-soluble polyrners and are generally water-soluble macromolecular structures having of both hydrophilic and hydrophobic components. Associative polymers can thicken surfactant solutions predomin~ntly via intermolecular association between the water-insoluble hydrophobic components on the water-soluble polymer backbone (discussed in detail by G. D. Shay in Polymers in Aqueous Media, Advances in Chernistry series 223, pp467. Edited by J. E. Glass).

As discussed in herein before, associative thickeners are known to build viscosity in the presence of low levels of water-soluble surfactants (i.e., less than about 1% w/w), as described in EP-A-0,412,706, and the litcralure reports on the interaction of such associative thickeners with specific surfactants (Sau and Landoll, 'Polyrners in Aqueous Media', Advances in Chemistry Series No. 223, pp 343-364, Edited by J.E.
Glass).

Hydrophobically modifed polymer, as defined herein, means, a water soluble (hydrophilic) associative polymer which has been modified by the addition of hydrophobic groups to ellh~nce its thickening potential (as ~licc~lsse~l in Sau and Landoll ~olymers in Aqueous Media', Advances in Ch~ sLy Series No. 223, Chapters 8, 17, 18, edited by J.E. Glass).
The generally accepted model of product thickening, in terms of hydrophobically modified water-soluble nonionic polymers, is that thicl~nin~ results ~om interrnolecular association between the hydrophobic groups on the polymer (Sau and Landoll, 'Polyrners in Aqueous Media', Advances in Chemistry Series No. 223, pp 343-364, edited by J.E. Glass). In particular, the effect of simple anior.uc surfactant, e.g. SDS, and nonionic surfactant, e.g. CxEy, on hydrophobically modified hydroxy ethyl cellulose (~MHEC) (as .. . .. ......

CA 022~96~8 1998-12-30 WO 98,'(. ~19~ PCT/US97/1 1679 discussed in Sau & Landoll in 'Polymers in Aqueous Media', Advances in Chernistry Series No. 223, pp 343-364 and Tanaka et al. in Macromolecules, 1992, 25, pp 1304-1310) and hydrophobically modified ethoxy ~elllalle (~UR) ~Hulden, Colloids & Surfaces, 82 (1994), 263-277).

Pre~lled liquid cle~n~in~ compositions herein are based on a thicLenin~ system concistine essentially of hydrophobically modified water-soluble, nonionic polymer and polar oil having a re~uired HLB
value of at least about 12, in combination with a water-soluble, non-dilute surfactant system comprising polyhydroxy fatty acid arnide and auxiliary surfactants, and optionally polymeric skin conditioning agents. Water-soluble, in terms of hydrophobically modified water-soluble nonionic polymer, as defined herein, means, polymer having at least a water-soluble backbone and/or linlcages.

While not wishing to be bound to any particular theory, it is proposed herein that the hydrophobically modified water-soluble nonionic polymer and polar oil thickeners of the present invention, interact, in the presence of non-dilute, water-soluble surfactant systems comprising polyhydroxy fatty acid amide and auxiliary surf~ct~nts to deliver excellent product thickening characteristics.

Hydrophobically modified water-soluble nonionic polymers suitable for use in the thickening systems of the present invention include hydrophobically modified hydroxyalkyl cellulose polymers such as hydrophobically modified hydroxyethyl cellulose (~C), hydrophobically modified alkoxylated urethane polyrners, such as hydrophobically modified ethoxylated urethane (HEUR), and hydrophobically modified nonionic polyols.

Hydrophobicallv Modified H~/droxyalkyl Cellulose Thickener Cellulose ethers suitable for use herein, have, prior to hydrophobic modification, a sufficient degree of nonionic substitution selected from methyl, ethyl, hydroxyethyl and hydroxypropyl to cause them to be water-soluble. The ~,lefel-ed degree of nonionic substitution is in the WO ~8/0015~ PCT/US97/11679 range of ~om about 1.8 to about 4.0, preferably from about 2 to about 3, and especially from about 2.2 to about 2.8 by weight. The cellulose ethers are then further substituted with alkyl or alkenyl groups having from about 10 to about 24, preferably from about 14 to about 18 carbon atoms in an amount of from about 0.1 to about 1, prefc.ably from about 0.3 to about 0.8, and especially from about 0.4 to about 0.6 weight percent. The cellulose ether to be modified is l~re~lably one of low to medium molecular weight, i.e., less than 800,000 and Ille~.~bly between 20,000 and 700,000 (75 to 2500 D.P.). Degree of polymerisation (D.P.) as defined herein, means, the average number of glycoside units in the polymer.

~ efe.led cellulose ethers for use herein are selected from cornmercially available nonionic cellulose ethers such as hydroxy ethyl cellulose, hydroxy propyl methyl cellulose, hydroxy methyl cellulose, ethyl hydroxy ethyl cellulose and mixtures thereof.

The plefel-ed cellulose ether substrate, for use herein, is a hydroxyethyl cellulose (~C) of from about 50,000 to about 700,000 molecular weight. Hydroxyethyl cellulose of this molecular weight level is the most hydrophilic of the materials completed. Accordingly, control of the modification process and control of the properties of the modified product can be more precise with this substrate. Hydrophilicity of the most commonly used nonionic cellulose ethers varies in the general direction: hydroxyethyl > hydroxypropyl > hydroxypropyl methyl >
methyl.

The long chain alkyl modifier, for the cellulose ether, can be attached to the cellulose ether substrate via an ether, ester or urethane linL-~g. The ether linkage is l.refe--ed. Although the modified cellulose ether materials are referred to as being "alkyl modified ", (the term alkyl as used generally herein also includes using alkenyl) it will be recognised that except in the case where modification is effected with an alkyl halide, the modifier is not a simple long chain alkyl group. The group is actually an alphahydroxyalkyl radical in the case of an epoxide, a urethane radical in the case of an isocyanate, or an acyl radical in the WO 981(.~ t~9 PCT/US97/11679 case of an acid or acyl chloride. General methods for m~king modified cellulose ethers are taught in Landoll ('277) at column 2, lines 36-65.

Highly p lefe-led hydrophobically modified hydroxy ethyl cellulose (~C) polymers suitable for use herein have a 1% aqueous viscosity in the range of from about 8,000 to about 50,000 mPas (Brookfield LVT
viscometer, spindle No. 4, speed 4).

Commercially available materials prefe.led for use herein include NATROSOL PLUS Grade 330 CS (TM), a hydrophobically modified hydroxyethylcellulose available from Aqualon Co,l~ y, Wilmington, Delaware. This material has a C16 alkyl substitution of from 0.4% to 0.8% by weight. The hydroxyethyl molar substitution for this material is from 3.0 to 3.7. The average molecular weight for the water-soluble cellulose prior to modification is approximately 300,000. Also suitable for use herein is NATROSOL PLUS Grade 430 CS (TM) Another material of this type is sold under the trade name NATROSOL PLUS CS Grade D-67 (TM), by Aqualon Company, Wilmington, Delaware. This material has a C16 substitution of from 0.50% to 0.95%, by weight. The hydroxyethyl molar substitution for this material is from 2.3 to 3.7. The average molecular weight for the water soluble cellulose prior to modification is approximately 700,000. Highly ~refelled for use herein are C14 - Clg alkyl and alkenyl modified hydroxy ethyl cellulose polymers having a degree of ethoxylation of from about 1.8 to about 3.2, preferably from about 2.0 to about 3.0, more l~refe.ably from about 2.2 to about 2.8 and an alkyl and alkenyl substitution level of from about 0.3 to about 0.8, l~lefeiably from about 0.4 to about 0.7, most ~u~efel~bly ~om about 5.5 to about 0.7 and especially about 0.65. Highly preferred are cetyl modified hydroxy ethyl cellulose polymers as available from the Aqualon Co. under the trade names Polysurf 67 (TM) having a molecular weight of about 700,000.

. . .

Hydrophobicallv Modified Alkoxvlate Urethane Thickener Hydrophobically modified water-soluble nonionic alkoxylated urethane polymers suitable for use herein are particularly valuable for providing excellent stability characteristics over normal temperature ranges (5~C to about 50~C) as well as delivering near Newtonian rheology behaviour at low shear rates in matrices comprising high surfact~nt levels, and for delivery of improved product thickening characteristics and rheological behaviour in combination with polar oil, having a re~uired HLB of at least 12, in a water-soluble, non-dilute surfactant system comprising polyhydroxy fatty acid amide and auxiliary surfactants.

Hydrophobically modified water-soluble nonionic alkoxylated urethane polymers are made by prepolyrnerisation of a diisocyanate with a polyol followed by end capping with primary amines or primary.
alcohols. The resulting molecule is usually a linear block copolymer, with internal and terminal hydrophobes but branched and cross linked polymer can also be obtained.
The polyrnerisation process is very complex and various resulting polyrner structures can be formed as reviewed in the literature by Hulden (Colloids & Surfaces, 82, 263-277), K~c~n~rski et al. (Polyrn. Mater.
Sci. Eng., 67, 282-283), and Kar~n~sen~ et al. (Polymers in aqueous media, Advances in Chemistry Series, 223, 495-52S). Further details on hydrophobically modified water-soluble nonionic alkoxylated urethane polymers as thickeners are discussed in the paper titled 'Polymers in Cosmetics', preserlte-l by Rohm & Haas as part of 'The Procee~ings of the 20th National Congress of the Society of Italian Cosmetic Chemists 1993' at p29.

I~efe..ed hydrophobically modi~ed water-soluble nonionic aL~coxylated urethane polymers for use herein are described by K~cml~rski et al. as linear block copolymers (which can be obtained by a step - growth process) and can have the following general structures:

R2-NHCO-NH-Rl [NH-CO-O-En-CH2CH20CONH-R 1 ]X-NHCO-NH-, . . ... , ~, ., R2-0-CONH-R 1 ~NH-CO-O-En-CH2CH20CONH-R 1 ]X-NH-CO-O-R2 wherein: En is a polyol having the general formula, (CH2 CH2 O) n, n can vary from 10 to 10,000, ~lefwably from 10 to 1,000, and more l)refe~bly from 50 to 500; Rl includes straight or branched chain alkyl, alkenyl or aromatic groups cont~inin~ pending functional groups e.g.
COOH; R2 includes straight or branched chain alkyl, alkenyl or aromatic groups cont~ining pending functional groups e.g. COOH and wherein R2 is ,vre~elably selected from NH2 or OH and wherein x represents the degree of polymerisation.

P'~cfe~led hydrophobically modified water-soluble nonionic alkoxylated urethane polymers suitable for use herein are those sold by Rohm & Haas under Acrysol 44 (TM), by Berol Nobel under Bermodol 2101 (TM), 2130 (TM) and Bermodol Pur 2100 (TM) and by Servo under the name Ser-Ad-FX-100 (TM).

Hydrophobically Modified Nonionic Polyols Also suitable for use herein as thickeners are hydrophobically modified water-soluble nonionic polyols. Suitable hydrophobically modified water-soluble nonionic polyols for use herein are fatty acid esters of glucosides such as PEG 120 methyl glucoside dioleate (available from Amercol under the trade name Gl--c~ te DOE 120), PEG-150 pentaerythrityl tetrastearate (available from Croda under the trade name Crothix (IM)), PEG-75 dioleate (available from Kessco under the trade name PEG-4000 dioleate (I~I)) and PEG-150 distearate (available from Witco under the trade name Witconal L32 (TM)).

Polar Oil A further essential feature of the thickening systems of the present invention is polar oil having a required HLB of at least 12. Polar oil is present in the cle~n.~in~ compositions herein at a level of from about , .

WO 98/00499 PCTtUS97/11679 0.01% to about 3%, preferably from about 0.01% to about 2%, more prefelably from about 0.1% to about 1%, most preferably from about 0.2% to about 0.8% by weight.

Polar oil as defined herein, means, an organic oil, in liquid or waxy form, having one or more hydrophilic or polar functionalities, and which, can interact with associative polymer, in the presence of a water-soluble, non-dilute surf~ct~nt system comprising polyhydroxy fatty acid amide and auxiliary surf~.t~nt~ to deliver excellent product thickening and rheology attributes.

Polar oils suitable for use as thickeners herein have a required HLB value of about at least 12, preferably from about 12 to about 15, more l~re~elably from about 12 to about 14. Required HLB value, as defined herein, represents the "Required Hydrophile / Lipophile Balance"
and can be ~sesse~l by the standard technique well known in the art. The HLB concept in general, and specifically the required HLB, is also described more fully in "The HLB System", published by ICI Americas lnc., Wilmin~on Delaware.

Exemplary polar oils suitable for use in the compositions according to the present invention include natural and synthetic fatty alcohols and fatty acids having an average carbon chain length of from about 10 to 18 carbon atoms. Fatty alcohols suitable for use herein include decyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol and mixtures thereof. Additional polar oils include fatty acids having an average carbon chain length of from about 12 to 16 carbon atoms, such as lauric acid and myristic acid.

Applicant has also found that the carbon chain length of the polar oil has an impact on the degree of product thickening delivered to water-soluble, non-dilute surfactant systems comprising polyhydroxy fatty acid amide and auxiliary surfactants by the thickening systems of the present invention. In general, I,,efe.red polar oils suitable for use herein have an average carbon chain length which is in the range of from about 10 to about 18, preferably from about 12 to about 16 and especially from about 12 to about 14 carbon atoms. Particularly preferred for use herein are systems wherein the average carbon chain length of the polar oil is subst~nti~lly similar to the average carbon chain length of the water-soluble, non-dilute surfactant system comprising polyhydroxy fatty acid amide and auxiliary surfactants. Subst~nti~lly similar average carbon chain length, as defined herein, means, carbon chain lengths within two, ~refelably one, carbon units difference, i.e, C12 is defined herein as substantially similar to C 14 Polar oils having an average carbon chain length of from about 12 to about 14 carbon atoms on the alkyl chain are ,urerelled in the cle~n~ing compositions according to the invention, as surfactants having an average carbon chain length of from about 12 to about 14 carbon atoms are highly desirable for the delivery of good foaming properties.

As herein before discussed, particularly suitable for use in the thickening system of the present invention are polar oils having a chain length substanitally similar to that of the chosen surfactant system.
Preferred polar oils for use herein are Cl 2 to C 14 alcohols such as Lauryl Alcohol (Laurex NC (RTM) from Albright & Wilson), C12 to C13 alcohols (Dobanol 23 from Shell UK) and C 12 to C 15 alcohols (Dobanol 25 from Shell UK) and, C14 to Cls alcohols (Dobanol 45 from Shell UK) also available under the Neodol trademark from Shell US
Inc.

Applicant has also found that the level of polar oil thickener present in the thickening system of the invention has a finite effect on the increase in product thickening (i.e., as the level of polar oil increases, relative to the total surfactant level, the degree of thickening achieved in the surfactant matrix eventually reaches a plateau).

The present compositions can also comprise an auxiliary nonionic or anionic polymeric thickening component, especially a water-soluble polymeric materials, having a molecular weight greater than about 20,000. By "water-soluble polymer" is meant that the material will form a substantially clear solution in water at a 1% concentration at 25~C and the material will increase the viscosity of the water. Examples of water-soluble polymers which may desirably be used as an additional thickening component in the present compositions, are hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol (examples include PVA 217 from Kurary Chemical Co., Japan), polyvinyl pyrrolidone K-120, dextrans, for example Dextran purified crude Grade 2P, available from D&O Chemicals, carboxymethyl cellulose, plant exr~ tec such as ~C~&i~ ghatti, and tr~g~c~nth seaweed extracts such as sodium ~lgin~te, propylene glycol ~l~n~te and sodium carrageenan. Preferred as the additional thickeners for the present compositions are natural polys~cch~ride materials. Examples of such materials are guar gurn, locust bean gum, and ~nth~n gum. Also suitable herein preferred is hydroxyethyl cellulose having a molecular weight of about 700,000.

Polvhvdroxv Fatty Acid Amide Surfactant The compositions according to the present invention comprise, as an essential feature, a mild water-soluble polyhydroxy fatty acid amide nonionic surfactant at levels of from about 0.1% to about 20%, more lJlefe.~bly from about 0.1% to about 10%, and especially from about 1%
to about 8% by weight. Suitable for use herein are polyhydroxy fatty acid amide surfactants having the general formula (III).

O Rg The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to formula (III) are those in which R8 is Cs-C31 hydrocarbyl, preferably C6-C1g hydrocarbyl, including straight-chain and br~ he~l chain alkyl and alkenyl, or mixtures thereof and Rg is typically, hydrogen, C1-Cg alkyl or hydroxyalkyl, preferably methyl, or a group of formula-Rl-O-R2 wherein R1 is C2-Cg hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is efelably C2-C4 alkylene, R2 is C1-Cg straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is WO ~8/00159 PCT/US97111679 I)refer~bly C 1 -C4 allcyl, especially methyl, or phenyl. Z2 is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (prefelably ethoxylated or propoxylated) thereof.
Z2 I.re~.ably will be derived from a reducing sugar in a reductive ~m~nin~tion reaction, most ~referably Z2 is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilised 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 con.sistin~ of-CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)nI-CH2H, CH2(CHOH)2(CHOR')CHOH)-CH2OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly-saccharide, and alkoxylated derivatives thereof. As noted, most ~refelled 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 C6-CIg straight chain allcyl or allcenyl group. In compounds of the above formula, Rg-CO-N< can be, for example, cocoamide, stearamide, oleamide, laurarnide, myristamide, capricamide, p~lmi~mide, tallowamide, etc.

A ~,efclled process for m~kin~ the above compounds having formula (m) comprises reacting a fatty acid triglyceride with an N-subs~ihlte-l polyhydroxy amine in the substantial absence of lower (Cl-4) alcoholic solvent, but l~lefe.~bly with an alkoxylated alcohol or alkoxylated aLkyl phenol such as NEODOL and using an alkoxide catalyst at temperatures of from about 50~C to about 140~C to provide high yields (90-98%) of the desired products. Suitable processes for m~kin~ the desired polyhydroxy fatty acid amide compounds are ou~lined in US-A-5,194,639 and US-A-5,380,891.

. .

It is known that mild, nonionic surfactants such as polyhydroxy fatty acid amides and alkyl polyglycosides can deliver excellent skin mildness characteristics in combination with good lather and cle~n~ing attributes. However, Applicant has found that auxiliary, water-soluble, non-dilute surfactant system comprising polyhydroxy fatty acid amide and auxiliary surf~ct~nt~ at high (>1% w/w) levels can be relatively unresponsive or unstable in the presence of conventional thickening agents, such as electrolyte. For example, when improperly ~orrnulated, non-dilute, auxiliary, water-soluble surfactant systems comprising polyhydroxy fatty acid amide surfactants and electrolyte are water-thin and difficult to thicken.

In addition to the product thinnin~ and stability limit~tions of such conventional thickening agents, Applicant has also found that incorporation of alternative thickening agents, such as hydroxy ethyl cellulose"c~nth~n gum, guar gum, polyrner JR 30M (TM), into non-dilute, water-soluble surfactant matrices comprising polyhydroxy fatty acid amide surfactant can provide some thickening but at the expense of lather and rinsing performance.

Thus, it would be desirable to develop a thickening system for the formulation of mild, non-dilute, water-soluble surfactant systems comprising polyhydroxy fatty acid amide and/or alkyl polyglycoside which deliver good product thickening, rheology and stability attributes in combination with good lather and rinsing perforrnance.

Applicant has now found that the thickening system of the present invention is valuable for the delivery of excellent product thickening and rheology attributes in combination with good lather pc.~llllance and skin mildness attributes in non-dilute, water-soluble surf~ct~nt systems comprising mild polyhydroxy fatty acid amide and water-soluble auxiliary surfactants.

According to another aspect of the invention there is provided a personal cle~n~ing composition comprising:

(a) from about 0.01% to about 15% by weight of a thickening system which consists essentially of associative polymer and polar oil having a re~uired HLB of at least 12.

(b) from about 0.1% to about 20% by weight of a nonionic polyhydroxy fatty acid amide surfactant having the general formula (III):

wherein R8 is Cs-C3 1 hydrocarbyl, Rg is hydrogen, Cl-Cg alkyl or hydroxyalkyl and Z2 is a polyhydroxyhydrocarbyl moiety;

(c) from about 1% to about 60% by weight of water-soluble auxiliary surfactant other than the polyhydroxy fatty acid amide surfactant of (b), selected from anionic surfactant, nonionic, zwitterionic and arnphoteric surfactants and mixtures thereof; and (d) water.

wherein the average carbon chain length of the polar oil is from about 10 to about 18 carbon atoms and is substantially similar to the average carbon chain length of the combined polyhydroxy fatty acid amide and other mild surfactants in the water-soluble, non-dilute surfactant matrix.

Auxiliary Surfactant System As a further essential feature the compositions of the present invention comprise an auxiliary water-soluble, non-dilute surf~ct~nt system comprising polyhydroxy fatty acid amide and auxiliary surf~ct~ntc. Water-soluble, as defined herein, means a surfactant having a molecular weight of less than about 20,000 wherein the surfactant is - capable of forming a clear isotropic solution when dissolved in water at .. ..

0.2 % w/w under ambient conditions. Surfactants suitable for inclusion in compositions according to the present invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and can be selecte~l from anionic, nonionic, zwitterionic and amphoteric surf~ct~nt~ and mixtures thereof. The total level of surfactant is preferably from about 2% to about 40%, more preferably from about 3%
to about 15% by weight. The compositions preferably comprise a mixture of anionic with zwitterionic and/or amphoteric surfactants. The level of the individual anionic, zwitterionic and amphoteric surfactant components, where present, is in the range from about 1% to about 15%, and especially from about 1% to about 10% by weight of the composition, while the level of nonionic surfactant, where present, is in the range from about 0.1% to about 20% by weight, preferably from about 0.5% to about 16%, more preferably from about 1% to about 12%
by weight. The weight ratio of anionic surfactant: zwitterionic and/or amphoteric surfactant is in the range from about 1:10 to about 10:1, prefe.ably from about 1:5 to about 5:1, more preferably from about 1:3 to about 3:1. Other suitable compositions within the scope of the invention comprise mixtures of anionic, zwitterionic and/or amphoteric surfactants with one or more nonionic surfactants. Preferred for use herein are soluble or dispersible nonionic surfactants selected from ethoxylated animal and vegetable oils and fats and mixtures thereof, sometimes referred to herein as "oil-derived" nonionic surfactants.

The compositions of the invention can comprise an auxiliary, water-soluble anionic surfactant at levels from about 0.1% to about 20%, more ~l~r~,~bly from about 0.1% to about 10%, and especially from about 1%
to about 8% by weight.

Water-soluble auxiliary anionic surfactants suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include alkyl sulphates, ethoxylated alkyl sl~lf~tes, alkyl ethoxy carboxylates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl gl--~ tes, acyl isethion~tes, allcyl sulfosuccinates, alkyl ethoxysulphosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulphates, acyl ... .~ .

CA 022',96',8 l998-l2-30 W O 98/00499 PCTrUS97/11679 sarco.cin~tes and fatty acid/protein condensates, and rnixtures thereof.
Alkyl and/or acyl chain lengths for these surfactants are C 1 2-C22, pre~erably C12-C18 more preferably C 12 C14.

Surfactants of this class include short-chain alkyl sulphate surf~ct~nt.~ where 'short chain' as defined herein means an average carbon chain length of Clo or less. The short chain alkyl sulphate surf~ct~nt~ of the present invention are valuable in shower gel compositions for the delivery of improved skin mildness attributes and product rinsing benefits in combination with a desirable lather profile. Alkyl sulphate surfactants suitable for inclusion in the compositions of the present invention have the general formula (II);

wherein R is straight or branched chain alkyl, preferably straight chain, cont~inin~ on average from about 8 to about 10 carbon atoms, preferably about 10 carbon atoms and wherein M is selected from alkali metals, ammonium or other suitable monovalent cation or mixtures thereof. It should be understood that the definition of any particular carbon chain length, say C8 is an average value and as such may contain certain proportions of both higher and lower carbon cha~n lengths as a direct function of its synthesis. The level of such material can be achieved by modification of the process and the nature of the starting materials.
While Clo alkyl sulphate is the preferred surfactant in the compositions of the invention mixtures of short chain alkyl sulphates may also be used.
Especially prefe.,ed in the compositions herein is C1o alkyl sulphate rnaterial cont~inin~ at least about 80% by weight of the Clo, preferably at least about 90% Clo, more plefelably at least about 95% Clo and especially at least about 99% Clo alkyl sulphate. Suitable short chain alkyl sl-lph~te materials are available from Albright and Wilson under the trade names Empicol LC35 and Empicol 0758F.

Additional auxiliary, water-soluble anionic surfactants suitable for use in the compositions according to the present invention 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, arnrnonium and magnesium being the preferred counterions.
Particularly preferred are the alkyl ethoxy sulphates cont~ining from about 2 to 6, preferably 2 to 4 moles of ethylene oxide, such as sodium laureth-2 sulphate, sodiurn laureth-3 sulphate and magnesium sodiurn laureth-3.6 sl-lph~te. In preferred embodirnents, the anionic surfactant contains at least about 50% especially at least about 75% by weight of ethoxylated allcyl sulphate.

In addition to the broad range ethoxylated alkyl sl-lrh~te~ obtained via conventional sodium catalysed ethoxylation tec~lniques and subsequent sulphation processes, ethoxylated alkyl sl-lph~tes obtained from narrow range ethoxylates (NREs) are also suitable auxiliary, water-soluble anionic surfactants for use in the present compositions. Narrow range ethoxylated alkyl sulphates suitable for use herein are selected from sulphated allcyl ethoxylates containing on average from about 1 to about 6, ~)lefc.ably from about 2 to about 4 and especially about 3 moles of ethylene oxide such as NRE sodium laureth-3 sulphate. NRE materials suitable for use herein contain distributions of the desired ethylene oxide (E~n) in the ranges of from lS% to about 30% by weight of EOn~ from about 10% to about 20% by weight of EOn+l and from about 10% to about 20% by weight of EOn l . Highly preferred NRE materials contain less than about 9% by weight of ethoxylated alkyl sulphate having 7 or more moles of ethylene oxide and less than about 13% by weight of non-ethoxylated alkyl sulphate. Suitable laureth 3 sl-lph~te NRE materials are available from Hoechst under the trade names GENAPOL ZRO Narrow Range and GENAPOL Narrow Range.

The compositions of the present invention may contain, as an auxi~iary water-soluble anionic surfactant alkyl ethoxy carboxylate surfactant at a level of from about 0.5% to about 15%, ~ler~l~bly from about 1% to about 10%, more ~rerelably from about 1% to about 6% and especially from about 1% to about 4% by weight. Alkyl ethoxy carboxylate surf~ct~t is particularly valuable in the compositions according to the present invention for the delivery of excellent skin mildness at~ibutes in combination with excellent rinsing performance and desirable lather characteristics.

. .

WO 98~'C 159 PCTIUS97/11679 All~l ethoxy carboxylates suitable for use herein have the general formula (I):

R30(CH2CH2o)kCH2Coo-M+

wherein R3 is a Clo to Cl 5 alkyl or alkenyl group, preferably a Cl 1 Cls , more l~ref~r~bly a C12-C14 alkyl or C12-C13 alkyl group, k is an average value of ethoxylation ranging from 2 to about 7, ~refe.ably from about 3 to about 6, more prerc.~bly from about 3.5 to about 5.5, especially from about 4 to about 5, most preferably from about 4 to about 4.5, and M is a water-solubilizing cation, plefe.ably an alkali metal, alkaline earth metal, ammonium, lower alkanol ammonium, and mono-, di-, and tri-ethanol arnmonium, more preferably sodium, potassium and ammonium, most, rererably sodium and ammonium and mixtures thereof with m~ne~ium and calcium ions.

Particularly preferred as auxiliary, water-soluble anionic surf~ct~ns.~ suitable for use herein are alkyl ethoxy carboxylate surf~ct~nt.s having a selected distribution of alkyl chain length and/or ethoxylate. Thus, the alkyl ethoxy carboxylate surfactants suitable for use in the compositions according to the present invention may comprise a distribution of allcyl ethoxy carboxylates having different average values of R3 and/or k.

The average value of k will generally fall in the range of from - about 3 to about 6 when the average R3 is Cl1, C12, C13 or C14.
I~efel,ed auxiliary, water-soluble anionic allcyl ethoxy carboxylate surf~Gt~nts suitable for use herein are the C12 to C14 (average EO 3-6) ethoxy carboxylates and the C12 to C13 (average EO 3-6) ethoxy carboxylates. Suitable materials include salts of NEODOX 23-4 (RTM) available from Shell Inc. (Houston, Texas, USA). Highly l,lefelled for use herein are alkyl ethoxy carboxylate surfactants wherein, when R3 is a C12-C14 or C12-C13 alkyl group and the average value of k is in the range of from about 3 to about 6, more l)re~rably from about 3.5 to about 5.5, especially from about 4 to about 5 and most l)refel~bly from about 4 to about 4.5.
-... . .. . . ..

WO 98/n01~ PCT/US97/11679 The compositions according to the present invention may additionally comprise auxiliary water-soluble nonionic surfactant, other than polyhydroxy fatty acid amides as described herein before, at levels from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, and especially from about 1% to about 8% by weight.
Surf~ct~nts of this class include C12-C14 fatty acid mono-and ~ lk~nolarnides such as cocoethanolamide7 cocomonoisopropylamide, cocodiethanolamide and ethoxylated derivatives thereof, sucrose polyester surfactants and Clo-CIg alkyl polyglycosides.

The compositions for use herein may also contain a auxiliary, water-soluble arnphoteric surfactant. Amphoteric surfactants suitable for use in the compositions of the invention include:

(a) imidazolinium surfactants of formula (IV) C2H4~R2 , CH 2 Z
1--I 1~' +
N

wherein Rl is C7-C22 alkyl or alkenyl, R2 is hydrogen or CH2Z, each Z is indepen(len~ly C02M or CH2C02M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (V) RlCONH(CH2) 2N CH2Z

wherein Rl, R2 and Z are as def~ned above;

- (b) aminoalkanoates of formula (VI) WO 981'~ 1!19 PCTIUS97/11679 Rl NH(CH2)nC02M
imino~i~lk~noates of formula (VII) Rl N[(CH2)mC02M]2 and iminopoly~lk~no~tes of formula (Vm) Rl [N(CH2)p]qN[cH2c02M]2 wherein n, m, p, and q are nurnbers from 1 to 4, and Rl 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 Empigen and are understood to comprise a complex mixture of species. Traditionally, the Miranols have been described as having the general formula IV, although the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclic structure V
while the 4th Edition indicates yet another structural isomer in which R2 is O-linked rather than N-linked. In practice, a complex mixture of cyclic alld non-cyclic species is likely to exist and both definitions are given here for sake of completeness. PrefeITed for use herein, however, are the non-cychc specles.

Examples of suitable amphoteric surfactants of type (a) include compounds of formula IV andJor V in which Rl is CgH17 (especially iso-caplyl), CgHlg and CIlH23 alkyl. Especially p,efe.,ed are the compounds in which Rl is CgH19, Z is C02M and R2 is H; the compounds in which Rl is C1 1H23, Z is C02M and R2 is CH2C02M;
and the compounds in which Rl is Cl lH23, Z is C02M and R2 is H.

In CTFA nomenclature, materials suitable for use in the present invention include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, and especially cocoarnphoacetate and cocoarnphodiacetate (otherwise referred to as cocoarnphocarboxyglycinate). Specific commercial products include those sold under the trade narnes of Ampholak 7TX (sodium carboxy methyl tallow polypropyl arnine), 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 (Rhône-Poulenc); Alkateric 2CrB (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 nurnber of cornrnercially-available amphoteric surfactants of this type are m~nllf~ctured and sold in the forrn of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the slllf~te-l Cg-C1g alcohol, Cg-C1g ethoxylated alcohol or Cg-C1g acyl glyceride types. Preferred from the viewpoint of mildness and product stability, however, are compositions which are essenti~lly free of (non-ethoxylated) sulfated alcohol surfactants. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomplexed forms of the surfactants, any anionic surf~ct~nt counterions being considered as part of the overall anionic surf~ct~nt component content.

Exarnples of preferred amphoteric surfactants of type (b) include N-a~cyl poly~imethylene poly-, carboxyrnethylarnines sold under the trade names Arnpholak X07 and Arnpholak 7CX by Berol Nobel and also salts, especially the triethanolammoniurn salts and salts of N-lauryl-beta-amino propionic acid and N-lauryl-imino-di~ro~ionic acid. Such materials are sold under the trade narne Deriphat by Henkel and Mirataine by Rhône-Poulenc.

The compositions herein can also contain from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, and CA 022~96~8 1998-12-30 WO 98/00499 PCTtUS97/11679 especially from about 1% to about 8% by weight of a zwitterionic surfactant.

Water-soluble betaine surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines of the formula RsR6R7N+ (CH2)nC02M and amido betaines of the formula (IX) lR6 R5CON ( CH2 ) m IN ( CH2 ) nC~2M

wherein Rs is Cl l-C22 alkyl or alkenyl, R6 and R7 are independently Cl-C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m are each numbers from 1 to 4. ~lefel-ed betaines include cocoamidopropyldimethylcarboxymethyl betaine, laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine (RTM).
Water-soluble sultaine surfactants suitable for inclusion in the compositions of the present invention include alkylamido sultaines of the formula;

R1 CON(CH2)mN+(CH2)nCH(OH)CH2S03~M+
I

wherein Rl is C7 to C22 alkyl or aL~cenyl, R2 and R3 are independently C1 to C3 aL~cyl, M is H, alkali meta}, allcaline earth metal, ammonium or alkanolammoniurn and m and n are numbers from 1 to 4. Plerelled for use herein is coco amido propylhydroxy sultaine.

WO 98/001~3 PCT/US97/11679 Water-soluble amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide RsR6R7NO and amido amine oxides of the formula I

R5CON(CH2)mN ~
I

wherein Rs is Cl 1 to C22 alkyl or allcenyl, R6 and R7 are indepen~lçntly Cl to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammoniurn or alkanolarnmonium and m is a number from I to 4. Preferred amine oxides include cocoarnidopropylamine oxide, lauryl dirnethyl arnine oxide and myristyl dimethyl amine oxide.

Polvrneric Cationic Conditionin~ Agent The compositions according to the present invention can optionally include a polymeric cationic conditioning agent. Polymeric cationic conditioning agents are valuable in the compositions according to the present invention for provision of desirable skin feel attributes. The polymeric skin conditioning agent is preferably present at a level ~om about 0.01% to about 5%, prefel~bly from about 0.01% to about 3% and especi~lly from about 0.01% to about 2% by weight.

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 5,000,000, pr~felably from about 5,000 to about 3,000,000 more yrefel~bly from 100,000 to about 1,000,000).

Representative classes of polymers include cationic polys~Gch~rides; cationic homopolymers and copolymers derived ~om acrylic and/or methacrylic acid; cation~c cellulose resins; cationic ~ ... ,. .. . . .. ~

CA 022',96',8 1998-12-30 W O ~8/00133 PCTrUS97/11679 copolyrners of dimethyldiallylammonium chloride and acrylamide and or acrylic acid; catior~ic 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 trirnethyl 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 hydroxy ethyl cellulose ethers available commercially under the trade names Ucare Polymer JR-30M, JR-400, Catanal (~TM) and Celquat. Other suitable cationic polymers are homopolymers of dirnethyldiallylamrnoniurn chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acrylarnide, copolymers of dimethyldiallylamrnoniurn chloride and acrylamide, available commercially under the trade names Merquat 550 and Merquat S, acrylic acid/dimethyldiallylammonium chloridelacrylarnide copolyrners available under the trade narne Merquat 3330, quaternized vinyl pyrrolidone acrylate or methacrylate copolyrners of amino alcohol available comrnercially under the trade name Gafquat, for exarnple Poly~uaterniurn l l, 23 and 28 (quaternized copolymers of vinyl pyrrolidone and dirnethyl aminoethylmethacrylate - Gafquat 755N and quaternized copolymers of vinyl pyrrolidone and dimethyl aminoethylmethacrylarnide - HS-100), vinyl pyrrolidonelvinyl irnidazolium methochloride copolyrners available under the trade names Luviquat FC370, Polyquaternium 2, and polyalkyleneimines such as polyethylen~mine and ethoxylated polyethylenimine .

The compositions of the invention may also contain from about 0.1% to about 20%, preferably from about 1% to about 15%, and more prefelably from about 2% to about 10% by weight of an oil derived nonionic surfactant or mixture of oil derived nonionic surfactants. Oil derived nonionic surfactants are valuable in compositions according to the invention for the provision of skin feel benefits both in use and after .. ...
. . ....

use. Suitable oil derived nonionic surfactants for use herein include water soluble vegetable and animal-derived emollients such as triglycerides with a polyethyleneglycol chain inserted; ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives. One ~lefe.-ed class of oil-derived nonionic surfactants for use herein have the general formula (XII) RCOC~2 CH ( OH ) CH2 ( OCH2 CH2 ) nOH

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 on average from about 5 to 20 carbon atoms, preferably from about 7 to 18 carbon atoms.

Suitable ethoxylated oils and fats of this class 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 oil derived nonionic surfactants of this class are available from Croda Inc. (New York, USA) under their Crovol line of materials such as Crovol EP40 (PEG 20 evening primrose glyceride), Crovol EP 70 (PEG 60 evening primrose glyceride) Crovol A-40 (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) and under their Solan range of materials such as Solan E, E50 and X polyethoxylated lanolins and Aqualose L-20 (PEG 24 lanolin alcohol) and Aqualose W15 (PEG 15 lanolin alcohol) available from Westbrook Lanolin. Further suitable surfactants of this class are comrnercially available from Sherex Chemical Co. (Dublin, Ohio, USA) under their Varonic LI line of surf~ct~nts and from Rewo under their Rewodenn 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), Rewoderm LI5-20 (PEG-200 palmitate), Rewoderm LIS-80 (PEG-200 palrnitate with PEG-7 glyceryl cocoate) and Rewoderm LIS-75 (PEG-200 p~lmit~te with PEG-7 glyceryl cocoate) and mixtures thereof. Other oil-derived emollients suitable for use are PEG derivatives of corn, avocado, and b~b~cs~1 oil, as well as Softigen 767 (PEG(6) caprylic/capric glycerides).

Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermurn Karkii Kotschy) and derivatives thereof. This vegetable fat, known as Shea Butter is widely used in Central Africa for a variety of means such as soap m~king and as a barrier cream, it is marketed by Sederrna (78610 Le Perray En Yvelines, France). Particularly suitable are ethoxylated derivatives of Shea butter available from Karl.~h~mn Chemical Co. (Columbos, Ohio, USA) under their Lipex range of chernicals, such as Lipex 102 E-75 and Lipex 102 E-3 (ethoxylated mono, di-glycerides of Shea butter) and from Croda Inc. (New York, USA) under their Crovol line of materials such as Crovol SB-70 (ethoxylated mono, di-glycerides of Shea butter). Similarly, ethoxylated derivatives of Mango, Cocoa and Illipe butter may be used in compositions according to the invention. Although these are classified as ethoxylated nonionic surfactants it is understood that a certain proportion may remain as non-ethoxylated vegetable oil or fat.

Other suitable oil-derived nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran 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, h~elnut oil, olive oil, grapeseed oil, and sunflower seed oil.

Oil derived nonionic surfactants highly preferred for use herein from the viewpoint of optimum mildness and skin feel characteristics are Lipex 102-3 (RTM) (PEG-3 ethoxylated derivatives of Shea Butter) and Softigen 767 (RTM) (PEG-6 caprylic/capric glycerides).

~ _ . .. . . . .. .

Hvdlollo~e The compositions according to the present invention may contain as an optional feature a hydrotrope. Suitable for use herein as hydrotropes are those well known in the art, including sodiurn xylene sulphonate, ammoniurn xylene sulphonate, sodium cumene sulphonate, short chain alkyl sull)h~te and mixtures thereof. Hydrolrope may be present in the compositions according to the invention at a level of from about 0.01% to about 5%, preferably from about 0.1% to about 4%, more ~refe.~bly from about 0.5% to about 3% by weight. Hydrotrope, as defined herein, means, a material which, when added to a non-dilute, water-soluble surfactant system can modify its viscosity and rheological profile.

To achieve both good product thickening and rheological attributes in non-dilute, water-soluble surfactant matrices in the presence of hydrotrope can be a challenging process. Thus it would be desirable to develop a thickening system for the delivery of both good product thickening and rheological attributes in non-dilute, water-soluble surfactant systems which comprise a hydrotrope.

Applicant has found that thickening system of the present invention is valuable for the delivery of good product thck~ning and rheology attributes in water-soluble, non-dilute surfactant systems comprising polyhydroxy fatty acid amide and auxiliary surfactants in the presence of hy~l~otlo~e. Applicant has also found that excellent product thickening is delivered when the ratio of total water-soluble surfactant level to total hydl~o~ope level is in the range of from about 5: 1 to about 1: 5, ~fel~bly from about 3: 1 to about 1: 3, more preferably from about 1.5 : 1 to about 1: 1.5 and filrthermore that a ratio of total polyhydroxy fatty acid amide surfactant level to total hydrotrope level in the range of from about 3: 1 to about 1: 3, preferably from about 1.5: 1 to about 1: 1.5, more t)lefe.ably about 1: 1 is especially valuable for the delivery of good thickening attributes.

WO ~8/00199 PCT/US97/11679 According to a further aspect of the invention there is provided a personal cleansing composition comprising:

(a) from about 0.01% to about 15% by weight of a thickening system which consists essentially of associative polymer and polar oil having a required HLB of at least 12.

(b) from about 01% to about 20% by weight of a nonionic polyhydroxy fatty acid arnide surfactant having the general formula (III):

O Rg wherein R8 is Cs-C3 1 hydrocarbyl, Rg is hydrogen, C 1 -C8 alkyl or hydroxyalkyl and Z2 is a polyhydroxyhydrocarbyl moiety;

(c) from about 1% to about 60% by weight of water-soluble auxiliary surfactant other than the polyhydroxy fatty acid amide surfactant of (b), selected from anionic surfactant, nonionic, zwitterionic and arnphoteric surfactants and mixtures thereof; and (d) water.
wherein the average carbon chain length of the polar oil is from about 10 to about 18 carbon atoms and is subs~nti~l~y similar to the average carbon chain length of the combined polyhydroxy fatty acid amide and other surfactants in the water-soluble, non-dilute surfactant matrix, and wherein the ratio of total water-soluble surf~ct~nt level to total hydrotrope level is in the range of from about 5: 1 to about 1 :5.

The compositions according to the present invention can also comprise lipophilic eml-l.cifiers as sl~in care actives. Suitable lipophilic .. ..

CA 022~96~8 1998-12-30 WO !~8/nO~ PCl'/US97/11679 skin care actives include anionic food grade emulsifiers which comprise a di-acid mixed with a monoglyceride such as succinylated monoglycerides, monostearyl citrate, glyceryl monostearate diacetyl tartrate and mixtures thereof.

The compositions of the invention may also include an insoluble perfiltne or cosmetic oil or wax or a mixture thereof at a level up to about 10%, ~lefe,~bly up to about 3% by weight wherein the oil or wax is insoluble in the sense of being insoluble in the product matrix at a temperature of 25~C. Addition of such oils or waxes can provide emolliency, mildness and rinsibility characteristics to personal cle~ncing compositions according to the invention. It is a feature of the invention, however, that compositions having excellent emolliency and mildness together with desirable physical attributes (clarity etc.) can be delivered which contain less than about 1%, preferably less than 0.5% by weight of an added oil phase (other than the polar oil). Physically, preferred compositions of this type take the form of an optically-clear solution or microemulsion. In compositions including an additional perfume or cosmetic oil or wax, ~le~l~bly the weight ratio of oil-derived nonionic surfactant to added oil is at least about l :2, more especially at least about 3:1 .

Suitable insoluble cosmetic 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 quate~
ammonium modified silicones, rigid cross-linked and reinforced silicones and ll~ ures thereof, Cl-C24 esters of Cg-C30 fatty acids such as isopropyl myristate, myristyl myristate and cetyl ricinoleate, Cg-C30 esters of benzoic acid, beeswax, saturated and un.c~lrated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolaturn squalane and squalene, polybutene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil-like }anolin derivatives, anirnal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, rice bran oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palrn nuts, pistachio nuts, sesarne seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soyabean oil, 3~
avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil, and Cl-C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylm~l~te, diisostearyldimerate and triisostearyltrimerate .

The viscosity of the final composition (Brookfield DV ~I, 1 rpm with Cone CP41 or CP52, 25~C, neat) is ~referably at least about 500 cps, more plefe.ably from about 1,000 to about 50,000 cps, especially from about 1,000 to about 30,000 cps, more especially from about l,000 to about 15,000 cps.

The cle~n~ing compositions can optionally include other hair or skin moisturizers which are soluble in the cleansing composition matrix.
The l)ref~"~d level of such moisturizers is from about 0.5% to about 20%
by weight. In l,lefelled embodiments, the moisturizer is selected from essçnti~l amino acid compounds found naturally occurring in the stratum corneum of the skin and water-soluble nonpolyol nonocclusives and mixtures thereof.

Some examples of more preferred nonocclusive moisturizers are polybutene, squalane, sodium pyrrolidone carboxylic acid, D-panthenol, lactic acid, L-proline, guanidine, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel, acetamide MEA and l~ct~tnide MEA and mixtures thereof.

Compositions according to the present invention may also include an opacifier or pearlescing agent. Such materials may be included at a level of from about 0.01% to about 5%, preferably from about 0.2% to abo~t 1.3% by weight. A suitable opacifier for inclusion in the present compositions is a polystyrene dispersion available under the trade names Lytron 621 & 631 (RTM) from Morton International.

Additional opacifiers/pearlescers suitable for inclusion in the compositions of the present invention include: titaniurn dioxide, TiO2;
EUPERLAN 810 (RTM); TEGO-PEARL (RTM); long chain (C16 -C22) acyl derivatives such as glycol or polyethylene glycol esters of fatty acid having from about 16 to about 22 carbon atoms and up to 7 .. . . ... .... . . ...

ethyleneoxy units; allcanolamides of fatty acids, having from about 16 to about 22 carbon atoms, preferably about 16 to 18 carbon atoms such as stearic monoethanolamide, stearic diethanolatI.ude, stearic monoiso~ropanolamide and stearic monoethanolamide and alkyl (C16 -C22) dimethyl amine oxides such as stearyl dimethyl amine oxide.

In ~lefelred compositions the opacifier/pearlescer is present in the form of crystals. In highly preferred compositions the opacifier/pearlescer is a particulate polystyrene dispersion having a particle size of from about 0.05 microns to about 0.45 microns, fel~bly from about 0.17 microns to about 0.3 microns, such dispersions being ~refe~,ed from the viewpoint of providing optirnum rheology and shear-thinning behaviour. Highly preferred is stvrene PVP
copolymer and Lyton 631 (RTM).

A number of additional optional materials can be added to the cle~n~ing compositions each at a level of from about 0.1% to about 2%
by weight. Such materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives such as Dh~M Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate and bisabalol;
sodium benzoate and 2-phenoxyethanol; other moisturizing agents such as hyaluronic acid, chitin, and starch-grafted sodium polyacrvlates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Po~ ilh~ VA, USA and described in US-A-4,076,663; solvents; suitable anti-bacterial agents such as Oxeco (phenoxy isopropanol), Trichlorocarbanilide (TCC) and Triclosan and~; 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; TiO2 and TiO2-coated mica;
perfilmes and perfume solubilizers; and zeolites such as Valfour BV400 and derivatives thereof and Ca2+/Mg2+ sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates, EDTA etc, water softening agents such as sodium citrate and insoluble particulates such as zinc stearate and furned silica.
Water is also present at a level preferably of from about 5% to about WO !)8/OOt5~ PCT/US97/11679 99.89%, preferably from about 40% to about 90%, more preferably at least about 80% by weight of the compositions herein.

The pH of the compositions is ~refe,~bly ~om about 4 to about 10, more preferably from about 5 to about 9, especially from about 6 to about 8.

EXPERIMENTAL RESULTS

All viscosities are measured in mPa.s (cps) at 26. î~Celcius.
All level mentioned below are percentages weight by weight.

Method:
Brookfield Cone & Plate Model DV II with Spindle CP41.
Measurements are performed at 1 rpm or at the al,~ro~.iate speed to get the correct torque value. All measurements are given + 50 cps SURFACTANT SYSTEM:
Anionic (Sodium C12-13 Pareth-5 Carboxylate), Sodium Decyl Sulphate (Empicol LC 35); Nonionic (C12-14 N-Methyl Glucose Amide);
Amphoteric (Cocoamphodiacetate).
Total level of surfactants: 12 % by weight.

TABLE I
Interaction between associative pol~ners and polar oil Polymer Level Polar Oil Level Viscosity (cps) Natrosol Plus 430 0.5 C12-13 Alcohol 0.0 350 Natrosol Plus 430 0.0 C12-13 Alcohol 0.6 350 Natrosol Plus 430 0.5 C12-13 Alcohol 0.6 3,500 Acrysol 44 0.5 C12-13 Alcohol 0.0 150 .

Acrysol 44 0.0 C12-13 Alcohol 0.6 350 Acrysol 44 0.5 C12-13 Alcohol 0.6 1,000 TABLE II
Effect of de,eree (X) of ethoxvlation of polar oil Polyrner Level PolarOil Level Viscosity (cps) Acrysol 44 1.0C12-14 0 EO (Laurex NC) 0.7 1,200 Acrysol 44 1.0C12-14 3 EO (Genapol L3) 0.7 300 Acrysol 44 1.0C12-14 7 EO (Empicol KBE 7) 0.7 50 The compositions according to the present invention are illustrated by the following non-limiting exarnples. In the examples, all concentrations are on a 100% active basis and the abbreviations have the following designation:

Anionic 1 Sodiurn C12-C13 Pareth-4-carboxylate (the sodium salt derived from the alkyl ether carboxylic acid NEODO~ 23-4 from Shell US Inc.) - Anionic 2 SodiurnLaureth-4 Carboxylate Anionic 3 Sodium decyl alkyl sulphate Anionic 4 Sodium Laureth-2 sulphate Amphoteric Disodiurn Cocoamphodiacetate Betaine Cocoamidopropylbetaine.

Nonionic Polyhydroxy fatty acid amide of ~orrnula IX in which R8 is C I 1 -C 17 alkyl, Rg is methyl, and Z2 is CH2(CHOH)4CH20H

HEUR 1 Acrysol 44.

HEUR 2 Berrnodol 2130 HMHEC 1 Natrosol Plus 430 HMHEC 2 Polysurf 67 HNP Ghlc~tn~te DOE

Polar Oil 1 Dobanol 23 Polar Oil 2 Laurex NC/E

Examples I to VIII

The following are personal cle~n.~in~ compositions in the form of shower gel or bath foarn products and which are representative of the present lnvention:

II III IV V VI VII VIII
- Anio~ic 1 4.0 6.0 4.0 3.0 -Anionic 2 - - - - 4.0 6.0 Anionic 3 2.0 3.0 1.5 2.5 3.0 Anionic 4 - - - - - 3.0 12.0 8.0 Arnphoteric 1.0 1.0 0.5 0.2 1.0 1.0 - -Betaine - - - - - - 3.0 3.0 CA 022',96',8 1998-12-30 W O 98/00499 PCTrUS97/11679 Nonionic 4.0 2 0 2.5 3.0 3.0 2.0 0.5 5.0 HEUR 1 0.7 - - - 1.0 0.5 -HEUR 2 - - - 0.6 - - 0.5 HMHEC 1 - 0 . 5 HMHEC 2 - - 0.8 - - 0.5 - 0.5 HNP - - - ~ 5 PolarOil 1 0.6 0.3 0.5 1.0 - - 0.3 0.8 Polar Oil 2 - - - - 0.4 0.6 Water to 100 Compositions I to VIII can be prepared by firstly dispersing the water-soluble or colloidally water-soluble associative polymer in water at up to about 70 ~C either in a Tri-blender (IM) or by extçn~ed stirring and hydration. The surfactants are added to this mixture with mild agitation (continued heating at up to about 70~C can be used). It is preferable to add the polar oil following the surfactants. Skin care agents (where present) can then be added along with the rem~-ning water-soluble, oil-insoluble ingredients and finally the rem~ining water, preservative, opacifier and perfurne are added.

The compositions have a viscosity (Brookfield DV II, 1 rpm with Cone CP41 or CP52, 25~C, neat) in the range of from 500 to 50,000 cps, refc.ably from 1,000 to 15,000 cps.

The products provide excellent product thickening and rheological attributes, in storage, in dispensing and in-use, in combination with good efficacy benefits including excellent rinsibility, mildness, skin conditioning, skin moisturising, good product stability, cleansing and lathering.

Claims (27)

What is claimed is:
1. A liquid personal cleansing composition comprising:

(a) from about 0.01% to about 15% by weight of a thickening system which consists essentially of associative polymer and polar oil having a required HLB of at least 12.

(b) from about 0.1% to about 20% by weight of a nonionic polyhydroxy fatty acid amide surfactant having the general formula (III):

wherein R8 is C5-C31 hydrocarbyl, R9 is hydrogen, C1-C8 alkyl or hydroxyalkyl and Z2 is a polyhydroxyhydrocarbyl moiety;

(c) from about 1% to about 60% by weight of water-soluble auxiliary surfactant other than the polyhydroxy fatty acid amide surfactant of (b), selected from anionic surfactant, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; and (d) water.

wherein the average carbon chain length of the polar oil is from about 10 to about 18 carbon atoms and is substantially similar to the average carbon chain length of the combined polyhydroxy fatty acid amide and other surfactants in the water-soluble, non-dilute surfactant matrix.

wherein the polar oil has an average carbon chain length of from about 10 to about 18 carbon atoms and wherein the the water-soluble surfactants have an average carbon chain length of from about 10 to about 18 carbon atoms.
2. A composition according to Claim 1 wherein the total level of the thickening system is from about 0.01% to about 10%, preferably from about 0.05% to about 8%, more preferably from about 0.1%% to about 4%, most preferably from about 0.1% to about 2%, especially from about 0.5% to 1.5% by weight.
3. A composition according to Claim 1 or 2 wherein the ratio of associative polymer to polar oil is in the range of from about 1:5 to about 5:1, more preferably from about 1:3 to about 3:1, most preferably from about 1:2 to about 1:2.
4. A composition according to any of Claims 1 to 3 wherein associative polymer is present at a level of from about 0.01% to about 12%, preferably from about 0.01% to about 10%, more preferably from about 0.05% to about 8%, most preferably from.
about 0.1% to about 4%, especially from about 0.1% to about 2%
and most especially from about 0.5% to about 1.5% by weight..
5. A composition according to any of Claims 1 to 4 wherein the associative polymer has an average molecular weight in the range of from about 2,000 to about 2,000,000, preferably from about 10,000 to about 1,000,000, more preferably from about 20,000 to about 800,000.
6. A composition according to any of Claims 1 to 5 wherein the associative polymer is a hydrophobically modified water-soluble nonionic polymer selected from hydrophobically modified hydroxyalkyl cellulose polymers, hydrophobically modified alkoxylated urethane polymers, hydrophobically modified nonionic polyols and mixtures thereof.
7. A composition according to any of Claims 1 to 6 wherein the polar oil is present at a level of from about 0.01% to about 3%, preferably from about 0.01% to about 2%, more preferably from about 0.1% to about 1%, most preferably from about 0.2% to about 0.8% by weight.
8. A composition according to any of Claims 1 to 7 wherein the polar oil has a required HLB value of from about 12 to about 15, more preferably from about 12 to about 14.
9. A composition according to any of Claims 1 to 8 wherein the polar oil is selected from natural and synthetic fatty alcohols and acids having an average carbon chain length in the range of from about 10 to 18 carbon atoms, preferably from about 12 to about 16, more preferably from about 12 to about 14 carbon atoms.
10. A composition according to any of Claims 1 to 9 wherein the average carbon chain length of the polar oil is substantially similar to the average carbon chain length of the non-dilute, water-soluble surfactant system.
11. A composition according to any of the Claims 1 to 10 wherein the polar oil is lauryl alcohol.
12. A composition according to any of Claims 1 to 11 wherein the composition has a viscosity (Brookfield DV-II, 1 rpm with Cone CP41 or CP52, 25°C, neat) in the range from 500 to 50,000 cps, preferably 1,000 to 15,000 cps.
13. A composition according to any of Claims 1 to 12 wherein the total level of water-soluble polyhydroxy fatty acid amide surfactant is from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, and especially from about 1% to about 8% by weight.
14. A composition according to any of Claims 1 to 13 wherein the polyhydroxy fatty acid amide has the formula R8(CO)N(CH3)CH2(CHOH)4CH2OH wherein R8 is a C6-C19 straight chain alkyl or alkenyl group.
15. A composition according to any of Claims 1 to 14 wherein the total level of auxiliary water-soluble surfactant, other than the polyhydroxy fatty acid amide of (b), is from about 2% to about 40%, preferably from about 3% to about 15%.
16. A composition according to any of Claims 1 to 15 wherein the auxiliary, water-soluble anionic surfactant is selected from alkyl sulphates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, alkyl ethoxy carboxylates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxy sulphosuccinates, 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.
17. A composition according to any of Claims 1 to 16 wherein the auxiliary, water-soluble anionic surfactant is selected from alkyl sulfate, ethoxylated alkyl sulphate, alkyl ethoxy carboxylate and mixtures thereof.
18. A composition according to any of Claims 1 to 17 which additionally comprises from about 0.1% to about 20% by weight of an auxiliary, water-soluble nonionic surfactant selected from C12-C14 fatty acid mono-and di-ethanolarnides, such as cocoethanolamide, cocomonoisopropylamide, cocodiethanolamide and ethoxylated derivatives thereof, sucrose polyester surfactants, C10-C18 alkyl polyglycosides and mixtures thereof.
19. A composition according to any of Claims 1 to 18 wherein the auxiliary, water-soluble amphoteric surfactant is selected from:

(a) imidazolinium derivatives of formula [IV]

wherein R1 is C7-C22 alkyl or alkenyl, R2 is hydrogen of CH2Z, each Z is independently CO2 or CH2 CO2M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium;
and/or ammonium derivatives of formula [V]
wherein R1, R2 and Z are as defined above:
(b) aminoalkanoates of formula [VI]
R1NH(CH2)n CO2M
iminodialkanoates of formula [VII]

R1N[(CH2)m CO2M]2 and iminopolyalkanoates of formula (VIII) wherein n, m, p, and q are numbers from 1 to 4, and R1 and M are independently selected from the groups specified above; and (c) mixtures thereof.
20. A composition according to Claim 19 wherein the auxiliary, water-soluble amphoteric surfactant is selected from imidazolinium derivatives of formula IV and/or ammonium derivatives of formula V.
21. A composition according to any of Claims 1 to 20 wherein the auxiliary, water-soluble zwitterionic surfactant is selected from alkyl betaine, amido betaine, alkyl sultaine and mixtures thereof.
22. A composition according to any of Claims 1 to 21 comprising an optional polymeric cationic conditioning agent having a mass average molecular weight in the range from about 2000 to about 5,000,000 preferably between about 5000 to about 3,000,000.
23. A composition according to Claim 22 wherein the polymeric cationic conditioning agent is selected from cationic polysaccharides; cationic homopolymers and copolymers derived form acrylic and/or methacrylic acid; cationic cellulose resins;
cationic copolymers of dimethyldiallylammnonium 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 22 and 23 wherein the polymeric cationic conditioning agent is present at a level of from about 0.05% to about 4%, preferably from about 0.1% to about 2%
and especially from about 0.5% to about 1.5% by weight.
25. A composition according to any of Claims 1 to 24 comprising from about 0.1% to about 20% by weight of nonionic surfactant selected from ethoxylated oils or fats having the formula (XII) wherein n is from about 5 to 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having an average from about 5 to 20 carbon atoms, preferably from about 9 to 20 atoms, more preferably from about 11 to 18 carbon atoms, most preferably from about 12 to 16 carbon atoms.
26. A composition according to any of Claims 1 to 25 additionally comprising up to about 20% by weight of perfume or cosmetic oil.
27. A composition according to any of Claims 1 to 26 additionally comprising hydrotrope at a level of from about 0.01% to about 5%
by weight.
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CN1092042C (en) 2002-10-09
WO1998000499A1 (en) 1998-01-08
BR9710140A (en) 1999-08-10
CN1228805A (en) 1999-09-15
GB9613901D0 (en) 1996-09-04
EP1019471A4 (en) 2002-08-14
JPH11514003A (en) 1999-11-30

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