MXPA94005931A - Compositions of oil emulsion in water for personal cleaning - Google Patents

Compositions of oil emulsion in water for personal cleaning

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Publication number
MXPA94005931A
MXPA94005931A MXPA/A/1994/005931A MX9405931A MXPA94005931A MX PA94005931 A MXPA94005931 A MX PA94005931A MX 9405931 A MX9405931 A MX 9405931A MX PA94005931 A MXPA94005931 A MX PA94005931A
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Mexico
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ppg
ether
composition according
emulsion composition
group
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MXPA/A/1994/005931A
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Spanish (es)
Inventor
Endel Deckner George
Loren Mcmanus Richard
Marie French Dawn
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The Procter&Ampgamble Company
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Publication of MXPA94005931A publication Critical patent/MXPA94005931A/en

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Abstract

The present invention relates to oil-in-water emulsion compositions, which are useful in personal cleansing and for depositing an active ingredient on the surface of the skin. The active ingredient in compositions has a solubility parameter of about 7 to about 13. A preferred active ingredient is salicylate.

Description

Wet stamp that says: Number of shipping label of 'Express Mail "B469249649 Date of deposit August 3, 1993 I hereby certify that this document / right has been deposited in the" Post Office Express Mail to Recipient "Postal Service of the United States under 36 CFR .10 on the date indicated above and addressed to the Director of Patents and Trademarks Washington DC 20231 Anthony D. Sabatelli 34,714 Representative who sends the application Reg. No.
Signed Signature of the Proxy that sends the request Case 4969 COMPOSITIONS FOR PERSONAL CLEANING George End? L Deckner Richard Loren McManus Dawn Marie French TEQilCO FIELD The present invention relates to personal cleansing compositions, which clean the skin and deposit an active ingredient on the skin during the cleaning process. These cleaning compositions are in the form of oil-in-water emulsions. These compositions are useful for delivering a wide variety of active ingredients. Cleaning compositions containing salicylic acid as the active ingredient are highly preferred and are useful for cleansing the skin and for providing anti-acne and anti wrinkle benefits of the skin.
Waif iaíM? Ss PE I? IMVEM IOH There is a continuing interest in providing consumers with personal cleansing compositions, which not only cleanse the skin, but also provide additional skin care benefits. For example, it should be very advantageous to provide products which cleanse the skin completely, and which also deposit various active ingredients on the surface of the skin. during the cleaning procedure. These dual objectives of cleansing the skin and depositing an active ingredient are difficult to achieve from a single product, since the surfactant ingredients typically found in a skin cleansing product tend to inhibit the deposition of active ingredients. , and also tend to eliminate the active products that have been deposited. Therefore, there is a need to develop compositions which effectively achieve both of these cleaning and deposit objectives. A significant portion of the population suffers from acne. These individuals have special skin cleansing needs. Acne patients need to cleanse their skin to remove dirt, oils, bacteria and other foreign materials. Acne patients also need to treat their skin with various medications to alleviate existing acne lesions and to prevent future acne injuries. Even though cleaning products which contain various active ingredients are known, and which are targeted for those suffering from acne, many of these cleaning products do not effectively deposit therapeutic levels of the active ingredients on the skin. Therefore, those who suffer from acne, need to use two products separately, namely a cleaning product followed by an anti-acne medication, to obtain effective anti-acne protection.
Not only those who suffer from acne have the unfulfilled need to find products that cleanse and treat the skin. For example, a significant portion of the population is related to the effects of skin aging, ie, wrinkle formation, skin hanging, age spots and other skin changes related to age. These individuals also have special needs for cleansing the skin. These individuals need to keep their skin clean and also need to treat their skin to reduce the effects of aging, which have already occurred and to prevent and lessen the presentation of effects of future aging. In addition, these individuals also have the need to moisten their skin. As with acne patients, again there is a lack of products which clean and treat the skin, thus needing the use of products for the cleaning treatment separately.
A wide variety of active ingredients are currently known to treat various skin conditions. Representative of some active ingredients is salicylic acid. Salicylic acid is a well-known eratolytic agent, which is believed to help eliminate keratin plugs and aid in the skin's exfoliation process. Salicylic acid is further described in C. Huber et al., Arch. Derm. Res. 257, pp. 293-297, 1977). Salicylic acid is known for its anti-acne benefits, and is available in numerous products. See C. Huber et al., Arch. Derm. Res .. 257, pp. 293-297, 1977. Salicylic acid is known for its anti-aging skin benefits. See PCT Patent Application No. 9310755 to Blank et al., Published June 10, 1993 and Blank PCT Application No. 9310756, published June 10, 1993. However, it is difficult to provide effective acid levels. salicylic acid to the skin from conventional skin cleansing products. This stimulus is especially difficult in view of FDA regulations, which limit the level of salicylic acid in skin care products to only 2%. See "Topical Acne Drug Products For Over The Counter Human Use Final Monograph", 21 CFR 333, August 16, 1991. Thus, there is a need to develop products which completely cleans the skin and which also provide therapeutically effective levels of acid salicylic to the skin within the restrictions of the FDA formulation.
It has been found in the present invention that cleaning compositions in the form of emulsions, oil in water, can be formulated, which are useful for cleaning the skin and depositing effective levels of a wide variety of active ingredients during the cleaning process. It has been found that emulsions are useful for depositing active materials having a solubility parameter of about 7 to about 13. It has also been found that these emulsions are especially useful for depositing salicylic acid.
It is an object of the present invention to provide oil-in-water emulsion compositions for personal cleansing, which are useful for cleansing the skin and depositing the active ingredients on the surface of the skin during the cleaning process.
It is another object of the present invention to provide compositions which are useful for cleansing the skin and providing an anti-acne benefit.
It is another object of the present invention to provide compositions which are useful for cleansing the skin and providing an anti-aging benefit of the skin.
It is another object of the present invention to provide compositions which are useful for cleansing the skin and for depositing salicylic acid on the surface of the skin during the cleaning process.
It is another object of the present invention to provide methods for cleaning the skin and for depositing active ingredients on the surface of the skin.
These and other objects of this invention will become apparent in the light of the following description.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to an oil-in-water emulsion for personal cleansing, comprising: (a) from about 0.05% to about 20% of an active ingredient, having a solubility parameter of from about 7 to about 13; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula wherein R is selected from the group consisting of H and C- alkyl; .30 of straight chain or branched chain, m is an integer from 0 to about 6, R 'is selected from the group consisting of methyl and ethyl and n is an integer from about 3 to about 30; or an alkoxylated diether of the formula H (OCHjCH) qO- CH; CH2 p • Cr2 • 0 (HCH20) rH V wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each qyr is independently selected such that the sum is an integer from about 3 to about 30; (c) from about 0.05% to about 10% of an emulsifier; (d) from about 0% to about 10% of an auxiliary polymer for deposition; (e) from 0% to about 10% of a polymeric thickener; and (f) from about 25% to about 99.7% water. In another embodiment, the present invention relates to an oil-in-water emulsion composition useful for personal cleansing, comprising: (a) from about 0.05% to about 20% salicylic acid; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula wherein R is selected from the group consisting of H and a straight chain or branched chain C-, .30 alkyl, m is an integer from 0 to 6, R 'is selected from the group consisting of methyl and ethyl, and n is an integer from about 3 to about 30; or alkoxylated diether of the formula H (0CH2CH) q0- CH2 - jcH2jp - CH * - OHHCHÍO wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each q and r are independently selected, such that their sum is an integer from about 3 to about 30, (c) from about 0.05% to about 10% of an emulsifier, (d) from about 0% to about 10% of a deposition aid polymer, (e) from 0% to about 10% of a polymeric thickener and (f) from about 25% to about 99.7% water, wherein the composition has a pH of about 2 to about 7.
In still another embodiment, the present invention relates to an oil-in-water emulsion composition, useful for personal cleansing, comprising: (a) from about 0.05% to about 20% of an active ingredient having a solubility parameter of about 7 to about 13; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula wherein R is selected from the group consisting of H and C- alkyl; Linear chain or branched chain, is an integer from 0 to about 6, R 'is selected from the group consisting of methyl and ethyl and n is an integer from about 3 to about 30; or an alkoxylated diether of the formula H (0CH2CH) q0- CH2 - jcH2] p - CH2 - (XfHCH wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each qyr is independently selected, such that its sum is an integer from about 3 to about 30 (c) from about 0.05% to about 10% of an emulsifier; (d) from about 0.1% to about 10% of a deposition auxiliary polymer, which is a mixture of a hydroxy-terminated urethane polymer and a propylene glycol , wherein the weight / weight ratio of the hydroxy-terminated urethane polymer to the polypropylene glycol is from about 1: 1.5 to about 1.5: 1; (e) from 0% to about 10% of a polymeric thickener, and (f) from approximately 25% to approximately 99.7% water All percentages and ratios used herein are by weight of the total composition and all measurements made are at 25 ° C, unless otherwise designated. invention may comprise, or consist of, essential ingredients, as well as optional ingredients and components described herein.
DESCRIPTION PfiTftTiT-APft PE tA INVENCIC-N The emulsion compositions of the present invention are useful for cleaning the skin and for depositing an active ingredient on the skin during the cleaning process. These compositions are in the form of oil-in-water emulsions, whereby the oily phase and the aqueous phase may contain, in addition to the essential components described herein, a wide variety of ingredients known in the art. The active ingredients are deposited on the skin of the oil phase in the oil-in-water emulsion. The active ingredients for use herein, therefore, will have a solubility parameter of about 7 to about 13. These emulsions are normally used with water to clean the skin. When rinsing with water, these compositions are removed from the surface of the skin along with the soil, oils, bacteria and other foreign material, associated and leave the active ingredients deposited on the skin. The oil-in-water emulsions of the present have advantageous aesthetic properties such as an exquisite and creamy skin feel, not yet greasy. These emulsions can range in a wide consistency from light lotions to heavy creams. These emulsions typically have viscosities in the range of about 100 cps to about 500,000 cps, more preferably from about 1000 cps to about 150,000 cps, and most preferably from about 5,000 cps to about 100,000 cps. The emulsion compositions herein can be extended over a wide range of pH values which can be acidic, basic or neutral depending on the active material or particular active materials used. For example, for acidic active materials, the pH of the composition should be chosen carefully such that it is at or below the pKa of the active ingredient. By standard definitions, the pKa value for a compound is that pH value at which the material is 50 percent dissociated or ionized to produce its conjugate base and a proton (or hydrated proton). Without being limited to any theory when the pH of the formulation is below the pKa of the active ingredient, it is believed that the active ingredient will exist mainly in its un-ionized form, which should increase its subsequent deposit on the skin.
For example, salicylic acid has a pKa that reports 2.97 to 19 ° C in aqueous solution. Therefore, it would be useful to formulate compositions containing salicylic acid at or below a pH of about 2.97 to eliminate ionization and maximize the deposition of the emulsion. See CRC HandbQQk of Chercistry and Phvsics, 57 Edition, page D-150 (1976). For compositions containing salicylic acid it should be from about 2 to about 7, more preferably from about 2.5 to about 5, still more preferably from about 2.5 to about 4, and most preferably from about 2.5 to about 3. Even when the buffers can be used to help maintain the pH of the emulsion compositions, these components are not required but are only optional. (a) ACTIVE GLOBAL The emulsion compositions of the present invention comprise a safe and effective amount of an active ingredient, which is deposited on the surface of the skin during the cleaning process. These emulsions can. contain a mixture of two or more active ingredients. By the term "safe and effective amount" as used herein, it means an amount of an active ingredient sufficiently high to modify the condition to be treated or to provide the benefit of the desired skin, but low enough to avoid serious side effects in a reasonable ratio of benefit to risk within the scope of medical judgment. What is a safe and effective amount of the active ingredient, will vary with the specific active ingredient, the ability of the active ingredient to penetrate through the skin, the age, the state of health and condition of the user's skin and other similar factors . Normally, the active ingredients of the present invention, consist of from about 0.05% to about 20%, more preferably from about 0.1% to about 10% and most preferably from about 1% to about 5%. The active ingredients useful herein have a solubility parameter of from about 7 to about 13, preferably from about 7.5 to about 12.5 and most preferably from about 8 to about 12. The solubility parameters are well known to the formulations with ordinary skill in the art and are routinely used as a guide to determine the compatibilities and solubilities of materials in the formulation process. Without being limited by theory, it is believed that in the choice of active materials with solubility parameters in the ranges designated in the foregoing, that the active ingredients will tend to be hydrophobic, i.e., lipophilic, and therefore more soluble in water. the oil phase of the oil-in-water emulsions of the present invention. The lipophilic nature of the active ingredients should help to increase the deposition of the active ingredient on the skin of an oil-in-water emulsion by rinsing the emulsion with water. Generally, the active ingredients useful herein, will have a solubility in water at 25 ° C of at least about 1 gram per about 100 grams of water. The solubility parameter of a chemical compound, d, is defined as the square root of the density of the cohesive energy for this compound. Normally, a solubility parameter for a compound is calculated from the tabulated values of the additive group contributions for the heat of vaporization and molar volume of the components of that compound, using the following equation: where i2 E¿ = the sum of the heat of vaporization of the contribution of the additive group. is m = the sum of the molar volume of the contributions of the additive group. Standard tabulations of the heat of vaporization and molar volume of the contributions of the additive group to a wide variety of atoms and groups of atoms are collected in Barton, A.F..M. Handbook of Solubility Parameters. CRC Press, Chapter 6, Table 3, pp. 64-66 (1985), which is incorporated herein by reference in its entirety. The solubility parameters of the equation are described in Fedors, R.F., "A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids", Polvmer Enaineerina and Science. vol. 14, no. 2, pp. 147-154 (February 1974), which is incorporated herein by reference in its entirety. The calculated solubility parameters obey the laws of the mixtures, in such a way that the calculated solubility parameter for a mixture of materials is given by the heavy average of the solubility parameters calculated for each component of that mixture, see. Handbook of Chemistry and Physics. 57th Edition, CRC Press, p. C-726 (1976-1977), which is incorporated herein by reference in its entirety. In the formulation, they normally report and use the solubility parameters in units of (cal / crrr) ''. The tabulated values of the contributions of the additive group for the heat of vaporization in Handbook of Solubilitv Parameters are reported in units of kJ / mol. However, these tabulated vaporization heat values are easily converted to cal / mol using the following well-known relationships: 1 J / mol = 0.239006 cal / mol and 1000 J = 1 kJ. ease Gordon, A.J.- et al., The Chemist 's Companion. John Wiley & Sons, pp. 456-463, (1972), which is incorporated herein by reference in its entirety. The solubility parameters can be tabulated for a wide variety of chemical compounds. Fablers of solubility parameters are found in Handbgok gf SolubilitY Parameters »The active ingredients useful herein can be classified by their therapeutic benefit or their postulated form of action. However, it should be understood that the active ingredients useful herein may, in some cases, provide more than one therapeutic benefit or function by means of one or more means of action. Therefore, any of the classifications herein are made for the purpose of convenience are not intended to limit the active ingredient for that particular application or applications listed. Among the classes of active ingredients useful herein, based on therapeutic benefit or mode of action, are the following. Anti-acne active ingredients: Examples of anti-acne active ingredients include keratolytics, such as salicylic acid and resorcinol; retinoids such as retinoic acid and its derivatives (e.g., cis and trans); antibiotics and antimicriobials such as benzoyl peroxide, octopirox, erythromycin and its metal complexes (eg, zinc erythromycin), tetracycline, 2,4,4'-trichloro-2'-hydroxydiphenylether, 3,4,4'-trichlorobanilide, azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, ethyl acetate, clindamycin and eclocycline; cebostatic agents such as flavinoids; alpha and beta hydroxy acids and bile salts such as escimnol sulfate and its derivatives, deoxycholate and cholate. Anti-wrinkle and anti-atrophy active ingredients of the skin: Examples of anti-wrinkle and anti-atrophy active ingredients of the skin include retinoic acid, salicylic acid and skin release agents (e.g., phenol and the like) . Non-steroidal anti-inflammatory active ingredients (NSAIDs): Examples of NSAIDs include the following categories: propionic acid derivatives; acetic acid derivatives; phenamic acid derivatives; biphenylcarboxylic acid derivatives and oxicams. All of these NSAIDs are fully described in U.S. Patent 4,985,459 to Sunshine et al., Issued January 15, 1991, incorporated herein by reference. Examples of useful NSAIDs include acetylsalicylic acid, acetaminophen, ibuprofen, naprofen, benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozin, pranoprofen, miroprofen, thioxaprofen, suprofen, alminoprofen, thiaprofenic acid, fluprofen and bucilloxic acid. Also useful are steroidal, anti-inflammatory drugs including hydrocortisone and the like. Topical Anesthetics: Examples of topical anesthetic drugs include lidocaine, bupivacaine, chloroprocaine, dibucaine, etidocaine, epivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxin, phenol and their pharmaceutically acceptable salts. Antimicrobial and antifungal active ingredients: Examples of antimicrobial and antifungal active ingredients include ß-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amiccation, 2,4,4'-trichloro-2-hydroxy diphenylether, 3, 4,4'-trichlorobanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutol, hexamidine isethionate, metronidazole, penta idine, gentamicin, kanamycin, lineomycin, metacycline, methenamine, minocycline, neomycin, methylmycin, paromomycin, streptomycin, trobamycin, miconazole, tetracycline hydrochloride, erythromycin, zinc erythromycin, erythromycin estolate, erythromycin stearate, amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chlorhexidine hydrochloride, hydrochloride Chlortetracycline, oxytetracycline hydrochloride, hydrochloride indamicin, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, lineomycin hydrochloride, metacycline hydrochloride, methenamine hippurate, methenamine mandelate, minocycline hydrochloride, neomycin sulfate, netilmicin sulfate, parmozin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride, amanfadine sulfate, octopirox, parachloromethaxyleneol, nystatin, tolnaftate and clotri azole. Sunscreen agents: A wide variety of active sunscreening ingredients are useful herein and include those described in US Patent No. 5,087,445 to Haffey et al., Issued February 11, 1992.; 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., in Chapter VIII, pages 189 et seq., of Cos eticg Science nd TechUQlQg ?. all of which are incorporated herein by reference in their entirety. Non-limiting examples of active ingredients for sun protection include those selected from the group consisting of 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N, N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole acid. Sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-i-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 3-benzyldencafor, 3- (4-ethylbenzylidene) camphor, and mixtures thereof. Still other useful sunscreens are those described in U.S. Patent No. 4,937,370 to Sabatelli, issued June 26, 1990; and U.S. Patent No. 4,999,186 to Sabatelli et al., issued March 12, 1991; These two references are incorporated herein by reference in their entirety. The sun protection agents described herein have, in a single molecule, two different chromophore portions which have different spectra of absorption of ultraviolet radiation. One of the chromophore portions absorbs predominantly in the UV radiation range and the other absorbs strongly in the UVA radiation range. These agents for sun protection provide superior efficacy, wider UV absorption, lower skin penetration and long-lasting efficacy relative to conventional sunscreens. Especially preferred examples of these sunscreens include those selected from the group consisting of 4-N, N- (2-ethylhexyl) methylaminobenzoic acid, 2,4-dihydroxybenzophenone ester, 4-N, N- ( 2-ethylhexyl) methylaminobenzoic acid, ester with 4-hydroxydibenzoylmethane, 4-N, N- (2-etxl-hexyl) methylaminobenzoic acid, ester of 2-hydroxy-4- (2-hydroxyethoxy) benzophenone, acid 4,, N- (2-ethylhexyl) -methylaminobenzoic acid ester of 4- (2-hydroxyethoxy) -dibenzoylmethane and their mixtures. Preferred examples of active ingredients useful herein include those selected from the group consisting of salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, acetylsalicylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, cis-retinoic acid, trans-retinoic acid, azelaic acid, arachidonic acid, benzoyl peroxide, tetracycline, ibuprofen, naproxen, hydrocortisone, acetaminophen, erythromycin, zinc erythromycin, resorcinol, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, 2,4,4 '- trichloro-2'-hydroxydiphenylether, 3,4,4'-trichlorocarbanilide, octopirox, lidocaine hydrochloride, clotrimazole, miconazole, neocin sulfate, 2-ethylehexyl p-methoxycinnamate, N, N-dimethyl-p-aminobenzoate 2- ethylhexyl, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-i-butyl-dibenzoylmethane , 4-isopropyl-dibenzoylmethane, 3- benzylidenecamphor, 3- (4-methylbenzylidene) camphor, 4- N, N- (2-ethylhexyl) -methylaminobenzoic acid, 2,4-dihydroxybenzophenone ester, 4, N, N - (2-ethylhexyl) methylaminobenzoic acid with 4-hydroxydibenzoylmethane, 4-N, N- (2-ethylhexyl) methylaminobenzoic acid, 2-hydroxy-4- (2-hydroxyethoxy) benzophenone ester, 4, N, N, N- (2-ethylhexyl) -methyl-isobenzoic acid 4- (2-hydroxyethoxy) dibenzoylmethane and mixtures thereof. More preferred examples of the active ingredients useful herein, include those selected from the group consisting of salicylic acid, acetylsalicylic acid, cis-retinoic acid, trans-retinoic acid, azelaic acid, tetracycline, ibuprofen, naproxen, acetaminophen, hydrocortisone, erythromycin, zinc erythromycin, resorcinol, phenoxyethanol, phenoxypropanol, phenoxy-isopropanol, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-trichlorocarbanilidia, octopirox, p-methoxycinnamate of 3-ethylhexyl, 2-ethylhexyl n-N-dimethyl-p-aminobenzoate, 2-phenylbenzimidazole-5-sulfonice acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-butyl-benzyl - zoylmethane, 4-isopropyldibenzoylmethane, 3-benzylidenecamphor, 3- (4-methylbenzylidene) camphor, 4, N, N- (2-ethylhexyl) -methylaminobenzoic acid ester with 4- (2-hydroxy-ethoxy) dibenzoylmethane and its mixtures More preferred examples of the ingredients useful herein include those selected from the group consisting of salicylic acid, cis-retinoic acid, trans-retinoic acid, azelaic acid, erythromycin, resorcinol, ibuprofen, naproxen, hydrocortisone, phenoxyethanol, phenoxypropanol , phenoxyisopropanol, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-trichlorocarbanilide, 2-ethylhexyl p-methoxycinnamate, N, N-dimethyl-p-aminobenzoate 2- ethylhyexyl, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-i.-butyldibenzoyl ethane, 4-isopropyldibenzoylmethane, 3-benzylidenecamphor, 3- (4-methylbenzylidene) ) camphor, 4- (2-hydroxyethoxy) dibenzoylmethane ester and its mixtures 4, N- (2-ethylhexylmethylaminobenzoic ester) A salicylic acid is a particularly useful active ingredient here. (fr) ÉTERES Y PIETERES MiTOXI ftDQS The compositions of the present invention comprise from about 0.1% to about 25%, preferably from about 0.1% to about 15% and more preferably from about 6% to about 10% of an alkoxylated ether, which is useful for solubilizing the active ingredients in the oil phase of oil-in-water emulsions. The alkoxylated ethers and diethers useful herein generally have a solubility in water of less than about 1 gram per about 100 grams of water at 25 ° C. These compounds are typically formulated in the oil phase of the oil-in-water emulsions as described in the following Examples. The mixtures of alkoxylated ethers and diethers can be used herein. The alkoxylated ethers useful herein can be described by the following general formula R - TCH - CH2 - 0 < fHCH2?) rtH wherein R is selected from the group consisting of H and C 1-30 alkyl, straight chain or branched chain, m is an integer from 0 to about 6, R 1 is selected from the group consisting of methyl and ethyl, and is an integer from about 3 to about 30. Preferably R is selected from the group consisting of straight or branched chain C2-25 alkyl, m is an integer from 0 to about 2, R 'is methyl and n is an integer from about 5 to about 25. Most preferably R is selected from the group consisting of C2-20 alkyl, straight or branched chain, is an integer from 0 to about 1, R 'is methyl and n is a number whole from about 10 to about 20.
Non-limiting examples of the classes of alkoxylated ethers useful herein include propoxylated and butoxylated ethers of alcohols and polyols. These compounds can be described as PPG and PGB alkyl ethers, in which PPG and PBG are the designations commonly used for propylene glycol. and polybutylene glycol, respectively. The average number of PPG or PBG groups in these ethers is commonly given by a designation number after PPG or PBG. For example, PPG-14 butyl ether, would designate a butanol propylene glycol ether, in which the molecule has an average of 14 propylene glycol units. Non-limiting examples of alkoxylated ethers useful herein include PPG-10 butyl ether, PPG-11 butyl ether, PPG-12, butyl ether, PPG-13 butyl ether, PPG-14-butyl ether, PPG-15 butyl ether, PPG-15 butyl ether, PPG- 17 butyl ether, PPG-18 butyl ether, PPG-19 butyl ether, PPG-20 butyl ether, PPG-22 butyl ether, PPG-24 butyl ether, PPG-30 butyl ether, PPG-11 stearyl ether, PPG-15 stearyl ether, PPG-10 oleyl ether, PPG- 7 lauryl ether, PPG-30 isocetyl ether, PPG-10 glyceryl ether, PPG-15 glyceryl ether, PPG-10 butylene glycol ether, PPG-15 butylene glycol, PPG-27 glyceryl ether, PPG-30 cetyl ether, PPG-28 cetyl ether, PPG-10 cetyl ether, PPG- Hexylene glycol ether, PPG-15 hexylene glycol ether, PPG-10, 1,2,6-hexanetriol ether, PPG-15, 1, 2,6-hexanetriol ether and mixtures thereof. Preferred alkoxylated ethers are those selected from the group consisting of PPG-14 butyl ether, PPG-15 stearyl ether, PPG-11 stearyl ether, PPG-20 oleyl ether and its mixtures. Preferred alkoxylated ethers are those selected from the group consisting of PPG-14 butyl ether, PPG-15 stearyl ether, and mixtures thereof. PPG-14 butyl ether is available under the trade name Fluid AP from the Union Carbide Corporation. PPG-15 stearyl ether is available under the trade name Arla ol E from ICI Americas Corporation. Alkoxylated diethers are also useful herein. These compounds can be represented by the general formula: H (OCH2fH) qO- CH2. [cH2] p - CH2 - OffHCHtf wherein each R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6, and each qyr is independently selected such that sum is an integer from about 3 to about 30. Preferential R "is methyl, p is an integer from about 2 to about 4 and qyr are independently selected, such that their sum is an integer from about 5 to about 25. Most preferably R "is methyl, p is an integer of about 2. to about 4, and each qyr are independently selected such that their sum is an integer of from about 10 to about 20. Non-limiting examples of the alkoxylated diethers useful herein include those selected from the group consisting of PPG-10. 1,4-butanediol ether, PPG-12 1,4-butanediol ether, PPG-14 1,4-butanediol ether, PPG-2 butanediol ether, PPG-10 1,6-hexanediol ether, PPG-12 1,6-hexanediol ether, PPG- Hexanodioldiethher, PPG-20 hexanedioldiethier, and mixtures thereof Preferred are those selected from the group consisting of PPG-10 1,4-butanedioliether, PPG-.12 1,4-butanedioliether, PPG-10 1,6-hexanedioldiieter, and PPG-12 h exanodioldiéter, and their mixtures. The most preferred is PPG-10 1,4-butanediol ether. This compound is commercially available under the tradename Macol 57 from PPG / Mazer Corporation.
(C) BMüLSIgIGftPQR The compositions of the present invention, consist of from about 0.1% to about 10%, preferably from about 0.2% to about 5% and more preferably from about 0.25% to about 2.5% of at least one emulsifier. The emulsifier is used herein to emulsify the ingredients of the oil and water phase and to stabilize the resulting emulsion. Although the term "emulsifier" is used herein to describe these materials, this term is not intended to exclude those emulsifiers which also have surfactant properties. Emulsifiers useful herein may include any of a wide variety of nonionic, cationic, anionic and zwitterionic emulsifiers described in the above patents and other references. See McCutcheon's, Detergents and Emulsifieres. North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. 5,011,681 to Ciotti et al., Issued April 30, 1991; U.S. Patent No. 4,421,769 to Dixon et al., issued December 20, 1983; and U.S. Patent No. 3,755,560 to Dickert et al., issued August 28, 1973; These four references are incorporated herein by reference in their entirety. The exact emulsifier chosen will depend on the pH of the composition and the other components present. Suitable types of emulsifiers include tetraalkylammonium salts, glycerin esters, 4-propylene glycol esters, polyethylene glycol fatty acid esters, propylene glycol fatty acid esters, sorbitol esters, sorbitan anhydride esters, carboxylic acid copolymers, esters and glucose ethers, ethoxylated ethers, ethoxylated alcohols, algayl phosphates, polyoxyethylene fatty acid phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof. Preferred herein, especially when the emulsions have a pH of about 2 to about 7, are cationic emulsifiers. A wide variety of cationic emulsifiers and surfactants useful herein are described in U.S. Patent No. 5,151,209 to McCall et al., Issued September 29, 1992; U.S. Patent No. 5,151,210 to Steuri et al., issued September 29, 1992; U.S. Patent No. 5,120,532 to Wells et al., issued June 9, 1992; U.S. Patent No. 4,387,090, issued by Bolich, June 7, 1983; U.S. Patent No. 3,155,591, Hlfer, issued November 3, 1964; U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975; U.S. Patent No. 3,929,461 to Bailey et al., issued May 25, 1976; MeCuteheon 's. Deteraents & Emulsifiers (North American Edition 1979) M.C. Publishing Co.; and Schwartz, et al., Surface Active en es, Their Chemistrv d Te hndQCY, New York: Interscience Publishers, 1949; All documents are incorporated herein by reference in their entirety. Cationic emulsifiers useful herein include cationic ammonium salts such as those having the formula: where R- | , is selected from an alkyl group having from about 12 to about 22 carbon atoms, or aromatic, aryl or alkaryl groups, having from about 12 to about 22 carbon atoms; R2"R3 and R4 are independently selected from hydrogen, an alkyl group having from about 1 to about 22 carbon atoms, or aromatic, aryl or alkaryl groups, having from about 12 to about 22 carbon atoms; and X is an anion selected from chloride, bromide, iodide, acetate, phosphate, nitrate, sulfate, methyl sulfate, ethyl sulfate, tosylate, lactate, citrate, glycolate and mixtures thereof. Additionally, the alkyl groups may also contain ether linkages or substituents hydroxy group or amino group (eg, alkyl groups, ethylene glycol and polypropylene glycol portions) Most preferably, R- | is an alkyl group having from about 12 to about 22 -atoms of carbon, R2 is selected from H or an alkyl group having from about 1 to about 22 carbon atoms; R3 and R4 is independently selected from H or an alkyl group having from about 1 to about 3 carbon atoms; and X is as described in the previous paragraph.
More preferably, R- | is an alkyl group having from about 12 to about 22 carbon atoms; R2, R3 and R4 are selected from H or an alkyl group having from about 1 to about 3 carbon atoms; and X is as previously described. Alternatively, other useful cationic emulsifiers include amino-amides, wherein the structure R- | above is alternatively R5CO- (Chin in which R5 is an alkyl group having from about 12 to about 22 carbon atoms, and n is an integer from about 2 to about 6, more preferably from about 2 to about 4 and greater preferably from about 2 to about 3. Non-limiting examples of these cationic emulsifiers include stearoamidopropyl PG-diammonium phosphate chloride, stearoamidopropylethylimoniate ethanesulfate, stearamidopropyl dimethyl (myristyl acetate) ammonium chloride, stearamidopropyl dimethyltenetethylammonium tosylate, stearamidopropyl dimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate and their mixtures Non-limiting examples of the cationic emulsifiers of the quaternary ammonium salt include those selected from the group consisting of cetylammonium chloride, cetyl onium bromide, laurylammonium chloride, laurylammonium bromide, stearylamide chloride nium, stearylammonium bromide, cetyl dimethyl ammonium chloride, cetyl diimethylammonium bromide, lauryl dimethyl ammonium chloride, lauryl dimethyl ammonium bromide, stearyldimethylammonium chloride, stearyldimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, steariltrimium chloride - tilamonium, stearyltrimethylammonium bromide, lauryldimethylammonium chloride, stearyldimethyl-cetilditalow dimethylammonium chloride, dicetyl ammonium chloride, di-ethyl ammonium bromide, dilaurammonium chloride, diolaurylammonium bromide, distearylammonium chloride, distethylammonium bromide, dicetylmethylammonium chloride, dicetylmethylammonium chloride, dicetylmethylammonium bromide, dilaurylmethylammonium chloride, dilaurylmethylammonium bromide, methylammonium chloride, distearylmethylammonium bromide and mixtures thereof. Additional quaternary ammonium salts include those in which the C12 to C22 alkyl carbon chain is derived from a fatty acid of bait or of a coconut fatty acid. The term "bait" refers to an alkyl group derived from bait fatty acids (usually hydrogenated bait fatty acids), which generally have mixtures of alkyl chains in the range of C16 to C18. The term "coconut" refers to an alguyl group derived from a coconut fatty acid, which generally has mixtures of alkyl chains in the range of C12 to C14. Examples of quaternary ammonium salts, derived from these bait and coconut sources, include dikebo-dimethylammonium chloride, dikebo-dimethylammoniomethyl sulfate, di (hydrogenated bait) dimethylammonium chloride, di (hydrogenated bait) dimethylammonium acetate, dike phosphate - dipropylammonium, dikebo-dimethylammonium citrate, di (coconut alkyl) dimethylammonium chloride, di (coconut alkyl) dimethylammonium bromide, cebammonium chloride, cocoammonium chloride, stearamidopropyl PG-dimonium chloride phosphate, ethanolamidopropylethylimoniate ethoxide , Stearic Rampropyl Dimethyl (Ammonium Myristyl Acetate, Stearamidopropyldimethyltearylammonium Tosylate, Stearamidopropyldimethylammonium Chloride, Stearamidopropyldimethylammonium Lactate, and Their Mixtures The most preferred cationic emulsifiers are those selected from the group consisting of dilauryldimethylammonium chloride, distearyldimethylammonium chloride, dimyristyl dimethyl ammonium chloride , dipalmityldimethylammonium chloride, distearyldimethylammonium chloride, stearamidolpropyl PG-dimonium chloride phosphate, stearamidopropylethylimoniate ethosulfatestearamidepropyl (myristyl acetate) ammonium chloride, stearamidopropyl dimethyltearylammonium tosylate, stearamidopropyldimethylammonium chloride, stearamidopropyldimethylammonium lactate and mixtures thereof. The most preferred cationic emulsifiers are those selected from the group consisting of dilauryl dimethyl ammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, dipalmityldimethylammonium chloride, distearyldimethylammonium chloride, and mixtures thereof. (d) POLYMER TO HELP THE DEPOSIT The compositions of the present invention consist of from 0.1% to about 10%, preferably from about 0.1% to about 10%, more preferably from about 0.25% to about 7.55 and most preferably from about 0.50% to about 5% of a polymer to assist the deposit to increase the deposition of the active ingredient on the skin. Without being limited to any theory, the auxiliary polymer of the deposit is believed to aid in the deposition of the active ingredient from the oil phase of the oil-in-water emulsion whereby the active ingredient is deposited on the skin during the cleaning and assistance procedure. the active agent to adhere to the skin during the rinsing procedure. The auxiliary deposition polymers useful herein are typically formulated in the oil phase of the oil-in-water emulsions, as described in the following examples. A variety of polymers to aid deposition are useful herein and include those selected from the group consisting of hydroxy terminated urethane polymers, propylene glycols and mixtures thereof.
It has been ethical. I am interested in the fact that ßß obtains preferred high-mettlß emulsions when the polymer stops __yud__r _üpoßito is __na ßnacla dß a hydroxy-terminated urine polymer and a propylene glycol.
When these two types of deposition-assisting polymers are used in conjunction, the weight / weight ratio of the hydroxy-terminated urethane polymer to the polypropylene glycol polymer is from about 1: 1.5 to about 1.5: 1, preferably from about 1.25: 1 to about 1: 1 .25, more preferably about 1. 1: 1 to approximately 1: 1. 1 and more preferably approximately 1: 1. poTiTmamfí PE VBS ÍBO tBR? au_Dffi. TM G? T ?? T.O__T The hydroxy-terminated urethane polymers useful as deposit aids herein are those generally described in US Patent No. 5,051,260 to Chess et al., Issued September 24, 1991; U.S. Patent No. 5,045,317 to Chess et al, issued September 3, 1991; and U.S. Patent No. 4,971,800, to Chess et al., issued November 20, 1990; all of which are incorporated herein by reference in their entirety. These hydroxy-terminated urethane compounds are represented by the general formula (it should be understood that this formula represents a linear polymer chain and is illustrated as such, solely by convenience and space restrictions): O H H 0 H- (0- «l) • O - C - H - - M - C n O H H g (O-Rl) ß - O • C - N • R • N - - O • (R ^ -O), wherein R represents an alkyl or alkenyl radical having from about 1 to about 20 carbon atoms or a cycloalkyl or cycloalkenyl radical containing from about 5 to about 10 carbon atoms or a mononuclear or fused aryl ring radical containing about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more C1-C6 alkyl groups, C1-C6 alkoxy, C1-C6 alkoxy, substituted with C1-C6, nitro or amino or halogen atoms; R is the same radical or a different alkyl or alkenyl radical; m is a whole number selected to provide a portion (0-R1) having a molecular weight of from about 40 to about 6000, preferably from about 400 to about 2000; ynyn 'are integers equal or different from 0 to about 30 inclusive, correlated with to provide a hydroxy-terminated urethane compound having a molecular weight of up to about 200,000, preferably from about 220 to about 37,000 and preferably from about 1,000 to about 5000. The hydroxy-terminated urethane compounds are prepared using standard synthetic techniques from the reaction of linear alkylene or polyalkylene glycols or polyethers with monomeric organic diisocyanates. Alkylene or linear polyalkylene glycols or polyethers are represented by the general formula: H- (0-R1) m-0-H where R and m are as described in the preceding paragraph. Specific non-limiting examples of the polyalkylene glycol or polyether reagents include: diethylene glycol, triethylene glycol, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG -18, PEG-20, PEG-32, PEG-40, PPG-9, PPG-12, PPG-15, PPG-17, PPG-20, PPG-26, PPG-30, PPG-34, and polytetramethylene glycols they have molecular weights in the range of about 600 to 6000 similar. The terms "PEG" and "PPG" are the CTFA designations commonly used for polyethylene glycol and polypropylene glycol, respectively. The number after the designation indicates the average number of units of ethylene glycol or polypropylene glycol in the molecule. Also, the polyalkylene glycols or polyether mixtures described above may also be employed to prepare the hydroxy-terminated urethanes useful herein. The monomeric organic diisocyanates are represented by the general formula: O = C = N-R-N = C = 0 wherein R is an alkyl or alkenyl radical having from about one to about 20 carbon atoms or a cycloalkyl or cycloalkenyl radical containing from about 5 to about 10 carbon atoms or a mononuclear or fused ring aryl radical containing about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more C1-C6 alkyl groups, C1-C6 alkoxy, Cl-C6 alkoxy substituted with C1-C6, nitro or amino or halogen atoms. Non-limiting examples of the diisocyanates are aromatic diisocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4-t-butyl-m-phenylene diisocyanate, 4-methoxy-m-phenylene diisocyanate, 4-phenoxy-m-phenylene diisocyanate, 4-chloro -m-phenylene diisocyanate, toluene diisocyanates (either as a mixture of isomers, for example, the commercially available mixture of 80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate, or as individual isomers per se), m-xylidenediisocyanate, p-xylylene diisocyanate, cumen-2,4-diisocyanate, durendiisocyanate, 1,4-naphthylidene diisocyanate, 1,5-naphthylene diisocyanate, 1,8-naphthylidene diisocyanate, 2,6-naphthylene diisocyanate, 1,5-tetrahydronothylene diisocyanate, P, p'-diphenyldiisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4-diphenylhexan-1,6-diisocyanate, "bitolenediisocyanate" (3,3'-dimethyl-4,4'-biphenylene diisocyanate), " dianisidin-ediisocyanate "(3,3'-dimethoxy-4,4'-biphenylene diisocyanate); aliphatic diisocyanates such as methylene diisocyanates, ethylene diisocyanate, tri-tetra-, penta-, hexa-, octa-, nona and decamethylene-omega, omega-diisocyanates, 2-chloro-tr? methylene diisocyanate, 2,3-dimethyltetra-ethylene diisocyanate and the like, as also their mixtures. A preferred hydroxy-terminated urethane polymer useful herein is poly [oxy (methyl-1,2-ethanediyl)], alpha-hydro-omega-hydroxy-, which forms a polymer with 1, 1'-methylene -bis- (4-isocyanatocyclohexane). This material is also known by the CTFA designations as polyol-prepolymer-2 and is commercially available as Topicare 35A from Penederm Inc. through its distributor Barnet Products Corp. (Englewood Cliffs, NJ).
POLYPROPYLENGLICO ES The polypropylene glycols are useful as polymers to aid in the deposit. Polypropylene glycols are polymers which are normally formed from the polymerization of propylene oxide, polypropylene glycol, propylchlorohydrin, propylbromohydrin and other related materials. The polypropylene glycols are represented by the following formula: H (0CH2CH) n0H CH3 wherein n is an integer from about 10 to about 50, preferably wherein n is an integer from about 15 to about 40 and most preferably wherein n is an integer of about 20 to about 34. In the previous structure, even when an isomeric orientation is illustrated for convenience, this illustration is not intended to exclude other isomeric structures. Polypropylene glycols are commonly referred to as PPGs followed by a number that indicates the average number of periodic units in the structure. For example, the PPG-30 would correspond to the above structure, where n has an average value of about 30. Based on this nomenclature, the polypropylene glycols useful herein encompass those designated as PPG-10 to PPG-50, greater preference those designated as PPG-15 to PPG-40, and more preferably those designated as PPG-20 to PPG-34. An especially preferred PPG for use in the compositions herein is PPG-30, which is sold under the trade name Polyglycol P-4000 and is commercially available from Dow Chemical Corporation. (e) PQLIMERICQ THICKENER The compositions of the present invention consist of from 0% to about 10%, preferably from about 0.5% to about 5%, and most preferably from about 1% to about 4% of a polymeric thickener. A wide variety of thickeners can be employed herein with the choice depending on the pH of the formulation and the other chosen components of the emulsion. For compositions having a pH of about 2 to about 7, the thickeners should be stable within this pH range, ie, they should not degrade and should not lose their thickening capacity. Preferred thickeners include those selected from the group consisting of crosslinked polyacrylate polymers, alkyl-modified hydroxyalkyl cellulose polymers, quaternary ammonium hydroxyalkyl cellulose polymers and mixtures thereof.
PQLIACRILAMIDE POLYMERS Polyacrylamide polymers useful as thickeners include both cationic and nonionic polymers, cations being generally preferred. Examples of cationic polymers, useful and cross-linked cationic polyacrylate polymers, are those described in US Pat. No. 5,100,660, Hawe et al., Issued on March 31, 1992; US Patent L +, 649, 1 + 6"+, by Heard, issued July 1, 1969; North American Patent 4,635,206, Farrar et al., Issued May 30, 1969; US Patent 4,626,076, Glover et al., issued December 9, 1966, US Patent 4,599,379 to Flesher et al., issued July 6, 1966, and EP 226,666 to Farrar et al., published July 15, 1967, all the These cationic polymers are high molecular weight materials, containing cationic portions, usually quaternized nitrogen, These polymers can be characterized by the general formula: (A); L (B) , n (C) ", wherein (A) is a dialkylaminoalkyl acrylate monomer or its acid addition salt or quaternary ammonium salt (B), is a dialkylaminoalkyl methacrylate monomer or its addition salt of acid or quaternary ammonium salt (C) is a monomer having a carbon-carbon double bond, 1 is an integer of 0 or greater, is an integer of 0 or greater, n is an integer of O or greater. The monomer (C) can be selected from any of the monomers commonly used. Non-limiting examples of these monomers include ethylene, propylene, butylene, isobutylene, eicosene, maleic anhydride, acrylamide, methacrylamide, maleic acid, acrolein, cyclohexene, et vinyl ether, and methovinyl ether. In the cationic polymers of the present invention IC) it is preferably acrylamide. These polymers () (B), n (C),., Also consist of a crosslinking agent, which is more typically a material containing two or more unsaturated functional groups. In other words, these polymers expressly also intend to include the crosslinking agent in addition to the monomer units of (A), (B) and (C). As is well known to one skilled in the art of polymer science, a crosslinking agent is reacted with the monomeric units of the polymer and incorporated into the polymer so that they form links or covalent.es links, between two or more individual polymer chains, or between two or more sections of the same polymer chain. Non-limiting examples of suitable crosslinking agents include those selected from the group consisting of methyl mercapto-lamides, dialkali-lamon halides, polyalkyl polyether polyhydric alcohols, acellum acrylates, vinyloxyalkyl acrylates and polyfunctional vinylidenes. Specific examples of the crosslinking agents useful herein include those selected from the group consisting of methylebis, lipac, and lamimide., di (met) acplato de et i liclicol, di (met) acr? lick, cyanomethyl acllate, vimloxiet lly acrylate, vinyloptalene ethacrylate, allylpentaeptritol, tpmet i lolpropanodiali lter, allylsucrose, butadiene, isoprene, divinylbenzene, divinyl naphthalene, and vinyl ether, methyl vinyl ether, and acrylic acid. Other reticulators include for aldehyde and glyoxal. Preferred to be used herein as a crosslinking agent, in the methy lenbisacplamide. When the crosslinking agent is present, widely varied amounts thereof may be employed, depending on the desired properties in the final polymer, for example, effect of viscosity. Without being limited to the theory, it is believed that the incorporation of a crosslinking agent in these cationic polymers provides a material that is an agent to give more effective viscosity without negative effects, such as slip resistance and viscosity breaking in the presence of the electrolytes. The crosslinking agent, when present, may consist of about 1 ppm to about 1000 ppm, preferably about 25 ppm to about 500 ppm, more preferably about 100 ppm to about 500 ppm, and more preferably Approximately 250 ppm to approximately 500 ppm of the total weight of the polymer on a weight / weight basis. The polymerization is preferably conducted under known conditions, so that the polymers are soluble in water and have a high molecular weight, generally of 1 million, for example up to 30 million. The intrinsic viscosity of the cross-linked polymer, measured in a sodium chloride solution in a molar at 25 ° C, is generally above 6, preferably, from about 6 to about 14. These cationic polymers can be prepared by the polymerization of an aqueous solution containing from about 20% to about 60% ", generally, from about 25% to about 40% by weight of the monomer in the presence of an initiator (formally redox or thermal) until polymerization ends. When the polymer is going to be crosslinked, a suitable amount of the crosslinking agent is also added to the solution of the monomers to be polymerized to incorporate the crosslinking agent into the polymer In the polymerization reactions, the temperature at General begins low, .gr., approximately 0 ° C 95 ° C. The polymerization can be carried out by forming a reverse phase dispersion of a water phase. of the monomers (and also any of the crosslinking agents) in a non-aqueous liquid, for example mineral oil, and the like. All percentages describing the polymer in this section of the description herein are molars, unless otherwise specified. When the polymer contains acplamide, the molar ratio of the acrylamide, based on the total molar amount of acplamide, dialkylalkyl acrylate and methallylated dialkyl dialkali is generally from about 20% to about 99%, most preferably from approximately 50% to approximately 9U%. When the monomer A is present, the ratio of the monomer (A) to the monomer (B) used in this process, and thus the ratio of the groups A and B in the final polymer, on a molar basis is preferably about 99: 5 to about 15:65, more preferably from about 60:20 to about 20: 60. Alternatively, in another class of procedures, the ratio is about 5:95 to 50:50, ie, the monomer Cationic is mainly metacrical. In these procedures, the ratio is generally achieved on the scale of approximately 5:95 to approximately 25:75. In another alternative class of procedures, the ratio (A) :( B) is from about 50:50 to about 65:15, the cationic monomers being mainly acplato. Preferably the ratio (A) :( B) is from about 60:40 to about 65:15, most preferably from about 75:25 to about 65:15. It is most preferred when monomer (A) is not present and the ratio of monomer (B): monomer (C) is from about 30:70 to about 70:30, preferably from about 40:60 to about 60. : 40 and more preferably approximately 45:55 to about 55:45. A class of cationic polymers which are useful herein are especially preferred, are those which form the general structure (A) L (B), "(C) r, wherein 1 is zero, (B) is meta-plate of di-ethylamino quaternized, the ratio of (B) :( C) is approximately 45:55 to about 55:45, and the optional cross-linking agent is methylenbisacplamide. An example of such a cationic polymer is one that is commercially available as a dispersion in mineral oil (which may also include auxiliary dispersion spans, such as PPS-1 tpdecet-6) under the trade name Bal are "SC92 from Allied Colloids Ltd. (Norfoll ', Virginia) This polymer has the proposed CTFA designation "Polyquaternium 32 (and) Mineral Oil." Another class of cationic polymers useful herein are those that do not contain acrylamide monomer, ie, n is In these polymers, the monomeric components (A) and (B) are as described above.A particularly preferred group of these polymers that do not contain acplamide is one in which 1 is also zero. The polymer is essentially a homopolymer of a dialkylammoalkyl meta-platelet monomer or its quaternary ammonium salt or acid addition salt These dialkylammoalkyl metacrate polymers preferably contain a crosslinking agent as described in the above. A cationic polymer useful herein is one conforming to the general structure (A) L (B) m (C) r) wherein 1 is zero, (B) is dimethyl amine meta-platelet quaternized with methyl, n is zero , and the metilbisacplated crosslinking agent. An example of such homopolymer is commercially available as a mixture containing about 50% of the polymer, about 4% mineral oil and about 6% of PPG-1 tr? Decet-6 as a dispersion aid, from Allied Colloids Ltd, (Narfol.-, VA) under the trade name Saleare "SC95.This polymer has recently been given the CTFA designation of" Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Tr? Decet-6".
ALKYL HYDROXYL ALCOHOL E CELLULQSA The term "alkylhydroxyalkyl cellulose ethers" as used herein means polymer containing a cellulose backbone, ie, a polysaccharide skeleton of periodic glucose units. In these polymers, the hydroxy groups of the cellulose polymer are hydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) to form hydroxyalkylated cellulose which is then modified with a straight chain or branched chain alkyl group of C 10 -C 30 via a linkage. ether. Typically, these polymers are ethers of straight or branched chain alcohols of C 10 -C 30 with hydroxyalkyl celluloses. Examples of alkyl groups useful herein include those selected from the group consisting of stearate, isostearyl, lauplo groups. ipstyl, cetyl, isocetyl, cocoyl (i.e., alkyl groups derived from coconut oil alcohols) palmityl, oleyl, linoleoyl, lmolenyl, phenyloyl, behenyl, and mixtures thereof. Among the preferred alkylalhydroxyalkyl cellulose ethers is the material that is given the CTFA designation of cet i lhydroxyethyl cellulose, which is the ether of the cetyl alcohol and the hydroxyethyl cellulose. This material is sold under the trade name Natrosol CS Plus of the Aqualon Corporation.
POLYMERS OF QUATERNARY AMMONIUM HYDROXYCHLORCELULOSE By the term "quaternary ammonium hydroxyalkyl cellulose polymer" as used herein, we mean polymers that contain a cellulose backbone, ie, a backbone of polysaccharides of periodic glucose units. In these polymers, the hydro groups i of the cellulose polymer are hydroxyalkyl (preferably hydroxyethylated or hydroxypropylated) to form a hydroxyalkylated cellulose, which is further modified with a cationic or protonated quaternary ammonium group. Preferred cationic modification groups are those having at least one C10-20 alkyl chain and two shorter alkyl chains (ie, Cl or C2) in the nitrogen. The substituent on the cellulose polymer can thus be represented as - (X) NRR'R "wherein X is hyoxyalkyl <preferably - OCHBCHa.- or -0CH; i¡CHOHCH; B-), R and R 'are methyl or ethyl, and R "is C10-20 alkyl C, preferably lauplo, esteaplo, or cocoyl (ie, a mixture of alkyl groups derived from coconut oil)]. Alternatively it has been found that when R, R 'and R "are all methyl (ie, the tpmonium group) that useful cellulose polymers are also obtained.In other alternative structures, the substituent on the cellulose polymer can be presented. as - (O-OCI-.saCHa.-NRR 'R "wherein X is hydroxyalkyl (preferably -OCHaCHSA- or -OCHaCHOCH» -), R and R' are methyl or ethyl, and R "is C10 alkyl -20 C preferably lauryl, stearyl, or cocoyl (ie a mixture of alkyl groups derived from coconut oil)] Alternatively it has been found that when R, R 'and R "are all methyl (ie the tri onium group) Useful cellulose polymers are also obtained In still other alternative structures the cationic substituent in the cellulose contains both of the hydroxyethyl and hydroxypropyl groups, such that the portion can be represented as - < OCH-aCH-aO) -CHa , CH0HCH5aNRR'R ", wherein R, R 'and R" are methyl or ethyl and R "is C1 alkyl 0-20 Preferably lauryl, stearyl, or cocoyl (ie, a mixture of alkyl groups derived from coconut oil)] or alternatively wherein R, R 'and R "are all methyl (ie, the trimonium group). Commercially available cationic modified celluloses include: designated polyquaternium-24, by CTFA, which is the quaternary ammonium salt of hydroxyethylcellulose that reacts with an epoxide substituted with lauryldimethylammonium (wherein the formula - (X) ~ QCH: slCHs, -NRR'R ", X is -OCHa-CHa.-, R and R 'are methyl, and R" is stearyl). This material is sold under the trade name Quatrisoft Polymer LM-200 and is available from Amerchol Corporation.
Other commercially available cationic modified celluloses include: laurdimonium hydroxyethylcellulose (wherein in the above formula - (X) NRR'R ", X is -0CH.2CH12-, R and R 'are methyl and R" is lauplo), stearimonium hydroxyethylcellulose, in which in the formula above - (X) NRR'R ", X is, R and R 'are methyl and R" is stearate), and cocodi onium hydro? ethi -cellulose (in which in the formula above - (X) NRR'R ", X is -OCH ^ CH ^, -, R and R 'are methyl and R" is cocoyl). These three materials are known by the trade names Crodacel QL, Crodacel QS, and Crodacel QM, respectively, which are all commercially available from Croda Corp. Other cationic cellulose very useful in the hydroxypropyl cellulose (in which the group of modification in cellulose is - (OCH? aCHa.O) -CHa.CHaHCHí! NRR 'R ", in which RR' are methyl and R" is lauryl), which is available to eat only as Crodacel QL Special, of Croda Corp. Among the preferred hydroxyalkylene cellulose quaternary ammonium polymers is polyquatern? Um-23.
( / ) WATER The emulsions of the present invention, consist of from about 25% to about 99.7%, more preferably from about 65% to about 95%, and most preferably from about 70% to about 90% of water.
OPTIONAL COMPONENTS Each of the water and oil phases of the emulsions can consist of a wide variety of optional components. Typical of such optional components are: FATTY ACIDS An optional component of the present invention is a fatty acid. These fatty acids can be used to increase the viscosity of the emulsion and to provide a soft touch for the finished emulsion. When used herein, these fatty acids may consist of from about 0.1% to about 10%, more preferably from about 0.1% to about 7.5% and most preferably 0.1% to about 5% of the compositions. By the term "fatty acid" is meant any organic acid from natural or synthetic sources having from about 10 to about 40 carbon atoms, more preferably from about 10 to about 30 carbon atoms and more preferably from about 12 carbon atoms. to approximately 22 carbon atoms. The corresponding branched carbon chain materials are also included within this definition of fatty acid. Non-limiting examples of fatty alcohols include those selected from the group consisting of laupco acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, behenic acid, isostearic acid and mixtures thereof. Examples of fatty alcohols are described in CTFR International Cosmetic Ingredient Dictionarv Fourth Edition, which is incorporated herein for reference in its entirety. Also useful are the derivatives of the hydroxy substituted fatty acids described herein. Non-limiting examples of these materials include hydroxystearic acid, hydroxylalic acid, lauric hydroxy acid and mixtures thereof.
FATTY ALCOHOL An optional component of the present invention is a fatty alcohol. These fatty alcohols can be used to increase the viscosity of the emulsion and to provide a soft touch to the finished emulsion. When used herein, these fatty alcohols may consist of from about 0.1% to about 10%, more preferably from about 0.1% to about 7.5% and most preferably from 0.1% to about 5% of the compositions. . By the term "fatty alcohol" is meant any organic alcohol from natural or synthetic sources having from about 10 to about 40 carbon atoms, more preferably from about 10 to about 30 carbon atoms and more preferably from about 12 to about 22 carbon atoms. Branched carbon chain materials are also included within this definition of fatty alcohol, correspondent. Non-limiting examples of fatty alcohols include those selected from the group consisting of lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenic alcohol, ricinoleyl alcohol, behenyl alcohol, and mixtures thereof. Examples of fatty alcohols are described in CTFfl International Cosmetic Ingredient Dictionarv Fourth Edition, which is incorporated herein by reference in its entirety.
HUMIDANTS Another optional component of the compositions of the present invention is a humectant. When used herein, the humectant may be from 0.1% to about 20%, more preferably from about 0.5% to about 10% and more preferably from about 1% to about 5% of the compositions. Although these materials are defined herein as humectants, they may also possess hydration, skin conditioning and other related properties. Examples of humectants useful herein include materials such as urea; guanidine; glycolic acid and glycolate salts (for example, ammonium and quaternary alkylammonium); lactic acid and lactate salts (for example, ammonium and quaternary alkylammon), zabila in any of its variety of forms (for example, zabila gel); polyhydric alcohols such as sorbitol glycerol, low molecular weight polymers (for example, dipolypropylene glycol and tripepropyl glycol), hexanotopol, propylene glycol, butyl glycol, hexyl glycol and the like; polyethylene glycol; sugars and starches; sugar derivatives < the id (eg, alkoxylated glucose); yaluronic acid; what? , starch polyacrylate grafted with starch, such as Sanwet (RTM) IM-1000, IM-1500, and IM-2500 (available from Celanese Superabsorbent Materials, Ports outh, VA); lactamide monoethanolamine; acetamide monoethanolamine; propoxylated glycerol (as described in U.S. Patent No. 4,976,953 to Orr et al., issued Dec. 11, 1990, which is incorporated herein by reference in its entirety); and its mixtures. Preferred humectants useful in the compositions of the present invention are C3-C6 urea, diols and triols, low molecular weight polypropylene glycols and propoxylated glycerin. Preferred humectants include those materials selected from the group consisting of urea, propylene glycol, 1,3-dihydroxypropane, glycerin, butylene glycol, hexymethyl glycol, 1,4-dihydroxyhexane, 1,2,6-hexanetriol, dipropylene glycol, tripropylene glycol and mixtures thereof. . Most preferred are those selected from the group consisting of urea, glycerin, butylene glycol, hexylene glycol, glycerin, dipropylene glycol, triprop and glycol and their mixtures. Most preferred are urea, glycerin and mixtures thereof.
EMOLLIENTS The compositions of the present invention may also include an emollient. Examples of suitable emollients include, but are not limited to, volatile and non-volatile silicone oils (eg, ethylene, cycloethicon, dimethiconol, and the like), highly branched hydrocarbons and non-polar carboxylic acid and alcohol esters and mixtures thereof. The emollients useful in the present invention are further described in U.S. Patent No. 4,919,934 to Dect'ner et al., Issued April 24, 1990, which is incorporated herein by reference in its entirety. The emollients may typically consist of a total of from about 0.5% to about 50%, more preferably from about 0.5% to about 25% and more preferably from about 0.5% to about 15% by weight of the compositions of the compositions. the present invention.
ADDITIONAL INGREDIENTS A variety of additional ingredients can be incorporated into the compositions of the present invention. Non-limiting examples of these additional ingredients include / itamines and their derivatives (eg, tocopherol, tocopherol acetate and the like); other thickening agents (for example polyacrylamide and isoparaffipa of C 3-ii + and lauret-7, available as Sepigel 305 from Seppic Corp., homopolymers of acrylic acid cross-linked with an allyl ether of pentaerythritol or an allyl ether of sucrose, which are known by the carbomer designation by CTFA and are commercially available from BF Goodrich under the trademark Carbopol; and copolymers of C10-30 alkyl acrylates with acrylic acid, alkyl esters of acrylic acid, methacrylic acid, alkyl ethers of methacrylic acid, crosslinked with an allyl ether of sucrose or an allyl ether of pentaerythritol, which are known by the designation CTFA as acrylate / acrylate crospolymers of C10-30 and are commercially available as Carbopol 1342, Pemulen TR-1, and Pemulen TR-2 from BF Goodrich); resins; gums (for example, guar gum, xanthan gum and the like); waxes (synthetic and occurring naturally); polymers to assist the film formation properties and substantivity of the composition (such as a copolymer of eicosene and vinylpyrrolidone, an example of which is available from GAF Chemical Corporation as Ganex V-220R); preservatives to maintain the antimicrobial integrity of the compositions; skin penetration aids such as DMSO, 1-dodecylazacycloheptan-2-one (available as Azone from Upjohn Co.) and the like; artificial tanning ingredients and tanning accelerators such as dihydroxyacetone, tyrosine, tyrosine esters such as ethyl thirosmate and phospho-DOPA); skin whitening agents (or brighteners) including but not limited to hydroquinone, koic acid and sodium metabisulfite; anti-oxidants; chelating agents and eliminators; and aesthetic components such as fragrances, pigments, dyes, essential oils, skin sensitizers, astringents, skin pain relieving agents, skin healing agents and the like, non-limiting examples of these aesthetic components include panthenol and derivatives (for example, ethylapantenol), zabila, pantothenic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, entilo lactate, amamelis distillate, allantoin, bisabalol, dipotassium glycine, and the like.
METHODS FOR SKIN CLEANSING AND DEPOSIT OF ACTIVE INGREDIENT ON THE SKIN SURFACE The emulsion compositions of the present invention are useful for cleaning the skin and also for depositing an active ingredient on the skin during the cleaning process. Normally, an adequate amount of the cleaning composition is applied to the skin to be cleaned. It is preferred to pre-treat the skin with water. Alternatively, a suitable amount of the cleansing composition can be applied to the skin by means of the intermediate application of a cup, sponge or other application device. It has been found that the compositions of the present invention provide their optimal cleaning performance when combined with water during the cleaning process. To complete the cleaning procedure, the composition is rinsed directly from the skin with water, leaving the active ingredient on the surface of the skin. To clean the skin and deposit an active ingredient, an effective amount of the emulsion composition is used. In general, an effective amount of emulsion will depend on the needs and habits of use of the individual. The non-limiting effective amounts are in the range of about 0.5 mg / cm.sup.5 to about 5.0 mg / cm.sup.-5 of area of the skin to be cleaned.
EXAMPLES The following examples further describe and demonstrate the embodiments within the scope of the invention. The examples are given solely for the purpose of illustration and should not be construed as limitations of the present invention, since many variations thereof are possible without departing from the spirit and scope of the invention.
The ingredients are identified by the chemical name or the CTFA name.
EXAMPLES I-Iv CLEANING PRODUCTS CONTAINING SALICILIC ACID A cleaning emulsion containing salicylic acid is prepared by combining the following ingredients using conventional mixing techniques.
Ingredients% Weight / Weight II III IV Water qs 100 os ico QS ICO QSIOO PPG-14 Butyl Ether .0 7.0 ... 7.00 PPG-10 Butanediol 0 0 6.00? Glycerin 3.00 3.00 3.00 3.00 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2. 0 2.00 1.00 0 Stearyl Alcohol 2.00 2.00 1.50 3.00 Cetyl Alcohol 2. 0 2.00 1.50 3. 0 Polyol prepolymer-25a 1.00 .50 2.00 .50 PPG-30 1.00 0.50 0 0.50 Distearil dimet i 1 ammonium chloride 0.50 .50 0.50 1.00 Cetylhydroxyethyl elulosa3 0 0 0.50 0 Urea 0.50 0.50 0 0.50 Menthol 0.20 0.20 0.20 Fragrance 0.60 0.60 0.30 0.60 Disodium EDTA 0.01 0.01 0.01 O. 1 LD? Sponble as Saleare SC95, from Allied Colloids (Suffoll ', VA). Designation proposed by CTFA for poly Cox i (methylene, 2-ethanedyl)] -alpha-hydro-omega-hydroxy-polymer with 1,1'-meth i len-b? S- ( 4-? Soc? Anatoc? Clohe-xano), which is available as Topicare 35A from Penederm Inc. (Foster City, CA) through Barnet Product Corp. (Englewood Cliffs, N3). Applicable as Natrosol CS Plus, from Aqualon Corp (Wilmington, DE). An aqueous phase is first prepared by combining the glyce- pna, disodium EDTA, hydrocarboxylic acid (if any) and water (additional water is added, later in the procedure, when 96% of the water is used appropriately), and then the mixture is heated to 75-60 ° C with stirring. In a separate container, the PPG-14 butyl ether (if any), the PPG-IO butanediol, (if any), the PPG-30 (if any) the hydroxy-terminated urethane polymer are combined with agitation to form an oil phase. Next, salicylic acid is added to this phase in oil which is heated to 75-d0 ° C with agitation. Once the salicylic acid has dissolved, cetyl alcohol, stearyl alcohol and distearyldimethylammonium chloride are added to this phase in oil with stirring. Then, this phase is added to this phase in oil with agitation, the polyquaternium 37 (and) mineral oil (and) PPG-1 tridecet (if any). Right away, the emulsion is formed by adding the oily phase to the aqueous phase with stirring using a homogenization mill. The resulting emulsion is cooled to 40 ° C while mixing. In a separate container, urea is dissolved (if any) in the remaining water and then added to the emulsion with stirring. Then the emulsion is further cooled to 30 ° C and the fragrance (if any) and menthol (if any) are added. Then the emulsion is cooled to room temperature. The resulting emulsions are useful for application to the skin for cleaning purposes. When rinsing the skin, the composition provides salicylic acid and are useful for the treatment of acne, and also for the treatment of wrinkles and other skin conditions related to age.
EXAMPLE V CLEANING PRODUCT CONTAINING IBUPRQFEN A cleaning emulsion containing ibuprofen is prepared by combining the following ingredients using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-14 But i léter 6.00 Glice ina 3.00 Ibuprofen 2.00 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Tpdeceth 2.? O Stearyl alcohol 2. 0 Cetyl Alcohol 2. () Poliolprepol number-2 1.00 PPG-30 1.00 Distearil Chloride dimethylammonium 0.50 Urea 0.50 Menthol 0.20 Fragrance 0.60 Disodium EDTA 0.01 An emulsion is prepared using the general procedure given for Examples I-IV with 2% salicylic acid which is replaced with 2% ibuprofen. The resulting emulsion is used for application to the skin for cleaning purposes. By rinsing the skin, the composition delivers ibuprofen and is useful in providing an anti-inflammatory benefit.
EXAMPLE VI CLEANING PRODUCT CONTAINING 2.4.4 '-TRICL0R0-2' -HIDROXIDIFENILETER A cleaning emulsion containing 2,4,4'-trichloro-2 'hydroxydi phenyl ether (ie, triclosan) is prepared by combining the following ingredients using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-15 Stearyl ether 6.00 Glycerin 3.00 2,4,4'-trichloro-2 '-hydro diphenyl ether 0.50 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2.00 Stearyl Alcohol 2.00 Cetyl Alcohol 2.00 Pol iolprepol number-2 1.00 PPG-30 1.00 Distearil Chloride dimethylammonium 0.50 Urea 0.50 Menthol 0.20 Fragrance 0.60 Disodium EDTA 0.01 An emulsion is prepared using the general procedure given for Examples I-IV with 2% salicylic acid which has been replaced with 0.5% 2,4,4'-trichloro-2'-hydrodiphenyl ether. The resulting emulsion is useful for application to the skin for cleaning purposes. By rinsing the skin, the composition supplies 2,4,4'-tpchloro-2'h? Drox? D? Phenylether to the skin and is useful for treating acne and for providing an anti-microbial benefit.
EXAMPLE VII CLEANING PRODUCT CONTAINING RETINIC ACID A cleaning emulsion containing trans-nitric acid is prepared by combining the following ingredients, using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-14 But i léter 6.00 Gli ce ina 3.00 Trans-ret acid 0.10 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2.00 Stearyl Alcohol 1.50 Cetyl Alcohol 1.50 Pol iolprepolímero-2 1.00 PPG-30 1.00 Distearil Chloride dimet i 1amon io 0.50 Urea 0.50 Fragrance 0.30 Disodium EDTA 0.01 An emulsion is prepared using the general procedure given for Examples I-IV with 2% salicylic acid which is replaced with 0.1% trans-60 acid. retico inoico. The resulting composition is useful for application to the skin for cleaning purposes. By rinsing the skin, the composition provides trans-re-innocuous acid to the skin and is useful in providing treatment for acne, and also for treating wrinkles and other skin conditions related to age.
EXAMPLE VIII CLEANING PRODUCT CONTAINING FEN0XIIS0PR0PAN0L A cleaning emulsion containing phenoxy isopropanol prepared by combining the following ingredients is prepared using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-14 But i léter 0.50 Glicer ina 3.00 Phenoxy isopropanol 6.00 61 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2.00 Stearyl Alcohol 2.00 Cetyl Alcohol 2. 0 Pol iolprepol number-2 1.00 PPG-30 1.00 Distearyl dimethyl ammonium chloride 0.50 Urea 0.50 Menthol 0.20 Fragrance 0.40 Disodium EDTA 0.01 62 An emulsion is prepared using the general procedure given for Examples I-IV with 2% salicylic acid which is replaced with 6% phenoxy isopropanol. The resulting emulsion is useful for application to the skin for cleaning purposes. By rinsing the skin, the composition delivers trans-phenoxy isopropanol to the skin and is useful in providing treatment for acne, and to provide an anti-microbial benefit.
EXAMPLE IX CLEANING PRODUCT CONTAINING CLQTRIMAZOL A cleaning emulsion containing clotpmazole is prepared by combining the following ingredients using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-14 But i léter 6.00 Gli er ina 3. 0 Clortpmazol 1.00 63 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2.00 Stearyl Alcohol 1.50 Alcohol Cet Ilic 1.50 Pol iolprepol number-2 0.50 PPG-30 0.50 Distearil Chloride dimethylammonium 0.50 Urea 0.50 Disodium EDTA 0.01 An emulsion is prepared using the general procedure given for Examples 1-IV with 2% salicylic acid which is replaced with 1% clortrimazole. 64 The resulting emulsion is useful for the application for cleaning purposes. By rinsing the skin, the composition provides clortrimazole to the skin and is useful in providing an anti-fungal benefit.
EXAMPLE X CLEANING PRODUCT CONTAINING SUN PROTECTION A cleaning emulsion containing sun protectants is prepared by combining the following ingredients, using conventional mixing techniques.
Ingredients% Weight / Weight Water QS 100 PPG-14 Butyl Ether 0.10 Glycerin 3.00 p-methoxynamate 2- Etilhe ilo 7.50 Oxybenzone 3.00 65 Polyquaternium 37 (y) Mineral Oil (y) PPG-1 Trideceth 2.00 Stearyl Alcohol 2.00 Cetyl Alcohol 2. 0 Pol iolprepol number-2 1.00 PPG-30 1.00 Distearyl dimethyl ammonium chloride 0.50 Urea 0.50 Menthol 0.20 Fragrance 0. 0 66 Disodium EDTA 0.01 An emulsion is prepared using the general procedure given for Examples I-IV with 2% salicylic acid which is replaced with a mixture of 7.5% 2-ethexyl p-methoxycinnamate and 3% oxybenzone. The resulting emulsion is useful for application to the skin for cleaning purposes. By rinsing the skin, the composition delivers the 2-ethylhexyl p-methoxycinnamate and oxybenzoate to the skin and is useful in providing protection against the sun's ultraviolet rays.

Claims (16)

67 WHAT IS REVINDED IS: 1. An oil-in-water emulsion composition useful for personal cleansing, characterized in that it comprises: (a) from about 0.05% to about 20% of an active ingredient, having a solubility parameter of from about 7 to about 13; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula R - C..2?) NH wherein R is selected from the group consisting of H and straight chain or branched chain alkyl, m is an integer from 0 to about 6, R 'is selected from the group consisting of methyl and ethyl and n is an integer from about 3 to about 30; an alkoxylated diether of the formula H (0CH2CH) Q0- CH2 -! Cr_2 D, - CH2 - 0 (CHCIl2?) RH / • I R "" R "66 wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each q and r are independently selected such that the sum is an integer from about 3 to about 30; (c) from about 0.05% to about 10% of an emulsifier, (d) from about 0% to about 10% of a polymer auxiliary for deposition, (e) from 0% to about 10% of a thickener polymer, and (f) from about 25% to about 99.7% water 2. An emulsion composition according to claim 1, characterized in that the active ingredient is selected from the group consisting of salicylic acid, acid c. -noic acid, trans-retinoic acid, azelaic acid, eptromicin, resorcinol, ibuprofen, naproxen, hydrocortisana, f-enoxethanol, phenoxypropanol, phenoxy isopropanol, 2,4,4'-tr? -chlor-2 'diphenylether -hydroxy, 3,4,4 ' -tr-chlorocarbon, p-methoxycinnamate 2-ethylhexylo, N, Nd? met? lp-aminobenzoate 2-ethexyl, 2-f acid in l-benz imidazole-5-sulfon-ico, octocplene, oxybenzone, salicylate of homomenthyl, octyl salicylate, 4,4'-methoxy? -t.-but i ldibenzoi methane, 4-1soprop ldibenzoyl ethane, 3-benzyl idencanfor, 3 ~ (4-meth i lbenzylidene) -canfor , ester of 4 - N, N - (2 - et i _ hex 11) -meth and the indobenzoic acid of 4- (2-hydroxyethoxy? ) d ibben-zoi l ethane and their mixtures. 9 3. An emulsion composition according to claim 2, characterized in that the emulsifier is a cationic ammonium salt having the formula: R? ~ + - N - R2, x - R4 __, wherein R is an alkyl group having from about 12 to about 22 carbon atoms, Rffi is H or an alkyl group having from about 1 to about 22 carbon atoms, R: 3 and Rt + are independently selected from H or a alkyl group having from about 1 to about 3 carbon atoms, and X is an anion selected from chloride, bromide, iodide, acetate, phosphate, nitrate, sulfate, methylsulfate, etiisulfate, tasilate, lactate, citrate, glycolate and mixtures thereof . 4. An emulsion composition according to claim 3, characterized in that the auxiliary polymer for deposition is selected from the group consisting of urethane polymers terminated by hydroxy, propylene glycols and mixtures thereof. 5. An emulsion composition according to claim 4, characterized in that the hydroxy-terminated urethane polymer of the formula: O H H O 1 (? -Rl) m.- o - C - N - R - N - C? N O H 'H O - (O-Rl) m - O - C - N - R - N - C - O - (R ^ OJm - «I 11 - C U C (Rl-O) m-n '"' < wherein R represents an alkyl or alkenyl radical having from about 1 to about 20 carbon atoms or a cycloalkyl or cycloalkyl radical containing from about 5 to about 10 carbon atoms or a mononuclear or fused mononuclear ring radical which contains from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more C1-C6 alkyl groups, Cl-C0 alkoxy, C1-C6 alkoxy, substituted with C1-C6, nitro or amino or carbon atoms. halogen; Rx is the same radical or a different alkyl or alkenyl radical; is an integer selected to provide a portion (0-R having a molecular weight of about UO to about 6000, and yn 'are integers equal to or different from 0 to about 30 inclusive, correlated with to provide a hydroxy-terminated urethane compound having a molecular weight of from about 220 to about 37,000 6. An emulsion composition according to claim 4, characterized in that the polypropylene glycol is of the formula: H (0CH2CH) n0H CH3 wherein n is an integer from about 10 to about 50. 7. An emulsion composition according to claim 5, characterized in that the alkoxylated ether or alkoxylated diether is selected from the group consisting of PPG-10 butyl ether, PPG -11 butyl ether, PPG 1 2 butyl ether, PPG-13 butyl ether, PPG-14 butyl ether, PPG 15 butyl ether, PPG-ló butyl ether, PPG-17 butyl ether, PPG-16 butyl ether, PPG-19 butyl ether, PPG-20 butyl ether, PPG- 22 butyl ether, PPG-24 butyl ether, PPG-30 butyl ether, PPG-11 esteapléte, PPG-15 stearate, PPG-10 oleyl ether, PPG-7 lauplether, PPG-30 isoceti l ether, PPG-10 gl amyl ether, PPG-15 glyceryl ether , PPG-10 but i tongue, PPG-15 butylene glycol ether, PPG-27 glycerol, PPG-30 cetyl ether, PPG-26 cetyl ether, PPG-10 cetyl ether, PPG-10 hex i lengl icol ether, PPG-15 hexylene glycol ether, PPG-10 1, 2,6-hexane-polyester, PPG-15, 1,2,6-hexane-polyester, PPG-10 1, 4-butand-oleyter, PPG-12, 1,4-butane r, PPG-14 1, 4-butanold? ether, PPG-2 butanedioldieter, PPG-10 1, 6-hexand? old? ether, PPG-12 1,6-he? andioldiéter, PPG-14 hexandioldiéter, PPG-20 hexandioldiéter and their mixtures. 6. An emulsion composition according to claim 7, characterized in that the alkoxylated ether or alkoxylated ether is selected from the group consisting of PPG-14 butyl ether, PPG-15 stearatether, PPG-11 stearate ether, PPG-20 olefin lter, PPG-10 1, 4-butane-oleyter, PPG-12 1,4-butane-old ?, ether-PPG-10 1, 6-hexand-old-ether, and PPG-12-hexanediol-diether, and mixtures thereof. 9. An emulsion composition according to claim 6, characterized in that the alkoxylated ether or alkoxylated diether is selected from the group consisting of PPG-14 butyl ether, PPG-15 stearatether, PPG-10 1, 4-butand? old? ether, and their mixtures. 10. An emulsion composition according to claim 9, characterized in that the cationic e i i f f se se se se se se se a a a a cloruro on on on on on on on on on on on cloruro cloruro cloruro cloruro cloruro cloruro cloruro 10. 10. 10. 10. 10. 10. 10. 10. cloruro Imir ist i ldimet i la on 10, dipal chloride I nd J et i lamon i v and mixtures thereof. 11. An emulsion composition according to claim 10, characterized in that the polymeric thickener is selected from the group consisting of cationic polyacrylamide polymers, alkylhydroxyalkylcellulose ethers, quaternary ammonium hydroxyalkylcellulose polymers and mixtures thereof. 12. An emulsion composition according to claim 11, characterized in that the cationic polyacrylamide polymer is a crosslinked polymer of the formula: (A) .1. (B) m (C) r ,, wherein (A) is a dialkylaminoalkyl acrylate monomer or its acid addition salt to quaternary ammonium salt thereof, (B), is a dialkylaminoalkyl methacrylate monomer or its acid addition salt or quaternary ammonium salt thereof, (C) is acrylamide, 1 is an integer of 0 or greater, m is an integer of 1 or greater, n is an integer of O or greater, and wherein said polymer contains a crosslinking agent and said crosslinking agent is met i len ( bis) acrylamide. 13. An emulsion composition according to claim 11, characterized in that the alkylhydroxycellulose ether is cetyl hydroxyethylcellulose. 14. An emulsion composition according to claim 11, characterized in that the quaternary ammonium hydroxyalkyl cellulose polymer is selected from the group consisting of polyquaternium-2, laurdiamonium hydroxyethyl cellulose, steardiamonium hydroxyethyl cellulose, hydroxyethyl cellulose and cocaine dioxide, and its mixtures. 15. An emulsion composition according to claim 12, further characterized in that it comprises from about 0.1% to about 10% of a fatty alcohol. 16. An emulsion composition according to claim 15, characterized in that the fatty alcohol is selected from the group consisting of lauryl alcohol, ipstolic alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleic alcohol, linolenic alcohol, phenylelic alcohol, behenyl alcohol, and mixtures thereof. 17. An emulsion composition according to claim 16, characterized in that it comprises from about 1% to about 5% of a humectant. 16. An emulsion composition according to claim 17, characterized in that it consists of urea, qlicepna, propagated glyce- pic, butylene glycol, dipropylene glycol, tri- propylene glycol, hexylene glycol and mixtures thereof. 19. An emulsion composition according to claim 20, characterized in that it comprises from about 1% to about 10% of an emollient, selected from the group consisting of valatic oils of silicone, non-volatile silicone oils, hydrocarbons very branched, and their mixtures. 20. An oil-in-water emulsion composition useful for personal cleansing characterized in that it comprises: (a) from about 0.05% to about 20% salicylic acid; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula wherein R is selected from the group consisting of H and straight chain or branched chain alkyl, m is an integer from 0 to about 6, R 'is selected from the group consisting of methyl and ethyl and n is a whole number from about 3 to about 30; an alkoxylated diether of the formula or H (0CH2CH) q0- r ": - JCH?.}. p - CH2 - 0 (CHCH20) rH 'R" k J. F. wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each q and r are independently selected such that the sum is an integer from about 3 to about 30; < c) from about 0.05% to about 10% of an emulsifier; (d) from about 0% to about 10% of an auxiliary polymer for deposition; (e) from 0% to about 10% of a thickener polymer, and (f) from about 25% to about 99.7% water, wherein the composition has a pH from about 2 to about 7. 21. An emulsion composition according to claim 20, characterized in that it has a pH of about 2.5 to about 5. 22. An emulsion composition according to claim 21, characterized in that it has a pH of about 2.5 to about 4. 23. A conformal emulsion composition. ad with claim 22, characterized in that it has a pH of about 2.5 to about 3. 24. An emulsion composition according to claim 23, characterized in that the emulsifier is a cationic ammonium salt having the formula: l -i + R2 -N- R3 j R4 J wherein R ± is an alkyl group having from about 12 to about 22 carbon atoms, R. ^ is H or an alkyl group having from about 1 to about 22 atoms of carbon, R; 3 and Rl + are independently selected from H or an alkyl group having from about 1 to about 3 carbon atoms, and X is an anion selected from chloride, bromide, iodide, acetate, phosphate, nitrate , sulfate, methyl sulfate, ethyl sulfate, tosylate, lactate, citrate, glycolate, and mixtures thereof. 25. An emulsion composition according to claim 24, characterized in that the auxiliary polymer for the deposition is selected from the group consisting of hydroxy terminated urethane polymers, polypropylene glycols and mixtures thereof. 26. An emulsion composition according to claim 25, characterized in that the hydroxy-terminated urethane polymer is of the formula: (O-Rl) m - 0 - C - N - R - N - C - n 'O H II 0 (O-R1) !!,. - 0 - C - M - R - .N - C (R'-O) r ! 0 HH 0"" I ll.! T - N - R - N - C - O - (Hl - O) mi - n '- H wherein R represents an alkyl or alkenyl radical having from about 1 to about 20 carbon atoms or a cycloalkyl or cycloalkylene radical containing from about 5 to about 10 carbon atoms or a mononuclear or fused mononuclear ring radical containing from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more C1-C6 alkyl groups, C1-C6 alkoxy, C1-C6 alkoxy, substituted with C1-C6, nitro or ino or halogen atoms; R is the same radical or a different alkyl or alkenyl radical; m is an integer selected to provide a portion (0-R1) having a molecular weight of about 40 to about 6000, and yn 'are integers equal to or different from 0 to about 30 inclusive, correlated with m to provide a compound finished hydroxy urethane that has a molecular weight of about 220 to about 37.0 < > 0. 27. An emulsion composition according to claim 25, characterized in that the polyglot lengl icol is of the formula: H (0CH2CH) n0H CH3 wherein n is an integer from about 10 to about 50. 26. An emulsion composition according to claim 27, characterized in that the cationic polyacrylamide polymeric thickener is a crosslinked polymer of the formula: (A) t (B) m (C) ", wherein (A) is a monomer of dialkylaminoalkyl acrylate or eu-acid addition salt or quaternary ammonium salt thereof, (B), is a dialkylaminoalkyl methacrylate monomer or its acid addition salt or quaternary ammonium salt thereof, (C) is acrylamide , 1 is an integer of 0 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and wherein said polymer contains a crosslinking agent and said crosslinking agent is methylene (bis) acr i licked. 29. An oil-in-water emulsion composition useful for personal cleansing characterized in that it comprises: (a) from about 0.05% to about 20% of an active ingredient having a solubility parameter of from about 7 to about 13; (b) from about 0.1% to about 25% of an alkoxylated ether of the formula wherein R is selected from the group consisting of H and straight-chain or branched-chain alkyl, m is an integer from 0 to about 6, R 'is selected from the group consisting of methyl and ethyl, and is an integer from about 3 to about 30; an alkoxylated diether of the formula H (0CH2CH) q0- CH2 - [CH1"| ^ - CH2-0 (CHCH2?) RH 'RM' ', Fi¬ wherein R "is selected from the group consisting of methyl and ethyl, p is an integer from about 1 to about 6 and each q and r are independently selected such that the sum is an integer from about 3 to about 30; (c) from about 0.05% to about 10% of an emulsifier; (d) from about 0% to about 10% of an auxiliary polymer for deposition, which is a hydroxy-terminated urethane polymer and a polypropylene glycol in that the weight / weight ratio of the hydroxy-terminated urethane polymer to polypropylene glycol is from about 1: 1.5 to about 1.5: 1; (e) from 0% to about 10% of a polymeric thickener, and (f) from about 25% to approximately 99.7% water. 30. An emulsion composition according to claim 29, characterized in that the hydroxy-terminated urethane polymer is of the formula: O H H, 0 H - (° -Rl) - 0 - C - N - R - Ñ - C- 0 • H, 0 II (O-Rl), • i N - R C - 0 (R1-0) " n '- H wherein R represents an alkyl or alkenyl radical having from about one to about 20 carbon atoms or a cycloalkyl or cycloalkenyl radical containing from about 5 to about 10 carbon atoms or a mononuclear or fused aryl ring radical containing about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more C1-C6 alkyl groups, Cl-Co alkoxy, C1-C6 alkoxy, substituted with C1-C6, nitro or amino or halogen atoms; R is the same radical or a different alkyl or alkenyl radical; m is a whole number selected to provide a portion (0-R having a molecular weight of from about 40 to about 6000, and yn 'are integers equal to or different from 0 to about 30 inclusive, correlated with m to provide a finished urethane compound in hydroxy having a molecular weight of approximately 220 to approximately 37,000, and where the polypropylene glycol is of the formula: H { 0CH2CH) "0H Cr) 3 wherein n is an integer from about 10 to about 50. 31. An emulsion composition according to claim 30, characterized in that the active ingredient is selected from the group consisting of salicylic acid, cis-ret inoic acid, trans -retinoic acid, azelaic acid, epromycin, resorcinol, ibuprofen, naproxen, hydrocortisone, phenoxyethanol, phenapropanol, phenoxy isopropapol, diphenylether 2, 4,4'-tpcloro-2 '-hydroxy, 3,4,4'-tr-chlorocarbamide, 2-ethylhexyl p-methoxyamate, N, Nd? Metl-p-amnobenzoate 2-eti Ihexyl, 2-phenylebenzaminodazole-5-sulphonic acid, octocrylene, oxybenzone, ornyl omilicate silicate, octyl salicylate, 4,4'-methoxy-1-butylbenzoate, 4 - Isopropyl l-dibenzoylmethane, 3-benzyl idenef, 3- (4-methylenebenzylidene Jcanor, 4-, N, N- (2-ethylhexyl) -methylaminobenzoic acid ester of 4- (2-hydroxyethane) dibenzoylmethane, and its mixtures 32. An emulsion composition according to claim 31, characterized in that the emulsifier is a cationic ammonium salt having the formula: where Ra. is an alkyl group having from about 12 to about 22 carbon atoms, Ra is H or an alkyl group having from about 1 to about 22 carbon atoms, R3 and R ^. are independently selected from H or an alkyl group having from about 1 to about 3 carbon atoms, and X is an anion selected from chloride, bromide, iodide, acetate, phosphate, nitrate, sulfate, methylisulf, etiisulfate, tosylate, lactate , citrate, glycolate and their mixtures. 33. An emulsion composition according to claim 32, characterized in that the alkoxylated ether or alkoxylated diether is selected from the group consisting of PPG-10 butyl ether, PPG-11 butyl ether, PPG 12 butyl ether, PPG-13 butyl ether, PPG -14 butyl ether, PPG 15 butyl ether, PPG-16 butyl ether, PPG-17 butyl ether, PPG-16 butyl ether, PPG-19 butyl ether, PPG-20 butyl ether, PPG-22 buffer, PP6-24 but i ether, PPG-30 buter, PPG-11 stearate, PPG-15 stearate, PPG-10 oleyl ether, PPG-7 laurel ether, PPG-30 isocet ether, PPG-10 glycerol, PPG-15 glyceryl ether, PPG-10 butylene glycol ether, PPG-15 butylene glycol ether, PPG-27 glycerol ether, PPG-30 cetyl ether, PPG-26 cetyl ether, PPG-10 cetyl ether, PPG-10 hexylene glycol ether, PPG-15 hexylene glycol ether, PPG-10 1, 2,6-hexanotrol ether, PPG -15, 1,2,6-hexane-polyester, PPG-10 1, 4-butand-oleyter, PPG-12, 1,4-butaned? Old? Ether, PPG-14 1, 4-butanold? Ether, PPG-2 butanodioldiéter, PPG-10 1, 6-hexan d? old? ether, PPG-12 1,6-he? andioldiéter, PPG-14 he? andioldiéter, PPG-20 hexandioldiéter and their mixtures. 34. An emulsion composition according to claim 33, characterized in that the polymeric thickener is selected from the group consisting of polymers of cationic polyaprylamide, alkylhydroxyalkylcellulose ethers, polymers of hydroxyalkylene-1-quaternary ammonium cellulose and mixtures thereof. . 35. An emulsion composition according to claim 34, characterized in that the cationic polycarp lamide polymer is a crosslinked polymer of the formula: (A), (B), "(C) r,, wherein (A) is a dyalkylaminoalkyl acrylate monomer or its acid addition salt or quaternary ammonium salt thereof, (B), is a dialkylaminoalkyl methacrylate monomer or its acid addition salt or quaternary ammonium salt of the same, (C) is acrylamide, 1 is an integer of 0 or greater, is an integer of 1 or greater, n is an integer of 0 or greater, and wherein said polymer contains a cross-linking agent and said cross-linking agent is met ilen (bis) acri lick. 36. An emulsion composition according to claim 34, characterized in that the alkylhydroxycellulose ether is cetyl hydroxyethylcellulose. 37. An emulsion composition according to claim 34, characterized in that the quaternary ammonium hydroxyalkylcellulose polymer is selected from the group consisting of polyquaternium-2, laurdiamonium hydroxyethylcellulose, steardiamonium hydroxyethylcellulose, cocodimonium hydroxyethylcellulose, and mixtures thereof . 36. An emulsion composition according to claim 35, characterized in that the active ingredient is salicylic acid and in which the emulsion has a pH of approximately 2 to approximately 7. 39. An emulsion composition according to claim 36 , characterized in that the emulsion has a pH of about 2.5 to about 3. 40. A method for cleaning the skin and depositing an active ingredient on the surface of the
1. 06 skin, characterized in that the method comprises topically applying and subsequently rinsing the skin with an effective amount of a composition according to claim 1. 41. A method for cleansing the skin and depositing an active ingredient on the surface of the skin , characterized in that the method comprises topically applying and subsequently rinsing the skin with an effective amount of a composition according to claim 20. 4
2. A method for cleansing the skin and depositing an active ingredient on the surface of the skin , characterized in that the method comprises topically applying and subsequently rinsing the skin with an effective amount of a composition according to claim 29. ABSTRACT The present invention relates to oil-in-water emulsion compositions, which are useful for personal cleansing and for depositing an active ingredient on the surface of the skin. The active ingredient in compositions has a solubility parameter of about 7 to about 1
3. A preferred active ingredient is salicylic acid.
MXPA/A/1994/005931A 1993-08-03 1994-08-03 Compositions of oil emulsion in water for personal cleaning MXPA94005931A (en)

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Application Number Priority Date Filing Date Title
US08/100,957 1993-12-02

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MXPA94005931A true MXPA94005931A (en) 2000-07-01

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