CA2152640C

CA2152640C - Cosmetic compositions with keratolytic and anti-acne activity

Info

Publication number: CA2152640C
Application number: CA002152640A
Authority: CA
Inventors: Barbara Ann Wolf; Florence Snyder
Original assignee: Revlon Consumer Products LLC
Current assignee: Revlon Consumer Products LLC
Priority date: 1994-08-09
Filing date: 1995-06-26
Publication date: 1999-09-14
Anticipated expiration: 2015-06-26
Also published as: ZA955621B; US5449519C1; NZ272727A; NO953114D0; JPH0859425A; US5449519A; GB2292080B; PE32096A1; HK1013251A1; NO953114L; IL114487A; AU2179895A; CA2152640A1; FI953743A; BR9503559A; AU690251B2; FI953743A0; KR960006912A; GB2292080A; EP0696451A1

Abstract

A cosmetically acceptable composition with anti-acne or keratolytic activity comprising:
0.01 to 25% by weight of a keratolytic compound complexed to a carrier molecule,75-99.95% by weight of a diluent.

Description

21526~p COSMETIC COMPOSITIONS HAVING KERATOLYTIC AND
ANTI-ACNE ACTIVITY

2 Technical Field 3 The invention is in the field of cosmetic compositions having keratolytic and anti-acne 4 activity.
S Back~ound of the Invention 6 Acne vulgaris is reported to be the most common skin disease, affecting approximately 7 eighty percent of the teenage population, and in some cases persisting into the third and fourth 8 decades of life. The pathology of acne is believed to first involve the formation of comedones, 9 which are solid, horny masses of tightly packed keratinized cells which plug follicles. These comedone plugs are first white when formed (whiteheads), but through continued growth and 11 deposition of melanin become blackheads. As the comedo enlarges through continued 12 accumulation of keratinized cells, pressure builds up within the follicles and they eventually 13 rupture, dumping the contents (consisting of horny material, sebum, and bacteria) into the skin.
14 This provokes an inflammatory response; when the rupture is small pustules or pimples develop, and when the follicle completely ruptures cystic nodules result.
16 It is well known that acne vulgaris can be treated by application of agents which dry and 17 peel the skin to remove keratinous plugs. Well known keratolytic agents are sulfur, resorcinol, 18 benzoyl peroxide, salicylic acid, and hexachlorophene. Benzoyl peroxide is an antimicrobial 19 agent which effectively suppresses the acne bacillus Propionibacterium acnes, an organism . 2152640 i~ ~ which has an important causual role in acne. In addition to being an effective keratolytic agent, 2 salicylic acid also interferes with the formation of blackheads, whiteheads, and the horny masses 3 which clog follicles.
4 Salicylic acid, benzoyl peroxide, and resorcinol have been incorporated into various anti-s acne preparations for years. However, due to the acidic nature of these ingredients, they often 6 exert undesireable effects on the carrier formulation. Salicylic acid, for example, is not water 7 soluble; it can only be solubilized in oils or alcohol. When salicylic acid is incorporated into 8 these preparations at a pH of above 3, it converts to salicylate and causes stability problems in 9 the formulation. Also, salicylic acid is light sensitive above a certain pH.
Make-ups made with salicylic acid are known to fade on exposure to light and can be slightly irritating in sensitive 11 skinned individuals who are prone to skin irritations. There is therefore a need for anti-acne 12 preparations having improved stability and aesthetic properties.
13 ~~r of the Invention 14 The invention is directed to a cosmetically acceptable composition with anti-keratolytic activity comprising:
16 0.01 to 25 % by weight of a keratolytic compound complexed to a carrier molecule, 17 75-99. 99 % by weight of a diluent.
18 The invention is also directed to a method for treating acne vulgaris comprising:
19 a) complexing a keratolytic compound to a carrier molecule, b) adding an effective amount of said complex of (a) to a cosmetically acceptable diluent.
., 2 1 The invention is further directed to a cosmetic formulation comprising from about 0.01 2 to about 30% by weight of the total formulation of a keratolytic compound selected from the 3 group consisting of resorcinol, benzoyl peroxide, salicylic acid, or a mixture thereof, complexed 4 to a complexing molecule having at least one free amino or hydroxy functional group; and from about 70 to about 99.99% by weight of the total formulation of a cosmetically acceptable Garner.
6 The invention is further directed to a method for preparing a cosmetic formulation 7 comprising a) complexing a keratolytic compound selected from the group consisting of 8 resorcinol, benzoyl peroxide, salicylic acid, or a mixture thereof with a complexing molecule 9 having at least one free amino or hydroxy functional group; and b) b r i n g i n g s a i d c o m p 1 a x produced by step (a) into association with a cosmetically acceptable Garner.
11 Detailed Description 2a x A

z~ 52s~o 1 It has most unexpectedly been discovered that if keratolytic compounds, particularly those 2 known to also have anti-acne activity are bound to a certain Garner molecules, the resulting 3 complex will remain stable in cosmetic preparations. When the complex is applied to the skin in 4 a cosmetic composition, the keratolytic compound becomes disassociated from the carrier molecule on the skin and is absorbed into the skin to provide the desired anti-acne effect. In the 6 case of salicylic acid, the complexation of the salicylic acid in the cosmetic preparation is 7 believed to prevent the conversion of salicylic acid to salicylate, and enhances the stability and 8 aesthetics of the cosmetic preparation. The various ingredients of the cosmetically acceptable 9 composition according to the invention are described in more detail below.
The term "keratolytic compound" means a chemical compound having keratolytic and/or 11 anti-acne activity.

13 The keratolytic compounds which are suitable for use with the invention contain an acid 14 group or tend to be acidic and are capable of binding with the free amino group of a protein or polymer. The binding may be ionic, covalent, or through Van Der Waals forces.
Anti-acne 16 ingredients capable of forming ionic bonds include salicylic acid and resorcinol. Benzoyl 17 peroxide will bond to carrier molecules, or bind through Van der Waals forces.
18 THE C RR1RR MO . . TT F
19 A wide variety of Garner molecules are suitable, so long as the carrier molecule possesses at least one free amino group.

'21 52640 1 Animal protein or peptides such as collagen, placental proteins, serum proteins, amylase, 2 casein, urease, keratin, silk, hydrolyzed animal protein, albumin, etc. are well known in the 3 cosmetic art and are capable of ionic binding to the keratolytic compound.
The preferred carrier 4 molecule comprises hydrolyzed animal protein, collagen, or keratin.
Vegetable or plant proteins or polyamino saccharides containing free amino groups are 6 also suitable, such as soya, corn, sweet corn, lupin, wheat gluten, guar, oat, extensins, 7 hydrolyzed vegetable proteins, and so on, as well as polymers of amino sugars such as chitosan.
8 The preferred carrier molecule in this category comprises hydrolyzed vegetable protein, or 9 extensins.
A wide variety of synthetic polymers have free amine groups are also suitable as the 11 carrier molecule. Particularly desireable are branched polyamidoamines as set forth in U.S.
12 patents 4,435,548, 4,737,550, 4,871,779) 4,857,599, 4,713,975, 4,694,064, 4,690,985, 13 4,631,337, 4,599,400, 4,587,329, 4,568,737, 4,558,120, and 4,507,466. These patents disclose 14 and claim dense star-type polymers with dendritic branches which have highly reactive substitutent groups.
16 Other synthetic polymers such as polya.mides, polya.nilines, polyureas, polyurethanes, and 17 contain at least one free amino group and would be suitable carrier molecules. Certain other 18 polymers with free hydroxyl groups, such as polyvinyl alcohols, poly (2-HEMA) and poly (2-19 HPMA) will bind by Van tier Waals forces.
COMPLEXATION OF THE KERATOLYTIC COMPOUND TO THE CARRIER
21 MOLEC~
4 _ . 21 52640 ' 1 The keratolytic compound is attached to the carrier molecule employing a variety of 2 chemical reactions depending on the carrier molecule and the anti-acne active used. The term 3 "complex" refers to the keratolytic compound complexed or bound to the carrier molecule.
4 Salicylic acid and resorcinol have free acid groups which will ionically bond to the free amino groups of proteins or polymers. Binding of the salicylic acid to vegetable or animal 6 proteins is achieved by simply combining approximately equal parts of both ingredients in 7 suitable vessel. The salicylic acid will react with the free amino groups on the carrier molecule 8 to form a complex. Sometimes a slight degree of heat will hasten the reaction, or the addition of 9 small amounts of acid such as hydrochloric acid. Salicylic acid may also be complexed to various carriers such as hydrolyzed vegetable proteins as described in French patent no. 2667072 11 In particular, a concentrated solution of salicylic acid in alcohol is mixed with a concentrated 12 solution of hydrolyzed vegetable protein in water. The resulting dispersion is mixed under 13 shear or alternatively by ultrasonic agitation. Depending on the type of protein selected, the 14 complex may precipitate upon forming or may be recovered by vacuum distillation or lyophilization by method known to those skilled in the art. The resulting powder effectively 16 solubilizes the complexed salicylic acid which can be recovered and analyzed as salicylic acid 17 by traditional wet chemistry. Alternatively, the salicylic acid can be rendered more water 18 soluble by using a metal alkali salt such as sodium or potassium and complexing at a pH of S.5 19 to 6.5. The powdered hydrolyzed protein is then added to a dispersion of the salicylate in a buffered water solution.

Z 15r 1 Salicylic acid can be complexed with the dendritic polymers disclosed herein. Dendritic 2 polymers are constructed to vary in size and shape depending upon the initiator and the molecule 3 used to grow the shell. Of particular interest are the starburst dendrimers of the polyamidoamine 4 (PAMAM) type because the outer shell is covered with amino groups which will complex with salicylic acid. As in example one, the starting point can be either a water dispersion of 6 dendrimer to which is added salicylic acid in a volatile solvent, or a solution of salicylate at pH
7 5.5 to 6.5 to which is added crystals of dendrimers. The size of the dendrimer will allow 8 multiple sites for complexation, but not so large that solubility in water is hindered. Dendrimers 9 having 1-10 generations are ideal. Since the dendrimers can develop holes or irregularities, some salicylic acid may be sequestered within the shell as well as complexed to the surface. As 11 with the protein, a high complexation ratio is desireable.
12 Salicylic acid will also bind to synthetic polymers which have free amino groups in a 13 manner similar to binding to proteins. Such polymers include: polyamides -(R-CO-NH)n , 14 polyanilines -(C6H5-NH)n , polyureas (-R-NHCONH)n, and polyurethanes -(CO-OR-OCO-NH-R'-NH)", where the branched or terminal groups have free amino groups 16 and the interior amine groups are also available.
17 Other polymers with free hydroxy groups will bind to salicylic acid by Van der Waals 18 forces. Such polymers are polyvinyl vinyl alcohols -(CH2CHOH)-, poly(2-HEMA), 19 (-CH2-C(CH3)(COOCH2CH(OH)-)", and poly(2-HPMA), (-CH2-C(CH3)(COOCH2CHZOH-)" and (-CH2-C(CH3)(COOCH2CH(OH)CH3)". Such bonds are 21 weaker, but may be enhanced by shared electrons across the aromatic ring of salicylic acid.

1. Benzoyl peroxide will only form Van der Waals bonds with proteins or polymers. The 2 complexation of benzoyl peroxide to proteins is achieved by sharing electrons across the 3 peroxide moiety and the amido moiety in the polymer.
4 It is generally preferred that the complex be comprised of 40-50 % by weight of anti-acne active and 50-60% by weight of carrier molecule. Ratios may vary depending on the effect 6 desired. For example, in some cases it may be desired to have small levels of the anti-acne 7 active deposited on the skin, in which case more appropriate ratios might range from 10-40 %
8 anti-acne active/60-90 % carrier molecule, or vice versa.
9 It may be desired to encapsulate the complex to provide additional properties such as time release. Standard encapsulation methods are suitable, such as the methods disclosed in U.S.
11 Patent no. 5,194,262.
12 ~~"HE DILUENT
13 The term "diluent" generally refers to a composition applied externally to the skin or hair 14 of the human body for the purpose of cleansing, beautifying, conditioning or protecting the body surface. A wide variety of diluents is suitable including but not limited to water-in-oil or oil-in-16 water emulsions in cream or lotion form, sunscreens, toners, astringents, facial make-ups, 17 pressed or loose powder, skin cleansing compositions, and so on. In some cases it may be 18 desired to apply the complex to the scalp to achieve keratolytic effects, so suitable diluents can 19 also include shampoos and conditioners. In general, the cosmetically acceptable compositions of the invention contain about 0.1-30 % of the complex and about 70-99.9 %
diluent. Preferably the 21 compositions comprise about 0.1-10 % complex and 90-99.9 % diluent.

~21 ~Zb~.O
1 The complex may be incorporated into creams. Creams generally contain about 2 water and 10-90 % oil. The oil may be low or high viscosity surface oils, volatile silicones, 3 nonvolatile silicones, or amine functional silicones. Creams may also contain humectants, 4 emollients, surfactants, emulsifiers, preservatives and fragrances. About 5-10 % humectant, 5-20 % emollient, and about 0. S-10 % surfactant or emulsifier is suggested.
6 The diluent may be a lotion. Lotions are generally comprised of 20-80 % oil and 10-80 7 water in an emulsion form. In addition, lotions may contain humectants, emollients, surfactants, 8 fragrances, preservatives and so forth. About 5-10 % humectant, about 5-20 %
emollient, and 9 about 0.5-10% surfactant are suggested.
The diluent may be a make-up. Make-ups generally comprise about 5-70% oil, 10-11 water, and about 5-40 % pigment. In addition, the makeup may contain surfactants, silicones as 12 part of the oil phase, humectants, emollients, preservatives, fragrances, etc. Generally 0.1-10 13 surfactant, 0.1-50 % silicone, 0.1-20 % humectant, 0.1-30 % emollient, and 0.1-5 % preservative 14 is suggested. In the preferred embodiment of the invention the diluent is a make-up comprising 0.01-SO % silicone, 30-60 % water, 0.01-4.0 % pigment, and 5~0 % oil. The preferred 16 composition may also comprise 0.1-20% humecta.nt, 0.1-10% surfactant, and 0.1-5%
17 preservative.
18 The make-up of the invention provides improved properties over the anti-acne make-ups 19 currently available in that it does not change color or fade. Normally anti-acne actives, salicylic acid in particular, react with the iron oxide pigments commonly used in make-up. However, 1 because the anti-acne active is bound to a carrier molecule, such reaction does not occur in the 2 make-up composition of the invention.
3 The diluent may also be a blush, face powder, or other anhydrous makeup.
Generally 4 blushes contain about 5-75 % pigment, 1-50 % oil, and 1-20 % wax. They may additionally contain one or more of 10-60 % water, 0.5-30 % surfactant, 1-10 % humectants, 0.1-5 %
6 preservative, and 0.1-20% silicone. Anhydrous makeups and concealers generally comprise one 7 or more of 0.1-10 % surfactant, 0.1-50 % silicone, 0-20 % humectant, 0.1-30 % emollient, 0.1-8 50 % pigment and 0.1-5 % preservative. Face powders comprise 5-75 % powder, 0.1-20 % wax, 9 and 0.01-20 % pigments. They may also contain one or more of 10-60 % water, 0.5-30 surfactant, 1-10% humectants, 0.1-5% preservative, and 0.1-20% silicone.
11 The diluent may be a shampoo when it is desired to apply the anti-acne active (which also 12 has keratolytic activity) onto the scalp. Suitable shampoo compositions contain 1-40 % of a 13 cleansing surfactant and 10-90 % water. Preferably the surfactants are anionic or amphoteric.
14 The shampoo may also contain any one of ingredients such as surfactants, colorants, preservatives, fragrance, emulsifiers, viscosity adjusters, and conditioning agents. If present, 16 suitable ranges are 0.01-30 % surfactant, 0.001-5 % colorant, 0.001-5 %
preservative, 0.01-15 17 emulsifiers, 0.01-10 % viscosity adjusters, and 0.1-20 % conditioning agents .
18 The diluent may also be a hair conditioner. Suitable hair conditioning formulations 19 include 10-95 % water, 0.5-30 % conditioning ingredients such as quaternary ammonium compounds or amphoteric polymers, proteins, etc. , and 1-40 % surfactants.
Hair conditioners 21 may also contain volatile or nonvolatile silicones; an amount of about 0.5-15 % is suggested.

1 The diluent may be a toner which generally comprises about 0-85 % alcohol, 0.01-5 %
2 surfactant, and 0.1-5 % humectants, 0.1-85 % water.
3 The diluent may also be pharmaceutical type vehicles such as ointments ) gels or 4 solutions. Suitable ointments are hydrophilic ointments (USP) or petrolatum.
Solutions are made by mixing the anti-acne active/carrier molecule complex in deionized water. Gels 6 generally comprised about 1-90 % water and about 1-90 % of a suitable polymer such as 7 polypropylene, etc.
8 Suitable emollients include glyceryl stearate, cetyl alcohol, stearyl alcohol, isopropyl 9 stearate, stearyl stearate, isopropyl stearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, sebacates, myristates, palmitates, squalenes, glyceryl monooleate, oleic acids, 11 lanolin, acetylated lanolin alcohols, petrolatum, mineral oils, palmitic acids, isostearyl 12 neopentanoate, etc. , as well as those set forth on pages 79-81 of the C .
T . F . A. Cosmetic 13 Ingredient Handbook, First Edition, 1988.
14 Suitable humectants include glycerin, butylene glycol, propylene glycol, glucose, fructose, glucuronic acid, glucamine, glutamic acid, glycereth-7, glycereth-12, glycereth-26, 16 histidine, honey, lactose, mannitol, methyl gluceth, sodium PCA, PEG-10 propylene glycol, 17 urea, xylitol, TEA-lactate, TEA-PCA, sucrose, sorbitol, PCA, sodium lactate, or mixtures 18 thereof, as well as those set forth on page 75 of the ~ T F.A. Cosmetic Ln~redient Ha_n_dbook, 19 First Edition, 1988.
A variety of surfactants may be used in the diluent including amphoteric, anionic, 21 cationic or nonionic surfactants. Suitable amphoteric surfactants include imidazolines, betaines, '' 10 _ 1 and amino acid salts. Suitable anionic surfactants include fatty acid soaps, salts of higher alkyl 2 sulfates, n-acyl sarcosinates, salts of phosphates, sulfosuccinates salts, alkyl benzene sulfonates) 3 salts of N-acyl glutamate, polyoxyethylene alkyl ether carboxylic acids, and so on. Cationic 4 surfactants include alkyl trimethyl ammonium salts, alkyl pyridinium salts, alkyl quaternary ammonium salts, polyamine fatty acid derivatives, etc. Suitable anionic and amphoteric 6 surfactants also include those designated as "cleansing agents" as set forth on pages 87-90 of the 7 C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988. Nonionic surfactants include 8 lipophilics such as sorbitan fatty acid esters, glycerol fatty acids, propylene glycol fatty acid 9 esters; hydrophilics such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, pluronics, 11 polyoxyethylene alkyl phenyl ethers, polyoxyethylene propylene glycol fatty acid esters, and 12 so on. Examples of nonionic surfactants include those set forth in pages 90-94 of the C.T.F.A.
13 Cosmetic Ingredient Handbook, First Edition, 1988. Suitable cationic surfactants are set forth 14 on page 97 of the C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988.
Suitable pigments include organic and inorganic pigments such as talc, mica, titanium 16 dioxide, titanated mica, iron oxides, ultramarines, chromium oxides, carmine, D&C and FD&C
17 colors and lakes, ferric and ferrous oxides, and so on, as set forth on pages 33 and 63 of the 18 C.T.F.A. Cosmetic Ingredient Handbook, First Edition, 1988.

.w 2152640 1 Suitable preservatives include the areas such as imidazolidinyl urea, diazolidinyl urea, the 2 parabens, quaternium 15, benzyl alcohol, phenoxyethanol and so on.
3 Suitable waxes include beeswax, cetyl esters, carnauba, ceresin, microcrystalline, lanolin, 4 paraffin, ozokerite, lanolin alcohol, acetylated lanolin, candelilla, cetyl alcohol, cocoa butter, petrolatum, hydrogenated castor oil, spenmacetic, bran wax, capok wax, bayberry, hydrogenated 6 jojoba oil, hydrogenated jojoba wax, hydrogenated rice bran wax, Japan wax, jojoba butter, 7 jojoba oil, mink, montan acid, montan, ouricury, shellac, etc.
8 Suitable silicones include cyclomethicone, dimethicone, stearoyl dimethicone, phenyl 9 trimethicone, dimethiconol, dimethicone copolyols, etc.
In the preferred embodiment of the invention the anti-acne active/carrier molecule 11 complex comprises 40-50 % by weight plant protein (hydrolyzed vegetable protein) and 45-SS
12 salicylic acid. The preferred diluent is a make-up or skin care product.

14 A concentrated solution of hydrolyzed vegetable protein in water is mixed with a 50 salicylic acid solution in ethanol. The resulting dispersion is mixed under shear. The mixture is 16 allowed to stand for approximately 24 hours. Lyophilization is performed to yield a powdered 17 material which comprises salicylic acid complexed to the hydrolyzed vegetable protein.

19 A water dispersion of about 50 wt % polyamidoamine methacrylate crystals in water is prepared. A solution of 50 % salicylic acid in ethanol is slowly added to the crystals with stirring 1 for a half hour. The mixture is vacuum distilled to yield crystals having salicylic acid complexed 2 thereto.

4 A concentrated dispersion of polyacrylamide in water is mixed with a 50 %
solution of S salicylic acid in ethanol with high shear mixing. After 24 hours the resulting dispersion is 6 lyophilized to yield crystals having salicylic acid complexed thereto.
7 FXAMPT .R d 8 A 50 % solution of benzoyl peroxide in ethanol is mixed with a 25 % solution of 9 hydrolyzed vegetable protein. The mixture is allowed to stand for 24 hours.
The mixture is then lyophilized to obtain a powder. The powder comprises hydrolyzed vegetable protein having 11 benzoyl peroxide complexed thereto.

13 The salicylic complex of Example 1 was used to prepare a make-up composition as 14 follows:
wow 17 Salicylic acid/hydrolyzed veg. protein1.00 complex 18 Trisodium EDTA 0.15 19 Benzoic acid 0.20 1, 3-butylene glycol 5 , pp 21 Sodium polymethacrylate 1,00 22 Sorbitan sesquioleate 0.50 23 Simethicone 0.15 24 Glycerin 5 , pp Magnesium aluminum silicate 1.25 26 Methyl paraben 0.30 27 Ethyl paraben 0.10 28 Polyethylene 2.00 1 Nylon 12 ; _ pp 2 Rutile titanium dioxide 5,00 3 Black iron oxide/talc 0.53 4 Red iron oxideltalc 0.92 Yellow iron oxide 0.69 6 Talc 3,q.4 7 Xanthan gum 0.35 8 Cyclomethicone 15.00 9 Diisopropyllinoleate 3.50 Polysorbate 20 1,00 11 Water 0.70 12 Imidazolidinyl urea 0.30 14 Water was heated to 60-65° C. Salicylic acid/hydrolyzed vegetable protein complex, trisodium ETDA, benzoic acid, 1,3-butylene glycol, sodium polymethacrylate, sorbitan 16 sesquioleate, simethicone, glycerin, magnesium aluminum silicate, methyl paraben, ethyl 17 paraben, polyethylene, nylon 12, the oxides, talc and xanthan gum were mixed in a colloid mill 18 until all ingredients were dispersed. The mixture was then heated in a steam bath to 68-70° C .
19 using a sweep mixer. Next combined were the oil phase ingredients:
cyclomethicone, diisopropyl linoleate and polysorbate 20. The mixture was heated in a steam bath to 68-70° C.
21 When the water and oil phases were at the same temperature, they were mixed with sweep action 22 to form the emulsion. Sweep mixing was continued at the maintenance temperature for 15-20 23 minutes . The mixture was then removed from the bath and allowed to cool while maintaining 24 mining. The urea was added when the batch temperature reach 40-45°
C.
26 An oil in water moisturizing lotion is made as follows:
27 w/w %

29 Glyceryl stearate 3.0 1 PPG-10 lanolin ether 0.5 2 Mineral oil 6.3 3 Lanolin alcohol 0,7 4 Oleic acid 2,7 Isocetyl stearate 10.00 6 Triethanolamine 1.3 7 Carbomer 941 0.1 8 Glycerin 4.0 9 Preservative 0.4 Salicylic acid/hydrolyzed vegetable protein complex 5.00 11 QS water 100,00 13 The lotion was made by mixing into about 30 grams of water the remaining ingredients.
14 The composition was emulsified and water added to 100 grams.

18 An oil-in-water moisturizing cream is made as follows:

w/w %%

22 Glyceryl stearate ~ 5.0 23 Cetyl alcohol 2.0 24 Stearyl alcohol 2.0 Isopropyl stearate 4.0 26 Mineral oil 12.0 27 Polysorbate 60 1.0 28 Glycerin g,0 29 Xanthan gum 0.25 Preservative 0.60 31 Salicylic acid/hydrolyzed vegetable protein complex 5.00 32 Water QS 100,00 The ingredients were combined and mixed to emulsify.

37 Ex 39 An anhydrous makeup with salicylic acid was made as follows:

2 15~~~0 1 Stearoyl dimethicone 12.00 2 Phenyl trimethicone 16.00 3 Octyldodecanol 12.00 4 Dimethicone 4,00 BHA 0.10 6 Phenoxyethanol 0.70 7 Titanium dioxide 15.00 8 Black iron oxide/talc 0.26 9 Red iron oxide/talc 2.00 Yellow iron oxide/talc 5.00 11 Talc 6.94 12 Lecithin treated mica 6.00 13 Hydrogenated coco glycerides 10.00 14 Ceresin wax 1,00 Tribehenin g,pp 16 Salicylic acid/hydrolyzed vegetable protein 17 protein complex 1.00 19 All ingredients except the complexed salicylic acid/protein was mixed in a steam bath until waxes were molten. The entire batch was roller milled until pigments were dispersed. The 21 mixture was then returned to the steam bath and the salicylic acid complex was added. The 22 batch was prop mixed until cooled to room temperature.

24 An anhydrous concealer stick was made as follows:
w/w 26 Ceresin wax 15.00 27 Carnauba 2,00 28 Wax blend 4,00 29 Microcrystalline wax 2.50 Ester blend 30.00 31 Prepolymer 2 10.00 32 Octyldodecanol 13.00 33 Sorbitan sesquioleate 1,00 34 Octyldodecyl stearoyl stearate2.00 Bismuth oxychloride 2,00 ~ 152~~-U
1 Polymethylinethacrylate 3.00 2 Talc 5.70 3 Lecithin treated black LO. 1.00 4 Lecithin treated red L O. 2.00 Lecithin treated yellow L O. 5.00 6 Phenoxyethanol 0.70 7 BHA 0.10 8 Salicylic acid/hydrolyzed vegetable protein 9 complex 1.00 11 All ingredients except the salicylic acid/protein complex were mixed in a steam bath until 12 waxes were molten. The entire batch was roller milled until pigments were dispersed. The 13 batch was returned to the steam bath and the salicylic acid complex was added. The batch was 14 prop mixed until it cooled to room temperature.
16 A shampoo composition was made as follows:
17 w/w Q/

19 Ammonium lauryl sulfate 10.00 Cocamide diethanolamine 4.00 21 Cocamidopropyl betaine 4.00 22 Ammonium chloride 0.80 23 Citric acid 0.10 24 Salicylic acid/hydrolyzed vegetable 5.00 protein complex Water QS 100,00 27 ~pLE 1 1 29 A creme rinse hair conditioner was made as follows:

31 wow 33 Stearalkonium chloride 2.0 34 Cetyl alcohol 1.0 _ 215 ~ ~> ~-(~
1 Stearyl alcohol 0.5 2 Ceteareth 20 2.0 3 Xanthan gum 0.5 4 Citric acid 0.3 Dimethicone 0.2 6 Salicylic acid/hydrolyzed vegetable protein complex 5.00 7 Water QS 100.00 11 A toner composition was made as follows:

13 wow Polysorbate 20 1.0 16 Ethyl alcohol 50.00 17 Perfume 8,00 18 Salicylic acid/hydrolyzed vegetable protein complex 10.00 19 Water QS 100.00 22 .

23 A cleansing cream was made as follows:

w/w 27 Mineral oil 20.00 28 Beeswax 2,00 29 Polysorbate 40 8.00 PEG 20 sorbitan beeswax 2,00 31 Stearic acid 10.00 32 Petrolatum 4,00 33 Sorbitol 5,00 34 Perfume 1, pp Preservative 0.50 36 Salicylic acid/hydrolyzed veg. protein10.00 complex 37 Water QS 100,00

Claims

1. A cosmetically acceptable composition with keratolytic activity comprising:
0.01 to 25% by weight of a keratolytic compound complexed to a carrier molecule, 75-99.99% by weight of a diluent.

2. The composition of claim 1 wherein the keratolytic compound is resorcinol, benzoyl peroxide, salicylic acid, or mixtures thereof.

3. The composition of claim 2 wherein the carrier molecule is hydrolyzed vegetable protein, hydrolyzed animal protein, a branched polyamidoamine, a polyamide, polyaniline, polyurea, polyurethane, polyvinyl alcohol derivative, or mixtures thereof.

4. The composition of claim 3 wherein the carrier molecule is complexed to the keratolytic compound by ionic, covalent, or Van der Waals bonding.

5. The composition of claim 4 wherein the diluent is a cream, lotion, make-up, blush, skin cleanser, sunscreen, toner, astringent, or powder.

6. The composition of claim 4 wherein the complex comprises 10-40% by weight of the complex of keratolytic compound and 60-90% by weight of the complex of carrier molecule.

7. The composition of claim 6 comprising 0.01 - 20% by weight of the total composition of the keratolytic ingredient/carrier molecule complex and 80-99.9% by weight of the total composition of diluent.

8. The composition of claim 7 wherein the diluent is a makeup containing 5-70%
oil, 10-95%
water, and 5-40% pigment.

9. The composition of claim 8 wherein the makeup comprises 0.01-50% silicone, 30-60%
water, 0.01-40% pigment and 5-40% oil.

10. The composition of claim 9 wherein the make-up additionally comprises 0.1-20%
humectant, 0.1-10% surfactant, and 0.1-5% preservative.

11. A method for treating acne vulgaris comprising:
a) complexing a keratolytic compound to a carrier molecule, b) adding an effective amount of said complex of (a) to a cosmetically acceptable diluent.
c) applying the composition of (b) to a subject's face at least once per day.

12. The method of claim 11 wherein the keratolytic compound is an salicylic acid.

13. The method of claim 12 wherein the diluent is a make-up.

14. The method of claim 13 wherein the carrier molecule is hydrolyzed vegetable protein.

15. The method of claim 14 wherein the salicylic acid is ionically bound to hydrolyzed vegetable protein.

16. The method of claim 15 wherein the make-up comprises 5-70% oil, 10-95%
water, and 5-40% pigment.

17. The composition of claim 16 wherein the make-up comprises 0.01-50%
silicone, 30-60%
water, 0.01-40% pigment and 5-40% oil.

18. A facial make-up composition having anti-keratolytic activity comprising:
0.01-50 % silicone 0.01-10% of salicylic acid ionically bound to hydrolyzed vegetable protein, 0.01-40% pigment, and 5-40% oil wherein when the make-up composition is applied to the face the ionic bond between the salicylic acid and hydrolyzed vegetable protein is ruptured and the free salicylic acid is absorbed onto the skin.

19. The composition of claim 18 further comprising 0.1-10% surfactant, 0.1-20%
humectant, 0.1-30% emollient, or mixtures thereof.

20. The composition of claim 19 wherein the silicone is a mixture of volatile and nonvolatile silicone.

21. A cosmetic formulation comprising from about 0.01 to about 30% by weight of the total formulation of a keratolytic compound selected from the group consisting of resorcinol, benzoyl peroxide, salicylic acid, or a mixture thereof, complexed to a complexing molecule having at least one free amino or hydroxy functional group; and from about 70 to about 99.99%
by weight of the total formulation of a cosmetically acceptable carrier.

22. A formulation according to claim 21 wherein the complexing molecule is a hydrolyzed vegetable protein, a hydrolyzed animal protein, a branched polyamidoamine, a polyamide, a polyaniline, a polyurea, a polyurethane, polyvinyl alcohol derivative, or a mixture thereof.

23. A formulation according to claim 21 or claim 22 wherein the cosmetically-acceptable carrier is in the form of a cream, lotion, make-up or foundation, blusher, skin cleanser, sunscreen, toner, astringent, powder, shampoo or conditioner.

24. A formulation according to claim 21, 22 or 23 wherein the formulation comprises 10 to 40% by weight of the complex of the keratolytic compound and 60 to 90% by weight of the complex of the complexing molecule.

25. A formulation according to claim 21, 22, 23 or 24 comprising 0.1 to 10% by weight of the total formulation of the complex and 90 to 99.9% by weight of the total formulation of the carrier.

26. A formulation according to claim 21, 22, 23, 24 or 25 wherein the keratolytic compound is salicylic acid.

27. A formulation according to claim 21, 22, 23, 24, 25 or 26 wherein the complexing molecule is a hydrolyzed vegetable protein.

28. A formulation according to any of claims 21 to 27 wherein the carrier is in the form of a make-up or foundation.

29. A formulation according to any of claims 21 to 28 wherein the carrier comprises 5 to 70%
w/w oil, 10 to 95% w/w water, and 0.01 to 40% w/w pigment.

30. A formulation according to any of claims 21 to 29 wherein the carrier comprises 5 to 40%
w/w oil, 30 to 60% w/w water, 5 to 40% w/w pigment and 0.01 to 50% w/w silicone.

31. A formulation according to any of claims 21 to 30 for use as an anti-keratolytic and/or anti-acne comprising:
0.01 to 50% w/w silicone 0.01 to 10% w/w of salicylic acid complexed with hydrolyzed vegetable protein, 0.01 to 40% w/w pigment, and to 40% w/w oil

32. A formulation according to any of claims 21 to 31 further comprising 0.1 to 10% w/w surfactant, 0.1 to 20% w/w humectant, 0.1 to 30% w/w emollient, or mixtures thereof.

33. A formulation according to any of claims 10 to 12 wherein the silicone is a mixture of volatile and non-volatile silicones.

34. A formulation according to an of claims 21 to 32 for use as a medicament.

35. A formulation according to any of claims 21 to 33 for use as a keratolytic and/or for treating acne vulgaris.

36. A method for preparing a cosmetic formulation comprising:
a) complexing a keratolytic compound selected from the group consisting of resorcinol, benzoyl peroxide, salicylic acid, or a mixture thereof with a complexing molecule having at least one free amino or hydroxy functional group; and b) bringing said complex produced by step (a) into association with a cosmetically acceptable carrier.

37. A method of cosmetically making-up skin which method comprises applying to the skin a cosmetic formulation according to any of claims 21 to 33.

38. A pack comprising a formulation according to any of claims 21 to 33 in a container therefor and instructions for the use thereof according to claims 34 or 35.