WO1999055300A1 - Skin care cosmetic compositions - Google Patents

Skin care cosmetic compositions Download PDF

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Publication number
WO1999055300A1
WO1999055300A1 PCT/EP1999/002519 EP9902519W WO9955300A1 WO 1999055300 A1 WO1999055300 A1 WO 1999055300A1 EP 9902519 W EP9902519 W EP 9902519W WO 9955300 A1 WO9955300 A1 WO 9955300A1
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WO
WIPO (PCT)
Prior art keywords
skin
composition
cosmetic
branches
exxal
Prior art date
Application number
PCT/EP1999/002519
Other languages
French (fr)
Inventor
John Steven Bajor
Manisha Narayan Mahajan
Stewart Paton Granger
Stephan Samuel Habif
Laura Rose Palanker
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Unilever Plc, Unilever N.V., Hindustan Lever Limited filed Critical Unilever Plc
Priority to AU38165/99A priority Critical patent/AU3816599A/en
Publication of WO1999055300A1 publication Critical patent/WO1999055300A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/70Biological properties of the composition as a whole

Definitions

  • Cosmetic methods and compositions for conditioning human skin by topical application to the skin of cosmetic compositions containing branched fatty alcohols Cosmetic methods and compositions for conditioning human skin by topical application to the skin of cosmetic compositions containing branched fatty alcohols.
  • Cosmetic products which improve the appearance of skin are increasingly popular with consumers. Frequently, consumers seek to alleviate or delay the signs of aged or photoaged skin, such as fine lines and wrinkles, dry and sagging skin. Consumers also seek other benefits in addition to anti-aging.
  • a frequent, undesirable skin condition is "oily skin,” the condition which results from the excessive amount of sebum on the skin.
  • Sebum is skin oil which is produced by sebocytes (cells of the sebaceous glands in the skin) and is then secreted to the skin surface.
  • Oily skin is associated with a shiny, undesirable appearance and a disagreeable tactile sensation. Oily skin affects various age groups. Cosmetic products which provide both sebum control and anti- aging benefits are highly desirable.
  • US Patent 4,496,536 discloses a cosmetic preparation for treating oily hair or seborrhea, which contains at least one long-chain alkanol and at least one anti-oxidant .
  • the long-chain alkanol is described as having 2 -
  • compositions according to the present invention include alcohols that differ from the Moller alcohols at least in the minimum chain length and the minimum number and length of the branches . Contrary to the experimental showing in the Moller patent, the alcohols included in the present invention suppress sebum excretion, even when used alone.
  • compositions according to the invention employ a combination of the alcohol with an oil- absorbing powder, e.g. silica, which provides an immediate relief from sebum accumulation on the skin. If silica alone is employed, high amounts are needed to provide effective oil control. Unfortunately, the use of high levels of silica is not practical since it results in whitening of the skin.
  • an oil absorbing powder e.g. silica
  • the inventive compositions can contain an oil -absorbing powder in an amount which does not result in whitening of the skin, yet compositions are effective for sebum suppression.
  • US Patent 5,344,850 discloses topical compositions for treating or preventing acne, the compositions containing C18 saturated or unsaturated alcohol with four methyl branches.
  • an anti-acne agent does not necessarily possess antisebum activity.
  • benzoyl peroxide and salicylic acid are well-established anti-acne agents, but they do not decrease sebum output. See Cunliffe, et al .
  • the present invention includes a skin care cosmetic composition comprising:
  • the present invention also includes a cosmetic method of controlling or preventing an oily skin condition, especially in the facial area, by applying to the skin a composition from 0.001% to 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches.
  • the invention also includes a cosmetic method of reducing, preventing or controlling sebum secretion from sebocytes by applying a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
  • the invention also includes a cosmetic method of stimulating collagen and glycosaminoglycan synthesis by fibroblasts in the skin, by applying a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
  • the invention also includes a cosmetic method of treating or delaying chronoaged, photoaged, dry, lined or wrinkled skin, shielding the skin from harmful UVA and UVB light (sunscreening) , increasing stratum corneum firmness and flexibility, and generally increasing the quality of skin by applying to the skin the inventive composition.
  • the present invention also comprises the cosmetic use of the inventive skin care composition for providing a skin care benefit selected from the following; reducing or preventing oily skin conditions; reducing or preventing sebum secretion from sebocytes; stimulating collagen and glycosaminoglycan synthesis by fibroblasts in skin; and/or treating aged, photoaged, dry, lined and/or wrinkled skin.
  • inventive cosmetic methods, compositions and uses provide control of sebum secretion from sebocytes, improved 6 -
  • skin as used herein includes amongst others the skin on the face, neck, chest, back, arms, hands and scalp.
  • the inventive methods and compositions include an alcohol containing a total of at least 9 carbon atoms, generally from 9 to 15 carbon atoms, and at least two branches.
  • the preferred alcohols contain a total of at least 10 carbon atoms, in order to obtain maximum efficacy.
  • the most preferred alcohols according to the invention contain from 2 to 5 branches, in order to maximize efficacy at minimum cost.
  • the branches are methyl branches, due to commercial availability.
  • the alcohol may contain a mix of various chain lengths' alcohols. Such mixed alcohol is suitable for use in the present invention, as long as the predominant alcohol in the mix contains a total of at least 9 carbon atoms and at least two branches.
  • the alcohol is employed in the inventive methods in an amount of from 0.001% to about 100%, preferably from 0.001% to 50% and more preferably from 0.1% to 20%, most preferably from 0.1% to 10%.
  • compositions include an oil-absorbing powder, in addition to the alcohol. Consequently, alcohol is employed in an amount of from 0.001% to 50%, preferably from 0.1% to 20%, most preferably from 0.1% to 10%, in order to accommodate the oil-absorbing powder and the cosmetically acceptable vehicle.
  • branched alcohols within the scope of the invention are commercially available, e.g. from Exxon or Henkel .
  • inventive compositions and the preferred inventive methods also include an oil-absorbing powder.
  • suitable oil -absorbing powder include but are not limited to silica (preferably fumed) , talcum, and clay.
  • the preferred oil-absorbing powder is fumed silica, due to its superior oil-absorbing capacity.
  • the oil-absorbing powder provides an immediate sebum control, but not a long-term relief, since it cannot be used in large amounts without whitening the skin.
  • the oil-absorbing powder is present in an amount of no greater than 1%, generally from 0.01% to 1%, preferably from 0.1% to 1%, most preferably from 0.5% to 1%.
  • the alcohol employed in the inventive methods and compositions is liquid, and thus the invention is effective even in the absence of the carrier, the compositions according to the invention comprise a cosmetically acceptable vehicle to act as a diluant, dispersant or carrier for branched alcohol and for oil- absorbing powder in the composition, so as to facilitate their distribution when the composition is applied to the skin.
  • the vehicle may be aqueous, anhydrous or an emulsion.
  • the compositions are aqueous or an emulsion, especially water-in-oil or oil-in-water emulsion.
  • Water when present will be in amounts which may range from 5 to 99%, preferably from 40 to 90%, optimally between 60 and 90% by weight .
  • relatively volatile solvents may also serve as carriers within compositions of the present invention.
  • Most preferred are monohydric C 1 -C 3 alkanols.
  • the amount of monohydric alkanol may range from 1 to 70%, preferably from 10 to 50%, optimally between 15 and 40% by weight.
  • Emollient materials may also serve as cosmetically acceptable carriers. These may be in the form of silicone oils and synthetic esters. Amounts of the emollients may range anywhere from 0.1 to 50%, preferably between 1 and 20% by weight . - 9 -
  • Silicone oils may be divided into the volatile and non-volatile variety.
  • volatile refers to those materials which have a measurable vapor pressure at ambient temperature.
  • Volatile silicone oils are preferably chosen from cyclic or linear polydimethylsiloxanes containing from 3 to 9, preferably from 4 to 5, silicon atoms. Linear volatile silicone materials generally have viscosities less than about 5 centistokes at 25°C while cyclic materials typically have viscosities of less than about 10 centistokes.
  • Nonvolatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers .
  • the essentially non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from about 5 to about 25 million centistokes at 25 °C.
  • polydimethyl siloxanes with viscosities of from about 5 to about 25 million centistokes at 25 °C.
  • preferred non-volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 10 to about 400 centistokes at 25°C.
  • ester emollients are:
  • Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms examples thereof include isoarachidyl neopentanoate , isononyl isonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate.
  • Ether-esters such as fatty acid esters of ethoxylated fatty alcohols.
  • Ethylene glycol mono and di- fatty acid esters diethylene glycol mono- and di- fatty acid esters, polyethylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly- fatty esters, ethoxylated glyceryl monostearate, 1,3 -butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters.
  • Wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate and arachidyl behenate.
  • Sterols esters of which cholesterol fatty acid esters are examples thereof .
  • Fatty acids having from 10 to 30 carbon atoms may also be included as cosmetically acceptable carriers for compositions of this invention.
  • Illustrative of this category are pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic and erucic acids.
  • Humectants of the polyhydric alcohol type may also be employed as cosmetically acceptable carriers in compositions 11
  • humectant aids in increasing the effectiveness of the emollient, reduces scaling, stimulates removal of built-up scale and improves skin feel.
  • Typical polyhydric alcohols include glycerol, polyalkylene glycols and more preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1 , 2 , 6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof.
  • the humectant is preferably propylene glycol or sodium hyaluronate .
  • the amount of humectant may range anywhere from 0.5 to 30%, preferably between 1 and 15% by weight of the composition.
  • Thickeners may also be utilized as part of the cosmetically acceptable carrier of compositions according to the present invention.
  • Typical thickeners include crosslinked acrylates (e.g. Carbopol 982), hydrophobically-modified acrylates (e.g. Carbopol 1382), cellulosic derivatives and natural gums.
  • useful cellulosic derivatives are sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl cellulose and hydroxymethyl cellulose.
  • Natural gums suitable for the present invention include guar, xanthan, sclerotium, carrageenan, pectin and combinations of these gums.
  • Amounts of the thickener may range from 0.0001 to 5%, usually from 0.001 to 1%, optimally from 0.01 to 0.5% by weight.
  • cosmetically acceptable carrier in amounts from 1 to 99.9%, preferably from 80 to 99% by weight.
  • An oil or oily material may be present, together with an emulsifier to provide either a water-in-oil emulsion or an oil-in-water emulsion, depending largely on the average hydrophilic-lipophilic balance (HLB) of the emulsifier employed.
  • HLB hydrophilic-lipophilic balance
  • Surfactants may also be present in cosmetic compositions of the present invention. Total concentration of the surfactant will range from 0.1 to 40%, preferably from 1 to 20%, optimally from 1 to 5% by weight of the composition.
  • the surfactant may be selected from the group consisting of anionic, nonionic, cationic and amphoteric actives.
  • Particularly preferred nonionic surfactants are those with a
  • C ⁇ o ⁇ C 2 o fatty alcohol or acid hydrophobe condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C 2 -C 10 alkyl phenols condensed with from 2 to 20 moles of alkylene oxide; mono- and di- fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di- C 8 -C 20 fatty acids; block copolymers (ethylene oxide/propylene oxide) ; and polyoxyethylene sorbitan as well as combinations thereof.
  • Alkyl polyglycosides and saccharide fatty amides are also suitable nonionic surfactants.
  • Preferred anionic surfactants include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, 13
  • Actives are defined as skin benefit agents other than emollients and other than ingredients that merely improve the physical characteristics of the composition. Although not limited to this category, general examples include additional anti-sebum ingredients and sunscreens.
  • Sunscreens include those materials commonly employed to block ultraviolet light.
  • Illustrative compounds are the derivatives of PABA, cinnamate and salicylate.
  • avobenzophenone Parsol 1789 ®
  • octyl methoxycinnamate and 2- hydroxy-4-methoxy benzophenone also known as oxybenzone
  • Octyl methoxycinnamate and 2-hydroxy-4-methoxy benzophenone are commercially available under the trademarks, Parsol MCX and Benzophenone-3 , respectively.
  • the exact amount of sunscreen employed in the compositions can vary depending upon the degree of protection desired from the sun's UV radiation.
  • Suitable preservatives include alkyl esters of p-hydroxybenzoic acid, hydantoin derivatives, propionate salts, and a variety of quaternary ammonium compounds. Particularly preferred preservatives of this invention are methyl paraben, propyl paraben, phenoxyethanol and benzyl 14
  • Preservatives will usually be employed in amounts ranging from about 0.1% to 2% by weight of the composition.
  • composition according to the invention is intended primarily as a product for topical application to human skin, especially as an agent for controlling or preventing excessive sebum secretion.
  • a quantity of the composition for example from 1 to 100 ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device.
  • the cosmetic skin composition of the invention can be in any form, e.g. formulated as a toner, gel, lotion, a fluid cream, or a cream.
  • the composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer.
  • a lotion or fluid cream can be packaged in a bottle or a roll-ball applicator or a propellant-driven aerosol device or a container fitted with a pump suitable for finger operation.
  • the composition is a cream, it can simply be stored in a non-deformable bottle or squeeze container, such as a tube or a lidded jar.
  • the invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined. 15
  • composition may also be included in capsules such as those described in U.S. Patent No. 5,063,057, incorporated by reference herein.
  • Exxal 7 Mixture of branched and straight chain isomers, about 40% dimethyl pentanols.
  • This example measured production of procollagen I by fibroblasts in response to treatment with various alcohols, - 16
  • Collagen is a predominant skin protein. Its synthesis decreases with aging or photodamage . The degradation or destruction of collagen increases the tensile strength of the skin causing wrinkles and laxity. Many studies involving human subjects have shown that collagen type I is decreased with increasing severity of photodamage (See Kligman, A., JAMA, (1969), 210, pp. 2377-2380; Lavker, R. , J. Inv Derm., (1979), 73, 79-66; Smith J. et al . , J. Inv. Derm., (1962), 39, pp. 347-350; and Shuster, S. et al . , Br. J. Dermatol . , (1975), 93, pp.
  • Neonatal human dermal fibroblasts were purchased from Clonetics Corp., San Diego, CA. All materials for cell culture were purchased from Life Technologies, NY (and used in passages 5-10) . Cells were seeded at a density of approximately 10,000/well in the inner 48 wells of a 96-well plate in a medium containing DMEM (Dulbecco's Modified
  • Test compounds were used at concentrations indicated in Table 1 below. Control did not contain a test compound. After 24 hours, the test compound solution or the control solution was removed and cells redosed with lOO ⁇ l of a solution of a test compound in serum-free DMEM. Test compounds were used at concentrations indicated in Table 1 below.
  • test compound solution was removed and stored over the weekend at 4°C with protease inhibitor (Aprotinin from Sigma) in a ratio of aprotinin to media of 1:200.
  • protease inhibitor Aprotinin from Sigma
  • the test compound solution was then diluted in DMEM (approximately 20 ⁇ l sample in 200 ⁇ l DMEM) .
  • TRIS buffered saline TRIS buffered saline
  • BioRad slot blot apparatus BioRad Labs, CA
  • 100ml TBS was added per well.
  • Vacuum was used to suck TBS through membrane.
  • the test compound solution or control was vortexed, then 100 ⁇ l was loaded per well and gravity filtered.
  • Procollagen from the test solution was bound to the membrane at this point in the procedure.
  • Membrane was removed from the apparatus, excess cut off, and bottom right corner notched for orientation.
  • the membrane was placed in blocking solution (5% milk powder in Dulbecco's phosphate buffered saline) overnight at 4°C, with shaking. The membrane was then incubated for 1.5 hrs at room temperature with 1.5mL Rat Anti-Human Procollagen Amino-Terminal Ab (Chemicon MAB1912) in TBS with 0.1% BSA (ratio of antibody to buffer/BSA was 1:100) in a sealed bag with shaking. The membrane was then removed; washed 3 times for 5 minutes in TBS/0.1% Tween.
  • blocking solution 5% milk powder in Dulbecco's phosphate buffered saline
  • BSA ratio of antibody to buffer/BSA was 1:100
  • the membrane was then incubated for 1 hour at room temperature in 2 mL of Biotinylated Anti-Rat Peroxidase-Conjugated Ab (Vector Labs) in TBS with 0.1% BSA (ratio of antibody to buffer/BSA was 1:1000) in a sealed bag with shaking.
  • the membrane was washed 3 times for 5 minutes in TBS/0. l%Tween. 3 mL PBS was incubated with 30 ⁇ l each of solutions A and B from Vectastain Kit for 30 minutes. The membrane was placed in the resulting solution for 30 minutes in a sealed bag with shaking. The membrane was then removed and washed twice for 5 minutes in TBS/ 0.1%Tween. The membrane was then stained using the following solution:
  • TGF-B is a positive control, ensuring the integrity of the assay: transforming growth factor beta is known to increase procollagen I in fibroblasts.
  • GAGs are a family of polysaccharides which (with the exception of hyaluronic acid (HA) ) can be linked to a protein core, forming a proteoglycan.
  • the main GAGs in the dermis are HA and dermatan sulfate, with chondroitin-4 -sulfate and chondroitin-6-sulfate present in small amounts.
  • GAGs are essential components of the extracellular matrix, although they make up only 0.2% of the dry weight of skin.
  • GAGs hydrate in the skin HA can hold up to lOOOx its mass in water) and maintain basement membrane integrity, regulate cellular interactions and nutrient transport, and are involved in collagen and possibly elastic fiber formation.
  • the proportion of GAGs (especially HA) in the dermis has been shown to be diminished with aging. See Perlish et al , "The Role of Glycosaminoglycans in Aging of the Skin.”
  • Retinoic acid the benchmark anti-aging active, has been shown to increase GAG content of the spinous and granular layers of the epidermis and the papillary dermis of aged skin in vivo. See Kligman et al . , "Effects of topical tretinoin on non-sun-exposed protected skin of the elderly, " J. Am Acad Dermatol 1993;29:25-33. 21
  • Neonatal human dermal fibroblasts were purchased from Clonetics Corp., San Diego, CA and used in passages 5-10. All materials for cell culture were purchased from Life Technologies, NY. Cells were seeded at a density of approximately 50,000/well in a 12-well plate in a medium containing DMEM (Dulbecco's Modified Eagle's Medium), high- glucose supplemented with 2 mM L-glutamine, 10% fetal bovine serum, and antibiotic and antimycotic solutions. Cells were then grown to confluence for 2 days. At confluence, each well was rinsed in serum- free DMEM and the cells dosed with test compounds (in triplicate) in 750 ⁇ L of serum-free DMEM. Test compounds were used at a concentration indicated in Table 2 below. Controls did not contain any test compounds.
  • DMEM Dulbecco's Modified Eagle's Medium
  • test compounds in triplicate
  • this medium was aspirated and the treatment step repeated. After a second 24 -hour period, this medium, containing the soluble GAGs, was collected and frozen until analysis .
  • TGF-B is a positive control, ensuring the integrity of the assay: transforming growth factor beta is known to increase production of GAGs by fibroblasts.
  • This example reports an in vitro analysis of sebum suppression by various test compounds.
  • Radioactive label was prepared by adding 100 ⁇ l of 14 C labeled - 24
  • acetic acid (Amersham, sodium salt, specific activity of 56 mCi/mmol) to 10 ml of 25 mM sodium acetate buffer. Then, 50 ⁇ l was added to each well containing the sebocytes and test agents . The cultures were returned to the incubator for four hours. Thereafter, the sebocytes were rinsed three times with fresh phosphate buffered saline (PBS) to remove unbound active and radioactive label. Radioactive label remaining in the cultured sebocytes was counted using a Beckman scintillation counter. The results were expressed as % reduction compared to control (ethanol) . The higher the number, the better the result.
  • PBS phosphate buffered saline
  • Exxal 10, Exxal 12, and Exxal 13 (within the scope of the invention) all were effective at suppressing sebum secretion.
  • the example demonstrates that the total chain length of at least 9 carbons is critical to attain sebum suppression.
  • Example 3 was repeated, using various concentrations of straight chain alcohols (no branching) which are outside the scope of the invention.
  • the results that were obtained are summarized in Table 4.
  • Example 3 was repeated, using various concentrations of alcohols which contain a single branch (outside the scope of the invention) .
  • the results that were obtained are summarized in Table 5.
  • Exxal 13 branched alcohol within the scope of the invention was an effective sebum suppressor (see Table 3) .
  • Example 3 was repeated, with the following changes: -PBS was used instead of DMEM during radiolabel incorporation; -quadruplicate samples were run, instead of triplicate; -50mM acetate buffer was used in place of 25mM to dilute the radiolabel .
  • This example reports an in-vivo assessment of skin whiteness following application of creams containing various levels of fumed silica.
  • sample cream Thirty milligrams of sample cream was applied on a 15 cm 2 circular area on the forearm of the subject. Two sites per forearm were used in the study. The creams were applied and 28 -
  • a chromameter (Minolta CR 10) was used to quantify the increase in skin whiteness.
  • the decrease in E value corresponds to an increase in skin whiteness.
  • the percent change in E value after application of the samples was calculated.
  • the samples containing silica were compared to the base formulation to evaluate the statistical significance of the increased whiteness due to addition of silica by calculating the p value using student's t-test.
  • the whiteness level was assessed visually and graded according to the following scale: (1) not white, (2) very slightly white, (3) slightly white, (4) white, (5) very white .
  • a simple cream (base formula) was prepared according to Table 7 below by heating phase A and phase B separately to 75C. Phase A was then added to phase B at 75C while mixing at 1000 rpm for 5 minutes. The sample was then homogenized 29
  • Examples 8 illustrates topical compositions according to the present invention.
  • the compositions can be processed in conventional manner. They are suitable for cosmetic use.
  • the compositions are suitable for application to oily, wrinkled, rough, aged and/or UV-damaged skin to improve the appearance and the feel thereof as well as for application to healthy skin to prevent or retard deterioration thereof .
  • Vitamine E Acetate tocopheryl acetate 0.1
  • CTFA Chemical Name weight % squalane 5 macadamia oil 5 pentaerythritol 15 tetraoctanoate petrolatum 5 glyceryl stearate 3 tocopherol acetate 0.5 butylated 0.05 hydroxytoluene methyl paraben 0.15 propyl paraben 0.15 sodium citrate 1 butylene glycol 2 glycerol 2 bentone clay 0.5 disodium EDTA 0.05 trimethyl nonanol 10 water to 100
  • CTFA or Chemical Name weight % glycerin 1 tetrasodium EDTA 0.1 cetyl alcohol 1 stearyl alcohol 1 mineral oil 5 dimethicone 1 dimethiconol 0.2 polyquaternium 37 2 steareth-21 1
  • CTFA Chemical Name weight % light mineral oil 10 stearoxytrimethylsilane 5 and stearyl alcohol dimethicone 2 stearyl stearate 10 quaternium-15 3 peg-22 dodecyl glycol 1 copolymer

Abstract

Cosmetic skin care methods and compositions containing branched alcohols. The inventive compositions provide control of sebum secretion from sebocytes, improved oil control and improved skin feel, prevent shine and stickiness, while also providing anti-aging benefits which results in reduced appearance of wrinkles and aged skin, improved skin color, treatment of photoaged skin, improvement in skin's radiance and clarity and finish, and an overall healthy and youthful appearance of the skin.

Description

SKIN CARE COSMETIC COMPOSITIONS
FIELD OF THE INVENTION
Cosmetic methods and compositions for conditioning human skin by topical application to the skin of cosmetic compositions containing branched fatty alcohols.
BACKGROUND OF THE INVENTION
Cosmetic products which improve the appearance of skin are increasingly popular with consumers. Frequently, consumers seek to alleviate or delay the signs of aged or photoaged skin, such as fine lines and wrinkles, dry and sagging skin. Consumers also seek other benefits in addition to anti-aging.
A frequent, undesirable skin condition is "oily skin," the condition which results from the excessive amount of sebum on the skin. Sebum is skin oil which is produced by sebocytes (cells of the sebaceous glands in the skin) and is then secreted to the skin surface. Oily skin is associated with a shiny, undesirable appearance and a disagreeable tactile sensation. Oily skin affects various age groups. Cosmetic products which provide both sebum control and anti- aging benefits are highly desirable.
US Patent 4,496,536 (Moller et al) discloses a cosmetic preparation for treating oily hair or seborrhea, which contains at least one long-chain alkanol and at least one anti-oxidant . The long-chain alkanol is described as having 2 -
12 to 26 carbon atoms and, preferably, one or more branches. 2- (1,3,3, -trimethylbutyl) -5,7, 7-trimethyloctanol (18 carbons total length, 4 branches: 3 methyl branches and the fourth branch itself containing 3 methyl branches) is mentioned among suitable alkanols. Unfortunately, 2- (1,3,3,- trimethylbutyl) -5, 7, 7-trimethyloctanol is structurally complex and does not appear to be commercially available. Even more importantly, experimental data provided in the patent demonstrates that an alcohol, when used alone, does not provide any sebum suppression. Furthermore, when used in combination with anti-oxidants, branched and non-branched alcohols are shown by Moller to be equally effective.
The compositions according to the present invention include alcohols that differ from the Moller alcohols at least in the minimum chain length and the minimum number and length of the branches . Contrary to the experimental showing in the Moller patent, the alcohols included in the present invention suppress sebum excretion, even when used alone.
Furthermore, the present invention is based, at least in part, on the discovery that the alcohols within the scope of the invention provide sebum suppression, but not immediately upon application. Thus, compositions according to the invention employ a combination of the alcohol with an oil- absorbing powder, e.g. silica, which provides an immediate relief from sebum accumulation on the skin. If silica alone is employed, high amounts are needed to provide effective oil control. Unfortunately, the use of high levels of silica is not practical since it results in whitening of the skin. By virtue of including a branched alcohol as herein defined, the inventive compositions can contain an oil -absorbing powder in an amount which does not result in whitening of the skin, yet compositions are effective for sebum suppression.
US Patent 5,093,112 (Birtwistle et al . ) discloses topical cleansing (detergent) compositions containing an alcohol and an alkyl or alkenyl phosphate salt. 6,6- dimethylheptan-1-ol is mentioned among suitable alcohols. Powders such as chalk, fullers earth, kaolin, starch, fumed silica, magnesium aluminum silicate, hydrated aluminum silicate, are listed as optional ingredients. Birtwistle does not teach or suggest either a problem of excessive sebum on the skin or any compositions for skin sebum control, or any compositions containing an oil-absorbing powder which are effective for sebum control, yet are non-whitening.
US Patent 5,344,850 (Hata et al . ) discloses topical compositions for treating or preventing acne, the compositions containing C18 saturated or unsaturated alcohol with four methyl branches. In this regard, it is important to note that although increased sebum production may be one of the many factors that lead to the formation of acne, an anti-acne agent does not necessarily possess antisebum activity. For instance, benzoyl peroxide and salicylic acid are well-established anti-acne agents, but they do not decrease sebum output. See Cunliffe, et al . , "Topical Benzoyl Peroxide Increases The Sebum Excretion Rate In Patients With Acne", British Journal of Dermatology (1983) 109, 577-579; William J. Cunliffe, "Acne", p. 256, Martin Dunitz Ltd. (1989) . See also Comparative Example 3 below. Hata et al . do not teach compositions containing an oil- absorbing powder or any compositions for sebum control.
US Patent 4,536,399 (Flynn et al . ) and US Patent 4,000,317 (Menda et al . ) disclose the use of silica for sebum adsorption (a total of 1-10% and 0.5-25%, respectively). The higher the level of silica, the better the oil removal ability. However, as mentioned above, a practical limit exists on the amount of silica that can be used without resulting in an unacceptable level of skin whitening due to deposits of high levels of silica powder. Unfortunately, the reduction in silica level results in a reduction in oil- removing efficacy.
SUMMARY OF THE INVENTION
The present invention includes a skin care cosmetic composition comprising:
(i) from 0.001% to 50% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches ; and
(ii) an oil-absorbing powder in an amount of not greater than 1%; and (iii) a cosmetically acceptable vehicle.
The present invention also includes a cosmetic method of controlling or preventing an oily skin condition, especially in the facial area, by applying to the skin a composition from 0.001% to 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches. The invention also includes a cosmetic method of reducing, preventing or controlling sebum secretion from sebocytes by applying a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
The invention also includes a cosmetic method of stimulating collagen and glycosaminoglycan synthesis by fibroblasts in the skin, by applying a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
The invention also includes a cosmetic method of treating or delaying chronoaged, photoaged, dry, lined or wrinkled skin, shielding the skin from harmful UVA and UVB light (sunscreening) , increasing stratum corneum firmness and flexibility, and generally increasing the quality of skin by applying to the skin the inventive composition.
According to a still further aspect, the present invention also comprises the cosmetic use of the inventive skin care composition for providing a skin care benefit selected from the following; reducing or preventing oily skin conditions; reducing or preventing sebum secretion from sebocytes; stimulating collagen and glycosaminoglycan synthesis by fibroblasts in skin; and/or treating aged, photoaged, dry, lined and/or wrinkled skin.
The inventive cosmetic methods, compositions and uses provide control of sebum secretion from sebocytes, improved 6 -
oil control and improved skin feel, prevent shine and stickiness, while also providing anti-aging benefits which results in reduced appearance of wrinkles and aged skin, improved skin color, treatment of photoaged skin, improvement in skin's radiance and clarity and finish, and an overall healthy and youthful appearance of the skin.
DETAILED DESCRIPTION OF THE INVENTION
All amounts in the specification are by weight of the oil-in-water emulsion, unless otherwise specified.
The term "skin" as used herein includes amongst others the skin on the face, neck, chest, back, arms, hands and scalp.
The inventive methods and compositions include an alcohol containing a total of at least 9 carbon atoms, generally from 9 to 15 carbon atoms, and at least two branches. The preferred alcohols contain a total of at least 10 carbon atoms, in order to obtain maximum efficacy. The most preferred alcohols according to the invention contain from 2 to 5 branches, in order to maximize efficacy at minimum cost. Preferably, the branches are methyl branches, due to commercial availability. The alcohol may contain a mix of various chain lengths' alcohols. Such mixed alcohol is suitable for use in the present invention, as long as the predominant alcohol in the mix contains a total of at least 9 carbon atoms and at least two branches. The alcohol is employed in the inventive methods in an amount of from 0.001% to about 100%, preferably from 0.001% to 50% and more preferably from 0.1% to 20%, most preferably from 0.1% to 10%.
The inventive compositions include an oil-absorbing powder, in addition to the alcohol. Consequently, alcohol is employed in an amount of from 0.001% to 50%, preferably from 0.1% to 20%, most preferably from 0.1% to 10%, in order to accommodate the oil-absorbing powder and the cosmetically acceptable vehicle.
The branched alcohols within the scope of the invention are commercially available, e.g. from Exxon or Henkel .
The inventive compositions and the preferred inventive methods also include an oil-absorbing powder. Examples of suitable oil -absorbing powder include but are not limited to silica (preferably fumed) , talcum, and clay.
The preferred oil-absorbing powder is fumed silica, due to its superior oil-absorbing capacity.
The oil-absorbing powder provides an immediate sebum control, but not a long-term relief, since it cannot be used in large amounts without whitening the skin. According to the present invention, the oil-absorbing powder is present in an amount of no greater than 1%, generally from 0.01% to 1%, preferably from 0.1% to 1%, most preferably from 0.5% to 1%. Although the alcohol employed in the inventive methods and compositions is liquid, and thus the invention is effective even in the absence of the carrier, the compositions according to the invention comprise a cosmetically acceptable vehicle to act as a diluant, dispersant or carrier for branched alcohol and for oil- absorbing powder in the composition, so as to facilitate their distribution when the composition is applied to the skin.
The vehicle may be aqueous, anhydrous or an emulsion. Preferably, the compositions are aqueous or an emulsion, especially water-in-oil or oil-in-water emulsion. Water when present will be in amounts which may range from 5 to 99%, preferably from 40 to 90%, optimally between 60 and 90% by weight .
Besides water, relatively volatile solvents may also serve as carriers within compositions of the present invention. Most preferred are monohydric C1-C3 alkanols.
These include ethyl alcohol, methyl alcohol and isopropyl alcohol . The amount of monohydric alkanol may range from 1 to 70%, preferably from 10 to 50%, optimally between 15 and 40% by weight.
Emollient materials may also serve as cosmetically acceptable carriers. These may be in the form of silicone oils and synthetic esters. Amounts of the emollients may range anywhere from 0.1 to 50%, preferably between 1 and 20% by weight . - 9 -
Silicone oils may be divided into the volatile and non-volatile variety. The term "volatile" as used herein refers to those materials which have a measurable vapor pressure at ambient temperature. Volatile silicone oils are preferably chosen from cyclic or linear polydimethylsiloxanes containing from 3 to 9, preferably from 4 to 5, silicon atoms. Linear volatile silicone materials generally have viscosities less than about 5 centistokes at 25°C while cyclic materials typically have viscosities of less than about 10 centistokes. Nonvolatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers . The essentially non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from about 5 to about 25 million centistokes at 25 °C. Among the preferred non-volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 10 to about 400 centistokes at 25°C.
Among the ester emollients are:
(1) Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms. Examples thereof include isoarachidyl neopentanoate , isononyl isonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate.
(2) Ether-esters such as fatty acid esters of ethoxylated fatty alcohols. 10
(3) Polyhydric alcohol esters. Ethylene glycol mono and di- fatty acid esters, diethylene glycol mono- and di- fatty acid esters, polyethylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly- fatty esters, ethoxylated glyceryl monostearate, 1,3 -butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters.
(4) Wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate and arachidyl behenate.
(5) Sterols esters, of which cholesterol fatty acid esters are examples thereof .
Fatty acids having from 10 to 30 carbon atoms may also be included as cosmetically acceptable carriers for compositions of this invention. Illustrative of this category are pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic and erucic acids.
Humectants of the polyhydric alcohol type may also be employed as cosmetically acceptable carriers in compositions 11
of this invention. The humectant aids in increasing the effectiveness of the emollient, reduces scaling, stimulates removal of built-up scale and improves skin feel. Typical polyhydric alcohols include glycerol, polyalkylene glycols and more preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1 , 2 , 6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. For best results the humectant is preferably propylene glycol or sodium hyaluronate . The amount of humectant may range anywhere from 0.5 to 30%, preferably between 1 and 15% by weight of the composition.
Thickeners may also be utilized as part of the cosmetically acceptable carrier of compositions according to the present invention. Typical thickeners include crosslinked acrylates (e.g. Carbopol 982), hydrophobically-modified acrylates (e.g. Carbopol 1382), cellulosic derivatives and natural gums. Among useful cellulosic derivatives are sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl cellulose and hydroxymethyl cellulose. Natural gums suitable for the present invention include guar, xanthan, sclerotium, carrageenan, pectin and combinations of these gums. Amounts of the thickener may range from 0.0001 to 5%, usually from 0.001 to 1%, optimally from 0.01 to 0.5% by weight.
Collectively, the water, solvents, silicones, esters, fatty acids, humectants and/or thickeners will constitute the 12
cosmetically acceptable carrier in amounts from 1 to 99.9%, preferably from 80 to 99% by weight.
An oil or oily material may be present, together with an emulsifier to provide either a water-in-oil emulsion or an oil-in-water emulsion, depending largely on the average hydrophilic-lipophilic balance (HLB) of the emulsifier employed.
Surfactants may also be present in cosmetic compositions of the present invention. Total concentration of the surfactant will range from 0.1 to 40%, preferably from 1 to 20%, optimally from 1 to 5% by weight of the composition. The surfactant may be selected from the group consisting of anionic, nonionic, cationic and amphoteric actives.
Particularly preferred nonionic surfactants are those with a
Cιo~C2o fatty alcohol or acid hydrophobe condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C2-C10 alkyl phenols condensed with from 2 to 20 moles of alkylene oxide; mono- and di- fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di- C8-C20 fatty acids; block copolymers (ethylene oxide/propylene oxide) ; and polyoxyethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and saccharide fatty amides (e.g. methyl gluconamides) are also suitable nonionic surfactants.
Preferred anionic surfactants include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, 13
C8-C20 acyl isethionates, acyl glutamates, C8-C20 alkyl ether phosphates and combinations thereof.
Various types of additional active ingredients may be present in cosmetic compositions of the present invention. Actives are defined as skin benefit agents other than emollients and other than ingredients that merely improve the physical characteristics of the composition. Although not limited to this category, general examples include additional anti-sebum ingredients and sunscreens.
Sunscreens include those materials commonly employed to block ultraviolet light. Illustrative compounds are the derivatives of PABA, cinnamate and salicylate. For example, avobenzophenone (Parsol 1789®) octyl methoxycinnamate and 2- hydroxy-4-methoxy benzophenone (also known as oxybenzone) can be used. Octyl methoxycinnamate and 2-hydroxy-4-methoxy benzophenone are commercially available under the trademarks, Parsol MCX and Benzophenone-3 , respectively. The exact amount of sunscreen employed in the compositions can vary depending upon the degree of protection desired from the sun's UV radiation.
Many cosmetic compositions, especially those containing water, must be protected against the growth of potentially harmful microorganisms. Preservatives are, therefore, necessary. Suitable preservatives include alkyl esters of p-hydroxybenzoic acid, hydantoin derivatives, propionate salts, and a variety of quaternary ammonium compounds. Particularly preferred preservatives of this invention are methyl paraben, propyl paraben, phenoxyethanol and benzyl 14
alcohol. Preservatives will usually be employed in amounts ranging from about 0.1% to 2% by weight of the composition.
The composition according to the invention is intended primarily as a product for topical application to human skin, especially as an agent for controlling or preventing excessive sebum secretion.
In use, a quantity of the composition, for example from 1 to 100 ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device.
Product Form and Packaging:
The cosmetic skin composition of the invention can be in any form, e.g. formulated as a toner, gel, lotion, a fluid cream, or a cream. The composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer. For example, a lotion or fluid cream can be packaged in a bottle or a roll-ball applicator or a propellant-driven aerosol device or a container fitted with a pump suitable for finger operation. When the composition is a cream, it can simply be stored in a non-deformable bottle or squeeze container, such as a tube or a lidded jar. The invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined. 15
The composition may also be included in capsules such as those described in U.S. Patent No. 5,063,057, incorporated by reference herein.
The following specific examples further illustrate the invention, but the invention is not limited thereto.
The following alcohols used in the Examples were obtained from Exxon:
Trade Name Branching
Exxal 7 Mixture of branched and straight chain isomers, about 40% dimethyl pentanols. Exxal 8 Methyl branching only, at least about 38% dimethyl hexanols.
Exxal 9 Dimethyl heptanols (41% - 57%)
®
Exxal 10 Trimethyl heptanols and dimethyl octanols
Exxal 12 Trimethyl nonanols
Exxal 13 Tetramethyl nonanols and trimethyl decanols
EXAMPLE 1
This example measured production of procollagen I by fibroblasts in response to treatment with various alcohols, - 16
Collagen is a predominant skin protein. Its synthesis decreases with aging or photodamage . The degradation or destruction of collagen increases the tensile strength of the skin causing wrinkles and laxity. Many studies involving human subjects have shown that collagen type I is decreased with increasing severity of photodamage (See Kligman, A., JAMA, (1969), 210, pp. 2377-2380; Lavker, R. , J. Inv Derm., (1979), 73, 79-66; Smith J. et al . , J. Inv. Derm., (1962), 39, pp. 347-350; and Shuster, S. et al . , Br. J. Dermatol . , (1975), 93, pp. 639-643); and some correlation in the histology of wrinkles and reduction in collagen levels in the sun-exposed skin has been reported. See Chen, S.; Kiss, I., J. Inv. Derm., (1992), 98. pp. 248-254. Voorhees and colleagues have supported these findings by showing the restoration of collagen type I in photo-damaged human skin by a topical treatment with tretinoin. See Christopher, E., et al . , The New Eng . Jou. of Medicine (1993), 329, pp. 530-535. Procollagen I is a precursor of collagen. Increased production of procollagen I in response to a test compound application is a marker of an increased collagen level.
Procollagen I Staining Protocol for Slot Blot
Neonatal human dermal fibroblasts were purchased from Clonetics Corp., San Diego, CA. All materials for cell culture were purchased from Life Technologies, NY (and used in passages 5-10) . Cells were seeded at a density of approximately 10,000/well in the inner 48 wells of a 96-well plate in a medium containing DMEM (Dulbecco's Modified
Eagle ' s Medium) , high-glucose supplemented with 2 mM L- - 17
glutamine, 10% fetal bovine serum, and antibiotic and antimycotic solutions. Cells were then grown to confluence for 2 days. At confluence, the medium was removed and cells were washed with serum- free DMEM, and each well dosed with 200μl of a solution of a test compound in serum-free DMEM. Each dosing was replicated in a total of six wells. Test compounds were used at concentrations indicated in Table 1 below. Control did not contain a test compound. After 24 hours, the test compound solution or the control solution was removed and cells redosed with lOOμl of a solution of a test compound in serum-free DMEM. Test compounds were used at concentrations indicated in Table 1 below. After 24 hours, the test compound solution or the control solution was removed and stored over the weekend at 4°C with protease inhibitor (Aprotinin from Sigma) in a ratio of aprotinin to media of 1:200. The test compound solution was then diluted in DMEM (approximately 20μl sample in 200μl DMEM) .
Nitrocellulose membrane and 3 sheets of filter paper were soaked in TRIS buffered saline (TBS, pH 7.3.). BioRad slot blot apparatus (BioRad Labs, CA) was set up with 3 sheets filter paper on bottom, membrane on top, and tightened tightened. 100ml TBS was added per well. Vacuum was used to suck TBS through membrane. The test compound solution or control was vortexed, then 100 μl was loaded per well and gravity filtered. Procollagen from the test solution was bound to the membrane at this point in the procedure. Membrane was removed from the apparatus, excess cut off, and bottom right corner notched for orientation. The membrane was placed in blocking solution (5% milk powder in Dulbecco's phosphate buffered saline) overnight at 4°C, with shaking. The membrane was then incubated for 1.5 hrs at room temperature with 1.5mL Rat Anti-Human Procollagen Amino-Terminal Ab (Chemicon MAB1912) in TBS with 0.1% BSA (ratio of antibody to buffer/BSA was 1:100) in a sealed bag with shaking. The membrane was then removed; washed 3 times for 5 minutes in TBS/0.1% Tween. The membrane was then incubated for 1 hour at room temperature in 2 mL of Biotinylated Anti-Rat Peroxidase-Conjugated Ab (Vector Labs) in TBS with 0.1% BSA (ratio of antibody to buffer/BSA was 1:1000) in a sealed bag with shaking.
The membrane was washed 3 times for 5 minutes in TBS/0. l%Tween. 3 mL PBS was incubated with 30μl each of solutions A and B from Vectastain Kit for 30 minutes. The membrane was placed in the resulting solution for 30 minutes in a sealed bag with shaking. The membrane was then removed and washed twice for 5 minutes in TBS/ 0.1%Tween. The membrane was then stained using the following solution:
12.5 mg 3 -amino 9-ethyl carbazole (Sigma)
3.125 (approximately) mL DMF (N,N- dimethylformamide, from
Sigma) 21.5 mL 0.2M NaOAc buffer, pH 5.2 12.5 μl H202
The membrane was stained until color developed and the reaction stopped with 2 washes for 10 minutes in tap water. The blot was scanned on a Bio-Rad GS700 Image Analysis densitometer . Percent change from control was calculated - 19
from densitometer readings as follows : [ (Reading for test compound-Reading for control) /Reading for control] * 100. Control has a reading of 100%. Statistical significance (p value) was calculated using student's t-test.
The results that were obtained are summarized in Table 1. TGF-B is a positive control, ensuring the integrity of the assay: transforming growth factor beta is known to increase procollagen I in fibroblasts.
TABLE 1
Sample % Increase p value (+) or % decrease (--) over control
Experiment 1
TGF-B +50* .0027
0.01% Exxal 7 -10* .026
0.01% Exxal 8 -30* .001493
Experiment 2
TGF-B +140* .001227
18)
0.01% Exxal 10 +50* .0025
IS)
0.01% Exxal 12 +40* .040
0.01% Exxal 13 +30* .042
Figure imgf000021_0001
*Statistically significant at p<0.05
It can be seen from the results in Table 1, that Exxal 7 and Exxal 8, which are not within the scope of the invention, did not increase collagen synthesis by fibroblasts. By contrast, the alcohols within the scope of the invention
® ® ®
(Exxal 10, Exxal 12, and Exxal 13) all increased collagen synthesis. - 20
EXAMPLE 2
This example measures production of glycosaminoglycans by fibroblasts in response to treatment with various test compounds. Glycosaminoglycans (GAGs) are a family of polysaccharides which (with the exception of hyaluronic acid (HA) ) can be linked to a protein core, forming a proteoglycan. The main GAGs in the dermis are HA and dermatan sulfate, with chondroitin-4 -sulfate and chondroitin-6-sulfate present in small amounts. Made by both keratinocytes and dermal fibroblasts, GAGs are essential components of the extracellular matrix, although they make up only 0.2% of the dry weight of skin. GAGs hydrate in the skin (HA can hold up to lOOOx its mass in water) and maintain basement membrane integrity, regulate cellular interactions and nutrient transport, and are involved in collagen and possibly elastic fiber formation. The proportion of GAGs (especially HA) in the dermis has been shown to be diminished with aging. See Perlish et al , "The Role of Glycosaminoglycans in Aging of the Skin."
Retinoic acid, the benchmark anti-aging active, has been shown to increase GAG content of the spinous and granular layers of the epidermis and the papillary dermis of aged skin in vivo. See Kligman et al . , "Effects of topical tretinoin on non-sun-exposed protected skin of the elderly, " J. Am Acad Dermatol 1993;29:25-33. 21
Protocol for measuring GAGs
Neonatal human dermal fibroblasts were purchased from Clonetics Corp., San Diego, CA and used in passages 5-10. All materials for cell culture were purchased from Life Technologies, NY. Cells were seeded at a density of approximately 50,000/well in a 12-well plate in a medium containing DMEM (Dulbecco's Modified Eagle's Medium), high- glucose supplemented with 2 mM L-glutamine, 10% fetal bovine serum, and antibiotic and antimycotic solutions. Cells were then grown to confluence for 2 days. At confluence, each well was rinsed in serum- free DMEM and the cells dosed with test compounds (in triplicate) in 750μL of serum-free DMEM. Test compounds were used at a concentration indicated in Table 2 below. Controls did not contain any test compounds.
After 24 hours, this medium was aspirated and the treatment step repeated. After a second 24 -hour period, this medium, containing the soluble GAGs, was collected and frozen until analysis .
A positively-charged Zeta Probe membrane was soaked in sterile water and placed into the Dot-Blot Apparatus (both
Bio-Rad Labs, Hercules, CA) . lOOμL of water was applied to each well and pulled through using a vacuum. After thawing, lOOμL of test solution samples or standards (Hyaluronic acid or Chondroitin Sulfate from bovine trachea, Sigma, St. Louis, MO) was applied to the membrane and allowed to gravity filter (about 1.5 - 2 hours) . GAGs were now bound to membrane. The membrane was blocked in 3% w/v fatty acid free bovine serum albumin (Sigma) in water for one hour. A dye solution of 0.5% w/v Alcian Blue dye (ICN Biochemicals, - 22
Cleveland, OH) in 3% acetic acid, pH approximately 2.3, was made. The membrane was washed twice in distilled water and then stained in the dye solution on a rotary shaker for 15 minutes. The dye was poured off and the membrane destained twice for 15 minutes each time in 3% acetic acid. The membrane was rinsed in water and left to dry overnight . The Bio-Rad GS 700 Image Analysis Densitometer was used to quantitate the intensity of color in each spot. Percent change from control was calculated from densitometer readings as follows: [(Reading for test compound-Reading for control) /Reading for control] * 100. Control has a reading of 100%. Statistical significance (p value) was calculated using student's t-test.
The results that were obtained are summarized in Table 2. TGF-B is a positive control, ensuring the integrity of the assay: transforming growth factor beta is known to increase production of GAGs by fibroblasts.
TABLE 2
Sample % Increase p value
(+) or % decrease (--) over control
TGF-B +200* 6.2 x 10"7
(!)
0.01% Exxal 7 +20* .017
0.01% Exxal 8 0* .096
0.01% Exxal 10 +10* .0050
(5)
0.01% Exxal 12 +30* .0006
0.01% Exxal : L3 +20* 5.6 x 10
Figure imgf000024_0001
*Statistically significant at p<0.05 - 23
It can be seen from the results in Table 2 that all the alcohols tested, including the alcohols within the scope of the invention, significantly increased GAGs production by fibroblasts.
EXAMPLE 3
This example reports an in vitro analysis of sebum suppression by various test compounds.
In Vi tro Sebocyte Lipogenesis Assay:
Human sebaceous glands were isolated from the nose of a male (age 60) and cultured using submerged tissue culture techniques (Bajor et al, J. Invest. Dermatol . 102: 1994, P. 564) . These sebocytes accumulate intracellular lipid droplets characteristic of mature human sebum.
Harvested and passaged sebocytes were added to each well of a 48 well tissue culture plate and incubated at 37 C in the presence of 7.5% C02 for 7 days. On the day of experimentation, the growth medium was removed and the sebocytes washed three times with Dulbecco's Modified Eagle's medium (DMEM; glucose free, phenol red free) . Fresh DMEM in 0.5 ml amount was added to each well and 5 μl of a test agent, at final concentrations indicated in the Tables below. Triplicate wells were utilized for each sample. Controls consisted of DMEM and ethanol (used to dilute alcohols) . All cultures were incubated at 37C/7.5% C02 for 30 minutes.
Radioactive label was prepared by adding 100 μl of 14C labeled - 24
acetic acid (Amersham, sodium salt, specific activity of 56 mCi/mmol) to 10 ml of 25 mM sodium acetate buffer. Then, 50 μl was added to each well containing the sebocytes and test agents . The cultures were returned to the incubator for four hours. Thereafter, the sebocytes were rinsed three times with fresh phosphate buffered saline (PBS) to remove unbound active and radioactive label. Radioactive label remaining in the cultured sebocytes was counted using a Beckman scintillation counter. The results were expressed as % reduction compared to control (ethanol) . The higher the number, the better the result.
The results that were obtained are summarized in Table 3 below. Statistical significance (p value) was calculated using student's t-test. Test compounds are considered to be effective at % reduction of at least 20%. Negative values indicate increase in sebum production.
TABLE 3
Sample % Reduction p value
0.01% Exxal 7 -9.1% .322
0.01% Exxal 8 3.1% .716
0.01% Exxal 9 23.4%* .026
0.01% Exxal 10 33.9%* .009
(!)
0.01% Exxal 12 32.0%* .014
0.01% Exxal 13 33.9%* .006
Figure imgf000026_0001
*Statistically significant at p<0.05 25
It can be seen from the results in Table 3 that Exxal 7
® and Exxal 8 (not within the scope of the invention) did not
® suppress sebum secretion by sebocytes, whereas Exxal 9,
® ® ®
Exxal 10, Exxal 12, and Exxal 13 (within the scope of the invention) all were effective at suppressing sebum secretion. The example demonstrates that the total chain length of at least 9 carbons is critical to attain sebum suppression.
COMPARATIVE EXAMPLE 4
Example 3 was repeated, using various concentrations of straight chain alcohols (no branching) which are outside the scope of the invention. The results that were obtained are summarized in Table 4.
TABLE 4
Sample % Reduction p value
0.01% 1-Dodecanol -21.0% .487
0.10% 1-Dodecanol 12.4% .211
0.01%1-Tridecanol -2.6% .701
0.10% 1-Tridecanol -7.0% .168
0.01% 1-Hexadecanol -5.6% .621
Figure imgf000027_0001
0.10% 1-Hexadecanol -27.8% .138
It can be seen from the results in Table 4 that straight chain, non-branched alcohols which are not within the scope of the invention, do not attain sebum supression. Thus, branched alcohols are critical in order to attain sebum suppression. 26
COMPARATIVE EXAMPLE 5
Example 3 was repeated, using various concentrations of alcohols which contain a single branch (outside the scope of the invention) . The results that were obtained are summarized in Table 5.
TABLE 5
Sample % Reduction p value
0.01% 1-Tridecanol -10.5% 0.033
0.010% 2-Tridecanol -2% 0.608
Figure imgf000028_0001
0.01% 4-Tridecanol 3% 0.503
It can be seen from the results in Table 5 that straight chain tridecanol variants of Exxal 13 were not effective
® sebum suppressors. By contrast, Exxal 13 (branched alcohol within the scope of the invention) was an effective sebum suppressor (see Table 3) .
COMPARATIVE EXAMPLE 6
Example 3 was repeated, with the following changes: -PBS was used instead of DMEM during radiolabel incorporation; -quadruplicate samples were run, instead of triplicate; -50mM acetate buffer was used in place of 25mM to dilute the radiolabel .
The results that were obtained are summarized in Table 6 27
TABLE 6
Treatment Concentration % Reduction p value
Phenol Red lOμM 34.1 0.018
Phenol Red lOOμM 52.4 0.0083
Dihydrotestosterone 0.00003% -28.8 0.0002 (1 μM)
Salicylic Acid 0.14% 3.6 0.205 (10.0 mM)
Figure imgf000029_0001
The results in Table 6 demonstrate that the sebocyte assay is a valid and reliable test for measuring sebum suppression, because Phenol Red (phenolsulfonphthalein) provided sebum suppression, as predicted from the other sources, whereas dihydrotestosterone (androgen) actually increased sebum production, as also predicted from other sources. Salicylic acid, a known anti-acne agent did not inhibit sebum output, demonstrating that an antiacne agent does not necessarily have antisebum activity.
EXAMPLE 7
This example reports an in-vivo assessment of skin whiteness following application of creams containing various levels of fumed silica.
Procedure:
Thirty milligrams of sample cream was applied on a 15 cm2 circular area on the forearm of the subject. Two sites per forearm were used in the study. The creams were applied and 28 -
rubbed in using a latex finger cot to prevent loss during rubbing. The sites were measured before application and 10 minutes after application to allow for drying.
A chromameter (Minolta CR 10) was used to quantify the increase in skin whiteness. The L, a, and b values were recorded and an E value was calculated using the following formula: E = square root of [(L-40)2 + a2 + b2] , where L, the luminescence, is measured on a scale from 0 to 100, a (the red-green axis) is measured from -60 (green) to +60 (red) , and b (the yellow-blue axis) is measured from -60 (blue) to +60 (yellow) . As can be seen from Table 8 below, the decrease in E value corresponds to an increase in skin whiteness. The percent change in E value after application of the samples was calculated. The samples containing silica were compared to the base formulation to evaluate the statistical significance of the increased whiteness due to addition of silica by calculating the p value using student's t-test.
The whiteness level was assessed visually and graded according to the following scale: (1) not white, (2) very slightly white, (3) slightly white, (4) white, (5) very white .
Samples :
A simple cream (base formula) was prepared according to Table 7 below by heating phase A and phase B separately to 75C. Phase A was then added to phase B at 75C while mixing at 1000 rpm for 5 minutes. The sample was then homogenized 29
for 10 minutes while cooling using an L4R Silverson homogenizer at half power, and transferred to a jar where it was allowed to cool to room temperature overnight. 200 g samples were prepared. The samples containing silica were prepared according to same procedure and following the same recipe as the base formula except that some water was removed from phase B to accommodate the fumed silica.
TABLE 7
Base formula
Phase Ingredient CTFA or Chemical t. % Name
A Pristerene 4911 stearic acid 15
A Lanette 16 NF cetyl alcohol 1
A propyl paraben same 0.1
B Aerosil 200 fumed silica 0
B methyl paraben same 0.1
B potassium same 1.5 hydroxide (25%)
Figure imgf000031_0001
B water same to 100
30
Results
TABLE 8
Sample E value E value change p value whiteness before after in E (compared score applicaapplicavalue to base tion tion (%) formula) base 21.64 20.81 - 3.8% - 2 formula
1% silica 21.34 19.74 - 7.5% 0.099 3 in base formula
2% silica 22.07 20.04 -9.2%* 0.018 4 in base formula
5% silica 21.48 17.37 -19.1%* 0.013 5 in base
Figure imgf000032_0001
formula
* Statistically significant at p<0.05
It can be seen from the results in Table 8 that a level of 2% fumed silica yielded a skin whiteness score of 4 , a whiteness level unacceptable for cosmetic applications.
Consequently it appears that a level of 1% fumed silica is the upper limit for use in cosmetic applications corresponding to a decrease in E value of no more than 8% in our test. The addition of 1% silica did not result in a significantly different change in E value when compared to the base formula with no silica. However the addition of 2% and 5% both resulted in a significant higher decrease in E value when compared to the base formula. 31
EXAMPLE 8
Examples 8 illustrates topical compositions according to the present invention. The compositions can be processed in conventional manner. They are suitable for cosmetic use. In particular the compositions are suitable for application to oily, wrinkled, rough, aged and/or UV-damaged skin to improve the appearance and the feel thereof as well as for application to healthy skin to prevent or retard deterioration thereof .
OIL-IN WATER EMULSION CREAM
Ingredient CTFA or Chemical Name weight %
Polawax Regular Emulsifiable Wax 5
® Exxal 12 isoalcohol 5
Myristyl myristate same 2
Dow Corning 3225 cyclomethicone and 2 dimethicone copolyol
Aerosil 200 silica 1
Sepigel 305 poyacrylamide and C13- 0.5 14 isoparaffin and laureth-7
Glycerine microsponges Methacrylate copolymer 0.5 with glycerine
Brij 58 ceteth-20 0.3 methyl paraben same 0.2 germall 115 imidazolidinyl urea 0.2 propyl paraben same 0.15
BHT butylated hydroxy 0.05 toluene water same to 100
Figure imgf000033_0001
32 -
OIL-IN-WATER EMULSION CREAM
Ingredient CTFA or Chemical Name weight %
Sequesterene Na2 disodium EDTA 0.05
Veegum Ultra magnesium aluminum silicate 0.6
Methyl Paraben methyl paraben 0.15
DC Antifoam Emulsion simethicone 0.01
Butylene Glycol 1,3 butylene glycol 1,3 3.0
Natrosol 250HHR hydroxyethylcellulose 0.5
Aerosil 200 fumed silica 0.5
Glycerine USP glycerine, USP 2.0
Keltrol 1000 xanthan gum 0.2
Triethanolamine 99% triethanolamine 1.2
Pristerene 4911 stearic acid 3.0
Propylparaben NF propyl paraben NF 0.1
Naturechem GMHS glyceryl hydrostearate 1.5
Lanette 18DEO stearyl alcohol 1.5
® isoalcohol 4.0 Exxal 13
Protachem ISP isostearyl palmitate 3.0
Hetester FAO C12-15 alcohols octanoate 2.0
Silicone Fluid 200(50cts) dimethicone 1.0
Cholesterol NF cholesterol NF 0.5
Sorbitan Stearate sorbitan stearate 1.0
Embanox BHT butylated hydroxytoluene 0.05
Vitamine E Acetate tocopheryl acetate 0.1
MYRJ 59 PEG-100 stearate 2.0
Pationic SSL sodium stearoyl lactylate 0.5
Alpha-bisabolol alpha-bisabolol 0.2 water same to 100
Figure imgf000034_0001
33
anhydrous composition
CTFA or Chemical Name weight % isostearyl neopentanoate 20 peg-8 caprylic/capric 16 glycerides cetyl octanoate 17 polyglyceryl-6 dioleate 15 cyclomethicone 20 glyceryl isostearate 0.5 talcum 0.5 ceramide III 0.1 ppg-5-cetheth-20 3 trimethyl heptanol 3 ethanol to 100
Figure imgf000035_0001
34
water-in-oil emulsion
CTFA or Chemical Name weight % squalane 5 macadamia oil 5 pentaerythritol 15 tetraoctanoate petrolatum 5 glyceryl stearate 3 tocopherol acetate 0.5 butylated 0.05 hydroxytoluene methyl paraben 0.15 propyl paraben 0.15 sodium citrate 1 butylene glycol 2 glycerol 2 bentone clay 0.5 disodium EDTA 0.05 trimethyl nonanol 10 water to 100
Figure imgf000036_0001
- 35
oil-in-water emulsion
CTFA or Chemical Name weight % glycerin 1 tetrasodium EDTA 0.1 cetyl alcohol 1 stearyl alcohol 1 mineral oil 5 dimethicone 1 dimethiconol 0.2 polyquaternium 37 2 steareth-21 1
Steareth-2 0.5
Trimethyl decanols (Exxal 13) 1
Cyclomethicone 0.5
Silica 0.6
Water to 100
Figure imgf000037_0001
- 3 <
water-in-oil emulsion
CTFA or Chemical Name weight % light mineral oil 10 stearoxytrimethylsilane 5 and stearyl alcohol dimethicone 2 stearyl stearate 10 quaternium-15 3 peg-22 dodecyl glycol 1 copolymer
Sorbitol 0.5
Methyl paraben 0.2 disodium EDTA 0.1 butylated 0.1 hydroxytoluene dimethyl heptanols 5 (Exxal" 9) silica 1 water to 100
Figure imgf000038_0001
It should be understood that the specific forms of the invention herein illustrated and described are intended to be representative only.

Claims

- 37CLAIMS
1. A skin care cosmetic composition comprising:
(i) from about 0.001% to about 50% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches; and
(ii) an oil-absorbing powder in an amount of not greater than about 1% ; and
(iii) a cosmetically acceptable vehicle.
2. The composition of claim 1 wherein the oil-absorbing powder is selected from the group consisting of silica, talcum, and clay.
3. A cosmetic method of reducing or preventing oily skin conditions, the method comprising applying to the skin a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
4. A cosmetic method of reducing or preventing sebum secretion from sebocytes, the method comprising applying to the skin a composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches.
5. A cosmetic method of stimulating collagen and glycosaminoglycan synthesis by fibroblasts in the skin, 38
the method comprising applying to the skin the composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches .
6. A cosmetic method of treating aged, photoaged, dry, lined or wrinkled skin, the method comprising applying to the skin the composition comprising from about 0.001% to about 100% of an alcohol containing a total of at least 9 carbon atoms and containing at least two branches.
7. Cosmetic use of a composition according to claim 1 for providing a skin care benefit selected from the following; reducing or preventing oily skin conditions; reducing or preventing sebum secretion from sebocytes; stimulating collagen and glycosaminoglycan synthesis by fibroblasts in skin; and/or treating aged, photoaged, dry, lined and/or wrinkled skin.
PCT/EP1999/002519 1998-04-23 1999-04-07 Skin care cosmetic compositions WO1999055300A1 (en)

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WO2002002067A1 (en) * 2000-06-30 2002-01-10 Unilever Plc Skin care cosmetic compositions containing carboxymethylates of branched alcohols and/or ethoxylates thereof
DE10063658A1 (en) * 2000-12-20 2002-07-04 Beiersdorf Ag Cosmetic or dermatological emulsion, useful for skin care, e.g. for treating rough skin, comprises sterols and/or fatty acids, polyol mono- and/or diesters, sorbitol monoester, ethoxylated fatty acids and fatty alcohols
DE10063660A1 (en) * 2000-12-20 2002-07-04 Beiersdorf Ag Cosmetic or dermatological emulsion, useful for e.g. treating rough skin, comprises sterols and/or fatty acids, polyol mono- and/or diesters, sorbitol monoester, ethoxylated fatty acids and fatty alcohols
DE10139580A1 (en) * 2001-08-10 2003-02-20 Beiersdorf Ag O/W emulsions useful e.g. cleansing, skin-care or anti-acne agents comprise a combination of steroids or fatty acids with optionally ethoxylated esters
DE10139582A1 (en) * 2001-08-10 2003-02-20 Beiersdorf Ag W/O/W emulsions useful e.g. cleansing, skin-care or anti-acne agents comprises a combination of steroids, fatty acids and optionally ethoxylated esters
WO2004006883A1 (en) * 2002-07-17 2004-01-22 Unilever Plc Skin care cosmetic compositions containing carboxyalkylates of branched alcohols and/or alkoxylates thereof
JP2004501951A (en) * 2000-06-30 2004-01-22 ユニリーバー・ナームローゼ・ベンノートシヤープ Skin care cosmetic compositions comprising a branched chain alcohol phosphate and / or sulfate and / or its ethoxylate

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DE10063660A1 (en) * 2000-12-20 2002-07-04 Beiersdorf Ag Cosmetic or dermatological emulsion, useful for e.g. treating rough skin, comprises sterols and/or fatty acids, polyol mono- and/or diesters, sorbitol monoester, ethoxylated fatty acids and fatty alcohols
DE10139580A1 (en) * 2001-08-10 2003-02-20 Beiersdorf Ag O/W emulsions useful e.g. cleansing, skin-care or anti-acne agents comprise a combination of steroids or fatty acids with optionally ethoxylated esters
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WO2004006883A1 (en) * 2002-07-17 2004-01-22 Unilever Plc Skin care cosmetic compositions containing carboxyalkylates of branched alcohols and/or alkoxylates thereof

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