WO1998022075A2 - Compositions cosmetiques - Google Patents
Compositions cosmetiques Download PDFInfo
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- WO1998022075A2 WO1998022075A2 PCT/US1997/021470 US9721470W WO9822075A2 WO 1998022075 A2 WO1998022075 A2 WO 1998022075A2 US 9721470 W US9721470 W US 9721470W WO 9822075 A2 WO9822075 A2 WO 9822075A2
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- WIPO (PCT)
- Prior art keywords
- skin
- silicone
- cosmetic composition
- sucrose
- ascorbic acid
- Prior art date
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- IYCHDNQCHLMLJZ-UHFFFAOYSA-N ONC(c1cnccc1)=O Chemical compound ONC(c1cnccc1)=O IYCHDNQCHLMLJZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/676—Ascorbic acid, i.e. vitamin C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Definitions
- the present invention relates to cosmetic compositions.
- cosmetic compositions which provide improved skin lightening and /or evenness efficacy together with skin softness, skin smoothness benefits, and rub-in and absorption characteristics.
- Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure.
- the outermost of these layers, referred to as the stratum corneum is known to be composed of 25nm protein bundles surrounded by 8nm thick layers.
- Anionic surfactants and organic solvents typically penetrate the stratum corneum membrane and, by delipidization (i.e. removal of the lipids from the stratum corneum), destroy its integrity. This destruction of the skin surface topography leads to a rough feel and may eventually permit the surfactant or solvent to interact with the keratin, creating irritation.
- UV ultra-violet
- melanin complex formation in melanocytes located in a basal layer of epidermis.
- Produced melanin is released from dendrites of a melanocyte, then diffused to keratinocytes, resulting in hyper-pigmentation of the skin, including spots, freckles, blotches and unwelcome general darkening and/or unevenness of the basal skin.
- L-ascorbic acids is not limited to components which enriches vitamin C as an essential nutritive element, but is extending in various applications. It is believed that due to the chemical structure and the physiological activities, L-ascorbic acid and its derivatives are useful as a sourcing agent, reductant, antioxidant, bleaching agent, and stabilizer in various chemical reagents, foods and beverages; in pharmaceuticals for susceptive diseases such as preventive and remedy for viral diseases, bacterial diseases and malignant tumors; and further as a reductant, UV-absorbent and melanin- formation inhibitor in cosmetics including skin-refining agent and skin-lightening and/or evenness agent.
- L-ascorbic acid and derivatives thereof tends to give difficulties to various compositions, particularly in skin care products. This is because of unpleasant product aesthetics from L-ascorbic acid (i.e., leaving sticky and draggy feel when applied), deterioration of the physiological activities mainly due to decomposition and oxidation of L-ascorbic acid, or poor physical stability of the compositions.
- the present invention is directed to a cosmetic composition
- a cosmetic composition comprising:
- liquid polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing from about 4 to about 8 hydroxyl groups, and wherein each carboxylic acid moiety has from about 8 to about 22 carbon atoms, and wherein said liquid polyol carboxylic acid ester has a complete melting point of less than about 30°C;
- R 1 is selected from H or CH3, R 2 , R3 and R 4 are independently selected from C1-C20 straight chain or branched chain alkyl, and x is an integer of from 1-20, and compounds having the formula (II): O R 5 — C— ORe (") wherein R 5 is selected from optionally hydroxy or C1-C4 alkyl substituted benzyl and RQ is selected from C1-C20 branched or straight chain alkyl; and mixtures thereof; and (c) an ascorbic acid compound.
- the cosmetic composition of the present invention comprises (a) a liquid polyol carboxylic acid ester, (b) an emollient material, and (c) a lightening and/or evenness agent.
- a liquid polyol carboxylic acid ester for a liquid polyol carboxylic acid ester
- an emollient material for a liquid polyol carboxylic acid ester
- a lightening and/or evenness agent e.g., a lightening and/or evenness agent.
- Such composition provides a pleasant skin lightening and/or evenness together with skin conditioning feeling such as skin softness, skin smoothness benefits, and rub-in and absorption characteristics.
- skin conditioning feeling is an overall sensation of the skin when the product is put onto the skin.
- the products applied onto skin tends to penetrate the stratum corneum of skin, resulting in providing desirable benefits to the skin.
- skin includes any cosmetic conditioning benefit to the skin including, but not limited to, lightening and/or evenness, moisturizing, humectancy (i.e. the ability to retain or hold water or moisture in the skin), emolliency, visual improvement of the skin surface, soothing of the skin, softening of the skin, improvement in skin feel, and the like.
- complete melting point means a melting point as measured by the well-known technique of Differential Scanning Calorimetry (DSC).
- the complete melting point is the temperature at the intersection of the baseline, i.e., the specific heat line, with the line tangent to the trailing edge of the endothermic peak.
- a scanning temperature of 5°C/minute is generally suitable in the present invention for measuring the complete melting points. However, it should be recognised that more frequent scanning rates may be deemed appropriate by the analytical chemist skilled in the art in specific circumstances.
- a DSC technique for measuring complete melting points is also described in US Patent No. 5,306,514, to Letton et al., issued, April 26, 1994, incorporated herein by reference.
- non-occlusive means that the component as so described does not substantially or block the passage of air and moisture through the skin surface.
- An essential component of the cosmetic compositions of the present invention comprises a liquid polyol carboxylic acid ester.
- the liquid polyol carboxylic acid ester herein is present from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 1% to about 10% by weight of the composition.
- the level of polyol ester by weight of the oil in the composition is preferably from about 1% to about 30%, more preferably from about 5% to about 20%.
- the weight ratio of the liquid carboxylic acid polyol ester to the emollient material is preferably in the range of from about 5:1 to about 1 :5, more preferably in the range of from 2:1 to about 1:2.
- the polyol ester preferred for use herein is a non-occlusive liquid or liquifiable polyol carboxylic acid ester.
- These polyol esters are derived from a polyol radical or moiety and one or more carboxylic acid radicals or moieties. In other words, these esters contain a moiety derived from a polyol and one or more moieties derived from a carboxylic acid.
- These carboxylic acid esters can also be derived from a carboxylic acid.
- These carboxylic acid esters can also be described as liquid polyol fatty acid esters, because the terms carboxylic acid and fatty acid are often used interchangeably by those skilled in the art.
- the preferred liquid polyol polyesters employed in this invention comprise certain polyols, especially sugars or sugar alcohols, esterified with at least four fatty acid groups. Accordingly, the polyol starting material must have at least four esterifiable hydroxyl groups.
- preferred polyols are sugars, including monosaccharaides and disaccharides, and sugar alcohols. Examples of monosaccharides containing four hydroxyl groups are xylose and arabinose and the sugar alcohol derived from xylose, which has five hydroxyl groups, i.e., xylitol.
- the monosaccharide, erythrose is not suitable in the practice of this invention since it only contains three hydroxyl groups, but the sugar alcohol derived from erythrose, i.e., erythritol, contains four hydroxyl groups and accordingly can be used. Suitable five hydroxyl group-containing monosaccharides are galactose, fructose, and sorbose. Sugar alcohols containing six -OH groups derived from the hydrolysis products of sucrose, as well as glucose and sorbose, e.g., sorbitol, are also suitable. Examples of disaccharide polyols which can be used include maltose, lactose, and sucrose, all of which contain eight hydroxyl groups. Preferred polyols for preparing the polyesters for use in the present invention are selected from the group consisting of erythritol, xylitol, sorbitol, glucose, and sucrose. Sucrose is especially preferred.
- the polyol starting material having at least four hydroxyl groups is esterified on at least four of the -OH groups with a fatty acid containing from about 8 to about 22 carbon atoms.
- fatty acids include caprylic, capric, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, arachidic, arachidonic, behenic, and erucic acid.
- the fatty acids can be derived from naturally occurring or synthetic fatty acids; they can be saturated or unsaturated, including positional and geometrical isomers. However, in order to provide liquid polyesters preferred for use herein, at least about 50% by weight of the fatty acid incorporated into the polyester molecule should be unsaturated. Oleic and linoleic acids, and mixtures thereof, are especially preferred.
- the polyol fatty acid polyesters useful in this invention should contain at least four fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acid, but it is preferable that the polyester contain no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterified with fatty acid, i.e., the polyol moiety is substantially completely esterified.
- the fatty acids esterified to the polyol molecule can be the same or mixed, but as noted above, a substantial amount of the unsaturated acid ester groups must be present to provide liquidity.
- sucrose fatty triester would not be suitable for use herein because it does not contain the required four fatty acid ester groups.
- a sucrose tetra-fatty acid ester would be suitable, but is not preferred because it has more than two unesterified hydroxyl groups.
- a sucrose hexa- fatty acid ester would be preferred because it has no more than two unesterified hydroxyl groups.
- Highly preferred compounds in which all the hydroxyl groups are esterified with fatty acids include the liquid sucrose octa-substituted fatty acid esters.
- glucose tetraoleate the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof.
- highly preferred polyol fatty acid esters are those wherein the fatty acids contain from about 14 to about 18 carbon atoms.
- the preferred liquid polyol polyesters preferred for use herein have complete melting points below about 30°C, preferably below about 27.5°C, more preferably below about 25°C. Complete melting points reported herein are measured by Differential Scanning Calorimetry (DSC).
- the polyol fatty acid polyesters suitable for use herein can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification of the polyol with methyl, ethyl or glycerol fatty acid esters using a variety of catalysts; acylation of the polyol with a fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. See U.S. Patent No. 2,831 ,854; U.S. Patent No. 4,005,196, to Jandacek, issued January 25, 1977; U.S. Patent No.4,005,196, to Jandacek, issued January 25, 1977.
- Emollient material A second essential component of the cosmetic compositions herein includes an emollient material selected from compounds having the formula (I):
- R 1 is selected from H or CH3
- R 2 , R 3 and R 4 are independently selected from C1-C20 straight chain or branched chain alkyl, and x is an integer of from 1-20, and compounds having the formula (II):
- R5 — C— OR6 ' wherein R 5 is selected from optionally hydroxy or C1-C4 alkyl substituted benzyl and R6 is selected from C1-C20 branched or straight chain alkyl; and mixtures thereof.
- Preferred for use herein include emollients having the general formula (I) and (II) wherein R-j is H, R2, R3, R4, are independently selected from C1-C4 straight chain alkyl and x is 10 to 18, and wherein R5 is unsubstituted benzyl and RQ is C12-C15 alkyl.
- Suitable emollients of the types indicated above include but are not limited to methyl isostearate, isopropyl isostearate, C12-15 alkyl benzoate, isostearyl neopentanoate.
- methyl isostearate particularly preferred for use herein in particularly from the viewpoint of achieving skin softness and smoothness is methyl isostearate, C12-15 alkyl benzoate and mixtures thereof.
- the emollient material is present in the compositions herein at a level of from about 0.1% to about 10%, preferably from about 0.1% to about 5%, especially from about 1% to about 3% by weight of composition.
- Ascorbic acid compound A third essential component of the cosmetic compositions of the present invention is an ascorbic acid compound.
- the ascorbic acid compound is selected depending upon its compatibility with the other ingredients, especially compatibility with the liquid polyol carboxylic acid ester and the emollient material.
- the ascorbic acid compound may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources.
- the ascorbic acid compound is preferably substantially pure, more preferably essentially pure.
- the cosmetic composition of the present invention comprises from about 0.01% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 1% to about 5% of the ascorbic acid compound.
- the high reduction capability of the ascorbic acid compound provides promotion of cell respiration, enzyme activation and antioxidation. Consequently, it is believed that topical application of the ascorbic acid compound will reduce oxidized melanin complex itself and its precursors as well as inhibit tyrosinase activity in melanosone, thereby providing skin benefits such as the prevention of melanin production and the reduction of age spots, blotches and freckles associated with skin hyperpigmentation.
- Ascorbic acid compound as used herein, means a compound having the formula (III):
- V and W are independently -OH; R is - CH(OH)-CH 2 OH; derivatives thereof; and salts of any of the foregoing.
- the ascorbic acid compound useful herein is an ascorbic acid salt.
- “Ascorbic acid salt,” as used herein, means the non-toxic alkali metal, alkalin earth metal and ammonium salts commonly known by those skilled in the art including, but not limited to, the sodium, potassium, lithium, calcium, magnesium, barium, ammonium and protamine salts which are prepared by methods well known in the art.
- the ascorbic acid salt useful herein is a metal ascorbate having the following formula (IV): wherein R 7 and R 8 are independently selected from hydrogen; linear or branched alkyl of 1 to 8 carbons; and M is metal; and x is an integer of from 1 to about 3. More preferably, R 7 and R 8 are independently selected from hydrogen or linear or branched alkyl of 1 to 3 carbons; M is sodium, potassium, magnesium, and calcium.
- Examples of other preferred ascorbic acid salts having the formula (IV) include monovalent metal salts (e.g., sodium ascorbate, potassium ascorbate), divalent metal salts (e.g., magnesium ascorbate, calcium ascorbate) and trivelent metal salts (e.g., aluminium ascorbate) of the ascorbic acid.
- monovalent metal salts e.g., sodium ascorbate, potassium ascorbate
- divalent metal salts e.g., magnesium ascorbate, calcium ascorbate
- trivelent metal salts e.g., aluminium ascorbate
- the ascorbic acid salt useful herein is a water soluble ascorbyl ester having the following formula (V):
- R 9 and R 10 are independently selected from hydrogen, linear or branched alkyl of 1 to 8 carbons; and M is metal; and y is an integer of 1 to 3. More preferably; R 9 and R 10 are independently selected from hydrogen or linear or branched alkyl of 1 to 3 carbons; M is sodium, potassium, magnesium, and calcium.
- Exemplary water soluble salt derivatives include, but are not limited to L- ascorbyl phosphate ester salts exemplifying sodium L-ascorbyl phosphate, potassium L-ascorbyl phosphate, magnesium L-ascorbyl phosphate, calcium L- ascorbyl phosphate, aluminium L-ascorbyl phosphate.
- L-ascorbyl sulfate ester salts can also be used as a water soluble ascorbic acid derivertives.
- Exapmles are sodium L-ascorbyl sulfate, potassium L-ascorbyl sulfate, magnesium L- ascorbyl sulfate, calcium L-ascorbyl sulfate and aluminium L-ascorbyl sulfate.
- the cosmetic composition of the present invention can be applied for any suitable purpose, particularly suitable for the skin.
- the skin care compositions can be in the form of creams, lotions, gels, and the like.
- the cosmetic compositions herein are in the form of an oil-in-water emulsion of one or more oil phases in an aqueous continuous phase, each oil phase comprising a single oily component or a mixture of oily components in miscible or homogeneous form but these different oil phases containing different materials or combinations of materials from each other.
- the overall level of oil phase components in the compositions of the invention is preferably from about 0.1% to about 60%, preferably from about 1% to about 30% and more preferably from about 1% to about 10% by weight.
- the pH of the compositions is preferably from about 6 to about 9, more preferably from about 7 to about 8.0.
- the balance of the composition is water or an aqueous carrier suitable for topical application to the skin.
- the water content of the compositions herein is generally from about 30% to about 98.89%, preferably from about 50% to about 95% and especially from about 60% to about 90% by weight.
- compositions of the invention are preferably in the form of a moisturizing cream or lotion, which can be applied to the skin as a leave-on product.
- the cosmetic composition of the present invention comprises as either all or a portion of the oil phase or oil phases referred to above a first silicone-containing phase comprising a crosslinked polyorganosiloxane polymer and a silicone oil, wherein the composition comprises 0.1% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 0.5% to about 5%, by weight of composition, of the combination of crosslinked silicone and silicone oil.
- the first silicone-containing phase comprises from about 10% to about 40%, more preferably from about 20% to about 30%, by weight of the first silicone-containing phase, of the crosslinked polyorganosiloxane polymer and from about 60% to about 90%, preferably from about 70% to about 80%, by weight of the first silicone-containing phase, of the silicone oil.
- the crosslinked polyorganosiloxane polymer comprises polyorganosiloxane polymer crosslinked by a crosslinking agent.
- Crosslinking agents for use herein include any crosslinking agents useful for the preparation of crosslinked silicones. Suitable crosslinking agents herein include those represented by the following general formula:
- is methyl, ethyl, propyl or phenyl
- crosslinking agent has the general formula:
- , R2 and z are as defined above.
- the crosslinking agent has the following general formula:
- z is in the range of from about 1 to about 1000, preferably from about 1 to about 100.
- the crosslinked polysiloxane polymer preferably comprises from about 10% to about 50%, more preferably from about 20% to about 30%, by weight the crosslinked polysiloxane polymer, of crosslinking agent.
- Suitable polyorganosiloxane polymers for use herein include those represented by the following general formula:
- R-j is methyl, ethyl, propyl or phenyl
- R3 and R4 are independently selected from methyl, ethyl, propyl and phenyl
- R is an end-gap, such as an optionally hydroxy-substituted alkyl group having from 1 to 50 carbon atoms, preferably an alkyl group having from 1 to 5 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms
- p is an integer in the range of from about 1 to about 2000, preferably from about 1 to about 500
- q is an integer in the range of from about 1 to about 1000, preferably from about 1 to about 500.
- , R2, R3, R4, p and q are as defined above.
- suitable polyorganosiloxane polymers for use herein include methyl vinyl dimethicone, methyl vinyl diphenyl dimethicone and methyl vinyl phenyl methyl diphenyl dimethicone.
- the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer having the general formula:
- the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer having the general formula:
- m is in the range of from about 1 to about 1000, preferably from about 200 to about 800.
- the first silicone-containing phase also comprises a silicone oil.
- a silicone oil Any straight chain, branched and cyclic silicones suitable for use in skin care compositions can be used herein.
- the silicone oils can be volatile or nonvolatile. Suitable silicone oils for use herein include silicone oils having a weight average molecular weight of about 100,000 or less, preferably about 50,000 or less.
- the silicone oil is selected from silicone oils having a weight average molecular weight in the range from about 100 to about 50,000, and preferably from about 200 to about 40,000.
- the silicone oil is selected from dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and phenyl methicone, and mixtures thereof, most preferably phenyl methicone.
- Suitable materials for use in the first silicone-containing phase are available under the tradename KSG supplied by Shinetsu Chemical Co., Ltd, for example KSG-15, KSG-16, KSG-17, KSG-18. These materials contain a combination of crosslinked polyoragnosiloxane polymer and silicone oil. Particularly preferred for use herein especially in combination with the organic amphiphilic emulsifier material is KSG-18.
- KSG- 15, KSG-16, KSG-17 and KSG-18 are Cyclomethicone Dimethicone/Vinyl Dimethicone Crosspolymer, Dimethicone Dimethicone/Vinyl Dimethicone Crosspolymer, Cyclomethicone Dimethicone/Vinyl Dimethicone Crosspolymer and Phenyl Trimethicone Dimethicone/Phenyl Vinyl Dimethicone Crosspolymer, respectively.
- compositions herein preferably also comprise a second non-crosslinked silicone-containing phase.
- the second silicone- containing phase is present in a level of from about 0.1% to about 20%, especially from about 0.1% to about 10% by weight of composition.
- Suitable silicone fluids for use in the second silicone-containing phase herein include water-insoluble silicones inclusive of non-volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, and mixtures thereof.
- the second silicone-containing phase comprises a silicone gum or a mixture of silicones including the silicone gum.
- silicone gum means high molecular weight silicone- based fluids having a mass-average molecular weight in excess of about 200,000 and preferably from about 200,000 to about 400,000. Silicone oils generally have a molecular weight of less than about 200,000. Typically, silicone gums have a viscosity at 25°C in excess of about 1 ,000,000 mm 2 /s.
- silicone gums include dimethicones as described by Petrarch and others including US-A-4, 152,416, May 1 , 1979 to Spitzer, et al, and Noll, Walter, Chemistry and Technology of SiliconeSi New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76.
- Silicone gums for use herein include any silicone gum suitable for use in a skin care composition. Suitable silicone gums for use herein are silicone gums having a molecular weight of from about 200,000 to about 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof. Dimethiconol-based silicones suitable for use herein can have the chemical structure (II):
- n is from about 2000 to about 40,000, preferably from about 3000 to about 30,000.
- exemplary fluorosilicones useful herein can have a molecular weight of from about 200,000 to about 300,000, preferably from about 240,000 to about 260,000 and most preferably about 250,000.
- silicone gums include polydimethylsiloxane, polydimethylsiloxane methylvinylsiloxane copolymer, poly dimethylsiloxane diphenyl methylvinylsiloxane copolymer and mixtures thereof.
- the silicone gum used herein can be incorporated into the composition as part of a mixture of silicones.
- the silicone gum preferably constitutes from about 5% to about 40%, especially from about 10% to 20% by weight of the silicone mixture.
- the silicone or silicone mixture preferably constitutes from about 0.1% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 0.1% to about 10% by weight of composition.
- Suitable silicone gum-based silicone mixtures for use in the second silicone-containing phase of the compositions herein include mixtures consisting 5 essentially of:
- the silicone-based carriers suitable for use herein include certain silicone 5 fluids.
- the silicone fluid can be either a polyalkyl siloxane, a polyaryl siloxane, a polyalkylaryl siloxane or a polyether siloxane copolymer. Mixtures of these fluids can also be used and are preferred in certain executions.
- the polyalkyl siloxane fluids that can be used include, for example, polydimethylsiloxanes with viscosities ranging from about 0.65 to o 600,000 mm 2 /s, preferably from about 0.65 to about 10,000 mm 2 /s at 25°C.
- siloxanes are available, for example, from the General Electric Company as the Viscasil (RTM) series and from Dow Corning as the Dow Corning 200 series.
- the essentially non-volatile polyalkylarylsiloxane fluids that can be used include, for example, polymethylphenylsiloxanes, having viscosities of about 5 0.65 to 30,000 mm 2 /s at 25°C.
- These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow
- Corning as 556 Cosmetic Grade Fluid. Also suitable for use herein are certain volatile cyclic polydimethylsiloxanes having a ring structure incorporating from about 3 to about 7 (CH3)2SiO moieties. 0 The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 29, 1970.
- the viscosity of the silicone blend constituting the second fluid phase ranges from about 500 mm 2 /s to about 100,000 mm 2 /s,. preferably from about
- An especially preferred silicone-gum based component for use in the compositions herein is a dimethiconol gum having a molecular weight of from about 200,000 to about 4,000,000 along with a silicone carrier with a viscosity of about 0.65 to 100 mm 2 /s.
- An example of this silicone component is Dow Corning Q2-1403 (85% 5 mm /s Dimethicone Fluid/15% Dimethiconol) and Dow Corning Q2-1401 available from Dow Corning.
- silicone suitable for use in the second silicone-containing phase herein include polydiorganosiloxane-polyoxyalkylene copolymers containing at least one polydiorganosiloxane segment and at least one polyoxyalkylene segment, said polydiorganosiloxane segment consisting essentially of: Rb Si °(4-b)/2 siloxane units wherein b has a value of from about 0 to about 3, inclusive, there being an average value of approximately 2 R radicals per silicon for all siloxane units in the copolymer, and R denotes a radical selected from methyl, ethyl, vinyl, phenyl and a divalent radical bonding said polyoxyalkylene segment to the polydiorganosiloxane segment, at least about 95% of all R radicals being methyl; and said polyoxyalkylene segment having an average molecular weight of at least about 1000 and consisting of from about 0 to about 50 mol percent polyoxypropylene units and from about
- Preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general formula:
- x and y are selected such that the weight ratio of polydiorgano-siloxane segments to polyoxalkalkylene segments is from about 2 to about 8, the mol ratio of a:(a+b) is from about 0.5 to about 1 , and R is a chain terminating group, especially selected from hydrogen; hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy, propoxy, butoxy; benzyloxy; aryloxy, such as phenoxy; alkenyloxy, such as vinyloxy and allyloxy; acyloxy, such as acetoxy, acryloxy and propionoxy and amino, such as dimethylamino. 5
- the number of and average molecular weights of the segments in the copolymer are such that the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in the
- Suitable copolymers are available commercially under the tradenames
- Belsil (RTM) from Wacker-Chemie GmbH, Geschafts Buffalo S, Postfach D-8000 Kunststoff 22 and Abil (RTM) from Th. Goldschmidt Ltd., Tego House, Victoria Road, Ruislip, Middlesex, HA4 OYL, for example Belsil (RTM) 6031 and Abil (RTM) B88183.
- a particularly preferred copolymer for use herein includes Dow Corning DC3225C which has the CTFA designation Dimethicone/Dimethicone
- a third oil phase is present in an amount of from about 0.1% to about 15%, more preferably from about 1% to about 10% by weight of composition.
- the third oil phase can be either a separate phase or can form one phase together with either or both of the first and second silicone
- the third oil phase is a separate phase.
- the third oil phase preferably comprises a non-silicone organic oil, such as a natural or synthetic oil selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, fatty acids and mixtures thereof, which ingredients are useful for achieving emollient cosmetic properties.
- a non-silicone organic oil such as a natural or synthetic oil selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, fatty acids and mixtures thereof, which ingredients are useful for achieving emollient cosmetic properties.
- first oil phase component is preferably essentially silicone-free, i.e., it contains no more than about 10%, preferably no more than about 5% by weight of silicone-based materials. It will be understood that the oil phase may contain, for example, up to about 25%, preferably up to only about 10% of oil phase soluble emulsifier ingredients. Such ingredients are not to be considered as oil
- the overall required HLB of the oil phase is from about 8 to about 12, especially from about 9 to about 11 , required HLB being determined by summing the individual required HLB values for each component of the oil phase multiplied by its W/W percentage in the oil phase
- Suitable first oil phase components for use herein include, for example, optionally hydroxy-substituted C8-C50 unsaturated fatty acids and esters thereof, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol and cetyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalane, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), lanolin and lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil,
- the mineral oils, petrolatums, unsaturated fatty acids and esters thereof and mixtures thereof are particularly preferred.
- Preferred embodiments herein comprise from about 0.1% to about 10% by weight of an unsaturated fatty acid or ester.
- Preferred unsaturated fatty acids and esters for use herein are optionally hydroxy substituted C8-C50 unsaturated fatty acids and esters, especially esters of ricinoleic acid.
- the unsaturated fatty acid or ester component is valuable herein in combination with the liquid crystal- forming emulsifier for improving the skin feel and rub-in characteristics of the compositon.
- Highly preferred in this respect is cetyl ricinoleate.
- a further preferred component of the compositions herein is an organic amphiphilic surfactant which is capable of forming smectic lyotropic crystals in product or when the product is being applied to the skin at ambient or elevated temperatures.
- the amphiphilic surfactant is capable of forming liquid crystals at a temperature in the range from about 20°C to about 40°C.
- the amphiphilic surfactant is capable of forming smectic lyotropic liquid crystals.
- liquid crystals may not be identifiable on the skin surface or stratum corneum.
- the amphiphilic surfactant is preferably present at a level of from about 0.1% to about 20%, preferably from about 0.1% to about 10%, by weight.
- liquid-crystal forming amphiphilic surfactants suitable for use herein contain both hydrophilic and lipophilic groupings and exhibit a marked tendency to adsorb at a surface or interface, i.e. they are surface-active.
- Amphiphilic surface-active materials for use herein include nonionic (no charge), anionic (negative charge), cationic (positive charge) and amphoteric (both charges) based on whether or not they ionize in aqueous media.
- liquid crystals are also referred to as anisotropic fluids, a fourth state of matter, surfactant association structure or mesophases. Those terms are often used interchangeably.
- the term "lyotropic" means a liquid crystalline system containing a polar solvent, such as water.
- the liquid crystals used herein are preferably lamellar, hexagonal, rod or vesicle structures or mixtures thereof.
- the liquid crystalline phase utilized in the compositions of the invention can be identified in various ways. A liquid crystal phase flows under shear and is characterised by a viscosity that is significantly different from the viscosity of its isotropic solution phase. Rigid gels do not flow under shear like liquid crystals.
- liquid crystals when viewed with a polarized light microscope, liquid crystals show identifiable birefringence, as, for example, planar lamellar birefringence, whereas when isotropic solutions and rigid gels are viewed under polarized light, both show dark fields.
- organic amphiphilic surfactant preferred for use herein can be described as a liquid semi-solid or waxy water-dispersible material having the formula X-Y where X represents a hydrophilic, especially nonionic moiety and Y represents a lipophilic moiety.
- Organic amphiphilic surfactants suitable for use herein include those having a weight average HLB (Hydrophilic Lipophilic Balance) in the range from about 2 to about 12, preferably from about 4 to about 8.
- HLB Hydrophilic Lipophilic Balance
- Preferred organic amphiphilic surfactants employed herein have a long saturated or unsaturated branched or linear lipophilic chain having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic or alkyl phenyl chains.
- the hydrophilic group of the amphiphilic material forming the liquid crystal phase is a nonionic group, a polyoxyethylene, a polyglycerol, a polyol ester, oxyalkylated or not, and, for example, a polyoxyalkylated sorbitol or sugar ester, can be employed.
- hydrophilic group of the amphiphilic surfactant forming the liquid crystal phase is an ionic group, advantageously there can be used, as the hydrophilic group, a phosphatidylcholine residue as found in lecithin.
- Hydrophilic moieties suitable for use herein are selected from:
- R (C2 R4 ⁇ ) ⁇ OH wherein R 1 is C12-C30 linear or branched alkyl or alkenyl and x averages from about 0 to about 20, preferably from about
- polyol esters and polyalkoxylated polyol esters and mixtures thereof, the polyols preferably being selected from sugars, C2-C6 alkylene glycols, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols and polypropylene glycols and wherein the polyalkoxylated polyol esters contain from about 2 to about 20 preferably from about 2 to about 4 moles of alkylene oxide (especially ethylene oxide) per mole of polyol ester;
- amphiphilic surfactants suitable for the use herein include
- Suitable amphoteric surfactants include, for example, N-alkyl amino acids (e.g., sodium N-alkylaminoacetate) and N-lauroylglutamic acid cholesterol ester (e.g., Eldew CL-301 Ajinomoto).
- N-alkyl amino acids e.g., sodium N-alkylaminoacetate
- N-lauroylglutamic acid cholesterol ester e.g., Eldew CL-301 Ajinomoto
- anionic surfactants include, for example, acylglutamates (e.g., disodium N-lauroylglutamate); sarcosinates (e.g., sodium lauryl sarcosinate. Grace, Seppic); taurates (e.g., sodium lauryl taurate.
- acylglutamates e.g., disodium N-lauroylglutamate
- sarcosinates e.g., sodium lauryl sarcosinate.
- Grace, Seppic Seppic
- taurates e.g., sodium lauryl taurate.
- carboxylic acids and salts e.g., potassium oleate; potassium laurate; potassium-10-undecenoate; potassium 11 -(p-styryl)- undecanoate
- ethoxylated carboxylic salts e.g., sodium carboxy methyl alkyl ethoxylate
- ether carboxylic acids phosphoric acid esters and salts (e.g., lecithin; DEA-oleth-10 phosphate)
- acyl isethionates e.g., sodium 2- lauroyloxyethane sulfonate
- alkane sulfonates e.g., branched sodium x-alkane sulfonate (x/1); sulfosuccinates (e.g., sodium dibutyl sulfosuccinate, sodium di-2- pentyl sulfosuccinate, Sodium di-2-ethylbutyl
- Nonlimiting examples of cationic surfactants include, for example, alkyl Imidazolines (e.g., alkyl hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline (supplier Akzo, Finetex and Hoechst)); ethoxylated amines (e.g., PEG-n alkylamine, PEG-n alkylamino propylamine, poloxamine, PEG- cocopolyamine, PEG-15 tallow amine); alkylamines (e.g., dimethyl alkylamine; dihydroxyethyl alkylamine dioleate).
- alkyl Imidazolines e.g., alkyl hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline (supplier Akzo, Finetex and Hoechst)
- ethoxylated amines e.g., PEG-n alkylamine, PEG-n alky
- Cationic surfactants herein also include, for example, quaternaries such as alkylbenzyl dimethylammonium salts (e.g., stearalkonium chloride); alkyl betaines (e.g., dodecyl dimethyl ammonio acetate, oleyl betaine); heterocylic ammonium salts (e.g., alkylethyl morpholinium ethosulfate); tetraalkylammonium salts (e.g., dimethyl distearyl quaternary ammonium chloride (Witco)); bis-isostearamidopropyl hydroxypropyl diammonium chloride (Schercoquat 21 AP from Scher Chemicals); 1.8-bis (decyldimethylammonio)-3, 6 dioxaoctane ditosylate.
- alkylbenzyl dimethylammonium salts e.g., stearalkonium chloride
- Nonlimiting examples of nonionic surfactants include, for example, ethoxylated glycerides; monoglycerides (e.g., monoolein; monolinolein; monolaurin; 1-dodecanoyl-glycerol monolaurin; 1 , 13-docosenoyl-glycerol monoerucin); diglyceride fatty acid (e.g., diglycerol monoisostearate Cosmol 41 , fractionated.
- monoglycerides e.g., monoolein; monolinolein; monolaurin; 1-dodecanoyl-glycerol monolaurin; 1 , 13-docosenoyl-glycerol monoerucin
- diglyceride fatty acid e.g., diglycerol monoisostearate Cosmol 41 , fractionated.
- polyglyceryl esters e.g., triglycerol monooleate (Grindsted TS-T122), diglycerol monooleate (Grindsted TST-T101); polyhydric alcohol esters and ethers (e.g., sucrose cocoate, cetostearyl glucoside (Montanol, Seppic), ⁇ octyl glucofuranoside esters, alkyl glucoside such C-JQ-C16 (Henkel)); diesters of phosphoric acid (e.g., sodium dioleyl phosphate); alkylamido propyl betaine (e.g., cocoamido propyl betaine); amide: (e.g., N-(dodecanoylaminoethyl)-2-pyrrolidone); amide oxide (e.g., 1 , 1- dihydroperfluorooctyldimethylamine oxide, do
- Preferred organic amphiphilic surfactants for use herein are nonionic amphiphilic surfactants having a hydrophilic moiety selected from polyol esters and polyalkoxylated polyol esters, and mixtures thereof, the polyols preferably being selected from sugars, C2-C6 alkylene glycols, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols and polypropylene glycols and wherein the polyalkoxylated polyol esters contain from about 2 to about 20 preferably from about 2 to about 4 moles of alkylene oxide (especially ethylene oxide) per mole of polyol ester, and a lipophilic moiety selected from long saturated or unsaturated branched chain or linear lipophilic chains having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic
- Highly preferred organic amphiphilic surfactants for use herein are selected from polyhydric alcohol esters and ethers.
- Especially preferred amphiphilic surfactants for use herein are sugar esters and polyalkoxylated sugar esters.
- the sugar esters for use in this invention can be classified as hydrocarbyl and alkyl polyoxyalkylene esters of cyclic polyhydroxy saccharides wherein one or more of the hydroxyl groups on the saccharide moiety is substituted with an acyl or polyoxyalkylene group.
- Hydrocarbyl sugar esters can be prepared in well-known fashion by heating an acid or acid halide with sugar, i.e., by a simple esterification reaction.
- the sugars employed in the preparation of the sugar esters include monosaccharides, di-saccharides and oligo-saccharides well known in the art, for example, the dextrorotatory and levorotatory forms of glucose, fructose, mannose, galactose, arabinose and xylose.
- Typical di-saccharides include maltose, cellibiose, lactose, and trehalose.
- Typical tri-saccharides include raffinose and gentianose. The di-saccharides are preferred for use herein, especially sucrose.
- Sucrose can be esterified at one or more of its eight hydroxyl groups to provide the sucrose esters useful herein.
- sucrose When sucrose is combined with an esterification agent in a 1 :1 mole ratio, sucrose monoesters are formed; when the ratio of esterification agent to sucrose is 2:1 , or greater, the di-, tri-, etc., esters are formed, up to a maximum of the octa-ester.
- Preferred sugar esters herein are those prepared by the esterification of sugars at a mole ratio of esterification agentsugar of 1 :1 and 3:1 i.e., the mono- acyl and di- or higher acyl sugar esters.
- the respective esters of di-saccharide sugars, especially sucrose, wherein the acyl groups contain from about 8 to about 20 carbon atoms are especially preferred.
- Preferred sugar esters herein are sucrose cocoate, sucrose monooctanoate, sucrose monodecanoate, sucrose monolaurate, sucrose monomyristate, sucrose monopalmitate, sucrose monostearate, sucrose monooleate, sucrose monolinoleate, sucrose dioleate, sucrose dipalmitate, sucrose distearate, sucrose dilaurate and sucrose dilinoleate, and mixtures thereof.
- Sucrose cocoate has been found to be particularly efficacious in the compositions herein.
- the mono- and di-acyl esters preferably comprise at least about 40%, more preferably from about 50% to about 95% by weight of the total sugar ester mixture.
- Other sugar esters suitable for use in the compositions of this invention are the alkyl polyoxyalkylene sugar esters wherein one hydroxyl group is substituted with a Cg-C-ig alkyl group and wherein one or more of the hydroxyl groups on the sugar molecule are replaced by an ester or ether substituent containing the moiety [(CH2) ⁇ -O]y wherein x is an integer from 2 to about 4, preferably 2, and wherein y is an integer from about 1 to about 50, preferably 8 to 30 polyoxyalkylene substituents.
- sugar esters wherein the polyoxyalkylene substituent is a polyoxyethylene substituent containing from about 8 to about 30 polyoxyethylene groups.
- Such materials wherein sorbitan is the sugar moiety are commercially available under the tradename "Tweens".
- Such mixed esters can be prepared by first acylating a sugar at a 1:1 mole ratio with a hydrocarbyl acid halide followed by reaction with the corresponding polyoxyalkylene acid halide or alkylene oxide to provide the desired material.
- the simple polyoxyalkylene ester of di-saccharides, especially sucrose, wherein the polyoxyalkylene groups contain up to about 20 alkylene oxide moieties are another useful class of sugar esters herein.
- a preferred sugar ester of this class is sorbitol trioleate ethoxylated with 20 moles of ethylene oxide.
- Mixtures of sugar esters with other polyol esters, eg. glycerol esters, are also suitable for use herein, for example, Palm Oil Sucroglyceride (Rhone-Poulenc).
- lecithin refers to a material which is a phosphatide.
- Naturally occurring or synthetic phosphatides can be used.
- Phosphatidylcholine or lecithin is a glycerine esterified with a choline ester of phosphoric acid and two fatty acids, usually a long chain saturated or unsaturated fatty acid having 16-20 carbons and up to 4 double bonds.
- Other phosphatides capable of forming lamellar or hexagonal liquid crystals can be used in place of the lecithin or in combination with it.
- phosphatides are glycerol esters with two fatty acids as in the lecithin, but the choline is replaced by ethanolamine (a cephalin), or serine ( -aminopropanoic acid; phosphatidyl serine) or an inositol (phosphatidyl inositol). While the invention herein is exemplified with lecithin, it is understood that these other phosphatides can be used herein.
- lecithins can be used.
- American Lecithin Company supplies a Nattermann Phospholipid, Phospholipan 80 and Phosal 75.
- Other lecithins which can be used alone or in combination with these are: Actifla Series, Centrocap series, Central Ca, Centrol series, Centrolene, Centrolex, Centromix, Centrophase and Centrolphil Series from Central Soya; Alcolec and Alcolec 439- C from American Lecithin; Canaspersa from Canada Packers, Lexin K and Natipide from American Lecithin; and L-Clearate, Clearate LV and Clearate WD from the W.A. Cleary Co.
- Lecithins are supplied dissolved in ethanol, fatty acids, triglycerides and other solvents. They are usually mixtures of lecithins and range from 15% to 50% of the solution as supplied.
- Natural lecithins are derived from oilseeds such as sunflower seeds, soybeans, safflower seeds and cottonseed. The lecithins are separated from the oil during the refining process.
- the organic amphiphilic surfactant has been found to be especially valuable herein for improving the stability and skin feel of the compositions of the invention.
- amphiphilic surfactant is preferably incorporated into the composition in an amount of from about 0.1 % to about 20% , preferably from about 0.1% to about 10%, and more preferably from about 0.1% to about 8% by weight of composition.
- a fatty acid ester blend based on a mixture of sorbitan or sorbitol fatty acid ester and sucrose fatty acid ester, the fatty acid in each instance being preferably C8-C24, more preferably C ⁇ ⁇ o-C2 ⁇ -
- the preferred fatty acid ester emulsifier from the viewpoint of moisturisation is a blend of sorbitan or sorbitol C15-C20 fatty acid ester with sucrose C-10-C16 fatty acid ester, especially sorbitan stearate and sucrose cocoate. This is commercially available from ICI under the trade name Arlatone 2121.
- a highly preferred ingredient of the compositions herein is urea which is preferably present in a level of from about 0.1% to about 20%, more preferably from about 0.5% to about 10% and especially from about 1% to about 5% by weight of composition.
- the oil phase and organic amphiphilic surfactant when present are premixed in water at a temperature above the Kraft Point of the organic amphiphilic surfactant (but preferably below about 60°C) to form a liquid crystal/oil in water dispersion prior to addition of the urea.
- the urea is found to be especially effective herein in combination with the amphiphilic emulsifier surfactant and the polyol fatty acid polyester for providing outstanding skin moisturisation and softening in the context of an oil-in-water skin care emulsion composition. Moreover, it is surprisingly found that the urea is rendered more stable to hydrolytic degradation, thereby allowing an increase in compositional pH.
- compositions of the present invention can also comprise a safe and effective amount of a vitamin B3 compound.
- the compositions of the present invention preferably comprise from about 0.01% to about 10%, more preferably from about 0.1% to about 5%, even more preferably from about 0.5% to about 5%, and still more preferably from about 1% to about 5%, most preferably from about 2% to about 5%, of the vitamin B3 compound .
- vitamin B3 compound means a compound having the formula:
- R is - CONH2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or - CH2OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing.
- CONH2 i.e., niacinamide
- COOH i.e., nicotinic acid
- CH2OH i.e., nicotinyl alcohol
- Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
- Suitable esters of nicotinic acid include nicotinic acid esters of C1-C22, preferably C ⁇
- the alcohols are suitably straight-chain or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic), and substituted or unsubstituted.
- the esters are preferably non-vasodilating.
- non-vasodilating means that the ester does not commonly yield a visible flushing response after application to the skin in the subject compositions (the majority of the general population would not experience a visible flushing response, although such compounds may cause vasodilation not visible to the naked eye).
- Non-vasodilating esters of nicotinic acid include tocopherol nicotinate and inositol hexanicotinate; tocopherol nicotinate is preferred.
- derivatives of the vitamin B3 compound are derivatives of niacinamide resulting from substitution of one or more of the amide group hydrogens.
- Nonlimiting examples of derivatives of niacinamide useful herein include nicotinyl amino acids, derived, for example, from the reaction of an activated nicotinic acid compound (e.g., nicotinic acid azide or nicotinyl chloride) with an amino acid, and nicotinyl alcohol esters of organic carboxylic acids (e.g., C1 - C18).
- nicotinuric acid C8H8N2O3
- nicotinyl hydroxamic acid C6H6N2O2
- nicotinyl alcohol esters include nicotinyl alcohol esters of the carboxylic acids salicylic acid, acetic acid, glycolic acid, palmitic acid and the like.
- vitamin B3 compounds useful herein are 2- chloronicotinamide, 6-aminonicotinamide, 6-methylnicotinamide, n-methyl- nicotinamide, n,n-diethylnicotinamide, n-(hydroxymethyl)-nicotinamide, quinolinic acid imide, nicotinanilide, n-benzylnicotinamide, n-ethylnicotinamide, nifenazone, nicotinaldehyde, isonicotinic acid, methyl isonicotinic acid, thionicotinamide, nialamide, 1 -(3-pyridylmethyl) urea, 2-mercaptonicotinic acid, nicomol, and n
- vitamin B3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Company (St. Louis, MO); ICN Biomedicals, Inc. (Irvin, CA) and Aldrich Chemical Company (Milwaukee, Wl).
- vitamin B3 compounds may be used herein.
- Preferred vitamin B3 compounds are niacinamide and tocopherol nicotinate. Niacinamide is more preferred.
- salts, derivatives, and salt derivatives of niacinamide are preferably those having substantially the same efficacy as niacinamide in the methods of regulating skin condition described herein. Salts of the vitamin B3 compound can also be useful herein.
- Nonlimiting examples of salts of the vitamin B3 compound useful herein include organic or inorganic salts, such as inorganic salts with anionic inorganic species (e.g., chloride, bromide, iodide, carbonate, preferably chloride), and organic carboxylic acid salts (including mono-, di- and tri- C1 - C18 carboxylic acid salts, e.g., acetate, salicylate, glycolate, lactate, malate, citrate, preferably monocarboxylic acid salts such as acetate).
- anionic inorganic species e.g., chloride, bromide, iodide, carbonate, preferably chloride
- organic carboxylic acid salts including mono-, di- and tri- C1 - C18 carboxylic acid salts, e.g., acetate, salicylate, glycolate, lactate, malate, citrate, preferably monocarboxylic acid salts such as acetate.
- Wenner "The Reaction of L-Ascorbic and D-losascorbic Acid with Nicotinic Acid and Its Amide", J. Organic Chemistry, VOL. 14, 22-26 (1949), which is incorporated herein by reference. Wenner describes the synthesis of the ascorbic acid salt of niacinamide.
- the ring nitrogen of the vitamin B3 compound is substantially chemically free (e.g., unbound and/or unhindered), or after delivery to the skin becomes substantially chemically free ("chemically free” is hereinafter alternatively referred to as "uncomplexed”). More preferably, the vitamin B3 compound is essentially uncomplexed. Therefore, if the composition contains the vitamin B3 compound in a salt or otherwise complexed form, such complex is preferably substantially reversible, more preferably essentially reversible, upon delivery of the composition to the skin. For example, such complex should be substantially reversible at a pH of from about 5.0 to about 6.0. Such reversibility can be readily determined by one having ordinary skill in the art.
- the vitamin B3 compound is substantially uncomplexed in the composition prior to delivery to the skin.
- Exemplary approaches to minimizing or preventing the formation of undesirable complexes include omission of materials which form substantially irreversible or other complexes with the vitamin B3 compound, pH adjustment, ionic strength adjustment, the use of surfactants, and formulating wherein the vitamin B3 compound and materials which complex therewith are in different phases. Such approaches are well within the level of ordinary skill in the art.
- the vitamin B3 compound contains a limited amount of the salt form and is more preferably substantially free of salts of a vitamin B3 compound.
- the vitamin B3 compound contains less than about 50% of such salt, and is more preferably essentially free of the salt form.
- the vitamin B3 compound in the compositions hereof having a pH of from about 4 to about 7 typically contain less than about 50% of the salt form.
- the vitamin B3 compound may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources.
- the vitamin B3 compound is preferably substantially pure, more preferably essentially pure. 4.
- the compositions of the present invention also contain a retinoid.
- the vitamin B3 compound and retinoid provide unexpected benefits in regulating skin condition, especially in therapeutically regulating signs of skin aging, more especially wrinkles, lines, and pores. Without intending to be bound or otherwise limited by theory, it is believed that the vitamin B3 compound increases the conversion of certain retinoids to trans-retinoic acid, which is believed to be the biologically active form of the retinoid, to provide synergistic regulation of skin condition (namely, increased conversion for retinol, retinol esters, and retinal).
- the vitamin B3 compound unexpectedly mitigates redness, inflammation, dermatitis and the like which may otherwise be associated with topical application of retinoid (often referred to, and hereinafter alternatively referred to as "retinoid dermatitis").
- retinoid dermatitis also referred to, and hereinafter alternatively referred to as "retinoid dermatitis"
- the combined vitamin B3 compound and retinoid tend to increase the amount and activity of thioredoxin, which tends to increase collagen expression levels via the protein AP-1. Therefore, the present invention enables reduced active levels, and therefore reduced potential for retinoid dermatitis, while retaining significant positive skin conditioning benefits.
- higher levels of retinoid may still be used to obtain greater skin conditioning efficacy, without undesirable retinoid dermatitis occurring.
- retinoid includes all natural and/or synthetic analogs of Vitamin A or retinol-like compounds which possess the biological activity of Vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds.
- the retinoid is preferably retinol, retinol esters (e.g., C2 - C22 alkyl esters of retinol, including retinyl palmitate, retinyl acetate, retinyl proprionate), retinal, and/or retinoic acid (including all-trans retinoic acid and/or 13-cis-retinoic acid), more preferably retinoids other than retinoic acid.
- retinol retinol esters
- retinyl esters e.g., C2 - C22 alkyl esters of retinol, including retinyl palmitate, retinyl acetate, retinyl proprionate
- retinal and
- Suitable retinoids 5 are tocopheryl-retinoate [tocopherol ester of retinoic acid (trans- or cis-), adapalene ⁇ 6-[3-(1-adamantyl)-4-methoxyphenyl]-2-naphthoic acid ⁇ , and tazarotene (ethyl 6-[2-(4,4-dimethylthiochroman-6-yl)-ethynyl]nicotinate).
- One or more retinoids may be used herein.
- Preferred retinoids are retinol, retinyl palmitate, retinyl acetate, retinyl proprionate, retinal and combinations thereof.
- ⁇ o More preferred are retinol and retinyl palmitate.
- the retinoid may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources.
- the retinoid is preferably substantially pure, more preferably essentially pure.
- compositions of this invention may contain a safe and effective amount of the retinoid, such that the resultant composition is safe and effective for regulating skin condition, preferably for regulating visible and/or tactile discontinuities in skin, more preferably for regulating signs of skin aging, even more preferably for regulating visible and/or tactile discontinuities in skin texture 0 associated with skin aging.
- the compositions preferably contain from or about 0.005% to or about 2%, more preferably 0.01% to or about 2%, retinoid.
- Retinol is most preferably used in an amount of from or about 0.01% to or about 0.15%; retinol esters are most preferably used in an amount of from or about 0.01% to or about 2% (e.g., about 1%); retinoic acids are most preferably used in an 5 amount of from or about 0.01% to or about 0.25%; tocopheryl-retinoate [tocopherol ester of retinoic acid (trans- or cis), adapalene ⁇ 6-[3-(1-adamantyl)-4- methoxyphenyl]-2-naphthoic acid ⁇ , and tazarotene are most preferably used in an amount of from or about 0.01% to or about 2%.
- the vitamin B3 compound is preferably used in an amount of 0 from or about 0.1% to or about 10%, more preferably from or about 2% to or about 5%.
- a pH buffering agent can be present in the cosmetic composition of the present invention.
- the pH buffering agent tends to prevent decomposition of the 5 ingredients, particularly ascorbic acid and its derivatives, leading to maximising product stability.
- An optimum pH is subject to the selection of the ascorbic acid compound.
- the cosmetic composition includes magnesium L-ascorbyl phosphate
- the optimum pH of the composition is around 7.0 to 8.0.
- Suitable pH buffering agents herein include acetate, phosphate, citrate, triethanolamine and carbonate.
- a combination of foregoing agent are often employed to adjust a specific pH optimized for the composition.
- Total level of the pH buffering ingredients are 0.01 to 5.0 %, preferably, 0.5 to 2.0 % in the component.
- the cosmetic composition of the present invention can also include a variety of antioxidants to improve product stability, especially for the purpose for preventing oxidation of ascorbic acid and its derivatives.
- Preferred antioxidants are d-delta tocopherol, tocopherol derivatives such as tocopherol acetate, sulfites, and sulfates.
- the levels of the antioxidant agents are 0.01 to 5.0 %, preferably 0.1 to 1.0 % in the composition. 7.
- a wide variety of other components can optionally be formulated into the cosmetic composition for the use of skin composition. These include a humectant, a gelling agent, and the like can be added together with the above.
- the skin composition herein may further include a humectant for the use of skin care composition. Suitable humectants for use herein include sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose derivatives, hexanetriol, glycerine, glycine, hyaluronic acid, arginine, Ajidew (NaPCA), water-soluble polyglycerylmethacrylate lubricants and panthenols.
- a preferred humectant herein is glycerine (sometimes known as glycerol or glycerin). Chemically, glycerine is 1 ,2,3-propanetriol and is a product of commerce. One large source of the material is in the manufacture of soap. Glycerine is especially preferred in the compositions of the invention from the viewpoint of boosting moisturisation. Also preferred for use herein is butylene glycol. Particularly preferred from the viewpoint of boosting moisturisation is a combination of glycerine and urea.
- the humectant is preferably present at a level of from about 0.1% to about 20%, more preferably from about 1% to about 15%, and especially from about 5% to about 15% by weight of composition.
- Lubrajel Suitable polyglycerylmethacrylate lubricants for use in the compositions of this invention are available under the trademark Lubrajel (RTM) from Guardian Chemical Corporation, 230 Marcus Blvd., Hauppage, N.Y. 11787.
- Lubrajels can be described as hydrates or clathrates which are formed by the reaction of sodium glycerate with a methacrylic acid polymer. Thereafter, the hydrate or clathrate is stabilized with a small amount of propylene glycol, followed by controlled hydration of the resulting product.
- Lubrajels are marketed in a number of grades of varying glycerate: polymer ratio and viscosity. Suitable Lubrajels include Lubrajel TW, Lubrajel CG and Lubrajel MS, Lubrajel WA, Lubrajel DV and so-called Lubrajel Oil.
- At least part (up to about 5% by weight of composition) of the humectant can be incorporated in the form of an admixture with a particulate lipophilic or hydrophobic carrier material.
- the carrier material and humectant can be added either to the aqueous or disperse phase.
- the cross-linked hydrophobic polymer is preferably in the form of a copolymer lattice with at least one active ingredient dispersed uniformly throughout and entrapped within the copolymer lattice.
- the hydrophobic polymer can take the form of a porous particle having a surface area (N2.BET) in the range from about 50 to 500, preferably 100 to 300m2.g-1 and having the active ingredient absorbed therein.
- the cross-linked hydrophobic polymer is preferably present in an amount of from about 0.1% to about 10% by weight and is preferably incorporated in the external aqueous phase.
- the active ingredient can be one or more or a mixture of skin compatible oils, skin compatible humectants, emollients, moisturizing agents and sunscreens.
- the polymer material is in the form of a powder, the powder being a combined system of particles.
- the system of powder particles forms a lattice which includes unit particles of less than about one micron in average diameter, agglomerates of fused unit particles of sized in the range of about 20 to 100 microns in average diameter and aggregates of clusters of fused agglomerates of sizes in the range of about 200 to 1 ,200 microns in average diameter.
- the powder material of this embodiment can be broadly described as a cross-linked "post absorbed" hydrophobic polymer lattice.
- the powder preferably has entrapped and dispersed therein, an active which may be in the form of a solid, liquid or gas.
- the lattice is in particulate form and constitutes free flowing discrete solid particles when loaded with the active material.
- the lattice may contain a predetermined quantity of the active material.
- a suitable polymer has the structural formula:
- the hydrophobic polymer is a highly crosslinked polymer, more particularly a highly cross-linked polymethacrylate copolymer.
- the material is manufactured by the Dow Corning Corporation, Midland. Michigan, USA, and sold under the trademark POLYTRAP (RTM). It is an ultralight free-flowing white powder and the particles are capable of absorbing high levels of lipophilic liquids and some hydrophilic liquids while at the same time maintaining a free- flowing powder character.
- the powder structure consists of a lattice of unit particles less than one micron that are fused into agglomerates of 20 to 100 microns and the agglomerates are loosely clustered into macro-particles or aggregates of about 200 to about 1200 micron size.
- the polymer powder is capable of containing as much as four times its weight of fluids, emulsions, dispersion or melted solids.
- Adsorption of actives onto the polymer powder can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active is added to the powder and the spoon is used to gently fold the active into the polymer powder.
- Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel containing the polymer and then tumbling the materials until a consistency is achieved. More elaborate blending equipment such as ribbon or twin cone blenders can also be employed.
- the preferred active ingredient for use herein is glycerine.
- the weight ratio of humectant : carrier is from about 1 :4 to about 3: 1.
- Microsponges 5647 is also suitable as a highly cross-linked polymethacrylate copolymer. This takes the form of generally spherical particles of cross-linked hydrophobic polymer having a pore size of from about 0.01 to about 0.05 ⁇ m and a surface area of 200-300nr ⁇ 2/g. Again, it is preferably loaded with humectant in the levels described above. 8. Hydrophilic thickening agent
- the skin composition of the present invention may also include a hydrophilic thickening agent for the use of skin care composition.
- the hydrophilic thickening agent is present at a level preferably from about 0.01% to about 10%, more preferably from about 0.02% to about 5%.
- the hydrophilic thickening agent preferably has a viscosity (20°C, Brookfield RVT) of at least about 4000 mPa.s, more preferably at least about 10,000 mPa.s and especially at least 20,000 mPa.s.
- hydrophilic thickening agents can generally be described as water-soluble or colloidally water-soluble polymers, and include cellulose ethers (e.g.
- Suitable hydrophilic thickening agent useful for the present invention is a colloidally water dispersible inorganic clay thickening agent (colloidal clay thickener).
- colloidal clay thickeners include, but not limited to, kaolinite, montmorillonite, zeoiyte, hectrite, smectite, saponite.
- the preferred colloidal clay thickener is a synthetic hectrite (Trade Name: Laponite) which is chemically identified as hydrous magnesium silicate.
- Peptizers including pyrophosphate, sulfate, acrylate, carbonate and hosphate are preferrably added with the foregoing clay thickeners when a water phase contain a high level of electrolyte.
- hydrophilic thickening agents are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 3.00% of a crosslinking agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 941, Carbopol 950, Carbopol 954, Carbopol 980, Carbopol 951 and Carbopol 981.
- Carbopol 934 is a water- soluble polymer of acrylic acid crosslinked with about 1 % of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule.
- suitable for use herein are hydrophobically-modified cross- linked polymers of acrylic acid having amphipathic properties available under the Trade Name Carbopol 1382, Carbopol 1342, Carbopol ETD2020, and Pemulen TR-1 (CTFA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer).
- a most preferred polymer is Carbopol ETD2020.
- a combination of the polyalkenyl polyether cross-linked acrylic acid polymer and the hydrophobically modified cross-linked acrylic acid polymer is also suitable and is preferred for use herein.
- the gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures. 9.
- panthenol moisturizer such as D-panthenol
- keratolytic agents/desquamation agents such as salicylic acid
- proteins and polypeptides and derivatives thereof water-soluble or solubilizable preservatives preferably at a level of from about 0.1% to about 5%, such as Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, EDTA, Euxyl (RTM) K400, Bromopol (2-bromo-2-nitropropane-1 ,3-diol) and phenoxypropanol; anti-bacterials such as Irgasan (RTM) and phenoxyethanol (preferably at levels of from 0.1% to about 5%); soluble or colloidally-soluble moisturising agents such as hylaronic acid and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000,
- the cosmetic composition herein can be also applied to a sunscreening composition.
- sunscreening agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11 , 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17, 1991 ; U.S. Patent No. 5,073,371 , to Turner et al. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology.
- sunscreens which are useful in the compositions of the instant invention are those selected from 2-ethylhexyl p-methoxycinnamate, 2- ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2- phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789, and mixtures thereof.
- sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra.
- One of the chromophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range.
- sunscreens include those selected from 4-N,N-(2- ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4- N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4- hydroxydibenzoylmethane, 4-N.N- (2-ethylhexyl)methylaminobenzoic acid ester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)- methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.
- the sunscreens can comprise from about 0.5% to about 20% of the compositions useful herein. Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema. See Federal Register. Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
- the compositions of the present invention can additionally comprise from about 0.1% to about 5% by weight of aluminium starch octenylsuccinate. Aluminium starch octenylsuccinate is the aluminium salt of the reaction product of octenylsuccinic anhydride with starch and is commercially available under the trade name from Dry Flo National Starch & Chemical Ltd.
- Dry Flo is useful herein from the viewpoint of skin feel and application characteristics.
- Others for the sunscreens herein include pigments which, where water- insoluble, contribute to and are included in the total level of oil phase ingredients.
- Pigments suitable for use in the compositions of the present invention can be organic and/or inorganic. Also included within the term pigment are materials having a low colour or lustre such as matte finishing agents, and also light scattering agents. Examples of suitable pigments are iron oxides, acyglutamate iron oxides, ultramarine blue, D&C dyes, carmine, and mixtures thereof. Depending upon the type of composition, a mixture of pigments will normally be used.
- the preferred pigments for use herein from the viewpoint of moisturisation, skin feel, skin appearance and emulsion compatibility are treated pigments.
- the pigments can be treated with compounds such as amino acids, silicones, lecithin and ester oils.
- Cosmetic compositions of the present invention are prepared from the following ingredients using conventional formulating techniques.
- Fatty acid ester of sugar 1 A C1-C30 monoester or polyester of sugars and one or more carboxylic acid moieties as described herein, preferably a sucrose polyester in which the degree of esterification is 7-8, and in which the fatty acid moieties are C18 mono- and/or di-unsatu rated and behenic, in a molar ratio of unsaturates:behenic of 1 :7 to 3:5, more preferably the octaester of sucrose in which there are about 7 behenic fatty acid moieties and about 1 oleic acid moiety in the molecule, e.g., sucrose ester of cottonseed oil fatty acids, e.g., SEFA Cottonate.
- sucrose ester of cottonseed oil fatty acids e.g., SEFA Cottonate.
- compositions above described are suitably made as follows:
- the embodiments disclosed and represented by the previous examples have many advantages. For example, they can provide improved skin feel such as skin lightening and/or evenness with skin smoothness, skin softness and skin care characteristics together with reduced greasiness and excellent rub-in and fast absorption characteristics.
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Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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JP10523950A JP2000505108A (ja) | 1996-11-22 | 1997-11-21 | 化粧用組成物 |
BR9713412-0A BR9713412A (pt) | 1996-11-22 | 1997-11-21 | Composição cosmética adequada para aplicação tópica à pele ou cabelo e processo de tratamento cosmético |
AU53608/98A AU726831B2 (en) | 1996-11-22 | 1997-11-21 | Cosmetic compositions |
CA002272634A CA2272634A1 (fr) | 1996-11-22 | 1997-11-21 | Compositions cosmetiques |
EP97950667A EP0941043A2 (fr) | 1996-11-22 | 1997-11-21 | Compositions cosmetiques |
CO98028759A CO4940355A1 (es) | 1997-05-23 | 1998-05-21 | Composiciones cosmeticas que proveen eficacia mejorada de aclaracion y/o uniformidad de la piel junto con ventajas de suavidad y tesura de la piel |
ARP980102391A AR015697A1 (es) | 1997-05-23 | 1998-05-22 | Composicion cosmetica util para aplicacion topica a la piel y metodo cosmetico de tratamiento de la piel |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB9624305.0 | 1996-11-22 | ||
GBGB9624305.0A GB9624305D0 (en) | 1996-11-22 | 1996-11-22 | Cosmetic compositions |
GBGB9710697.5A GB9710697D0 (en) | 1997-05-23 | 1997-05-23 | Cosmetic compositions |
GB9710697.5 | 1997-05-23 |
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WO1998022075A2 true WO1998022075A2 (fr) | 1998-05-28 |
WO1998022075A3 WO1998022075A3 (fr) | 1998-08-06 |
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PCT/US1997/020566 WO1998022085A1 (fr) | 1996-11-22 | 1997-11-13 | Compositions cosmetiques |
PCT/US1997/021470 WO1998022075A2 (fr) | 1996-11-22 | 1997-11-21 | Compositions cosmetiques |
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PCT/US1997/020566 WO1998022085A1 (fr) | 1996-11-22 | 1997-11-13 | Compositions cosmetiques |
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EP (2) | EP0941057A1 (fr) |
JP (2) | JP2001504486A (fr) |
KR (2) | KR20000057166A (fr) |
AU (2) | AU734338B2 (fr) |
BR (1) | BR9713412A (fr) |
CA (2) | CA2272306A1 (fr) |
CZ (1) | CZ181199A3 (fr) |
WO (2) | WO1998022085A1 (fr) |
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DE10128911A1 (de) * | 2001-06-15 | 2002-12-19 | Beiersdorf Ag | Verwendung von Ascorbinsäure zur Herstellung angiogenetisch wirksamer topischer Zubereitungen |
DE10128910A1 (de) * | 2001-06-15 | 2002-12-19 | Beiersdorf Ag | Verwendung von Wirkstoffkombinationen aus Arginin und Ascorbinsäure zur Hautstraffung |
US6759033B2 (en) | 2000-06-22 | 2004-07-06 | Access Business Group International Llc | Method for slowing the decomposition of a cosmetic composition |
US20070141003A1 (en) * | 2005-12-21 | 2007-06-21 | L'oreal | Cosmetic composition with a volumizing effect |
EP2275080A1 (fr) * | 2004-11-10 | 2011-01-19 | Cognis IP Management GmbH | Procédé de fabrication d'esters partiels d'hydrates de carbone |
EP1756077A4 (fr) * | 2004-04-23 | 2012-01-25 | M M P Inc | Systeme d'emulsion a cristaux liquides multi-lamellaires |
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GB9818123D0 (en) * | 1998-08-19 | 1998-10-14 | Procter & Gamble | Cosmetic compositions |
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WO2009107062A2 (fr) | 2008-02-25 | 2009-09-03 | The Procter & Gamble Company | Lotions capillaires comportant des polyesters de sucrose |
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US9676696B2 (en) | 2009-01-29 | 2017-06-13 | The Procter & Gamble Company | Regulation of mammalian keratinous tissue using skin and/or hair care actives |
CN106232097B (zh) | 2014-04-23 | 2020-08-07 | 宝洁公司 | 用于保湿皮肤的化妆品组合物 |
JP6419661B2 (ja) * | 2015-08-22 | 2018-11-07 | クローダジャパン株式会社 | 皮膚外用剤組成物および該皮膚外用剤組成物を含有する皮膚外用剤 |
JP6608310B2 (ja) * | 2015-09-16 | 2019-11-20 | 株式会社ファンケル | 水中油型乳化化粧料 |
WO2021130349A1 (fr) | 2019-12-23 | 2021-07-01 | Kaffe Bueno Aps | Compositions cosmétiques comprenant des mélanoïdines |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE19913427A1 (de) * | 1999-03-25 | 2000-09-28 | Wella Ag | Verwendung von reduzierenden Verbindungen zur Verstärkung und Strukturverbesserung von Keratin enthaltenden Materialien |
US6759033B2 (en) | 2000-06-22 | 2004-07-06 | Access Business Group International Llc | Method for slowing the decomposition of a cosmetic composition |
DE10128818A1 (de) * | 2001-06-15 | 2002-12-19 | Beiersdorf Ag | Verwendung von Wirkstoffkombinationen aus Ascorbinsäure und einem oder mehreren Biochinonen zur Herstellung angiogenetisch wirksamer topischer Zubereitungen |
DE10128911A1 (de) * | 2001-06-15 | 2002-12-19 | Beiersdorf Ag | Verwendung von Ascorbinsäure zur Herstellung angiogenetisch wirksamer topischer Zubereitungen |
DE10128910A1 (de) * | 2001-06-15 | 2002-12-19 | Beiersdorf Ag | Verwendung von Wirkstoffkombinationen aus Arginin und Ascorbinsäure zur Hautstraffung |
EP1756077A4 (fr) * | 2004-04-23 | 2012-01-25 | M M P Inc | Systeme d'emulsion a cristaux liquides multi-lamellaires |
EP2275080A1 (fr) * | 2004-11-10 | 2011-01-19 | Cognis IP Management GmbH | Procédé de fabrication d'esters partiels d'hydrates de carbone |
US9730879B2 (en) | 2004-11-10 | 2017-08-15 | Cognis Ip Management Gmbh | Method for producing carbohydrate partial esters |
US20070141003A1 (en) * | 2005-12-21 | 2007-06-21 | L'oreal | Cosmetic composition with a volumizing effect |
US9320693B2 (en) * | 2005-12-21 | 2016-04-26 | L'oreal | Cosmetic composition with a volumizing effect |
US10220223B2 (en) | 2005-12-21 | 2019-03-05 | L'oreal | Cosmetic composition with a volumizing effect |
Also Published As
Publication number | Publication date |
---|---|
KR20000069087A (ko) | 2000-11-25 |
CA2272634A1 (fr) | 1998-05-28 |
EP0941057A1 (fr) | 1999-09-15 |
WO1998022085A1 (fr) | 1998-05-28 |
JP2001504486A (ja) | 2001-04-03 |
AU5360898A (en) | 1998-06-10 |
BR9713412A (pt) | 2000-04-18 |
AU726831B2 (en) | 2000-11-23 |
WO1998022075A3 (fr) | 1998-08-06 |
CA2272306A1 (fr) | 1998-05-28 |
EP0941043A2 (fr) | 1999-09-15 |
KR20000057166A (ko) | 2000-09-15 |
JP2000505108A (ja) | 2000-04-25 |
AU5177298A (en) | 1998-06-10 |
AU734338B2 (en) | 2001-06-14 |
CZ181199A3 (cs) | 1999-10-13 |
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