WO1996003962A1 - Cosmetic make-up compositions - Google Patents
Cosmetic make-up compositions Download PDFInfo
- Publication number
- WO1996003962A1 WO1996003962A1 PCT/US1995/008340 US9508340W WO9603962A1 WO 1996003962 A1 WO1996003962 A1 WO 1996003962A1 US 9508340 W US9508340 W US 9508340W WO 9603962 A1 WO9603962 A1 WO 9603962A1
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- WO
- WIPO (PCT)
- Prior art keywords
- make
- composition according
- weight
- oil
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- 239000000203 mixture Substances 0.000 title claims abstract description 136
- 239000002537 cosmetic Substances 0.000 title description 12
- 239000000049 pigment Substances 0.000 claims abstract description 36
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- 239000003906 humectant Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007764 o/w emulsion Substances 0.000 claims abstract description 3
- -1 polydimethylsiloxanes Polymers 0.000 claims description 40
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
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- NEOZOXKVMDBOSG-UHFFFAOYSA-N propan-2-yl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC(C)C NEOZOXKVMDBOSG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229940057400 trihydroxystearin Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046001 vitamin b complex Drugs 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
Classifications
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
-
- 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
- A61K8/06—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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- 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
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- 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
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
-
- 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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- 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
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
Definitions
- the present invention relates to cosmetic make-up compositions and more particularly, to pigmented foundation make-up compositions having improved moisturisation effectiveness, application characteristics, skin feel and appearance, together with colour corrective characteristics.
- a foundation composition can be applied to the face and other parts of the body to even skin tone and texture and to hide pores, imperfections, fine lines and the like.
- a foundation composition is also applied to moisturize the skin, to balance the oil level of the skin and to provide protection against the adverse effects of sunlight, wind and the harsh environment.
- Make-up compositions are generally available in the form of liquid or cream suspensions, emulsions, gels, pressed powders or anhydrous oil and wax compositions.
- US Patent No. 3,444,291 discloses a method of filling and camouflaging skin cavities by applying a composition which includes 65 to 75 parts by weight of a microcrystalline wax and about 25 to 35 parts of a mineral oil.
- the composition includes a colourant, preferably a coal tar dye, for example, D &C Red No. 17, which matches the colour of the user's skin.
- a spreadable, flowable and greaseless cosmetic cover-up composition is taught in US Patent No 4,486,405. That composition is characterized by the presence of a first and a second alkoxylated surfactant present in substantially the same concentration.
- US Patent No. 4,804,532 recites a facial cosmetic powder which utilizes crystalline silica in much lower concentration than that employed in the then prior art compositions.
- This powder used as a blush or a facial coating, is said to be effective in hiding skin wrinkles, lines and pores.
- the composition is a mixture of a colour phase and a diluent phase.
- the colour phase is formed by blending crystalline silica with colourants.
- the resultant colour phase is mixed with the diluent phase, essentially formed from nacreous materials such as talc and mica, to form the composition.
- US Patent No. 4,659,562 discloses a cosmetic make-up composition which includes, as a binding agent therefore, an intimate mixture of from 5 to 95 weight percent of a mixture of finely divided silica and about 5 to 95 weight percent of finely divided polyethylene fibres.
- the composition is recited to maintain its uniformity over the areas of the skin to which it is applied. That is, it is said to be "creaseproof.
- the composition of the '562 patent includes colourant in admixture with nacreous agents.
- 5,143,722 discloses a cosmetic make-up composition
- a cosmetic make-up composition comprising water-in-oil emulsions comprising pigment coated with polysiloxane, a silicone phase, a water phase and a polydiorganosiloxane-polyoxyalkylene copolymeric surfactant.
- Metal oxide coated substrate nacreous pigments are known in the art and are exemplified by titanium dioxide and/or zirconium dioxide coated mica. Such pigments are described in US- A-3, 497,515, US-A- 3,418,146, US-A-3,087,828 and US- A-4,038,099. Depending on the thickness of the metal oxide coating, the pigments can exhibit interference or reflection colours of blue, green, yellow, red, etc.
- a make-up composition in the form of a water-in-oil or oil-in-water emulsion comprising: a) from about 1% to about 50% by weight of silicone oil selected from volatile silicones, non-volatile silicones and mixtures thereof, b) optionally up to about 30% by weight of humectant, c) from about 0.1 % to about 25% by weight of at least one coated or uncoated iron oxide-type pigment, and d) from about 0.1 % to about 10% by weight of a Ti ⁇ 2-coated platelet-type interference pigment material having a Ti ⁇ 2 layer thickness of from about 120nm to about 160nm or a whole number multiple thereof.
- the water-in-oil emulsions of the present invention provide improved colour corrective benefits together with good coverage, skin appearance and superior moisturisation.
- the make-up composition according to the present invention comprises a mixture of volatile and/or non- volatile silicones, iron oxide-type pigment, Ti ⁇ 2 platelet type interference pigment material and optionally humectant.
- the composition is in the form of a water-in-oil emulsion.
- a first essential component of the water-in-oil emulsion is a silicone oil which in preferred embodiments comprises a mixture of volatile silicones and non-volatile silicones.
- the silicone oil is present in an amount of from about 1% to about 50% by weight.
- Suitable volatile silicone oils include cyclic and linear volatile polyorganosiloxanes (as used herein, "volatile” refers to those materials which have a measurable vapour pressure at ambient conditions).
- cyclic silicones include polydimethylsiloxanes containing from about 3 to about 9 silicon atoms, preferably containing from about 4 to about 5 silicon atoms.
- Preferred linear silicone oils include the polydimethylsiloxanes containing from about 3 to about 9 silicon atoms.
- the linear volatile silicones generally have viscosities of less than about 5 centistokes at 25°C, while the cyclic materials have viscosities of less than about 10 centistokes.
- silicone oils useful in the present invention include: Dow Corning 344, Dow Corning 21330, Dow Corning 345, and Dow Corning 200 (manufactured by the Dow Corning Corporation): Silicone 7207 and Silicone 7158 (manufactured by the Union Carbide Corporation). SF:202 (manufactured by General Electric) and SWS-03314 (manufactured by Stauffer Chemical).
- Suitable non-volatile silicones preferably have an average viscosity of from about 1,000 to about 2,000,000 mm ⁇ r 1 at 25°C, more preferably from about 10,000 to about 1,800,000 mm ⁇ .s-l, even more preferably from about 100,000 to about 1,500,000 mm ⁇ .s"*.
- Lower viscosity non ⁇ volatile silicone conditioning agents can also be used. Viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
- Suitable non- volatile silicone fluids for use herein include polyalkyl siloxanes, polyaryl siloxanes, poly alky laryl siloxanes, polysiloxanes with amino functional substitutions, polyether siloxane copolymers, and mixtures thereof.
- the siloxanes useful in the present invention may be endcapped with any number of moieties, including, for example, methyl, hydroxyl, ethylene oxide, propylene oxide, amino and carboxyl.
- other silicone fluids having skin conditioning properties may be used.
- the non-volatile polyalkyl siloxane fluids that may be used include, for example, polydimethylsiloxanes.
- siloxanes are available, for example, from the General Electric Company as a Viscasil (RTM) series and from Dow Coming as the Dow Corning 200 series.
- the viscosity ranges from about 10 mm ⁇ .s -1 to about 100,000 mm 2 .s _ 1 at 25°C.
- the polyalkylaryl siloxane fluids that may be used also include, for example, polymethylphenylsiloxanes. 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.
- the polyether siloxane copolymer that may be used includes, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC- 1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
- a polypropylene oxide modified dimethylpolysiloxane e.g., Dow Corning DC- 1248
- ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
- Preferred non-volatile silicones for use herein include polydiorganosiloxane-polyoxyalkylene copolymers containing at least one polydiorganosiloxane segment and at least one polyoxyalkylene segment, said polydiorganosiloxane segment consisting essentially of
- 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 50 to about 100 mol percent polyoxyethylene units, at least one terminal portion of said polyoxyalkylene segment being bonded to said polydiorganosiloxane segment, any terminal portion of said polyoxyalkylene segment not bonded to said polydiorganosiloxane segment being satisfied by a terminating radical; the weight ratio of polydiorganosiloxane segments
- polydiorganosiloxane-polyoxyalkylene copolymers having the general formula:
- x and y are selected such that the weight ratio of polydiorganosiloxane segments to polyoxalkylene 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.
- 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 copolymer is preferably from about 2.5 to about 4.0.
- 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. Particularly preferred for use herein are Abil WE 09, Belsil (RTM) 6031, Abil (RTM) B88183 and DC3225C. A preferred silicone herein is known by its CTFA designation as dimethicone copolyol. 96/03962 P
- the silicone oil phase preferably comprises from about 2% to about 25%, more preferably from about 5% to about 15% by weight of composition of non- volatile silicones.
- humectant or mixture of humectants is preferably present in an amount of from about 0.1% to about 30%, more preferably from about 5% to about 25%, and especially from about 10% to about 20% by weight of composition.
- Suitable humectants are selected from glycerine and polyglycerylmethacrylate lubricant having a viscosity at 25°C of 300,000 to 1,100,000 cps; a specific gravity at 25°C of 1 to 1.2g/ml, a pH of 5.0 to 5.5; a bound water content of 33 to 58%; and, a free water content from 5 to 20%.
- the humectant can be incorporated at least partly into the oil phase of the water-in-oil emulsion so as to form a multiphase humectant-in-oil-in- water dispersion.
- the oil phase comprises from about 0.1% to about 10%, preferably from about 0.1% to about 3% by weight of humectant on a composition basis.
- the humectant is introduced into the oil phase in the form of a mixture with or incorporated within a paniculate lipophilic or hydrophobic carrier material, for example a cross-linked hydrophobic acrylate or methacrylate copolymer as described in detail hereafter.
- Suitable polyglycerylmethacrylate lubricants are marketed by Guardian Chemical Corporation under the trademark "Lubrajel”.
- the "Lubrajels” identified as “Lubrajel DV”, “Lubrajel MS”, and “Lubrajel CG” are preferred in the present invention.
- the gelling agents sold under these trademarks contain about 1% propylene glycol.
- humectants include sorbitol, panthenols, propylene glycol, butylene glycol, hexylene glycol, alkoxylated glucose derivatives, such as Glucam (RTM) E-20, hexanetriol, glucose ethers, sodium hyaluronate, and mixtures thereof.
- Urea is also suitably added as a humectant in the internal aqueous phase.
- the panthenol moisturiser can be selected from D-panthenol ([R]-2,4- dihydroxy-N-[3-hydroxypropyl)]-3,3-dimethylbutamide), DL-panthenol, calcium pantothenate, royal jelly, panthetine, pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B complex.
- the humectant is selected from glycerine and sodium hyaluronate, and mixtures thereof.
- glycerine is 1,2,3-propanetriol and is a product of commerce.
- sodium hyaluronate is preferably incorporated at a level of from about 0.05% to about 2% by weight. The mixtures are especially valuable herein from the viewpoint of providing enhanced moisturisation.
- iron oxide-type pigment Another essential component herein is at least one iron oxide-type pigment.
- the iron oxide-type pigment used herein can be either coated or uncoated.
- the pigments can be treated with compounds such as amino acids, silicones, lecithin and ester oils.
- the more preferred pigments are the silicone (polysiloxane) treated pigments.
- the total concentration of the iron oxide-type pigment in the composition is from about 0.1 to about 25% by weight and is preferably from about 1 to about 15% by weight of the total composition.
- the exact concentration of pigments in the composition is dependent to some extent upon the specific mixture of pigments selected for use in a foundation make-up or blusher to achieve the desired shades.
- the preferred compositions contain from about 2% to about 20% by weight of titanium dioxide and most preferably from about 5% to about 10% by weight of titanium dioxide.
- the interference pigment material comprises platelet type mica which is coated with Ti ⁇ 2- The colour of the reflected light varies depending on the thickness of the layer.
- the interference pigment material used in the present invention comprises at least a proportion of pigment material having a Ti ⁇ 2 layer thickness of from about 120nm to about 160nm or a whole number multiple thereof such that the pigment itself has an overall green appearance when applied to skin as a result of light reflection from the pigment platelets.
- Preferred interference pigment materials for use in the composition of the invention are those supplied by Merck under the trade name Timiron, especially Timiron Super Green.
- the Ti ⁇ 2-coated platelet type interference pigment material is used herein at a level of from about 0.1% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.5% to 3% by weight of composition.
- Suitable pigments for use herein can be inorganic and or organic. 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 other suitable pigments are acylglutamate iron oxides, ultramarine blue, D&C dyes, carmine, and mixtures thereof. Depending upon the type of make-up composition, whether foundation or blusher, a mixture of pigments will normally be used.
- the foundation composition can also include from about 0.1% to about 10% of at least one matte finishing agent.
- the function of the matte finishing agent is to hide skin defects and reduce shine.
- Such cosmetically acceptable inorganic agents i.e., those included in the CTFA Cosmetic Ingredient Dictionary, Third Ed., as spherical silica, hydrated silica, silicone-treated silica beads, mica, talc, polyethylene, titanium dioxide, bentonite, hectorite, kaolin, chalk, diatomaceous earth, attapulgite and the like may be utilized.
- a matte finishing agent is low lustre pigment such as titanated mica (mica coated with titanium dioxide) coated with barium sulfate.
- inorganic components useful as a matte finishing agent low lustre pigment, talc, polyethylene, hydrated silica, kaolin, titanium dioxide and mixtures thereof are particularly preferred.
- Materials suitable for use herein as light-scattering agents can be generally described as spherical shaped inorganic materials having a particle size of up to about 100 microns, preferably from about 5 to about 50 microns, for example spherical silica particles.
- spherical silica particles having a specific surface area (N2, BET) of at least 150 m 2 /g (ASTM-D3663-91) and a pore volume of at least 0.5 ml/g (ASTM-D4222-91).
- the balance of the composition of the present invention comprises deionized water.
- the composition preferably comprises from about 15% to about 95%, more preferably from about 20% to about 80% by weight of the oil phase, and from about 5% to about 85%, more preferably from about 20% to about 80% by weight of the water phase.
- the make-up compositions of the present invention can also comprise a paniculate cross-linked hydrophobic acrylate or methacrylate copolymer.
- This copolymer is particularly valuable for reducing shine and controlling oil while helping to provide effective moisturization benefits.
- 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 and having the active ingredient absorbed therein.
- the cross-linked hydrophobic polymer when used herein is in an amount of from about 0.1% to about 10%, preferably from about 0.3-3% by weight and is preferably incorporated in the external silicone-containing oil 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 the present invention which can be employed as the carrier for the active ingredient 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 paniculate 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.
- the polymer has the structural formula: where the ratio of x to y is 80:20, R' is -CH2CH2- and R" is (CH 2 )nCH 3 .
- 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, dispersions 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 200-3 OOm-2/g. Again, it is preferably loaded with humectant in the levels described above.
- compositions of the invention can also contain a hydrophilic gelling agent at a level preferably from about 0.01% to about 10%, more preferably from about 0.02% to about 2%, and especially from about 0.02% to about 0.5%.
- the gelling agent preferably has a viscosity (1% aqueous solution, 20°C, Brookfield RVT) of at least about 4000 mPa.s, more preferably at least about 10,000 mPa.s and especially at least 50,000 mPa.s.
- Suitable hydrophilic gelling agents can generally be described as water- soluble or colloidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, ⁇ olyquaternium-10, guar gum, hydroxypropyl guar gum and xanthan gum.
- cellulose ethers e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose
- polyvinylpyrrolidone polyvinylalcohol
- ⁇ olyquaternium-10 guar gum
- guar gum hydroxypropyl guar gum
- xanthan gum xanthan gum
- hydrophilic gelling 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 cross ⁇ nked polymer of acrylic acid crosslinked with from 0.75% to 2.00% of a crosslinking agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, 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. Also 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 and Pemulen TR-1 (CTFA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer). A combination of the polyalkenyl polyether cross-linked acrylic acid polymer and the hydrophobically modified cross-linked acrylic acid polymer is also suitable for use herein.
- the gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures.
- Neutralizing agents suitable for use in neutralizing acidic group containing hydrophilic gelling agents herein include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoe anolamine, diethanolamine and triethanolamine.
- the make-up compositions herein can additionally comprise an emollient.
- Emollients suitable for the compositions of the present invention include natural and synthetic oils selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, alkylene glycol and polyalkylene glycol ethers and esters, fatty acids and mixtures thereof.
- Suitable emollients for use herein include, for example, optionally hydroxy-substituted C8-C50 * unsaturated fatty acids and esters thereof, C 1-C24 esters of C8-C30 saturated fatty acids such as isopropyl myristate, cetyl palmitate and octyldodecylmyristate (Wickenol 142), 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, such as lanolin alcohol ethoxylated, hydroxylated and acetylated lanolins, cholesterol and derivatives thereof, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil
- Preferred emollients are selected from cetearyl isononanoate, isopropyl palmitate, isopropyl isostearate, cetyl octanoate, cetyl acetate, trioctyl citrate, PEG isoceteth-3 acetate, dioctyl maleate, propylene glycol dicaprylate/dicaprate, caprylic/ capric triglyceride, mineral oil, PPG-20 methylglucose ether, and lanolin alcohol, and mixtures thereof.
- These emollients may be used independently or in mixtures and may be present in the composition of the present invention in an amount from about 1% to about 30% by weight, and preferably are present in an amount from about 5% to about 15% by weight of the total composition.
- composition may also contain additional materials such as, for example, fragrances, fillers such as nylon, sun-screens, preservatives, proteins, antioxidants, chelating agents and water-in-oil emulsifiers as appropriate.
- additional materials such as, for example, fragrances, fillers such as nylon, sun-screens, preservatives, proteins, antioxidants, chelating agents and water-in-oil emulsifiers as appropriate.
- UV absorbing agents can be present in a concentration in the range of between about 1% and about 12% by weight, based on the total weight of composition.
- the UV absorbing agents constitute between about 2% and 8% by weight. More preferably, the UV absorbing agents can be present in the composition in a concentration range of between about 4% and about 6% by weight.
- benzophenone-3, octyl dimethyl PABA (Padimate O) and mixtures thereof are particularly preferred.
- Ultrafine Ti ⁇ 2 is also suitable for use herein.
- a chelating agent can also be incorporated in the make-up composition.
- a chelating agent is preferably present in the composition in a concentration in the range of between about 0.02% to about 0.10% by weight, based on the total weight of the composition.
- the chelating agent is present in a concentration in the range of between about 0.03% and about 0.07% by weight, based on the total weight of the composition.
- the chelating agents that may be included in the composition is trisodium EDTA.
- the preservative concentration in the foundation composition is in the range of between about 0.2% and about 0.8% by weight- preferably between about 0.4% and about 0.6% by weight Suitable preservatives for use herein include diazolidinyl urea, methyl paraben and ethyl paraben, and mixtures thereof.
- sebum spreading agent Another optional but preferred component of the foundation composition is a sebum spreading agent.
- the sebum spreader is present at a level of from about 0.01% to about 5% by weight of composition.
- a preferred sebum spreading agent is sodium Cg-Cig isoalkylsuccinyl lactoglobulin sulfonate (Biopol(RTM) OE).
- a lower (C1-G5) alcohol may also be present in the foundation of the present invention at a level of from about 0.5% to about 10% by weight of composition.
- Suitable lower alcohols for use herein include ethanol, hexylene glycol, butylene glycol, propanol and propylene glycol, preferably ethanol.
- the make-up compositions of the present invention can be in the form of foundations, blushers, concealers, compact powders, and the like, preferably as foundations and blushers.
- Titanium Dioxide 8.25 6.0 1.5 6.0 8.0 20.0 9.0 7.0
- Vitamin A 0.05 — — 0.0
- the various components listed in the Table have been segregated into groups, the constituents of each group being mixed together before being added to members of the remaining groups in accordance with the procedures set forth below.
- the mixture of components of phase A is stirred for approximately 5 minutes with sheer mixing until homogeneous.
- the materials of phase B are added gradually to A and the batch is mixed for 35 minutes until dispersed.
- phase C and then phase D are slowly added to the mixture of phases A and B with high shear mixing until dispersed.
- Silica is added at this point and dispersed through the mixture.
- phase E The components of phase E are added into the resulting batch which is then heated to 84°C and mixed until dispersed.
- the vessel is cooled to 45 °C and the premixed phase F is added.
- the batch is mixed until homogeneous.
- the mixture is cooled to 30°C and phase G is added.
- phase H is made by mixing all the components until completely dissolved. At 30°C the premix of phase H is added sparingly to the batch mixture with high shear, ensuring that there is no excess water on the surface. The mixture is then mixed for 15 minutes. Finally phases I, J, K, and L are added.
- the resulting make-up composition is ready for packing.
- the make-up compositions of the Examples exhibit improved moisturisation, application characteristics, skin feel and appearance, together with colour corrective characteristics.
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8506496A JPH10503515A (en) | 1994-07-30 | 1995-06-30 | Makeup makeup composition |
MX9700793A MX9700793A (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up compositions. |
AU29156/95A AU2915695A (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up compositions |
EP95924770A EP0774950A4 (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up compositions |
CZ97239A CZ23997A3 (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up preparations |
KR1019970700608A KR970704412A (en) | 1994-07-30 | 1995-06-30 | COSMETIC MAKE-UP COMPOSITIONS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9415451.5 | 1994-07-30 | ||
GB9415451A GB9415451D0 (en) | 1994-07-30 | 1994-07-30 | Cosmetic make-up compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996003962A1 true WO1996003962A1 (en) | 1996-02-15 |
Family
ID=10759182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/008340 WO1996003962A1 (en) | 1994-07-30 | 1995-06-30 | Cosmetic make-up compositions |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0774950A4 (en) |
JP (1) | JPH10503515A (en) |
KR (1) | KR970704412A (en) |
AU (1) | AU2915695A (en) |
CA (1) | CA2195961A1 (en) |
CZ (1) | CZ23997A3 (en) |
GB (1) | GB9415451D0 (en) |
MX (1) | MX9700793A (en) |
WO (1) | WO1996003962A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998009609A1 (en) * | 1996-09-06 | 1998-03-12 | Colgate-Palmolive Company | Non-aqueous antiperspirant composition |
US5849275A (en) * | 1995-06-26 | 1998-12-15 | Revlon Consumer Products Corporation | Glossy transfer resistant cosmetic compositions |
FR2791886A1 (en) * | 1999-04-07 | 2000-10-13 | Caster | HOMOGENEOUS LIQUID PERFUMING COMPOSITION BASED ON VOLATILE SILICONES |
WO2001051017A3 (en) * | 2000-01-13 | 2002-01-03 | Color Access Inc | Optical makeup composition comprising an interference pigment anda metal oxide pigment |
WO2004020530A1 (en) | 2002-08-30 | 2004-03-11 | Ciba Specialty Chemicals Holding Inc. | Coloured gloss pigments having at least one coating of siox, with x=0.03 to 0.95 for use in cosmetic and personal care formulations |
EP0701810B1 (en) * | 1994-09-14 | 2004-11-17 | Shiseido Company Limited | Skin-colour adjusting method, and coloured titanium oxide coated mica used therefor |
EP1047371B1 (en) * | 1998-06-24 | 2006-03-29 | Color Access, Inc. | Natural look cosmetic compositions |
US7122174B2 (en) | 2002-09-30 | 2006-10-17 | L'oreal S.A. | Compositions comprising at least one silicone compound and at least one amine compound, and methods for using the same |
WO2009068462A1 (en) * | 2007-11-27 | 2009-06-04 | Basf Se | Use of zero-order diffractive pigments |
US7780955B2 (en) | 2004-11-12 | 2010-08-24 | L'oreal | Cosmetic composition with a lightening effect |
US7939489B2 (en) | 2002-12-23 | 2011-05-10 | Avon Products, Inc. | Oil absorbent topical compositions and methods for using same |
EP1541126B2 (en) † | 2003-12-04 | 2015-08-05 | Beiersdorf AG | Cosmetic and dermatological composition comprising a combination of a green colouring agent and an antiinflammatory agent |
US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US11357714B2 (en) | 2020-07-21 | 2022-06-14 | Chembeau LLC | Diester cosmetic formulations and uses thereof |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9655835B2 (en) * | 2014-10-14 | 2017-05-23 | Elc Management Llc | Oil-controlling cosmetic powder |
WO2021065123A1 (en) * | 2019-10-04 | 2021-04-08 | 株式会社 資生堂 | Solid oil-in-water type emulsified cosmetic |
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US5064644A (en) * | 1984-08-27 | 1991-11-12 | Shiseido Company Ltd. | Water-in-oil emulsion type cosmetic composition |
US5066485A (en) * | 1987-02-06 | 1991-11-19 | Revlon, Inc. | Cosmetic compositions comprising oil-in-water emulsion containing pigment |
US5143722A (en) * | 1986-12-19 | 1992-09-01 | Revlon, Inc. | Cosmetic makeup compositions comprising water-in-oil emulsions containing pigment |
US5169442A (en) * | 1990-05-24 | 1992-12-08 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Bluish green pigment and method of preparing the same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5993894A (en) * | 1993-01-11 | 1994-08-15 | Procter & Gamble Company, The | Cosmetic compositions containing surface treated pigments |
JPH07309715A (en) * | 1994-05-17 | 1995-11-28 | Pola Chem Ind Inc | Makeup cosmetic |
-
1994
- 1994-07-30 GB GB9415451A patent/GB9415451D0/en active Pending
-
1995
- 1995-06-30 JP JP8506496A patent/JPH10503515A/en active Pending
- 1995-06-30 KR KR1019970700608A patent/KR970704412A/en not_active Ceased
- 1995-06-30 MX MX9700793A patent/MX9700793A/en unknown
- 1995-06-30 AU AU29156/95A patent/AU2915695A/en not_active Abandoned
- 1995-06-30 CZ CZ97239A patent/CZ23997A3/en unknown
- 1995-06-30 WO PCT/US1995/008340 patent/WO1996003962A1/en not_active Application Discontinuation
- 1995-06-30 CA CA002195961A patent/CA2195961A1/en not_active Abandoned
- 1995-06-30 EP EP95924770A patent/EP0774950A4/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5064644A (en) * | 1984-08-27 | 1991-11-12 | Shiseido Company Ltd. | Water-in-oil emulsion type cosmetic composition |
US5143722A (en) * | 1986-12-19 | 1992-09-01 | Revlon, Inc. | Cosmetic makeup compositions comprising water-in-oil emulsions containing pigment |
US5143722B1 (en) * | 1986-12-19 | 1999-08-24 | Revlon Consumer Prod Corp | Cosmetic makeup compositions comprising water-in-oil emulsions containing pigment |
US5066485A (en) * | 1987-02-06 | 1991-11-19 | Revlon, Inc. | Cosmetic compositions comprising oil-in-water emulsion containing pigment |
US5169442A (en) * | 1990-05-24 | 1992-12-08 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Bluish green pigment and method of preparing the same |
Non-Patent Citations (1)
Title |
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See also references of EP0774950A4 * |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0701810B1 (en) * | 1994-09-14 | 2004-11-17 | Shiseido Company Limited | Skin-colour adjusting method, and coloured titanium oxide coated mica used therefor |
US5849275A (en) * | 1995-06-26 | 1998-12-15 | Revlon Consumer Products Corporation | Glossy transfer resistant cosmetic compositions |
US5855877A (en) * | 1996-09-06 | 1999-01-05 | Colgate-Palmolive Company | Non-aqueous antiperspirant composition |
AU724176B2 (en) * | 1996-09-06 | 2000-09-14 | Colgate-Palmolive Company, The | Non-aqueous antiperspirant composition |
WO1998009609A1 (en) * | 1996-09-06 | 1998-03-12 | Colgate-Palmolive Company | Non-aqueous antiperspirant composition |
EP1047371B1 (en) * | 1998-06-24 | 2006-03-29 | Color Access, Inc. | Natural look cosmetic compositions |
FR2791886A1 (en) * | 1999-04-07 | 2000-10-13 | Caster | HOMOGENEOUS LIQUID PERFUMING COMPOSITION BASED ON VOLATILE SILICONES |
US6432912B1 (en) | 1999-04-07 | 2002-08-13 | Caster | Homogeneous liquid fragrancing composition based on volatile silicones |
EP1043015A3 (en) * | 1999-04-07 | 2001-01-24 | Caster | Homogeneous liquid fragrance composition based on volatile silicones |
WO2001051017A3 (en) * | 2000-01-13 | 2002-01-03 | Color Access Inc | Optical makeup composition comprising an interference pigment anda metal oxide pigment |
WO2004020530A1 (en) | 2002-08-30 | 2004-03-11 | Ciba Specialty Chemicals Holding Inc. | Coloured gloss pigments having at least one coating of siox, with x=0.03 to 0.95 for use in cosmetic and personal care formulations |
US7122174B2 (en) | 2002-09-30 | 2006-10-17 | L'oreal S.A. | Compositions comprising at least one silicone compound and at least one amine compound, and methods for using the same |
US7939489B2 (en) | 2002-12-23 | 2011-05-10 | Avon Products, Inc. | Oil absorbent topical compositions and methods for using same |
EP1541126B2 (en) † | 2003-12-04 | 2015-08-05 | Beiersdorf AG | Cosmetic and dermatological composition comprising a combination of a green colouring agent and an antiinflammatory agent |
US11497942B2 (en) | 2003-12-04 | 2022-11-15 | Beiersdorf Ag | Cosmetic or dermatological preparation comprising a combination of a dye and an anti-inflammatory active ingredient |
US7780955B2 (en) | 2004-11-12 | 2010-08-24 | L'oreal | Cosmetic composition with a lightening effect |
WO2009068462A1 (en) * | 2007-11-27 | 2009-06-04 | Basf Se | Use of zero-order diffractive pigments |
US20110008399A1 (en) * | 2007-11-27 | 2011-01-13 | Basf Se | Use of zero-order diffractive pigments |
US9168394B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168393B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9168209B2 (en) | 2013-03-13 | 2015-10-27 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
US11357714B2 (en) | 2020-07-21 | 2022-06-14 | Chembeau LLC | Diester cosmetic formulations and uses thereof |
US11491092B2 (en) | 2020-07-21 | 2022-11-08 | Chembeau LLC | Hair treatment formulations and uses thereof |
US11801211B2 (en) | 2020-07-21 | 2023-10-31 | Chembeau LLC | Hair treatment formulations and uses thereof |
US12214065B2 (en) | 2020-07-21 | 2025-02-04 | Chembeau LLC | Diester cosmetic formulations and uses thereof |
US12285508B2 (en) | 2020-07-21 | 2025-04-29 | Chembeau LLC | Hair treatment formulations and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
GB9415451D0 (en) | 1994-09-21 |
CA2195961A1 (en) | 1996-02-15 |
JPH10503515A (en) | 1998-03-31 |
CZ23997A3 (en) | 1997-07-16 |
AU2915695A (en) | 1996-03-04 |
MX9700793A (en) | 1997-05-31 |
EP0774950A1 (en) | 1997-05-28 |
KR970704412A (en) | 1997-09-06 |
EP0774950A4 (en) | 1998-12-23 |
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