CZ20002789A3 - A cosmetic composition suitable for topical application to the skin and a cosmetic treatment, as well as in the skin - Google Patents

Abstract

A cosmetic composition suitable for topical application to the skin comprises a) a liquid, a polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, the polyol moiety being selected from sugars and sugar alcohols containing 4 to 8 hydroxyl groups, each carboxylic acid moiety having from 8 to 22 carbon atoms, and said polyol carboxylic acid ester having a complete melting point of less than 30°C, and b) a branched aliphatic hydrocarbon chain having a weight average molecular weight of from 100 to 15,000. A cosmetic method of treating the skin is also described, according to which said cosmetic composition is applied to the skin.

Description

Cosmetic composition suitable for topical application to the skin and cosmetic method of skin treatment

Technical area

The present invention relates to a cosmetic composition suitable for topical application to the skin. It particularly relates to cosmetic compositions which improve moisturization, moisture retention, skin feel, skin softness, skin smoothness along with excellent * rubbing and absorption properties. These compositions also have excellent stability at normal and elevated temperatures.

State of the art

The epidermis consists of several layers of cells that coat and protect the keratin and collagen fibrous proteins that form the skeleton of this structure. The outermost of these layers, known as the stratum corneum (cornified layer), is known to consist of 25 nm protein bundles surrounded by 8 nm thick layers. Anionic surfactants and organic solvents typically penetrate the membrane of the stratum corneum and destroy its integrity by removing fats (delipidation, i.e., removing fats from the stratum corneum). This destruction of the topology of the skin surface leads to the feeling of roughness and can eventually allow the surfactant or solvent to interact with the keratin and cause irritation.

It is now recognized that maintaining an appropriate water gradient in the stratum corneum is important for its function. Most of this water, which is sometimes considered to be a softener of the stratum corneum, comes from the interior of the body. If the humidity is too low, as in cold weather, insufficient water remains in the outer layers of the stratum corneum to soften the tissue adequately, and the skin begins to peel and itch. The permeability of the skin may be somewhat reduced if there is insufficient water in the stratum corneum. On the other hand, too much water on the outer surface of the skin causes the stratum corneum to eventually absorb three to five times its own weight in bound water. The skin then swells and cracks, leading to an approximately two to threefold increase in the permeability of the skin to water and other polar molecules.

There is therefore a need for agents that will help the stratum corneum maintain its barrier and preserve its water retention function in an optimal manner despite the harmful interactions that can occur to the skin during washing, work and recreation.

Conventional cosmetic compositions in the form of creams and lotions, as described, for example, in Sagarin: Cosmetics Science and Technology, Second Edition, Volume 1, Wiley Interscience (1972) and Encyclopedia of Chemical Technology, Third Edition, Volume 7, are known to provide varying degrees of emollient, barrier maintenance and water retention (moisturizing). However, they also have negative consequences in terms of skin feel (i.e., they do not provide the desired softness and smoothness of the skin) and exhibit poor rub-in and low absorption into the skin.

There remains a need, therefore, for compositions that will assist the stratum corneum in maintaining a water gradient, but which will do so with improved skin feel, skin softness and smoothness, and improved absorption into the skin.

Polyester polyol fatty acid compounds are known to be used in skin care compositions. For example, European Patent Application A 458 600, European Patent Application A 466 410, European Patent Application A 519 727 and European Patent Application A 587 288 describe compositions containing polyester polyol fatty acid compounds for use in skin care compositions.

Additionally, branched chain hydrocarbons such as isohexadecane are known to be used for use in skin care products.

• · • · • ·

It has now been surprisingly found that by incorporating a suitable polyester polyol and fatty acid material into a cosmetic emulsion composition together with a suitable branched chain hydrocarbon such as isohexadecane, a composition is obtained which provides improved skin feel and improved skin softness and smoothness. The compositions of the invention also have excellent properties in terms of wetting, rub-in and absorption.

The essence of the invention

According to one aspect of the present invention, there is obtained a cosmetic composition suitable for topical application to the skin or hair, which comprises:

a) a liquid, polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing 4 to 8 hydroxyl groups, each carboxylic acid moiety having from 8 to 22 carbon atoms, and said liquid polyol carboxylic acid ester having a complete melting point of less than 30°C, and

(b) a branched chain hydrocarbon with a weight average molecular weight of 100 to 15,000.

The compositions of the invention provide improved skin feel, skin softness and skin smoothness and/or improved rub-in and absorption properties.

According to another aspect of the present invention, there is provided a cosmetic method for treating the skin, according to which the composition according to the present invention is applied to the skin.

In the following part of the description, the invention will be described in detail.

The compositions of the present invention comprise a liquid polyol carboxylic acid ester component together with a branched chain hydrocarbon and also the various optional components listed above. All amounts and ratios are by weight of the total composition unless otherwise stated. The chain length and degree of ethoxylation are also specified on an average weight basis.

The term skin conditioning agent, as used herein, refers to a material that provides beneficial properties that improve the condition of the skin. The term skin conditioning beneficial properties, as used herein, refers to any cosmetic beneficial properties related to the condition of the skin, including, but not limited to, moisturizing, moisture retention (i.e., the ability to retain or hold water or moisture in the skin), emollient, visual improvement of the skin surface, skin smoothing, skin softening, improved skin feel, and the like.

The term complete melting point, as used herein, means the melting point that has been measured according to the well-known method of differential scanning calorimetry (DSC). The complete melting point is the temperature at the intersection of the base line, i.e., the specific heat line, with the tangent line to the descending end of the endothermic maximum. A scanning rate of 5°C/minute is usually a suitable temperature for measuring the complete melting point according to the present invention. However, it should be understood that in specific cases, more frequent scanning may be performed appropriately by an analytical chemist skilled in the art. The DSC technique for measuring complete melting points is also described in U.S. Patent No. 5,306,514 to Lettona et al., issued April 26, 1994.

The term non-occlusive, as used herein, means that the component so described does not substantially block or obstruct the passage of air and moisture across the skin surface.

Liquid polyol carboxylic acid ester: The compositions of the invention contain, as an essential component, a liquid polyol carboxylic acid ester.

The compositions of the present invention preferably contain from 0.01 to 20, more preferably from 0.1 to 15 and particularly preferably from 0.5 to 10% by weight of the polyol ester.

tt • · ·· ♦···· ·«·· ···· ·· ·· ·· ··

The weight amount of polyol ester based on the amount of oil in the composition is preferably from 1 to 85, more preferably from 5 to 75% by weight. In order to obtain improved softness and improved skin smoothness, the weight ratio of liquid polyol ester and carboxylic acid to emollient material is preferably in the range of 5:1 to 1:5, more preferably in the range of 3:1 to 1:3.

The polyol ester preferred for use in the present invention means a non-occlusive liquid or liquefiable ester of a polyol and a carboxylic acid. These polyol esters are derived from polyol groups or moieties and one or more carboxylic acid groups or moieties. In other words, these esters contain a polyol-derived moiety and one or more carboxylic acid-derived moieties. These carboxylic acid esters may also be derived from carboxylic acids. These carboxylic acid esters may also be described as liquid polyol-fatty acid esters, since the terms carboxylic acid and fatty acid are often used interchangeably by those skilled in the art.

Preferred liquid polyol polyesters used in the present invention contain certain polyols, particularly sugars or sugar alcohols, esterified with at least four fatty acid groups. The polyol starting material must therefore have at least four esterifiable hydroxyl groups. Examples of preferred polyols are sugars, including monosaccharides and disaccharides, and sugar alcohols. Examples of monosaccharides containing four hydroxyl groups are xylose and arabinose, and a sugar alcohol derived from xylose, which has five hydroxyl groups, i.e., xylitol. The monosaccharide erythrose is not suitable for the practice of the present invention because it contains only three hydroxyl groups, but a sugar alcohol derived from erythrose, i.e., erythritol, contains four hydroxyl groups and can therefore be used. Suitable monosaccharides containing five hydroxyl groups are galactose, fructose, and sorbose. Also suitable are sugar alcohols containing six hydroxyl groups, derived from the hydrolysis products of sucrose, as well as glucoses and sorboses, e.g. sorbitol. Examples of disaccharide polyols that can be used include maltose, lactose and sucrose, all containing eight hydroxyl groups.

·· 99 • · 9 · • · * · • · 9999 9999

Preferred polyols for the production of polyesters for use in the present invention are selected from the group consisting of erythritol, xylitol, sorbitol, glucose and sucrose. Sucrose is particularly preferred.

A polyol starting material having four hydroxyl groups is esterified at at least four hydroxyl groups with a fatty acid having 8 to 22 carbon atoms. Examples of such fatty acids include caprylic, caproic, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, oleostearic, arachidic, arachidonic, behenic and erucic acids. The fatty acids may be derived from naturally occurring or synthetic fatty acids. They may be saturated or unsaturated, including positional and geometric isomers. However, in order to obtain liquid polyesters useful for use in the invention, at least 50% by weight of the fatty acid included in the polyester molecule should be unsaturated. Oleic acid, linoleic acid and mixtures thereof are particularly preferred.

The fatty acid polyol polyesters useful in the present invention should contain at least four fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with the fatty acid, but it is preferred that the polyester contain no more than two unesterified hydroxyl groups. More preferably, substantially all of the hydroxyl groups of the polyol are esterified with the fatty acid, i.e., the polyol portion is substantially completely esterified. The fatty acids esterified by the polyol molecule may be the same or mixed, but, as noted above, a substantial amount of unsaturated acid must be present in the ester to achieve fluidity.

To illustrate the above, a sucrose fatty triester would not be suitable for use in the present invention because it does not contain the required number of four fatty acid ester groups. A sucrose fatty acid tetraester would be suitable but is not preferred because it has more than two unesterified hydroxyl groups. Sa·· 99 99 99 99 99

9 9 9 9 9 9 9 9 ^··

9 9 9 9 · 9 · 9 9

9 9 9 9 9 9 9 9 9 9 9 9 9 · 9 9 9 9 9 9 9

9999 9999 ·· 99 99 99 a sucrose hexaester of a fatty acid would be preferred because it has no more than two unesterified hydroxyl groups. Highly preferred compounds in which all hydroxyl groups are esterified with fatty acids include liquid octasubstituted sucrose fatty acid esters.

The following are non-limiting examples of specific polyol fatty acid polyesters containing at least four fatty acid ester groups suitable for use in the present invention; glucose tetraoleate, tetraesters of glucose with (unsaturated) soybean fatty acids, mannose tetraesters of mixed soybean fatty acids, galactose tetraesters of oleic acid, arabinose tetraesters of linoleic acid, xylose tetralinolate, galactose pantooleate, sorbitol tetraoleate, sorbitol hexaesters of unsaturated soybean fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, and mixtures thereof. As noted above, highly preferred polyol fatty acid esters are those in which the fatty acids contain from 14 to 18 carbon atoms.

Preferred liquid polyol polyesters for use in the invention have a complete melting point below 30°C, preferably below 27.5°C, more preferably below 25°C. The complete melting points reported herein are measured by differential scanning calorimetry (DSC).

Polyol-fatty acid polyesters suitable for use in the present invention can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification of the polyol with methyl, ethyl or glycerol esters of fatty acids using various catalysts, acylation of the polyol with a fatty acid chloride, acylation of the polyol with a fatty acid anhydride, and acylation of the polyol with the fatty acid itself. See U.S. Patent No. 2,831,854, U.S. Patent No. 4,005,196, Jandacek, issued January 25, 1977.

The second essential component of the present invention is a branched chain hydrocarbon with a weight average molecular weight of from 100 to 15,000, with

44 • 4 4 4 • 4 ·4 4

4 4 4 • 4 4 4 4

4444 4444 44 44

44

4 4 4

4 4 · ·4 4

4 4 4

44 preferably from 100 to 1000. Preferred for use in the compositions of the invention are branched chain hydrocarbons selected from isododecane, isohexadecane, isoeicosane, isooctahexacontane, isohexapentacontaheptane, isopentacontaoctane and mixtures thereof, especially isohexadecane and isooctacontane and mixtures thereof. Branched chain aliphatic hydrocarbons are preferred according to the invention in terms of achieving improved skin feel and improved absorption properties.

Suitable for use in the present invention are branched chain aliphatic hydrocarbons sold under the trade name Permethyl (RTM) and commercially available from Presperse Inc., P.O. Box 735, South Plainfield, N.J. 07080, USA. Particularly suitable for improved skin feel, spreadability and application is a mixture of isohexadecane and isooctahexacontane.

The branched chain hydrocarbon is present in the compositions according to the invention in an amount of from 0.1 to 15, preferably from 0.1 to 10, especially from 0.1 to 5% by weight of the composition.

The present compositions may be used for any suitable purpose. The present compositions are particularly suitable for topical application to the skin or hair. In particular, the skin care compositions may be in the form of creams, lotions, gels and the like. Preferably, the cosmetic compositions of the invention are in the form of an oil-in-water emulsion of one or more oil phases in an aqueous continuous phase, each oil phase comprising a single oil component or a mixture of oil components in miscible or homogeneous form, but said different oil phases comprising different materials or combinations of materials. The total amount of oil phase components in the compositions of the invention is preferably from 0.1 to 60, preferably from 1 to 30 and more preferably from 1 to 10% by weight.

The present compositions preferably comprise either as a whole or as a part of the oil phase or oil phases referred to above as the first silicone-containing phase comprising a crosslinked polyorganosiloxane polymer and a silicone oil, with ... 99

9

9999 9999

99

9 9 9 «9 ·

9 999 · ·

9·

99

9 9 «

9 9 9 · ♦ 9

9 9 9 wherein the composition contains 0.1 to 20, preferably from 0.5 to 10, more preferably from 0.5 to 5% by weight of the composition of a combination of crosslinked silicone and silicone oil.

The first silicone-containing phase comprises from 10 to 40, more preferably from 20 to 30% by weight of the first silicone-containing phase of a crosslinked polyorganosiloxane polymer and from 60 to 90, preferably up to 70 to 80% by weight of the first silicone-containing phase of silicone oil.

The crosslinked polyorganosiloxane polymer comprises a polyorganosiloxane polymer crosslinked with a crosslinking agent. Crosslinking agents for use in the present invention include any crosslinking agent useful for the production of crosslinked silicones. Suitable crosslinking agents for use in the present invention include those of the following general formula (R) ₃ Si-O

Ri

AND

Si-0

AND

R ₂ •Si(R) ₃ , in which Ri represents methyl, ethyl, propyl or phenyl, R ₂ represents a hydrogen atom or the group -(CH ₂ ) _n CH=CH ₂ , where n represents a number in the range from 1 to 50, z represents a number in the range from 1 to 1000, preferably from 1 to 100, and R represents an alkyl group with 1 to 50 carbon atoms.

The cross-linking agent preferably means an agent of the general formula

9 ·· • * · • · • · 9 • ·

9999 ···· »9 99 • 9 9 · • 9 · 9

9,999

9 9

99 • 9 «9 ♦ «9 9

9 9 9

9 9 9 9

9 9 * *9

Ri I (CH ₃ ) ₃ Si - O Si - o I r ₂

Si(CH ₃ ) ₃ , in which R 1 , R ₂ and az are as defined above.

In particularly preferred embodiments, the crosslinking agent means an agent of the general formula (CH ₃ ) ₃ Si - O

Ri

AND

Si-0

AND

R ₂

Si(CH ₃ ) ₃ , in which z represents a number in the range from 1 to 1000, preferably from 1 to 100.

The crosslinked polysiloxane polymer preferably contains from 10 to 50, more preferably from 20 to 30% by weight of the crosslinking agent based on the weight of the crosslinked polysiloxane polymer.

Any polyorganosiloxane polymers suitable for use in skin care compositions may be used in accordance with the invention. Suitable polyorganosiloxane polymers for use in accordance with the invention include polymers of the following general structural formula

9« »9 **

I · » 9 9

9 9 • · 9 9 • · 9 ► 9*9 »999 99 • 9 »9 • 9 · 9 »9 9

9 9 9 9 9 9

9*9*9 99 9

9 9 9 9 9

99 99 (R) ₃ Si - O

<*· — - r ₃ Ri | Yes - O I | -Si-0 I 1 year ₄ 1 year ₂ P

Si(R) ₃ , in which Ri represents methyl, ethyl, propyl or phenyl, R ₂ represents a hydrogen atom or the group -(CH ₂ )„CH=CH ₂ , where n represents a number in the range from 1 to 50, R ₃ and R ₄ are independently selected from methyl, ethyl, propyl and phenyl, R represents an end cap, such as an alkyl group, optionally substituted by hydroxyl, with 1 to 50 carbon atoms, preferably an alkyl group with 1 to 5 carbon atoms, more preferably an alkyl group with 1 or 2 carbon atoms, p represents a number in the range from 1 to 2000, preferably from 1 to 500, q represents a number in the range from 1 to 1000, preferably from 1 to 500.

In preferred embodiments, the polyorganosiloxane is selected from polymers of the following general formula (CH ₃ ) ₃ Si - O

r ₃ Ri 1 Si-0 | Si-0 1 I r ₄ r ₂ P

Si(CH ₃ ) ₃ , in which R 1 , R ₂ , R ₃ , R ₄ , p and q are as defined above.

As stated in this invention, p and q represent the number of Si-O bonds in the polymer chain and R 1 , R ₂ , R ₃ and R ₄ may vary from one monomer unit to another. For example, suitable polyorganosiloxane polymers for use in the invention include methylvinyldimethicone, methylvinyldiphenyldimethicone and methylvinylphenylmethyldiphenyldimethicone.

4»· »· • · * » • Φ

Φ Φ Φ • ·

Φ

ΦΦΦΦ

Φ Φ Φ · • · Φ · • φ ΦΦΦ · • Φ Φ • Φ ΦΦ

ΦΦ ΦΦ Φ * Φ Φ

Φ Φ Φ Φ

ΦΦΦ

ΦΦΦΦ

In order to achieve crosslinking between the polyorganosiloxane polymer and the crosslinking agent, the (Si-H) group must be crosslinked with a -Si-(CH ₂ ) n CH=CH ₂ group such that for any specific crosslinking, the R ₂ group must be different in the polyorganosiloxane polymer and the crosslinking agent. For example, for any specific crosslinking, if R ₂ is a (CH ₂ ) _n CH=CH ₂ group in the polyorganosiloxane polymer, R ₂ must be a hydrogen atom in the crosslinking agent and vice versa. However, mixtures of R ₂ for both the polyorganosiloxane polymer and the crosslinking agent may exist. In preferred embodiments, the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer of the general formula

means a number in the range from 0 to 1000, preferably from 0 to 500, and n means a number in the range from 1 to 1000, preferably from 1 to 100.

In particularly preferred embodiments, the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer of the general formula

wherein I, m and n are as defined above. In preferred embodiments, m is a number from 1 to 1000, preferably from 200 to 800.

• · · · · · · · · · · · · • · ···· ···· • · ·· ·· ····· ·

The first phase, which contains silicone, also contains silicone oil. Any branched silicones, cyclic silicones and straight chain silicones suitable for use in skin care compositions may be used in the present invention. Silicone oils may be volatile or non-volatile. Suitable silicone oils for use in the present invention include silicone oils having a weight average molecular weight of 100,000 or less, preferably 50,000 or less. Preferably, the silicone oil is selected from silicone oils having a weight average molecular weight in the range of 100 to 50,000, preferably 200 to 40,000. In preferred embodiments, the silicone oil is selected from dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and phenylmethicone and mixtures thereof, most preferably phenylmethicone.

Suitable materials for use in the first phase containing silicone are available under the trade name KSG, supplied by Shinetsu Chemical Co., Ltd., for example KSG-15, KSG-16, KSG-17, KSG-18. These materials comprise a combination of a crosslinked polyorganosiloxane polymer and a silicone oil. Particularly preferred for use in accordance with the invention, especially in combination with an organic amphiphilic emulsifying material, is KSG-18. The INCI names for KSG-15, KSG-16, KSG-17 and KSG-18 are cyclomethicone-dimethicone/vinyl dimethicone crosspolymer, dimethicone-dimethicone/vinyl dimethicone crosspolymer, cyclomethicone-dimethicone/vinyl dimethicone crosspolymer and phenyl-trimethicone-dimethicone/phenyl vinyl dimethicone crosspolymer.

The compositions of the invention preferably also comprise a second phase comprising uncrosslinked silicone. In preferred embodiments, this second phase comprising silicone is present in an amount of from 0.1 to 20, in particular from 0.1 to 10% by weight of the composition.

Suitable silicone fluids for use in the second silicone-containing phase of the invention include water-insoluble silicones, including nonvolatile polyalkyl and polyarylsiloxane resins and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amine and quaternary ammonium modified silicones, and mixtures thereof.

In preferred embodiments, the second silicone-containing phase comprises a silicone resin or a mixture of silicones including a silicone resin. The term silicone resin, as used herein, refers to high molecular weight silicone-based fluids having a weight average molecular weight greater than 200,000 and preferably from 200,000 to 400,000. Silicone oils generally have a molecular weight of less than 200,000. Silicone resins typically have a viscosity at 25°C greater than 1,000,000 mm ² s ^-1 . Silicone resins include dimethicones described by Petrarca et al. including U.S. Patent 4,152,416.1 . May 1979, Spitzer et al., and Noll Walter Chemistry and Technology of Silicones, New York, Academic Press 1968. Silicone resins are also described in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54, and SE 76.

Silicone resins for use in the present invention include any silicone resin suitable for use in a skin care composition. Suitable silicone resins for use in the present invention are silicone resins having a molecular weight of from 200,000 to 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof.

Dimethiconol-based silicones suitable for use according to the invention have the chemical structure

HO(CH ₃ ) ₂ SiO[(CH ₃ ) ₂ SiO] _n (CH ₃ ) ₂ SiOH, where n is a number from 2000 to 40,000, preferably from 3000 to 30,000.

Examples of fluorosilicones useful in the invention have a molecular weight of from 200,000 to 300,000, preferably from 240,000 to 260,000, and most preferably about 250,000.

• · • · · · ♦ · ···· • · · · · · ····· ·· · • · ··

Specific examples of silicone resins include polydimethylsiloxane, (polydimethylsiloxane)(methylvinylsiloxane) copolymer, (polydimethylsiloxane)(diphenyl)(methylvinylsiloxane) copolymer, and mixtures thereof.

The silicone resin used in the invention may be included in the composition as part of a silicone mixture. If the silicone resin is included as part of a silicone mixture, the silicone resin preferably represents 5 to 40, especially 10 to 20% by weight of the silicone mixture. The silicone or silicone mixture preferably represents from 0.1 to 20, more preferably from 0.1 to 15, especially from 0.1 to 10% by weight of the composition.

Suitable silicone resin-based silicone compositions for use in the second silicone-containing phase of the compositions of the invention include compositions consisting essentially of.

i) a silicone with a molecular weight of from 200,000 to 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof, and ii) a silicone-based carrier having a viscosity of from 0.65 to 100 mm ² .s'\ wherein the ratio of ad to ad ii) is from 10:90 to 20:80 and the silicone resin-based component has a final viscosity of from 500 to 10,000 mm ² .s' ¹ .

Silicone-based carriers suitable for use in the present invention include certain silicone fluids. The silicone fluid may be either a polyalkylsiloxane, a polyarylsiloxane, a polyalkylarylsiloxane, or a polyether/siloxane copolymer. Mixtures of these fluids may also be used, and in some embodiments, mixtures of these fluids are preferred.

Polyalkylsiloxane fluids that can be used include, for example, polydimethylsiloxanes with viscosities ranging from 0.65 to 600,000, preferably from 0.65 to 10,000 mm ² s ¹ at 25° C. These siloxanes are available, for example, from General Electric Company as the Viscasil (RTM) series and from Dow Corning as the Dow Corning 200 series. Substantially non-volatile polyalkylarylsiloxane fluids that can be used include,

4 · ·

4 4

4

44

4 4 ·

4 4 4

44444

4444 4444 44 44 44 44 include, for example, polymethylphenylsiloxanes with viscosities from 0.65 to 30,000 mm ² .s' ¹ at 25 °C. These siloxanes are available, for example, from General Electric Company as SF 1075 methylphenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid. Also suitable for use in the invention are certain volatile cyclic polydimethylsiloxanes with a ring structure containing from 3 to 7 (CH ₃ ) 2 SiO moieties.

Viscosity can be measured with a glass capillary viscometer as described in Dow Corning Corporate Test Method CTM0004, July 29, 1970. The viscosity of the silicone composition constituting the second liquid phase is preferably in the range of from 500 to 100,000, preferably from 1,000 to 10,000 mm ² .s ^-1 .

A particularly preferred silicone resin component for use in the compositions of the invention is a dimethiconol resin having a molecular weight of from 200,000 to 4,000,000 together with a silicone carrier having a viscosity of from 0.65 to 100 mm ² .s ¹ . Examples of such silicone components are Dow Corning Q2-1403 (85% dimethiconol liquid, 5 mm ² .s' ¹ , 15% by weight dimethiconol) and Dow Corning Q2-1401 available from Dow Corning.

Another group of silicones suitable for use in the second silicone-containing phase of the invention are polydiorganosiloxane-polyoxyalkylene copolymers comprising at least one polydiorganosiloxane segment and at least one polyoxyalkylene segment, said polydiorganosiloxane segment consisting essentially of R _b SiO ₍ 4-by2 siloxane units, wherein b has a value from 0 to 3, inclusive, with an average value of about 2 R radicals per silicone for all siloxane units in the copolymer. R is a group selected from methyl, ethyl, vinyl, phenyl and a divalent group linking said polyoxyalkylene segment to the polydiorganosiloxane segment, at least 95% of all R groups being methyl. Said polyoxyalkylene segment has an average molecular weight of at least 1000 and consists of from 0 to 50 mol% polyoxypropylene units and from 50 to 100 mol% polyoxyethylene units, at least one terminal portion of said polyoxyalkylene segment being linked to said polydiorganosiloxane segment not linked to said polydiorganosiloxane segment which is terminated by a terminating group. The weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in said copolymer is from about 2 to about 8. These polymers are described in U.S. Patent No. 4,268,499.

Preferred for use according to the invention are polydiorganosiloxane/polyoxyalkylene copolymers of the general formula

CH ₃ ch ₃ ch ₃ ch ₃ lili CH ₃ -Si - O - (Si - O),-(Si - O)y — Si - CH ₃ , lili ch ₃ ch ₃ c ₃ h ₆ ch ₃

AND

O-(C ₂ H ₄ O) _and (C ₃ H ₆ O) b R in which x and a are selected such that the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments is from 2 to 8, the molar ratio a:(a+b) is from 0.5 to 1 and R represents a chain terminating group, in particular a group selected from hydrogen, hydroxyl, alkyl, such as methyl, ethyl, propyl, butyl, benzyl, aryl, such as phenyl, alkoxy groups, such as methoxy, ethoxy, propoxy, butoxy, benzyloxy groups, aryloxy groups, such as phenoxy, akenyloxy groups, such as vinyloxy and allyloxy, acyloxy groups, such as acetoxy, acryloxy and propionyloxy, and amine groups, such as dimethylamino.

The number and average molecular weights of the segments in the copolymer are such that the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in the copolymer is preferably from 2.5 to 4.0.

Suitable copolymers are commercially available under the trade names Belsil (RTM) from Wacker-Chemie GmbH, Geschaeftsbereich S, Postfach D-8000, Munich 22, and Abil (RTM) from Th. Goldschmidt Ltd., Tego House, Victoria Road, Ruislip,

Μ • · · • · 9 • · · · ·· « «9 · · 9 «

9 9 « • 9 9 ·

9*

Middlesex, ΗΑ4 OYL, for example Belsil (RTM) 6031 and Abil (RTM) B88183. Particularly preferred copolymers for use in the invention include Dow Corning DC3225C, which has the CTFA designation dimethicone/dimethicone copolymer.

In preferred embodiments, the third oil phase is present in an amount of from 0.1 to 15, more preferably from 1 to 10% by weight of the composition. The third oil phase may be either a separate phase or may be a single phase together with either or both of the first and second silicone phases. The third oil phase preferably means a separate phase.

This oil phase preferably comprises a non-silicone organic oil, such as a natural or synthetic oil selected from mineral, vegetable and animal oils, fats and waxes, fatty acid esters, fatty alcohols, fatty acids and mixtures thereof, components which are useful for achieving emollient cosmetic properties. The first oil phase component is preferably a component which is essentially silicone-free, i.e. contains no more than 10, preferably no more than 5% by weight of silicone-based materials. It will be understood that the oil phase may contain, for example, up to 25, preferably up to only 10% by weight of the oil phase of soluble emulsifying component. These components are not considered to be components of the oil phase for the purpose of determining the amount of oil phase and the desired HLB. In preferred embodiments, the overall desired HLB of the oil phase is from 8 to 12, especially from 9 to 11. The desired HLB is determined as the sum of the individual desired HLB values for each component of the oil phase multiplied by the weight percent of that component in the oil phase (see ICI literature on the HLB system: ICI Reference Paper 51/0010/303/15m., first printed 1976, revised 1984 and May 1992).

Suitable components of the first oil phase for use according to the invention include, for example, optionally hydroxyl-substituted unsaturated fatty acids having 8 to 50 carbon atoms and their esters, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol and cetyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalene, fatty esters of sorbitan (see U.S. Patent 3,988,255, Seiden,

99 99 • 9 9 9 9 9

9 9 9

9 9 9 9

9 9 9

9999 9999 99

99 ··

9 9 · 9 · • · 9·99

99999 99 9

9 9 9 · •9 99 99 issued on October 26, 1976), oils containing more than 20% by weight. cholesterol esters, lanolin and lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, apricot kernel oil, walnut oil, palm kernel oil, pistachio oil, sesame seed oil and rapeseed oil, and other oils such as corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapefruit seed oil, shea butter, sunflower oil and esters of dimer and trimer acids with 1 to 24 carbon atoms such as diisopropyl dimerate, diisostearyl malate, diisostearyl dimerate and triisostearyl trimerate. Of the above, mineral oils, petrolatums, unsaturated fatty acids and their esters, and mixtures thereof are highly preferred.

Preferred embodiments of the invention contain 0.1 to 10% by weight of unsaturated fatty acid or ester. Preferred unsaturated fatty acids and esters for use in the invention are optionally hydroxyl-substituted unsaturated fatty acids and esters having 8 to 50 carbon atoms, especially ricinoleic acid esters. The unsaturated fatty acid or ester component is valuable in the invention in combination with a liquid crystal-forming emulsifier to improve the feel on the skin and to improve the spreadability of the composition. Cetyl ricinoleate is highly preferred in this regard.

Amphiphilic Surfactant: Another preferred component of the compositions of the invention is an organic amphiphilic surfactant that is capable of forming smectite lyotropic crystals either in the product or when the product is applied to the skin at room temperature or at elevated temperatures. The amphiphilic surfactant is preferably capable of forming liquid crystals at a temperature in the range of 20 to 40°C. Preferably, the amphiphilic surfactant is capable of forming smectite lyotropic liquid crystals. Once the product has been applied to the skin, the liquid crystals may not be identifiable on the skin surface or in the stratum corneum. The amphiphilic surfactant is preferably present in an amount of from 0.1 to 20, preferably from 0.1 to 10% by weight.

*· ·· • 9 9 9

9

9 9 • · ···· ····

• · · · · · · 99 • 9 9 9

9 9 9

9 9 9

9 9 9

99

Amphiphilic liquid crystal forming surfactants suitable for use in the present invention contain both hydrophilic and lipophilic moieties and exhibit a significant tendency to adsorb to surfaces or at the interface, i.e., are surface active. Amphiphilic surfactant materials for use in the present invention include nonionic (uncharged), anionic (negatively charged), cationic (positively charged), and amphoteric (both charged) agents based on whether or not they are ionized in an aqueous environment.

In the literature, liquid crystals are also referred to as anisotropic liquids, fourth states of matter, surface-active association structures or mesophases. These terms are often used interchangeably. The term lyotropic means a liquid crystalline system containing a polar solvent such as water. The liquid crystals used according to the invention are preferably lamellar, hexagonal, rod-like or vesicle-like structures or mixtures thereof.

The liquid crystal phase used in the compositions of the invention can be identified in various ways. The liquid crystal phase flows under shear and is characterized by a viscosity that is significantly different from that of its isotropic phase in solution. Solid gels do not flow under shear like liquid crystals. Also, when viewed with a polarized light microscope, liquid crystals exhibit identifiable birefringence, such as planar laminar birefringence, while isotropic solutions and solid gels appear as dark fields under polarized light. Other suitable methods for identifying liquid crystals include X-ray diffraction, NMR spectroscopy, and transmission electron microscopy.

In general terms, organic amphiphilic surfactants useful for use in the invention may be described as a liquid, semi-solid or waxy, water-dispersible material of the general formula X-Y, where X represents a hydrophilic, particularly non-ionic, moiety and Y represents a lipophilic moiety.

9 9 9 9 9 * · · 9 9 9 · I « 9 » · 99 9 9 9 9 · · 99 ·

9 99 99999

9999 9999 99 99 99 99

Organic amphiphilic surfactants suitable for use in the invention include those having a weighted average HLB (hydrophilic lipophilic balance) in the range of 2 to 12, preferably 4 to 8.

Preferred organic amphiphilic surfactants used in the present invention have a long saturated or unsaturated, branched or linear lipophilic chain with 12 to 30 carbon atoms, such as oleic, lanolin, tetradecyl, hexadecyl, isostearyl, lauric, coco, stearic and alkylphenyl chains. When the hydrophilic group of the amphiphilic liquid crystal phase forming material is a nonionic group, polyoxyethylene, polyglycerol, polyol ester, oxyalkylated or not, and for example polyoxyalkylated sorbitol or sugar ester can be used. When the hydrophilic group of the amphiphilic liquid crystal phase forming surfactant is an ionic group, a phosphatidylcholine residue as found in lecithin can be used as the hydrophilic group.

Hydrophilic moieties suitable for use according to the invention are selected from:

1) linear or branched polyglycerol ethers of the general formula R-(Gly) _n -OH, in which n represents an integer between 1 and 6, R is selected from aliphatic, linear or branched, saturated or unsaturated chains with 12 to 30 carbon atoms, hydrocarbon groups of lanolin alcohols and 2-hydroxyalkyl residues with a long chain of alpha-diols, and Gly represents a glycerol group,

2) polyethoxylated fatty alcohols, for example alcohols of the general formula R ¹ (C ₂ H 4 o) x OH, in which R ¹ represents a linear or branched alkyl or alkenyl with 12 to 30 carbon atoms and x represents an average number from 0 to 20, preferably from 0.1 to 6, more preferably from 1 to 4,

3) mono-, di- or tri-esters of a polyol, optionally polyalkoxylated, in which the polyols are preferably selected from sugars, alkylene glycols with 2 to 6 carbon atoms, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols and polypropylene glycols, and in which the esters of the polyalkoxylated • ·

99 99 99

9 9 9 9 9 9 9

9 9 9 9 9

9 99 99999

9 9 9 9

9999 9999 99 99 • ·

I» · • · polyol contain from 2 to 20, preferably from 2 to 4 moles of alkylene oxide (especially ethylene oxide) per mole of polyol ester, and

4) natural and synthetic phosphoglycerides, glycolipids and sphingolipids, for example cerebrosides, ceramides and lecithin.

Examples of amphiphilic surfactants suitable for use in the invention include amphoteric, anionic, cationic and nonionic surfactants containing alkyl and acyl groups of 8 to 30 carbon atoms, as set forth below.

Amphoteric agents:

N-alkyl amino acids (e.g. sodium N-alkylaminoacetate), N-lauroylglutamic acid cholesterol ester (e.g. Eldew CL-301

Ajinomoto).

Anionic reagents:

acylglutamates (e.g. disodium N-lauroylglutamate), sarcosinates (e.g. sodium lauroylsarcosinate, Grace, Seppic), taurates (e.g. sodium lauryltaurate, sodium methylcocolaurate), carboxylic acids and salts (e.g. potassium oleate, potassium laurate, potassium 10-undecenoate, 11-(p-styryl)-undecanoate), salts of ethoxylated carboxylic acids (e.g. sodium carboxymethylalkylethoxylate), carboxylic acid ethers, phosphoric acid esters and salts (e.g. lecithin, DEA-(oleth-10)-phosphate), acyl isethionates (e.g. sodium 2-lauroyloxyethanesulfonate), alkanesulfonates (e.g. sodium branched x-alkanesulfonate (x/1), sulfosuccinates, e.g.

Sodium dibutyl sulfosuccinate, sodium di-2-pentyl sulfosuccinate, sodium di-2-ethylbutyl sulfosuccinate, sodium dihexyl sulfosuccinate, φφ φ* «φ φφ φ* φφ φ φ φ φ φ φ φφφφ φφφφ • · φ φ φ · · φ φφφ φ φ φ φ φ · φφφφ φ φφ φφ φφ sodium di-2-ethylhexyl sulfosuccinate (ΑΟΤ), sodium di-2-ethyldodecyl sulfosuccinate, sodium di-2-ethyloctadecyl sulfosuccinate, disodium dioctyl sulfosuccinate and disodium laureth sulfosuccinate (MacKanate El, Mclntyre Group Ltd.), sulfuric acid esters (e.g., sodium 2-ethylhept-6-enyl sulfate, sodium 11-heneicosyl sulfate, sodium 9-heptadecyl sulfate) and alkyl sulfates (e.g. MEA alkyl sulfates such as MEA-lauryl sulfate).

Cationic reagents:

alkylimidazolines (e.g. alkylhydroxyethylimidazoline, stearylhydroxyethylimidazoline (supplied by Akzo, Finetex and Hoechst), ethoxylated amines (e.g. PEG-alkylamine, PEG-alkylaminopropylamine, poloxamine, PEG-cocopolyamine, PEG-15-tallowamine), alkylamines (e.g. dimethylalkylamine, dihydroxyethylalkylamine dioleate), quaternary agents:

alkylbenzyldimethylammonium salts (e.g. stearalkonium chloride), alkylbetaines (e.g. dodecyldimethylammonioacetate, oleylbetaine), heterocyclic ammonium salts (e.g. alkylethylmorpholinium methosulphate), tetraalkylammonium salts (e.g. dimethyldistearyl-quaternary ammonium chloride (Witco))>

bis-isostearamidopropyl-hydroxypropyl-diammonium chloride (Schercoquat 21 AP from Scher Chemicals) and 1,8-bis(decyldimethylammonio)-3,6-dioxaoctane ditosylate.

Nonionic surfactants: ethoxylated glycerides, monoglycerides (e.g. monoolein, monolinolein, monolaurin, 1-dodecanoylglycerol monolaurin, 1,13-docosenoylglycerol monoerucin, fatty acid diglyceride (e.g. Cosmol 41 diglycerol monoisostearate, fractionated, Nisshin Oil Mills Ltd.), • 9 99 99 99 99 99

99 9 9 99 9 9 «9 9

9 9999 9999

9 99 999999 99 9

9 99 99999

99«9 9999 99 99 99 99 polyglyceryl esters (e.g. triglycerol monooleate (Grindsted TS-T122), diglycerol monooleate (Grindsted TST-T101), polyalcohol esters and ethers (e.g. sucrose cocoate, ketostearyl glucoside (Montanol, Seppic), β-octyl-glucofuranoside esters, alkyl glucoside such as alkyl glucoside with 10 to 16 carbon atoms (Henkel)), phosphoric acid diesters (e.g. sodium dioleyl phosphate), alkylamidopropyl betaine (e.g. coconut amidopropyl betaine), amides (e.g. N-(dodecanoylaminoethyl)-2-pyrrolidone), amine oxide, e.g.

1,1-dihydroperfluorooctyldimethylamine oxide, dodecyldimethylamine oxide,

2-hydroxydodecyldimethylamine oxide,

2-Hydroxydodecyl-bis(2-hydroxyethyl)amine oxide

2-hydroxy-4-oxahexadecyldimethylamine oxide, ethoxylated amides (e.g. PEG-acylamide), ammonium phosphates (e.g. didecanoylecithin), amine (e.g. octylamine), ammonium amides, e.g.

N-trimethylammonium decanamidate and N-trimethylammonium dodecanamida, ammoniocarboxylates, e.g.

dodecyldimethylammonioacetate a

6-didocelldimethylammoniohexanoate, esters and amides of phosphorous and phosphoric acid, e.g. methyl-N-methyl-dodecylphosphonamidate, dimethyl-dodecylphosphonate, dodecylmethylmethylphosphonate and Ν,Ν-dimethyl-dodecylphosphonic acid diamide, ethoxylated alcohols, polyoxyethylene (with 8 carbon atoms), e.g.

pentaoxyethylene glycol p-octylphenyl ether,

About 99 99 *999 9 9 • 9 · ·

9 9 9 9

9 · 9

9999 9999 99

99 »9

9 9 9 9 «

9 9 9 9 9

999 99 99 ·

9 9 9 9

9999 hexaoxyethylene glycol-p-octylphenyl ether and nonaoxyethylene glycol-p-octylphenyl ether, polyoxyethylene (with 10 carbon atoms), e.g.

pentaoxyethylene glycol p-decylphenyl ether, decylglyceryl ether of 4-oxatetradecane-1,2-diol and p-decylphenyl ether of nonaoxyethylene glycol, polyoxyethylene (with 11 carbon atoms), e.g. undecyl ether of tetraoxyethylene glycol, polyoxyethylene (with 12 carbon atoms), e.g.

3,6,9,13-tetroxapentacosane-1,11-diol,

3,6,10-trioxadocosan-1,8-diol,

3,6,9,12,16-pentaoxaoctacosane-1,14-diol,

3.6.9.12.15- pentaoxanonacosan-1,17-diol,

3,7-dioxanonodecane-1,5-diol,

3.6.12.15.19- hexaoxahentriacontane-1,16-diol, dodecyl ether of pentaoxyethylene glycol and p-dodecylphenyl ether of nonaoxyethylene glycol, polyoxyethylene (with 14 carbon atoms), e.g.

3.6.9.12.16- pentaoxaoctacosan-1,14-diol a

3.6.9.12.15.19- hexaoxatriacontane-1,17-diol, sulfondiimines, e.g.

decyl-methyl-sulfondiimine, sulfoxides, e.g.

3-decyloxy-2-hydroxypropyl-methyl sulfoxide a

4-decyloxy-3-hydroxybutyl-methylsulfoxide and sulfoximines, e.g.

N-methyl-dodecylmethylsulfoximine.

Preferred organic amphiphilic surfactants for use in the invention are nonionic amphiphilic surfactants with a hydrophilic portion as mentioned in 3) above and a lipophilic portion selected from long saturated or unsaturated 99 ·· · 99 99 • 9 9 9 9999 9 9 9 9 • * 9999 9999 • 9999 999 99 99 · • · · 9 9999«

9999 9999_____ 99 99 ·9 9« saturated branched chain or linear lipophilic chains with 12 to 30 carbon atoms, such as oleic, lanolin, tetradecyl, hexadecyl, isostearyl, lauric, coco, stearic or alkylphenyl chain.

Highly preferred organic amphiphilic surfactants for use according to the invention are selected from esters and ethers of polyalcohols. Particularly preferred amphiphilic surfactants for use according to the invention are sugar esters and polyalkoxylated sugar esters.

Sugar esters for use in the present invention can be classified as hydrocarbon and alkylpolyoxyalkylene esters of cyclic polyhydroxysaccharides in which one or more hydroxyl groups on the saccharide moiety are substituted by an acyl or polyoxyalkylene group. Hydrocarbon sugar esters can be prepared in a well-known manner by heating an acid or acid halide with a sugar, i.e., by a simple esterification reaction.

Sugars used in the preparation of sugar esters include monosaccharides, disaccharides and oligosaccharides well known in the art, for example, the dextrorotatory and levorotatory forms of glucose, fructose, mannose, galactose, arabinose and xylose. Typical disaccharides include maltose, cellobiose, lactose and trehalose. Typical trisaccharides include raffinose and gentianose. Preferred disaccharides for use in the invention are, in particular, sucrose.

Sucrose can be esterified at one or more of its eight hydroxyl groups to provide sucrose esters useful in the present invention. When sucrose is combined with an esterifying agent in a molar ratio of 1:1, sucrose monoesters are produced. When the ratio of esterifying agent to sucrose is 2:1, a diester is produced. Particularly preferred are mono-, di- and tri-acyl esters of sugars and mixtures thereof, in which the acyl substituents contain 8 to 24, preferably 8 to 20 carbon atoms, and 0, 1 or 2 unsaturated moieties. Particularly preferred of the mono-acyl and diacyl esters of sugars are esters of disaccharide sugars, especially sucrose, in which the acyl groups are «9 * 9 · • 9 • 9 9

9 ?··· ··»» < 9 9 · • 9 9 9 • 9 9 99

9 9

99

99

9 9 9

9 9 9

9 9 » • 9 9 9

99 groups with 8 to 20 carbon atoms. Preferred sugar esters according to the invention include sucrose cocoate, sucrose monooctanoate, sucrose monodecanoate, sucrose monolaurate, sucrose monomyristate, sucrose monopalmitate, sucrose monostearate, sucrose monooleate, sucrose monolinoleate, sucrose dioleate, sucrose dipalmitate, sucrose distearate, sucrose dilaurate and sucrose dilinoleate and mixtures thereof. Sucrose cocoate has been found to be particularly effective in the compositions according to the invention. In mixtures of monoacyl-diacyl- and triacyl esters of sugars, the monoacyl esters and diacyl esters are preferably present in an amount of at least 40, more preferably from 50 to 95% by weight of the total weight of the sugar ester mixture.

Other sugar esters suitable for use in the compositions of the present invention are alkyl-polyoxyalkylene sugar esters in which one hydroxyl group is substituted with an alkyl group of 8 to 18 carbon atoms and in which one or more hydroxyl groups on the sugar molecule are substituted with an ester or ether substituent containing a group of the general formula [(CH ₂ ) x O] y , where x is a number from 2 to about 4, preferably 2, and where y is a number from 1 to 50, preferably 8 to 30 polyoxyalkylene substituents. Particularly preferred according to the invention are sugar esters in which the polyoxyalkylene substituent is a polyoxyethylene substituent containing from 8 to 30 polyoxyethylene groups. Such materials in which sorbitan represents the sugar moiety are commercially available under the trade name Tweeny. These mixed esters can be prepared by first acylating the sugar in a 1:1 molar ratio with a hydrocarbon acid halide. Subsequent reaction with the corresponding polyoxyalkylene acid halide or alkylene oxide provides the desired material. A simple polyoxyalkylene ester of disaccharides, especially sucrose, in which the polyoxyalkylene groups contain up to 20 alkylene oxide moieties, is another useful group of sugar esters according to the invention. A preferred sugar ester of this group is sorbitol trioleate ethoxylated with 20 moles of ethylene oxide. Also suitable for use according to the invention are mixtures of sugar esters with other polyol esters, for example glycerol esters, for example Palm Oil Sucroglyceride (Rhone-Poulenc).

00 0 0 0 • · · · · ··· 0 · 0 · · • · · · 0 0 0 · 0

0000 0000 00 00 00 00_______

The term lecithin, as used herein, refers to a material that is a phosphatide. Naturally occurring or synthetic phosphatides may be used. Phosphatidylcholine or lecithin is a glycerin esterified with the choline ester of phosphoric acid and two fatty acids, usually long chain saturated or unsaturated fatty acids of 16 to 20 carbon atoms and up to 4 double bonds. Other phosphatides capable of forming lamellar or hexagonal liquid crystals may be used instead of or in combination with lecithin. These phosphatides are esters of glycerol with two fatty acids, as in lecithin, but the choline is replaced by ethanolamine (cephalin), serine (-aminopropanoic acid, phosphatidylserine) or inositol (phosphatidylinositol). Although the invention is exemplified herein with lecithin, it is to be understood that these other phosphatides may be used herein.

Various lecithins can be used. The American Lecithin Company supplies Nattermann Phospholipid, Phospholipan 80, and Phosal 75. Other lecithins that can be used alone or in combination with these phospholipids are the Actifla series, the Centrocap series, Central Ca series, the Central, Centrolen, Centrolex, Centromix, Centrophase, and Centrophil series from Central Soya, Alcolec and Alcolec 439-C from American Lecithin, Canaspersa from Canada Packers, Lexin K and Natipide from American Lecithin, and L-Clearate, Clearate LV, and Clearate WD from W.A.Cleary Co. Lecithins are supplied dissolved in ethanol, fatty acids, triglycerides, and other solvents. They are usually mixtures of lecithins. They are supplied as solutions of 15 to 50% by weight. Both natural and synthetic lecithins can be used. Natural lecithins are derived from oilseeds such as sunflower seeds, soybeans, safflower seeds, and cottonseeds. Lecithins are separated from the oil during the refining process.

It has been found that an organic amphiphilic surfactant is particularly valuable in the present invention for improving the stability of the skin care compositions of the present invention. It is preferred to include it in the composition in an amount of from 0.1 to 20, preferably from 0.1 to 10, and more preferably from 0.1 to 8% by weight of the composition.

• · ···· · · · · • · ·· ····· · · · · • · · ····· ····· ·· · · · · · · ·

Highly preferred here is a mixture of fatty acid esters based on a mixture of sorbitan or sorbitol fatty acid esters and sucrose fatty acid esters, the fatty acid in each case being an acid having 8 to 24, more preferably 10 to 20 carbon atoms. A preferred fatty acid ester emulsifier from a wetting point of view is a mixture of a sorbitan or sorbitol fatty acid ester having 16 to 20 carbon atoms with a sucrose fatty acid ester having 10 to 16 carbon atoms, in particular sorbitan stearate and sucrose cocoate. This mixture is commercially available from ICI under the trade name Arlatone 2121.

A highly preferred component of the compositions according to the invention is urea, which is preferably present in an amount of from 0.1 to 20, more preferably from 0.5 to 10 and especially from 1 to 5% by weight of the composition.

In preferred embodiments, the oil phase and the organic amphiphilic surfactant, if present, are premixed in water at a temperature above the Kraft point of the organic amphiphilic surfactant (but preferably below 60°C). This forms a liquid crystal/oil-in-water dispersion before the urea is added. Urea has been found to be particularly effective herein in combination with an amphiphilic emulsifying surfactant and a polyol-fatty acid polyester to provide exceptional skin moisturization and softening in the context of an oil-in-water emulsion skin care composition. In addition, it has surprisingly been found that urea is more stable to hydrolytic degradation, allowing the pH of the composition to be increased.

Various optional ingredients may be added to the skin compositions of the invention, such as additional emollients, non-occlusive humectants, humectants, gelling agents, neutralizing agents, perfumes, coloring agents, and surfactants.

The compositions of the present invention may contain softening materials which are selected from compounds of the general formula

• · · · ♦ · ···· • · ·· ····· · · · · • · ·· ·

R ² O i ^{1 11}

R ¹ -C-(CH ₂ ) _x - c R ³ OR ⁴ wherein R ¹ is selected from hydrogen or CH ₃ , R ² , R ³ and R ⁴ are independently selected from straight or branched chain alkyl of 1 to 20 carbon atoms and x is a number from 1 to 20. Preferred plasticizers for use according to the invention are described in WO 98/22085 . Particularly preferred plasticizers for use according to the invention are isononyl isononanoate, methyl isostearate, isopropyl isostearate or mixtures thereof. The plasticizing material is preferably present in the compositions in an amount of from 0.1 to 10, preferably from 0.1 to 5, particularly preferably from 1 to 3 wt. % of the composition.

The compositions of the invention may contain a humectant. Such suitable humectants for use in the invention include sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose derivatives, hexanetriol, glycerin, hyaluronic acid, arginine, Ajidew (NaPCA), water-soluble polyglyceryl methacrylate lubricants and panthenols. A preferred humectant in the invention is glycerin (sometimes known as glycerol or glycerine). Glycerin is particularly preferred in the compositions of the invention for its ability to increase moisturization. Butylene glycol is also preferred for use in the invention. A combination of glycerin and urea is particularly preferred for its ability to increase moisturization.

In the present compositions, the humectant is preferably present in an amount of from 0.1 to 20, more preferably from 1 to 15, and most preferably from 5 to 15% by weight of the composition.

Suitable polyglyceryl methacrylate lubricants for use in the compositions of the present invention are available under the trade name Lubrajel (RTM) from Guardian Chemical Corporation, 230 Marcus Blvd., Hauppage, N.Y. 11787, USA. Lubrajels can generally be described as hydrates or clathrates which are prepared by reacting sodium glycerate with a polymer of methacrylic acid. The hydrate or clathrate is then stabilized with a small amount of propylene glycol, followed by controlled hydration of the resulting product. Lubrajels are prepared with varying degrees of glycerate:polymer ratio and with varying viscosities. Suitable Lubrajels include Lubrajel TW, Lubrajel CG and Lubrajel MS, Lubrajel WA, Lubrajel DV and the so-called Lubrajel Oil.

At least a portion (up to 5% by weight of the composition) of the humectant may be included in the composition in the form of a mixture with the appropriate crosslinked hydrophobic acrylate or methacrylate copolymer itself, preferably present in an amount of from 0.1 to 10% by weight, which may be added to either the aqueous phase or the disperse phase. This copolymer is particularly valuable for reducing shine and controlling oil, thereby helping to achieve effective wetting, and is described in detail in WO 96/03964, which is incorporated herein by reference.

The compositions according to the invention may also contain a hydrophilic gelling agent in an amount preferably from 0.01 to 10, more preferably from 0.02 to 2, particularly preferably from 0.02 to 0.5% by weight. The gelling agent preferably has a viscosity (1% (w/w) aqueous solution, 20°C, Brookfield RVT) of at least 4 Pa.s, more preferably at least 10 and particularly preferably at least 50 Pa.s.

Suitable hydrophilic gelling agents can be generally described as water-soluble or colloidally water-soluble polymers. These include cellulose ethers (e.g., hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose), polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropylguar gum, and xanthan gum.

Preferred hydrophilic gelling agents of the invention are acrylic acid/ethyl acrylate copolymers and carboxyvinyl polymers sold by B. F. Goodrich Company under the trade name Carbopol resin. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked acrylic acid polymer crosslinked with 0.75 to 2.00 wt. % of a crosslinking agent, • ·

such as polyallyl sucrose or polyallylpentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 954, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble acrylic acid polymer crosslinked with 1% (w/w) polyallyl ether of sucrose with an average of 5.8 allyl groups per sucrose molecule. The most preferred polymer is Carbopol 954. Also suitable for use in the invention are hydrophobically modified crosslinked acrylic acid polymers with amphipathic properties available under the trade names Carbopol 1382, Carbopol 1342 and Pemulen TR-1 (CTFA designation: crosslinked acrylates/10-30 alkyl acrylate polymer). A combination of a polyalkenylpolyether crosslinked acrylic acid polymer and a hydrophobically modified crosslinked acrylic acid polymer is also preferred and suitable for use in the invention. The gelling agents of the invention are particularly valuable for achieving excellent stability at both normal and elevated temperatures.

Other useful gelling agents of the invention are nonionic polyacrylamide polymers, which may be substituted, branched or unbranched. These polymers are nonionic water-dispersible polymers which may be prepared from a variety of monomers including acrylamide and methacrylamide which are unsubstituted or substituted with one or two alkyl groups (preferably with 1 to 5 carbon atoms). Preferred are acrylate amides and methacrylate amides in which the amide nitrogen is unsubstituted or substituted with one or two alkyl groups having 1 to 5 carbon atoms (preferably methyl, ethyl or propyl), for example acrylamide, methacrylamide, N-methacrylamide, N-methylmethacrylamide, N,N-dimethylmethacrylamide and N,N-dimethylacrylamide. These monomers are generally described in U.S. Patent No. 4,963,348 to Bolich ml. et al., issued October 16, 1990, which is incorporated herein by reference. These copolymers may optionally be prepared using conventional neutral crosslinking agents such as dialkenyl compounds. The use of these crosslinking agents for cationic polymers is described in U.S. Patent No. 4,628,078, Glover et al., issued December 9, 1986, and in U.S. Patent No. 4,599,379, Flesher et al., issued July 8, 1986, both of which are incorporated herein by reference. These nonionic copolymers have a molecular weight greater than • · · · · · · ·

I · · 4 • 4

000,000, preferably greater than 1,500,000 and in the range up to 30,000,000. Preferably, as a result of being synthesized by reverse phase emulsion polymerization, these nonionic polyacrylamides are predispersed in a water-immiscible solvent, such as mineral oil and the like, containing a high HLB surfactant (HLB of 7 to 10), which helps to facilitate the dispersibility of the polyacrylamide in water. Most preferred for use in the present invention is the nonionic polymer under the CTFA designation: polyacrylamide and isoparaffin and laureth-7, available under the trade name Sepigel 305 from Seppic Corporation. Other polyacrylamide polymers useful in the present invention include multiblock copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids. Commercially available examples of these multiblock copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H from Lipo Chemicals, Inc. (Patterson, NJ.).

Neutralizing agents suitable for neutralizing the acidic group of the hydrophilic gelling agents of the invention include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine.

The compositions of the invention are in the form of an emulsion and are preferably formulated so that the viscosity of the product is at least 4 Pa.s, preferably from 4 to 300, more preferably from 8 to 200, particularly preferably from 10 to 100 and even more preferably from 10 to 50 Pa.s (25 °C, neat, Brookfield RVT Spindle No. 5).

The compositions of the invention may also contain from 0.1 to 10, preferably from 1 to 5% by weight of a panthenol humectant. The panthenol humectant may be selected from D-panthenol ([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]-3,3-dimethylbutamide), DL-panthenol, calcium pantothenate, royal jelly, pathetin, pathothein, panthenyl ethyl ether, pangamic acid, pyridoxine, pantoyl lactose and vitamin B complex. Highly preferred from the point of view of skin care and tack reduction is D-panthenol.

99 9· ·· • 99 9 9 99 9 • 9 9 9 « 9

9 99 9999

9 9 9 9

99999999 99 ·9

The compositions of the present invention may further comprise from 0.001 to 0.5, preferably from 0.002 to 0.05, more preferably from 0.005 to 0.02% by weight of carboxymethylchitin. Chitin is a polysaccharide present in the integument of lobsters and crabs and is a mucopolysaccharide with beta(1-4) linkages of N-acetyl-D-glucosamine. Carboxymethylchitin is prepared by reacting purified chitin material with alkali and subsequently with monochloroacetic acid. It is commercially sold as a dilute (approximately 0.1 to 0.5% (w/w)) aqueous solution under the name Chitin Liquid, available from A & E Connock Ltd., Fordingbridge, Hampshire, England.

Other optional materials include keratolytic/desquamating agents such as salicylic acid, proteins and polypeptides and their derivatives, water-soluble or solubilizable protective agents, preferably in amounts of from 0.1 to 5% by weight, such as Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, EDTA, Euxyl(RTM) K400, Bronopol (2-bromo-2-nitropropane-1,3-diol) and phenoxypropanol, antibacterial agents such as Irgasan (RTM) and phenoxyethanol (preferably in amounts of from 0.1 to 5% by weight), soluble or colloidally soluble humectants such as hyaluronic acid and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500, available from Celanese Superabsorbent Materials, Portsmith, VA, USA, and described in U.S. Patent No. 4,076,663, vitamins such as vitamin A, vitamin C, vitamin E and vitamin K, alpha- and beta-hydroxy acids, aloe vera, sphingosines and phytosphingosines, cholesterol, skin whitening agents, N-acetylcysteine, coloring agents, perfumes and perfume solubilizing agents, other surfactants/emulsifiers such as fatty alcohol ethoxylates, ethoxylated polyol fatty acid esters, where the polyol may be selected from glycerin, propylene glycol, ethylene glycol, sorbitol, sorbitan, polypropylene glycol, glucose and sucrose. Examples include glyceryl monohydroxystearate and stearyl alcohol ethoxylated with an average of 10 to 200 moles of ethylene oxide per mole of alcohol and PEG-6 caprylic/capric glycerides.

Tanning agents are also useful herein. Various tanning agents are described in U.S. Patent No. 5,087,445, Haffey et al., issued February 11, 1992, U.S. • · • · ·

I» • · U.S. Patent No. 5,073,372, Turner et al., issued December 17, 1991, U.S. Patent No. 5,073,371, Turner et al., issued December 17, 1991, and Segarin et al., Chapter Vlil, page 189 et seq. in Cosmetics Science and Technology. Preferred of these tanning agents useful in the compositions of the present invention are those selected from 2-ethylhexyl-p-methoxycinnamate, 2-ethylhexyl-N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomentyl salicylate, octyl salicylate, 4,4'-methoxy-tert-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 3-benzylidenecamphor, 3-(4-methylbenzylidene)camphor, titanium dioxide, zinc oxide, silicon dioxide, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789 and mixtures thereof.

Still other useful tanning agents are those described in U.S. Patent No. 4,937,370, Sabatelli, issued June 26, 1990, and in U.S. Patent No. 4,999,186, Sabatelli et al., issued March 12, 1991. The tanning agents described herein have two different chromophore moieties in a single molecule that exhibit different ultraviolet absorption spectra. One of the chromophore moieties absorbs predominantly in the UFB radiation region and the other absorbs strongly in the UFA radiation region. These tanning agents provide higher efficacy, broader UF absorption, lower skin penetration, and longer-lasting efficacy than conventional tanning agents. Particularly preferred examples of these tanning agents include those selected from 2,4-dihydroxybenzophenone ester with 4-N,N-(2-ethylhexyl)methylaminobenzoic acid, 4-hydroxydibenzoylmethane ester with 4-N,N-(2-ethylhexyl)methylaminobenzoic acid, 2-hydroxy-(4-(2-hydroxyethoxy)benzophenone ester with 4-N,N-(2-ethylhexyl)methylaminobenzoic acid, 4-(2-hydroxyethoxy)dibenzoylmethane ester with 4-N,N-(2-ethylhexyl)methylaminobenzoic acid, and mixtures thereof.

Typically, sunscreen agents are present in compositions useful in the present invention in amounts ranging from 0.5 to 20% by weight. The exact amounts will vary depending on the sunscreen agent selected and the desired sun protection factor (SPF). SPF is

• ·· · ···· usually used to measure the photoreaction of tanning agents to erythema. See Federal Register August 25, 1978, 43 (166), 38206-38269.

The compositions of the present invention may further comprise from 0.1 to 5% by weight of starch aluminum octenyl succinate. This compound is the aluminum salt of the reaction product of octenyl succinic anhydride with starch and is commercially available under the trade name Dry Flo from National Starch & Chemical Ltd. Dry Flo is useful in the present invention for skin feel properties and application.

Other optional materials of the invention include pigments which, if insoluble in water, contribute to the total amount of the oil phase components and are included therein. Suitable pigments for use in the compositions of the present invention may be organic and/or inorganic. The term pigment also includes such materials which have a low color or luster, such as matting agents for finishing as well as light scattering agents. Examples of suitable pigments are iron oxides, acylglutamate iron oxides, ultramarine blue, D&C dyes, carmine and mixtures thereof. Depending on the type of composition, a mixture of pigments is normally used. Preferred pigments for use in the invention in terms of wetting, skin feel, skin appearance and emulsion compatibility are processed pigments. These pigments may be reacted with such compounds as amino acids, silicones, lecithin and ester oils.

The compositions of the invention may also contain colorants. In this regard, β-carotene is particularly preferred, which may be used in amounts of from 0.00001 to 0.005% by weight. In higher amounts, β-carotene is also valuable as an antioxidant to reduce free radical damage to the skin.

The compositions of the present invention may also contain a safe and effective amount of a vitamin B ₃ compound. The compositions of the present invention preferably contain from 0.01 to 50, more preferably from 0.1 to 10, even more preferably from 0.5 to • « • ·

10, more preferably from 1 to 5 and most preferably from 2 to 5% by weight of the vitamin B ₃ compound.

A vitamin B ₃ compound, as used herein, means a compound of the general formula wherein R is a group -CONH ₂ (i.e. niacinamide), COOH (i.e. nicotinic acid) or -CH ₂ OH (i.e. nicotinyl alcohol), derivatives thereof, and salts of any of the foregoing. Examples of derivatives of the foregoing vitamin B ₃ compounds include nicotinic acid esters including non-vasodilating nicotinic acid esters, nicotinylaminoacetic acid, nicotinyl alcohol esters with carboxylic acids, nicotinic acid N-oxide, and niacinamide N-oxide.

Suitable nicotinic acid esters include nicotinic acid esters with alcohols having 1 to 22, preferably 1 to 16, more preferably 1 to 6 carbon atoms. These alcohols are preferably straight or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic) and substituted or unsubstituted. The esters are preferably non-vasodilating esters. The term non-vasodilating, as used herein, means that the ester does not typically produce a visible flushing response upon application of the subject composition to the skin (most of the general population do not desire a visible flushing response, although such compounds may cause vasodilation invisible to the naked eye). Non-vasodilating nicotinic acid esters include tocopherol nicotinate and inositol hexanicotinate, with tocopherol nicotinate being preferred. A more complete description of vitamin B ₃ compounds is provided in WO 98/22085.

Examples of the above vitamin B ₃ compounds are well known in the art and are commercially available from numerous sources, e.g., from Sigma Chemical Com• ·

pany (St. Louis, Mo.), ICN Biomedicals, Inc. (Irvin, Ka.), and Aldrich Chemical Company (Milwaukee, Wi.). One or more vitamin B ₃ compounds may be used in the present invention. Preferred vitamin B ₃ compounds are niacinamide and tocopherol nicotinate. Niacinamide is more preferred.

Retinoids: In a preferred embodiment, the compositions of the present invention also comprise a retinoid. The vitamin B ₃ compound and the retinoid provide unexpected beneficial properties in regulating the condition of the skin, particularly in the therapeutic regulation of signs of skin aging, particularly the formation of wrinkles, lines and pores. Without wishing to be bound by theory, it is believed that the vitamin B ₃ compound increases the conversion of some retinoids to trans-retinoic acid, which is believed to be the biologically active form of retinoids and provides synergistic regulation of the condition of the skin (specifically, increased conversion to retinol, retinol esters and retinal). Furthermore, the vitamin B ₃ compound unexpectedly reduces redness, inflammation, dermatitis and the like, which may otherwise be associated with topical application of retinoids (often referred to and hereinafter also referred to as retinoic dermatitis). Furthermore, the combination of the vitamin B ₃ compound and retinoids tends to increase the amount and activity of thioredoxin, which tends to increase the level of collagen expression via the AP-1 protein. The present invention therefore allows for reduced effective amounts and thus reduced potential for retinoid dermatitis while maintaining significant positive skin condition modification. Furthermore, higher levels of retinoids may be useful to obtain greater efficacy in skin condition modification without the undesirable occurrence of retinoid dermatitis.

Retinoid, as used herein, includes all natural and/or synthetic vitamin A analogs or retinol-like compounds that have the biological activity of vitamin A in the skin as well as geometric isomers and stereoisomers of these compounds. Retinoid preferably means retinol, retinol esters (e.g., alkyl esters of 2 to 22 carbon atoms of retinol including retinyl palmitate, retinyl acetate, retinyl propionate), retinal and/or retinoic acid (including all-trans retinoic acid and/or 13-cis-retinoic acid), more preferably retinoids other than retinoic acid. These compounds are well known in the art and are commercially available from a variety of sources, e.g., Sigma Chemical Company (St. Louis, Mo.) and Boehringer Mannheim (Indianapolis, IN).

...

• ·

polis, In.). Preferred retinoids are retinol, retinyl palmitate, retinyl acetate, retinyl propionate, retinal and combinations thereof. More preferred are retinol and retinyl palmitate. The retinoid may be included in the composition essentially as a pure material or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g. plant) sources.

The compositions preferably contain 0.005 or from 0.005 to 2, more preferably from 0.01 to 2% by weight of retinoid. Retinol is most preferably used in an amount of 0.01 or from 0.01 to 0.15% by weight, retinol esters are most preferably used in an amount of 0.01 or from 0.01 to 2% by weight (e.g. about 1% by weight).

The pH of the compositions is preferably from 4 to 9, more preferably from 6 to 8.0. The composition is supplemented with water or an aqueous carrier suitable for topical application to the skin. The water content of the compositions according to the invention is usually from 30 to 98.89, preferably from 50 to 95, particularly preferably from 60 to 90% by weight.

The compositions of the invention are preferably prepared in the form of a moisturizing cream or lotion which can be applied to the skin as a removable product.

The invention is illustrated by the following examples.

Examples of embodiments of the invention

Examples I to IV

An oil-in-water emulsion is prepared from the following ingredients (in wt%) by conventional formulation methods.

* «

folder pr.1 ex.2 ex.3 ex.4 cetyl alcohol 0.72 0.72 0.72 0.72 cetaryl alcohol 0.48 0.48 0.48 0.48 stearic acid 0.1 0.1 0.1 0.1 PEG-100 stearate 0.1 0.1 0.1 0.1 Arlatone2121 ¹ 1.0 1.0 1.0 1.0 isohexadecane 1.33 1.33 1.33 1.5 silicone Q21403 ² 2.0 2.0 2.0 2.0 sugar and fat ester- acids ³ 0.67 0.67 0.67 1.5 glycerin 7.0 7.0 7.0 9.0 urea 2.0 0 0 2.0 Carbopol 954 ⁴ 0.68 0.5 0.5 0.68 Carbopol 1382 ⁵ 0.1 0.1 0.1 0.1 TiO ₂ 0.75 0.75 0.75 0.15 D-panthenol 0 0 0.5 0 tocopherol acetate 0 0 0.5 0 niacinamide 2.0 2.0 2.0 0 retinol 0 0 0.04 0 BHT 0 0 0.05 0 Glydant Plus 0.1 0.1 0.1 0.1 EDTA 0.1 0.1 0.1 0.1 NaOH 0.1 0.1 0.1 0.1 NaCl 0.02 0.02 0.02 0.02 distilled water q.s. q.s. q.s. q.s.

·· • :* > • 9 ♦ * • · 9 9 9 9 9 9

Examples 5 to 10

folder ex.5 ex.6 ex.7 ex.8 ex.9 ex.1O deionized water .added t to 100.......... glycerin 9.00 5.00 8.00 6.50 7.50 9.00 urea 1.40 1.80 2.20 1.98 1.60 2.00 Kronos (TiO ₂ ) ⁶ 0.15 0.15 0.15 0.15 0.15 0.15 Arlatone 2121 ¹ 0.0 0.50 1.50 0.60 0.50 1.00 Carbopol 1382 ⁵ 0.05 0.20 0.08 0.12 0.05 0.09 Carbopol 954 ⁴ 0.70 0.63 0.68 0.60 0.70 0.61 NaOH (40% solution) 0.80 1.00 0.80 0.85 0.75 0.90 hydrofolic acid 0.08 0.09 0.10 0.12 0.13 0.10 Myrj 59 ⁷ 0.09 0.10 0.09 0.12 0.10 0.10 stearyl alcohol 0.50 0.38 0.40 0.32 0.48 0.48 cetyl alcohol 1.20 0.85 1.00 0.72 0.72 0.72 propylparaben 0.29 0.25 0.15 0.15 0.18 0.00 FinsoIvTN ⁸ 0.00 1.2 0.00 0.5 0.5 0.00 SEFA Cottonate ⁹ 0.2 1.50 1.50 0.75 1.80 1.50 isohexadecane 1.33 0.2 0.75 2.25 1.00 1.00 methylparaben 0.20 0.20 0.20 0.20 0.20 0.00 phenoxytol 0.40 0.40 0.40 0.40 0.40 0.00 EDTA 0.10 0.10 0.10 0.10 0.10 0.10 DC Q2-14O3 ¹⁰ 2.00 1.60 1.60 1.80 1.50 3.00 NaCl 0.02 0.02 0.02 0.02 0.02 0.00 isononyl isononanoate 0.00 0.00 0.00 0.00 0.00 1.50 Glydant Plus 0.00 0.00 0.00 0.00 0.00 0.10

Examples 11 to 12

folder ex.11 ex.12 Sepigel 305 1.0 1.0 xantham gum 1400 CP1 0.28 0.28 glycerin 7.0 7.0 urea 2.0 2.0 PEG-30 2.4 2.4 glyceryl monostearate 1.5 1.5 propylene glycol monostearate 1.5 1.5 cetearyl alcohol 1.0 1.0 polyglyceryl-2-sesquilsostearate 0.8 0.8 isohexadecane 12.0 4.0 SEFA Cottonate ⁹ 2.0 2.0 lanolin oil 4.0 8.0 DC 345 1.0 1.0 dimethicone 350 1.0 1.0 Kronos (TiO ₂ ) ⁶ - 0.5 β-carotene 0.0015 0.0015 tetrasodium EDTA 0.1 0.1 methylparaben 0.3 0.3 phenoxyethanol 0.4 0.4 propylparaben 0.1 0.1 distilled water q.s. up to 100

supplied by ICI Surfactans, PO Box 90, Wilton Centre, Middlesborough, Cleveland, TS6 8JE supplied by Dow Corning, Kings Court, 185 Kinds Rd., Reading, Berks, RG1 4EX »· ·0 • · * · • · • 0 • · « · · * · ♦ · 0

a monoester of 1 to 30 carbon atoms or a polyester of sugars and one or more carboxylic acids as described herein, preferably a sucrose polyester with a degree of esterification of 7 to 8 and with residues of fatty acids of 18 carbon atoms, mono- and/or di-unsaturated and behenic acid, with a molar ratio of unsaturated: behenic from 1:7 to 3:5, more preferably an octaester of sucrose, in which there are 7 parts of behenic acid and 1 part of oleic acid per molecule, e.g. an ester of sucrose and cottonseed oil fatty acids, e.g. SEFA Cottonate ⁴ BF Goodrich, 9911 Brecksville Road, Brecksville, Oh. 44141, USA ⁵ BF Goodrich, 9911 Brecksville Road, Brecksville, Oh. 44141, USA ⁶ supplied by Kronos, 4 Pl. Ville Marie No. 500, Montreal, Quebec, Canada ⁷ PEG 100 stearate supplied by ICI, PO Box 90, Wilton Centre, Middlesborough,

Cleveland, TS6 8JE ⁸ alkyl (12 to 15 carbon atoms) benzoate ester supplied by Finetex lne., PO Box

216, Elmwood Park, New Jersey 07470, USA ⁹ supplied by Procter & Gamble, Winton Hill Technical Centre, Cincinnati, Oh.,

US ¹⁰ supplied by Dow Corning, Kings Court, 185 Kinds Rd., Reading, Berks, RG1 4EX

The compositions shown in Examples 1 to 10 are prepared by the following procedure: First, a pre-mix of thickening agents, methylparaben, if present, glycerin/ _TiO2 masterbatch, Arlaton 2121, if present, and other water-soluble ingredients in addition to urea is prepared by mixing in water and heating to a temperature of about 80°C. A second masterbatch of oil phase ingredients, which contains emulsifiers, oil-soluble preservatives, other than silicone resin, is prepared by mixing and heating and added to the aqueous masterbatch.

The silicone resin is added to the resulting mixture and the mixture is then cooled to 60°C. Then, to the resulting oil-in-water emulsion, NaOH solution, Glydant Plus, if present, EDTA, silicone resin and urea solution (1 g dissolved in 1 ml • « water) are added. The emulsion is cooled before the minor components are added. The composition is ready for packaging.

The compositions of Examples 11 and 12 are prepared as follows: A first premix of thickening agents (except Sepigel, if present), methylparaben, glycerin/ _TiO2 masterbatch, Arlaton 2121, if present, and other water-soluble ingredients except urea is prepared by mixing in water and heating to a temperature of about 80°C. A second premix of oil phase ingredients, which contains emulsifiers, oil-soluble preservatives other than silicone resin and cyclomethicone, is prepared by mixing and heating and added to the aqueous masterbatch. This mixture is homogenized.

The silicone resin is added to the resulting mixture and the mixture is then cooled to 60°C. Sepigel and cyclomethicone, if present, are then added to the resulting oil-in-water emulsion. EDTA and urea solution (1 g dissolved in 1 ml of water) are then added to the mixture. The mixture is neutralized with NaOH, if necessary. The mixture is further cooled with stirring before the minor ingredients are added. The composition is ready for packaging.

The compositions exhibit improved skin feel, skin smoothness, skin softness and skin care properties along with reduced greasiness, excellent rub-in and rapid absorption.

Claims (20)

PATENT CLAIMS A cosmetic composition suitable for topical application to the skin, comprising: (a) a liquid, a polyol ester and a carboxylic acid having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing 4 to 8 hydroxyl groups, each carboxylic acid group having from 8 to 22 carbon atoms and said liquid polyol-carboxylic acid ester has a total melting point of less than 30 ° C, and (b) a branched chain aliphatic hydrocarbon having a weight average molecular weight of 100 to 15,000. A cosmetic composition suitable for topical application to the skin of claim 1, wherein the branched hydrocarbon chain has an average molecular weight of from 200 to 1000. Cosmetic composition suitable for topical application to the skin according to claim 1 or 2, characterized in that the branched hydrocarbon chain is selected from isododecane, isohexadecane, isoeicosan, iso-octahexacontane, isoheptane-kontahectan, isopentane-kontaoctane and mixtures thereof. Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 3, characterized in that the branched hydrocarbon chain is isohexadecane. A cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 4, characterized in that it comprises from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.1 to 5%. wt. branched aliphatic hydrocarbon chain. ·· · 9 · · 9 · 9 · 9 9 999 99 99 9 9 9 9 9 Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 5, characterized in that the liquid ester of the polyol and the carboxylic acid contains no more than 2 free hydroxyl groups. A cosmetic composition suitable for topical application to the skin of any one of claims 1 to 6, wherein the carboxylic acid moieties contain from 14 to 18 carbon atoms. Cosmetic composition suitable for topical application to the skin of any one of claims 1 to 7, wherein the polyol moiety is selected from erythritol, xylitol, sorbitol, glucose, sucrose and mixtures thereof. A cosmetic composition suitable for topical application to the skin of any one of claims 1 to 8, wherein the polyol moiety is sucrose. A cosmetic composition suitable for topical application to the skin of any one of claims 1 to 9, wherein the liquid polyol-carboxylic acid ester has a complete melting point below 27.5 ° C. Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 10, characterized in that the liquid polyester of the polyol and the carboxylic acid has a complete melting point below 25 ° C. A cosmetic composition suitable for topical application to the skin of any one of claims 1 to 11, wherein the liquid polyol carboxylic acid ester is selected from sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, and mixtures thereof. • 99 9 9 9 99999 Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 12, characterized in that it comprises from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.1 to 5%. wt. a liquid polyol ester and a carboxylic acid. Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 13, characterized in that the weight ratio of the liquid polyol ester and the carboxylic acid to the branched chain aliphatic hydrocarbon is in the range of 5: 1 to 1: 5, preferably 3: 1 to 1: 3. Cosmetic composition suitable for topical application to the skin according to any one of claims 1 to 14, characterized in that it is in the form of an emulsion, preferably an oil-in-water emulsion. A cosmetic composition suitable for topical application to the skin of claim 15, further comprising a silicone-containing phase. A cosmetic composition suitable for topical application to the skin according to claim 16, wherein the silicone-containing phase comprises silicone or a mixture of silicones in an amount of from 0.1 to 20, preferably from 0.1 to 15, more preferably from 0, 1 to 10 wt. by weight of the composition, wherein the silicone or silicone composition comprises a silicone resin having a molecular weight of from 200,000 to 4,000,000. A cosmetic composition suitable for topical application to the skin of any one of claims 1 to 17, further comprising an oil component containing 20% or more by weight of the composition. cholesterol esters. * r 19. A cosmetic composition suitable for topical application to the skin of claim 18 wherein the oil component is selected from lanolin and lanolin derivatives. A cosmetic skin treatment method comprising applying a cosmetic composition according to any one of claims 1 to 19 to the skin.