The invention is in the field of color cosmetic compositions, preferably those containing water, and how to improve certain aesthetic properties such as moisturization, hydration, and feel of such compositions.
Most cosmetics contain water. However, such water-containing cosmetics are more often found in a liquid emulsion form. Other types of color cosmetic products such as lipsticks are less often found in an emulsion form. Water is a well known hydrating and moisturizing agent. Surprisingly, however, the most hydrating and moisturizing lipsticks are anhydrous compositions. Typical water containing lipsticks tend to be drying on the lips. Such products generally feel hydrating when applied to the lips, but when the water in the formula evaporates it tends to dry out the lip surface. In some cases, after prolonged use, such lipsticks can be considerably drying to the lips particularly for users that have problems with dry lips.
Lipsticks that have treatment benefits such as moisturizing, hydrating, and treating the lips are very desirable from a commercial point of view. As water is the best hydration agent of all it is advantageous to sell products that contain water. However, in order for such products to be successful they must also deliver the moisturization, hydration, and treatment benefits claimed. They must also feel comfortable on the lips.
Lipsticks containing water are known in the art. For example, U.S. Pat. Nos. 4,226,889; 4,322,400; and 4,507,279 teach soap based sticks. Such sticks are suggested for use as antiperspirants, although a colored pigment based stick is also disclosed.
U.S. Pat. Nos. 5,197,814; 5,310,547; 5,466,457 teach lipsticks containing up to 30% water. However, no mention is made of the moisturizing or hydrating properties of the sticks.
U.S. Pat. No. 5,645,903 teaches oil in water solid cosmetic compositions containing large amounts of water.
U.S. Pat. No. 6,162,421 describes water in oil emulsion lipsticks containing water, a volatile solvent, hydrocarbon wax, and fluorinated oil. While the lipsticks taught in this patent have improved moisturization and hydration benefits, they are still not optimal in this regard.
There is still considerable room for improvement in water based lipsticks. In particular, there is a need to make them as comfortable and moisturizing as the standard anhydrous lipophilic products. It has been discovered that formulating water based lipsticks with a sufficient amount of an occlusive material that remains on the lips during and after evaporation of the water present in the lipstick greatly improves the moisturization properties of the lipstick.
It is an object of the invention to provide water based lipsticks that provide the same degree of moisturization, hydration, and treatment benefits as found with standard highly lipophilic anhydrous lipsticks.
It is a further object of the invention to improve the moisturization and hydration properties of water based lipsticks by formulating them with an occlusive ingredient that remains on the lip surface to form a protective barrier once the water present in the formula has evaporated.
It is a further object of the invention to provide a method for moisturizing and hydrating lips with a water based lipstick containing at least one occlusive polymer that will form a barrier on the lips during and after the water present in the formula has evaporated.
It is a further object of the invention to provide lipstick compositions containing a phenyl silicone of a certain viscosity and an oil having a molecular mass of less than about 500 grams/mol.
The invention comprises a structured color cosmetic composition comprising water, a high viscosity phenyl-substituted silicone, a nonionic surfactant, and particulates. Preferably the composition is in the form of a solid or semi-solid, and further preferred is a solid color cosmetic in stick form.
The invention further comprises a structured color cosmetic composition comprising a high viscosity phenyl-substituted silicone and an oil having a molecular weight of less than 500 grams/mole.
The invention comprises a method for moisturizing and hydrating lips comprising applying to the lips a lipstick composition comprising water and at least one occlusive oil capable of forming a barrier layer on the lips after the lipstick composition has been applied to the lips.
The invention further comprises a method for improving the moisturization and hydration properties of a lipstick containing water comprising formulating said composition with an occlusive oil in an amount sufficient to form a barrier layer on the lips when the lipstick is applied to the lips and the water present in the formula begins to evaporate.
I. The Composition
A. The High Viscosity Phenyl Silicone Oil
The composition comprises at least one high viscosity silicone oil. The term “high viscosity” means that the silicone oil has a viscosity of greater than about 650 centipoise, more preferably a viscosity of greater than about 850 centipoise at 25° C. The high viscosity phenyl substituted silicone is present in amounts ranging from about 0.1-85%, preferably from about 0.5-75%, more preferably from about 1-45% by weight of the total composition. The preferred high viscosity silicone has the general formula:
wherein OR′ is SiMe3 wherein Me is methyl, and y and z are each independently 1-1000. One example of such a silicone is sold under the tradename PDM 1000 by Wacker-Belsil having the INCI name trimethylsiloxyphenyl dimethicone.
B. Water
The compositions of the invention contain water. Preferably, water is present in amounts ranging from about 0.5 to 85%, preferably from about 1 to 50%, more preferably from about 2 to 45% by weight of the total composition.
C. Nonionic Surfactant
The compositions of the invention may comprise about 0.01-20%, preferably from about 0.1-15%, more preferably from about 0.5-10% by weight of the total composition of a nonionic surfactant. Suitable nonionic surfactants or emulsifiers include alkoxylated alcohols, or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide. Preferably the alcohol is either a fatty alcohol having 6 to 30 carbon atoms. Examples of such ingredients include Beheneth 5-30, which is formed by the reaction of behenyl alcohol and ethylene oxide where the number of repeated ethylene oxide units is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, and so on. Other alkoxylated alcohols are formed by the reaction of fatty acids and mono-, di- or polyhydric alcohols with an alkylene oxide. For example, the reaction products of C6-30 fatty carboxylic acids and polyhydric alcohols which are monosaccharides such as glucose, galactose, methyl glucose, and the like, with an alkoxylated alcohol. Preferred are alkoxylated alcohols which are formed by the reaction of stearic acid, methyl glucose, and and ethoxylated alcohol, otherwise known as PEG-20 methyl glucose sesquiisostearate.
Also suitable as the nonionic surfactant are alkyoxylated carboxylic acids, which are formed by the reaction of a carboxylic acid with an alkylene oxide or with a polymeric ether. The resulting products have the general formula:
where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl, and n is the number of polymerized alkoxy groups. In the case of the diesters, the two RCO— groups do not need to be identical. Preferably, R is a C6-30 straight or branched chain, saturated or unsaturated alkyl, and n is from 1-100.
Also suitable as the nonionic surfactant are monomeric, homopolymeric and block copolymeric ethers. Such ethers are formed by the polymerization of monomeric alkylene oxides, generally ethylene or propylene oxide. Such polymeric ethers have the following general formula:
wherein R is H or lower alkyl and n is the number of repeating monomer units, and ranges from 1 to 500.
Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular, ethoxylation, of sorbitan provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates. Examples of such ingredients include Polysorbates 20-85, sorbitan oleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and so on.
Particularly preferred nonionic surfactants are silicone surfactants, which are defined as silicone polymers that have at least one hydrophilic radical and at least one lipophilic radical. The silicone surfactant used in the compositions of the invention are organosiloxane polymers that may be a liquid or solid at room temperature. The organosiloxane surfactant is generally a water-in-oil or oil-in-water type surfactant which is, and has an Hydrophile/Lipophile Balance (HLB) of 2 to 18. Preferably the organosiloxane is a nonionic surfactant having an HLB of 2 to 12, preferably 2 to 10, most preferably 4 to 6. The HLB of a nonionic surfactant is the balance between the hydrophilic and lipophilic portions of the surfactant and is calculated according to the following formula:
HLB=7+11.7×log Mw/Mo
where Mw is the molecular weight of the hydrophilic group portion and Mo is the
Examples of silicone surfactants are those sold by Dow Coming under the trade name Dow Coming 3225C Formulation Aid, Dow Coming 190 Surfactant, Dow Coming 193 Surfactant, Dow Coming Q2-5200, and the like are also suitable. In addition, surfactants sold under the trade name Silwet by Union Carbide, or a silicone surfactant blend sold by Goldschmidt Corporation under the trade name Abil, which is a mixture of cetyl dimethicone copolyol, polyglyceryl-4 isostearate, and hexyl laurate. Such types of silicone surfactants are generally referred to as dimethicone copolyols or alkyl dimethicone copolyols.
D. Structuring Agent The cosmetic composition of the invention is structured, meaning that it contains at least one structuring agent. Most preferred is where it is in the form of a semi-solid or solid. Most preferred is where the composition is in the form of a solid stick. The term “structuring agent” means an ingredient that causes an increase in viscosity, or thickens, a composition. Structuring agents include solid or semi-solid waxes, montmorillonite minerals, associative thickeners, and the like. The compositions of the invention may comprise one more structuring agents. The term “structuring agent” means an ingredient or combination of ingredients that increase the viscosity of, or thicken, the composition. Suggested ranges of structuring agent range from about 0.01-65%, preferably about 0.05-50%, more preferably about 0.1-45% by weight of the total composition. In the composition of the invention, the structuring agent may be found in the oil phase, water phase, or both phases.
1. Montmorillonite Minerals
One type of structuring agent that may be used in the composition comprises natural or synthetic montmorillonite minerals such as hectorite, bentonite, and quaternized derivatives thereof, which are obtained by reacting the minerals with a quaternary ammonium compound, such as stearalkonium bentonite, hectorites, quatemized hectorites such as Quaternium-18 hectorite, attapulgite, carbonates such as propylene carbonate, bentones, and the like. Particularly preferred is Quaternium-18 hectorite.
2. Associative Thickeners
Also suitable as structuring agents are various polymeric compounds known in the art as associative thickeners. Suitable associative thickeners generally contain a hydrophilic backbone and hydrophobic side groups. Examples of such thickeners include polyacrylates with hydrophobic side groups, cellulose ethers with hydrophobic side groups, polyurethane thickeners. Examples of hydrophobic side groups are long chain alkyl groups such as dodecyl, hexadecyl, or octadecyl; alkylaryl groups such as octylphenyl or nonyphenyl. Further specific examples include hydroxypropylcellulose, hydroxypropylethylcellulose, cellulose gums, and the like.
3. Silicas and Silicates
Another type of structuring agent that may be used in the compositions are silicas, silicates, silica silylate, and alkali metal or alkaline earth metal derivatives thereof. These silicas and silicates are generally found in the particulate form and include silica, silica silylate, magnesium aluminum silicate, and the like.
4. Silicone Elastomers
Also suitable as structuring agents are cross-linked organosiloxane compounds also known as silicone elastomers. Such elastomers are generally prepared by reacting a dimethyl methylhydrogen siloxane with a crosslinking group comprised of a siloxane having an alkylene group having terminal olefinic unsaturation, or with an organic group having an alpha or omega diene. Examples of suitable silicone elastomers for use as thixotropic agents include Dow Coming 9040, sold by Dow Coming, and various elastomeric silicones sold by Shin-Etsu under the KSG tradename including KSG 15, KSG 16, KSG 19 and so on.
5. Natural or Synthetic Organic Waxes
Suitable structuring agents include natural or synthetic waxes. A variety of waxes are suitable including animal, vegetable, mineral, or silicone waxes. Generally such waxes have a melting point ranging from about 28 to 125° C., preferably about 30 to 100° C. Examples of waxes include acacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnauba wax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, candelilla, grape wax, and polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or PEG-12 camauba wax; or fatty acids or fatty alcohols, including esters thereof, such as hydroxystearic acids (for example 12-hydroxy stearic acid), tristearin, tribehenin, and so on.
6. Silicone Waxes
Also suitable are various types of silicone waxes, referred to as alkyl silicones, which are polymers that comprise repeating dimethylsiloxy units in combination with one or more methyl-long chain alkyl siloxy units wherein the long chain alkyl is generally a fatty chain that provides a wax-like characteristic to the silicone such that is a solid or semi-solid at room temperature. Such silicones include, but are not limited to stearoxydimethicone, behenoxy dimethicone, stearyl dimethicone, cetearyl dimethicone, and so on. Suitable waxes are set forth in U.S. Pat. No. 5,725,845, which is hereby incorporated by reference in its entirety.
7. Polyamides and Silicone Polyamides
Also suitable as structuring agents are various types of polyamides or silicone polyamides including those set forth in U.S. patent publication nos. 2002/0114773 or 2003/0072730, both of which are hereby incorporated by reference in their entirety.
Silicone polyamides include those having moieties of the general formula:
wherein:
X is a linear or branched alkylene having from about 1-30 carbon atoms,
R1, R2, R3, and R4 are each independently C1-30 straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more C1-3 alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
Y is:
(a) a linear or branched alkylene having from about 1-40 carbon atoms which may be substituted with (i) one or more amide groups having the general formula R1CONR1, or (ii) C5-6 cyclic ring, or (iii) phenylene which may be substituted with one or more C1-10 alkyl groups, or (iv) hydroxy, or (v) C3-8 cycloalkane, or (vi) C1-20 alkyl which may be substituted with one or more hydroxy groups, or (vii) C1-10 alkyl amines; or
(b) TR5R6R7
wherein R5, R6, and R7, are each independently a C1-10 linear or branched alkylene, and T is CR8 wherein R8 is hydrogen, a trivalent atom N, P, or Al, or a C1-30 straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more C1-30 alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
and a and b are each independently sufficient to provide a silicone polyamide polymer having a melting point ranging from about 60 to 120° C., preferably about 85 to 105° C. and a molecular weight ranging from about 40,000 to 500,000 Daltons, preferably about 65,000 to 149,000 Daltons.
Preferred is where R1, R2, R3, and R4 are C1-10, preferably methyl; and X and Y is a linear or branched alkylene. Preferred are silicone polyamides having the general formula:
wherein a, b, and x are each independently sufficient to provide a silicone polyamide polymer having a melting point ranging from about 60 to 120° C., preferably about 85 to 105° C. and a molecular weight ranging from about 40,000 to 500,000 Daltons, preferably about 65,000 to 149,000 Daltons. One type of silicone polyamide that may be used in the compositions of the invention may be purchased from Dow Coming Corporation under the tradename Dow Coming 2-8178 gellant which has the INCI name nylon-611/dimethicone copolymer which is sold in a composition containing PPG-3 myristyl ether.
Preferred structuring agents are waxes such as polyethylene, ceresin, ozokerite, and the like.
E. Particulates
The compositions of the invention may contain particulate materials in the form of pigments, inert particulates, or mixtures thereof. If present, suggested ranges are from about 0.01-95%, preferably about 0.05-70%, more preferably about 0.1-65% by weight of the total composition. In the case where the composition may comprise mixtures of pigments and powders, suitable ranges include about 0.01-75% pigment and 0.1-75% powder, such weights by weight of the total composition.
1. Powders
The particulate matter may be colored or non-colored (for example white) non-pigmentations powders. Suitable non-pigmentations powders include bismuth oxychloride, titanated mica, fumed silica, spherical silica, polymethylmethacrylate, micronized teflon, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium aluminum silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate, calcium silicate, dextran, kaolin, nylon, silica silylate, silk powder, sericite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder, or mixtures thereof. The above mentioned powders may be surface treated with lecithin, amino acids, mineral oil, silicone, or various other agents either alone or in combination, which coat the powder surface and render the particles more lipophilic in nature.
2. Pigments
The particulate materials may comprise various organic and/or inorganic pigments. The organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthroquinone, and xanthine dyes which are designated as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc. Organic pigments generally consist of insoluble metallic salts of certified color additives, referred to as the Lakes. Inorganic pigments include iron oxides, ultramarines, chromium, chromium hydroxide colors, and mixtures thereof. Iron oxides of red, blue, yellow, brown, black, and mixtures thereof are suitable.
F. Other Ingredients
The compositions of the invention may contain a variety of other ingredients such as humectants, preservatives, additional film forming polymers, sunscreens, and so on. Some of such ingredients include, but are not limited to those set forth herein.
1. Sunscreens
In one preferred embodiment of the invention, it is desirable that the compositions contain sunscreens in an amount sufficient to confer an SPF ranging from about 1 to 25. Such sunscreens may be chemical or physical sunscreens, and if chemical may be UVA and UVB sunscreens including those set forth below.
(a). UVA Chemical Sunscreens
If desired, the composition may comprise one or more UVA sunscreens. The term “UVA sunscreen” means a chemical compound that blocks UV radiation in the wavelength range of about 320 to 400 nm. Preferred UVA sunscreens are dibenzoylmethane compounds having the general formula:
wherein R1 is H, OR and NRR wherein each R is independently H, C1-20 straight or branched chain alkyl; R2 is H or OH; and R3 is H, C1-20 straight or branched chain alkyl.
Preferred is where R1 is OR where R is a C1-20 straight or branched alkyl, preferably methyl; R2 is H; and R3 is a C1-20 straight or branched chain alkyl, more preferably, butyl.
Examples of suitable UVA sunscreen compounds of this general formula include 4-methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4′-diisopropylbenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane, 4,4′-diisopropylbenzoylmethane, 2-methyl-5-isopropyl-4′-methoxydibenzoymethane, 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane, and so on. Particularly preferred is 4-tert-butyl-4′-methoxydibenzoylmethane, also referred to as Avobenzone. Avobenzone is commercial available from Givaudan-Roure under the trademark Parsol 1789, and Merck & Co. under the tradename Eusolex 9020.
The composition may contain from about 0.001-20%, preferably 0.005-5%, more preferably about 0.005-3% by weight of the composition of UVA sunscreen. In the preferred embodiment of the invention the UVA sunscreen is Avobenzone, and it is present at not greater than about 3% by weight of the total composition.
(b). UVB Chemical Sunscreens
The term “UVB sunscreen” means a compound that blocks UV radiation in the wavelength range of from about 290 to 320 nm. A variety of UVB chemical sunscreens exist including α-cyano-β,β-diphenyl acrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which is hereby incorporated by reference in its entirety. One particular example of a α-cyano-β,β-diphenyl acrylic acid ester is Octocrylene, which is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In certain cases the composition may contain no more than about 10% by weight of the total composition Octocrylene. Suitable amounts range from about 0.001-10% by weight. Octocrylene may be purchased from BASF under the tradename Uvinul N-539.
Other suitable sunscreens include benzylidene camphor derivatives as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety. Such benzylidene camphor derivatives have the general formula:
wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred is 4-methylbenzylidene camphor, which is a lipid soluble UVB sunscreen compound sold under the tradename Eusolex 6300 by Merck.
Also suitable are cinnamate derivatives having the general formula:
wherein R and R1 are each independently a C1-20 straight or branched chain alkyl. Preferred is where R is methyl and R1 is a branched chain C1-10, preferably C8 alkyl. The preferred compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate or octyl methoxycinnamate. The compound may be purchased from Givaudan Corporation under the tradename Parsol MCX, or BASF under the tradename Uvinul MC 80. Also suitable are mono-, di-, and triethanolamine derivatives of such methoxy cinnamates including diethanolamine methoxycinnamate. Cinoxate, the aromatic ether derivative of the above compound is also acceptable. If present, the Cinoxate should be found at no more than about 3% by weight of the total composition.
Also suitable as UVB screening agents are various benzophenone derivatives having the general formula:
wherein R through R9 are each independently H, OH, NaO3S, SO3H, SO3Na, Cl, R″, OR″ where R″ is C1-20 straight or branched chain alkyl. Examples of such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Particularly preferred is where the benzophenone derivative is Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (also referred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium), and the like. Most preferred is Benzophenone 3.
Also suitable are certain menthyl salicylate derivatives having the general formula:
wherein R1, R2, R3, and R4 are each independently H, OH, NH2, or C1-20 straight or branched chain alkyl. Particularly preferred is where R1, R2, and R3 are methyl and R4 is hydroxyl or NH2, the compound having the name homomenthyl salicylate (also known as Homosalate) or menthyl anthranilate. Homosalate is available commercially from Merck under the tradename Eusolex HMS and menthyl anthranilate is commercially available from Haarmann & Reimer under the tradename Heliopan. If present, the Homosalate should be found at no more than about 15% by weight of the total composition.
Various amino benzoic acid derivatives are suitable UVB absorbers including those having the general formula:
wherein R1, R2, and R3 are each independently H, C1-20 straight or branched chain alkyl which may be substituted with one or more hydroxy groups. Particularly preferred is wherein R1 is H or C1-8 straight or branched alkyl, and R2 and R3 are H, or C1-8 straight or branched chain alkyl. Particularly preferred are PABA, ethyl hexyl dimethyl PABA (Padimate O), ethyldihydroxypropyl PABA, and the like. If present Padimate O should be found at no more than about 8% by weight of the total composition.
Salicylate derivatives are also acceptable UVB absorbers. Such compounds have the general formula:
wherein R is a straight or branched chain alkyl, including derivatives of the above compound formed from mono-, di-, or triethanolamines. Particular preferred are octyl salicylate, TEA-salicylate, DEA-salicylate, and mixtures thereof.
Generally, the amount of the UVB chemical sunscreen present may range from about 0.001-45%, preferably 0.005-40%, more preferably about 0.01-35% by weight of the total composition.
(c). Physical Sunscreens
The composition may also include one or more physical sunscreens. The term “physical sunscreen” means a material that is generally particulate in form that is able to block UV rays by forming an actual physical block on the skin. Examples of particulates that serve as solid physical sunblocks include titanium dioxide, zinc oxide and the like in particle sizes ranging from about 0.001-150 microns.
If desired, the compositions of the invention may be formulated to have a certain SPF (sun protective factor) values ranging from about 1-50, preferably about 2-45, most preferably about 5-30. Calculation of SPF values is well known in the art. Preferably, the claimed compositions have SPF values greater than 4.
3. Humectants
If desired, the compositions of the invention comprise 0.01-30%, preferably 0.5-25%, more preferably 1-20% by weight of the total composition of one or more humectants. Such humectants are preferably found in the water phase of the composition. Suitable humectants include materials such as glycols, sugars, and the like. Suitable glycols include polyethylene and polypropylene glycols such as PEG 4-240, which are polyethylene glycols having from 4 to 240 repeating ethylene oxide units; as well as C1-6 alkylene glycols such as propylene glycol, butylene glycol, and the like. Suitable sugars, some of which are also polyhydric alcohols, are also suitable humectants. Examples of such sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Preferably, the humectants used in the composition of the invention are C1-6, preferably C2-4 alkylene glycols, most particularly butylene glycol.
4. Botanical Extracts
It may be desirable to include one or more botanical extracts in the compositions. If so, suggested ranges are from about 0.0001 to 10%, preferably about 0.0005 to 8%, more preferably about 0.001 to 5% by weight of the total composition. Suitable botanical extracts include extracts from plants (herbs, roots, flowers, fruits, seeds) such as flowers, fruits, vegetables, and so on, including acacia (dealbata, farnesiana, senegal), acer saccharinum (sugar maple), acidopholus, acorus, aesculus, agaricus, agave, agrimonia, algae, aloe, citrus, brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear, lemon, lime, pea, seaweed, green tea, chamomile, willowbark, mulberry, poppy, and those set forth on pages 1646 through 1660 of the CTFA Cosmetic Ingredient Handbook, Eighth Edition, Volume 2. Further specific examples include, but are not limited to, Glycyrrhiza Glabra, Salix Nigra, Macrocycstis Pyrifera, Pyrus Malus, Saxifraga Sarmentosa, Vitis Vinifera, Morus Nigra, Scutellaria Baicalensis, Anthemis Nobilis, Salvia Sclarea, Rosmarinus Officianalis, Citrus Medica Limonum, and mixtures thereof.
5. Additional Oils
The composition of the invention may contain oils in addition to the at least one occlusive oil. If present, suggested ranges for such oils in the compositions of the invention are about 0.1-90%, preferably 0.5-75%, more preferably 1-60% by weight of the total composition. The oils used may be volatile or nonvolatile, and are pourable liquids at room temperature.
The term “volatile” means that the oil has a measurable vapor pressure, or a vapor pressure of at least about 2 mm. of mercury at 200° C. The term “nonvolatile” means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20° C.
(a). Volatile Oils
Suitable volatile oils generally have a viscosity of about 0.5 to 10 centipoise at 250° C. Suitable volatile oils include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof.
Cyclic silicones (or cyclomethicones) are of the general formula:
where n=3-6.
Linear volatile silicones in accordance with the invention have the general formula:
(CH3)3—Si—O—[Si—(CH3)2—O]n—Si—(CH3)3
where n=0-7, preferably 0-5.
Linear and cyclic volatile silicones are available from various commercial sources including Dow Coming Corporation and General Electric. The Dow Coming volatile silicones are sold under the trade names Dow Corning 244, 245, 344, and 200 fluids. These fluids comprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylhexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Examples of linear volatile silicones include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like.
Also suitable as the volatile oils are various straight or branched chain paraffinic hydrocarbons having 5 to 40 carbon atoms, more preferably 8-20 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and C8-20 isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference. Preferred volatile paraffinic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60-260 degrees C., and a viscosity of less than 10 cs. at 25 degrees C. Such paraffinic ydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Another C12 isoparaffin (isododecane) is distributed by Presperse under the tradename Permethyl 99A. Various C16 isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R), are also suitable. Transfer resistant cosmetic sticks of the invention will generally comprise a mixture of volatile silicones and volatile paraffinic hydrocarbons.
(b). Non-Volatile Oils
A wide variety of nonvolatile oils are also suitable for use in the cosmetic compositions of the invention. The nonvolatile oils generally have a viscosity of greater than about 5 to 10 centipoise at 25° C., and may range in viscosity up to about 1,000,000 centipoise at 25° C.
In one embodiment of the invention the oils present have a molecular mass of less than about 500 grams/mole. Preferably, the molecular mass ranges from 50 to 499 grams/mole, more preferably from about 100 to 450 grams/mole, and even more preferably from 200 to 400 grams/mole. Such oils include those set forth below.
(i). Esters
Suitable esters are mono-, di-, and triesters. The composition may comprise one or more esters selected from the group, or mixtures thereof.
(aa). Monoesters
Monoesters are defined as esters formed by the reaction of a monocarboxylic acid having the formula R—COOH, wherein R is a straight or branched chain saturated or unsaturated alkyl having 2 to 30 carbon atoms, or phenyl; and an alcohol having the formula R—OH wherein R is a straight or branched chain saturated or unsaturated alkyl having 2-30 carbon atoms, or phenyl. Both the alcohol and the acid may be substituted with one or more hydroxyl groups. Either one or both of the acid or alcohol may be a “fatty” acid or alcohol, and may have from about 6 to 30 carbon atoms. Examples of monoester oils that may be used in the compositions of the invention include hexyldecyl benzoate, hexyl laurate, hexadecyl isostearate, hexydecyl laurate, hexyldecyl octanoate, hexyldecyl oleate, hexyldecyl palmitate, hexyldecyl stearate, hexyldodecyl salicylate, hexyl isostearate, butyl acetate, butyl isostearate, butyl oleate, butyl octyl oleate, cetyl palmitate, cetyl octanoate, cetyl laurate, cetyl lactate, isostearyl isononanoate, cetyl isononanoate, cetyl stearate, stearyl lactate, stearyl octanoate, stearyl heptanoate, stearyl stearate, and so on.
(bb). Diesters
Suitable diesters are the reaction product of a dicarboxylic acid and an aliphatic or aromatic alcohol. The dicarboxylic acid may contain from 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated or unsaturated form. The dicarboxylic acid may be substituted with one or more hydroxyl groups. The aliphatic or aromatic alcohol may also contain 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated, or unsaturated form. The aliphatic or aromatic alcohol may be substituted with one or more substituents such as hydroxyl. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol, i.e. contains 14-22 carbon atoms. The dicarboxylic acid may also be an alpha hydroxy acid. Examples of diester oils that may be used in the compositions of the invention include diisostearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, di-C12-13 alkyl malate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, and so on.
(cc). Triesters
Suitable triesters comprise the reaction product of a tricarboxylic acid and an aliphatic or aromatic alcohol. As with the mono- and diesters mentioned above, the acid and alcohol contain 2 to 30 carbon atoms, and may be saturated or unsaturated, straight or branched chain, and may be substituted with one or more hydroxyl groups. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol containing 14 to 22 carbon atoms. Examples of triesters include triarachidin, tributyl citrate, triisostearyl citrate, tri C12-13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate, tridecyl cocoate, tridecyl isononanoate, and so on.
Esters suitable for use in the composition are further described on pages 1670-1676 of the C.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eighth Edition, 2000, which is hereby incorporated by reference in its entirety.
(ii). Hydrocarbon Oils
It may be desirable to incorporate one or more non-volatile hydrocarbon oils into the composition. The term “nonvolatile” means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20° C.
Suitable nonvolatile hydrocarbon oils include paraffinic hydrocarbons and olefins, preferably those having greater than 20 carbon atoms. Examples of such hydrocarbon oils include C24-28 olefins, C30-45 olefins, C20-40 isoparaffins, hydrogenated polyisobutene, polyisobutene, mineral oil, pentahydrosqualene, squalene, squalane, and mixtures thereof.
(aa). Lanolin Oil
Also suitable for use in the composition is lanolin oil or derivatives thereof containing hydroxyl, alkyl, or acetyl groups, such as hydroxylated lanolin, isobutylated lanolin oil, acetylated lanolin, acetylated lanolin alcohol, and so on.
(bb). Glyceryl Esters of Fatty Acids
Naturally occurring glyceryl esters of fatty acids, or triglycerides, are also suitable for use in the compositions. Both vegetable and animal sources may be used. Examples of such oils include castor oil, lanolin oil, C10-18 triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, walnut oil, and the like.
Also suitable are synthetic or semi-synthetic glyceryl esters, e.g. fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, acetylated castor oil, or mono-, di- or triesters of polyols such as glyceryl stearate, diglyceryl diiosostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryl trioctanoate, diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on.
(cc). Nonvolatile Silicones
Nonvolatile silicone oils, both water soluble and water insoluble, are also suitable for use in the composition. Such silicones preferably have a viscosity ranging from about 10 to 600,000 centistokes, preferably 20 to 100,000 centistokes at 25° C. Suitable water insoluble silicones include amine functional silicones such as amodimethicone; phenyl substituted silicones such as bisphenylhexamethicone, phenyl trimethicone, or polyphenylmethylsiloxane; dimethicone, alkyl substituted dimethicones, and mixtures thereof.
Such silicones have the following general formula:
wherein R and R′ are each independently C1-30 alkyl, phenyl or aryl, trialkylsiloxy, and x and y are each independently 0-1,000,000 with the proviso that there is at least one of either x or y, and A is siloxy endcap unit. Preferred is where A is a methyl siloxy endcap unit, in particular trimethylsiloxy, and R and R′ are each independently a C1-30 straight or branched chain alkyl, phenyl, or trimethylsiloxy, more preferably a C1-22 alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl, or trimethylsiloxy, and resulting silicone is dimethicone, phenyl dimethicone, or phenyl trimethicone. Other examples include alkyl dimethicones such as cetyl dimethicone, and the like wherein at least one R is a fatty alkyl (C12, C14, C16, C18, or C22), and the other R is methyl, and A is a trimethylsiloxy endcap unit.
(dd). Fluorinated Oils
Various types of fluorinated oils may also be suitable for use in the compositions including but not limited to fluorinated silicones, fluorinated esters, or perfluropolyethers. Particularly suitable are fluorosilicones such as trimethylsilyl endcapped fluorosilicone oil, polytrifluoropropylmethylsiloxanes, and similar silicones such as those disclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated by reference. Perfluoropolyethers include those disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated by reference, which are commercially available from Montefluos under the trademark Fomblin.
Fluoroguerbet esters are also suitable oils. The term “guerbet ester” means an ester which is formed by the reaction of a guerbet alcohol having the general formula:
and a fluoroalcohol having the following general formula:
CF3—(CF2)n—CH2—CH2—OH
wherein n is from 3 to 40,
with a carboxylic acid having the general formula:
R3COOH, or
HOOC—R3—COOH
wherein R1, R2, and R3 are each independently a straight or branched chain alkyl.
The guerbet ester may be a fluoro-guerbet ester, which is formed by the reaction of a guerbet alcohol and carboxylic acid (as defined above), and a fluoroalcohol having the following general formula:
CF3—(CF2)n—CH2—CH2—OH
wherein n is from 3 to 40.
Examples of suitable fluoro guerbet esters are set forth in U.S. Pat. No. 5,488,121 which is hereby incorporated by reference. Suitable fluoro-guerbet esters are also set forth in U.S. Pat. No. 5,312,968 which is hereby incorporated by reference. One type of such an ester is fluorooctyldodecyl meadowfoamate, sold under the tradename Silube GME-F by Siltech, Norcross, Ga.
6. Film Forming Polymers
If desired, the composition may comprise one or more additional film forming polymers. If present, suggested ranges are from about 0.1 to 75%, preferably from about 0.5 to 60%, more preferably from about 1-50% by weight of the total composition. Suitable film forming polymers may be water soluble or water dispersible and include organic polymers made from one or more ethylenically unsaturated monomers, copolymers of silicone and one or more organic monomers, or copolymers of ethylenically unsaturated monomers and one or more organic compounds.
(a). Silicone Film Forming Polymers
(i). Siloxane Polymeric Resins and Gums
Siloxane polymeric resins that comprise tetrafunctional or trifunctional units either alone or in combination with monofunctional units are suitable silicone film forming polymers for use in the composition. The term “siloxane polymeric resin” means that the siloxane is a polymer, or is comprised of repeating units or “mers”.
The term “resin” means that the siloxane polymer provides substantive, resinous, film forming properties when applied to skin. In the context of this invention, the term “resin” will mean a siloxane containing enough cross-linking to provide substantive, film forming properties. The term cross-linking means a moiety where the silicon atom is bonded to at least three, preferably four oxygen atoms when the moiety is polymerized with another siloxane unit.
The term “film forming” means that the siloxane resin is capable of forming a film, in particular, a substantive film, on the keratinous surface to which it is applied.
The term monofunctional unit means a siloxy unit that contains one silicon atom bonded to one oxygen atom, with the remaining three substituents on the silicon atom being other than oxygen. In particular, in a monofunctional siloxy unit, the oxygen atom present is shared by 2 silicon atoms when the monofunctional unit is polymerized with one or more of the other units. In silicone nomenclature used by those skilled in the art, a monofunctional siloxy unit is designated by the letter “M”, and means a unit having the general formula:
R1R2R3SiO1/2
wherein R1, R2, and R3 are each independently C1-30, preferably C1-10, more preferably C1-4 straight or branched chain alkyl, which may be substituted with phenyl or one or more hydroxyl groups; phenyl; alkoxy (preferably C1-22, more preferably C1-6); or hydrogen. The SiO1/2 designation means that the oxygen atom in the monofunctional unit is bonded to, or shared, with another silicon atom when the monofunctional unit is polymerized with one or more of the other types of units. For example, when R1, R2, and R3 are methyl the resulting monofunctional unit is of the formula:
When this monofunctional unit is polymerized with one or more of the other units the oxygen atom will be shared by another silicon atom, i.e. the silicon atom in the monofunctional unit is bonded to ½ of this oxygen atom.
The term “difunctional siloxy unit” is generally designated by the letter “D” in standard silicone nomenclature. If the D unit is substituted with substituents other than methyl the “D′” designation is sometimes used, which indicates a substituent other than methyl. For purposes of this disclosure, a “D” unit has the general formula:
R1R2SiO2/2
wherein R1 and R2 are defined as above. The SiO2/2 designation means that the silicon atom in the difunctional unit is bonded to two oxygen atoms when the unit is polymerized with one or more of the other units. For example, when R1 and R2, are methyl the resulting difunctional unit is of the formula:
When this difunctional unit is polymerized with one or more of the other units the silicon atom will be bonded to two oxygen atoms, i.e. will share two one-halves of an oxygen atom.
The term “trifunctional siloxy unit” is generally designated by the letter “T” in standard silicone nomenclature. A “T” unit has the general formula:
R1SiO3/2
wherein R1 is as defined above. The SiO3/2 designation means that the silicon atom is bonded to three oxygen atoms when the unit is copolymerized with one or more of the other units. For example when R1 is methyl the resulting trifunctional unit is of the formula:
When this trifunctional unit is polymerized with one or more of the other units, the silicon atom shares three oxygen atoms with other silicon atoms, i.e. will share three halves of an oxygen atom.
The term “tetrafunctional siloxy unit” is generally designated by the letter “Q” in standard silicone nomenclature. A “Q” unit has the general formula:
SiO4/2
The SiO4/2 designation means that the silicon shares four oxygen atoms (i.e., four halves) with other silicon atoms when the tetrafunctional unit is polymerized with one or more of the other units. The SiO4/2 unit is best depicted as follows:
The film forming siloxane resins that may be used in the compositions of the invention comprises D, T or Q units either alone or in combination with M units. In addition, there may be one or more of the other types of units present in the polymer.
The film forming polymeric siloxane resin may be a liquid, semi-solid, or solid at room temperature. Preferably, the siloxane polymeric resin is a semi-solid or solid at room temperature.
Typically T or MT silicones are referred to as silsesquioxanes, and in the case where M units are present methylsilsesquioxanes. Preferred are T silicones having the following general formula:
(R1SiO3/2)x
where x ranges from about 1 to 100,000, preferably about 1-50,000, more preferably about 1-10,000, and wherein R1 is as defined above. Such MT silicones are generally referred to as polymethylsilsesquioxane which are silsesquioxanes containing methyl groups.
Examples of specific polysilsesquioxanes that may be used are manufactured by Wacker Chemie under the Resin MK designation. This polysilsesquioxane is a polymer comprised of T units and, optionally one or more D (preferably dimethylsiloxy) units. This particularly polymer may have ends capped with ethoxy groups, and/or hydroxyl groups, which may be due to how the polymers are made, e.g. condensation in aqueous or alcoholic media. Other suitable polysilsesquioxanes that may be used as the film forming polymer include those manufactured by Shin-Etsu Silicones and include the “KR” series, e.g. KR-220L, 242A, and so on. These particular silicone resins may contain endcap units that are hydroxyl or alkoxy groups, which may be present due to the manner in which such resins are manufactured.
Also suitable are MQ resins, which are siloxy silicate polymers having the following general formula:
wherein R, R′ and R″ are each independently a C1-10 straight or branched chain alkyl or phenyl, and x and y are such that the ratio of (RR′R″)3SiO1/2 units to SiO2 units ranges from about 0.5 to 1 to 1.5 to 1. Preferably R, R′ and R″ are a C1-6 alkyl, and more preferably are methyl and x and y are such that the ratio of (CH3)3SiO1/2 units to SiO2 units is about 0.75 to 1. Most preferred is this trimethylsiloxysilicate containing 2.4 to 2.9 weight percent hydroxyl groups, which is formed by the reaction of the sodium salt of silicic acid, chlorotrimethylsilane, and isopropyl alcohol. The manufacture of trimethylsiloxysilicate is set forth in U.S. Pat. Nos. 2,676,182; 3,541,205; and 3,836,437, all of which are hereby incorporated by reference.
Trimethylsiloxysilicate as described is available from GE Silicones under the tradename SR-1000, which is a solid particulate material. Also suitable is Dow Coming 749 which is a mixture of volatile cyclic silicone and trimethylsiloxysilicate.
The film forming siloxane polymeric resins that may be used in the composition are made according to processes well known in the art. In general siloxane polymers are obtained by hydrolysis of silane monomers, preferably chlorosilanes. The chlorosilanes are hydrolyzed to silanols and then condensed to form siloxanes. For example, Q units are often made by hydrolyzing tetrachlorosilanes in aqueous or aqueous/alcoholic media to form the following:
The above hydroxy substituted silane is then condensed or polymerized with other types of silanol substituted units such as:
wherein n is 0-10, preferably 0-4.
Because the hydrolysis and condensation may take place in aqueous or aqueous/alcoholic media wherein the alcohols are preferably lower alkanols such as ethanol, propanol, or isopropanol, the units may have residual hydroxyl or alkoxy functionality as depicted above. Preferably, the resins are made by hydrolysis and condensation in aqueous/alcoholic media, which provides resins that have residual silanol and alkoxy functionality. In the case where the alcohol is ethanol, the result is a resin that has residual hydroxy or ethoxy functionality on the siloxane polymer. The silicone film forming polymers used in the compositions of the invention are generally made in accordance with the methods set forth in Silicon Compounds (Silicones), Bruce B. Hardman, Arnold Torkelson, General Electric Company, Kirk-Othmer Encyclopedia of Chemical Technology, Volume 20, Third Edition, pages 922-962, 1982, which is hereby incorporated by reference in its entirety.
Also suitable are linear, high molecular weight silicones that are semi-solids, solids, or gums at room temperature. Examples of such silicones include dimethicones having viscosities ranging from about 100,000 to 10 million, or 500,000 to 10 million centipoise or dimethicone copolyols having the same viscosity range.
Also suitable are silicone esters as disclosed in U.S. Pat. Nos. 4,725,658 and 5,334,737, which are hereby incorporated by reference. Such silicone esters comprise units of the general formula RaREbSiO[4−(a+b)/2] or R13xREySiO1/2, wherein R and R13 are each independently an organic radical such as alkyl, cycloalkyl, or aryl, or, for example, methyl, ethyl, propyl, hexyl, octyl, decyl, aryl, cyclohexyl, and the like, a is a number ranging from 0 to 3, b is a number ranging from 0 to 3, a+b is a number ranging from 1 to 3, x is a number from 0 to 3, y is a number from 0 to 3 and the sum of x+y is 3, and wherein RE is a carboxylic ester containing radical. Preferred RE radicals are those wherein the ester group is formed of one or more fatty acid moieties (e.g. of about 2, often about 3 to 10 carbon atoms) and one or more aliphatic alcohol moieties (e.g. of about 10 to 30 carbon atoms). Examples of such acid moieties include those derived from branched-chain fatty acids such as isostearic, or straight chain fatty acids such as behenic. Examples of suitable alcohol moieties include those derived from monohydric or polyhydric alcohols, e.g. normal alkanols such as n-propanol and branched-chain etheralkanols such as (3,3,3-trimethylolpropoxy)propane. Preferably the ester subgroup (i.e. the carbonyloxy radical) will be linked to the silicon atom by a divalent aliphatic chain that is at least 2 or 3 carbon atoms in length, e.g. an alkylene group or a divalent alkyl ether group. Most preferably that chain will be part of the alcohol moiety, not the acid moiety. Such silicones may be liquids or solids at room temperature.
(ii). Copolymers of Silicone and Ethylenically Unsaturated Monomers
Another type of film forming polymer that may be used in the compositions of the invention is obtained by reacting silicone moieties with ethylenically unsaturated monomers. The resulting copolymers may be graft or block copolymers. The term “graft copolymer” is familiar to one of ordinary skill in polymer science and is used herein to describe the copolymers which result by adding or “grafting” polymeric side chain moieties (i.e. “grafts”) onto another polymeric moiety referred to as the “backbone”. The backbone may have a higher molecular weight than the grafts. Thus, graft copolymers can be described as polymers having pendant polymeric side chains, and which are formed from the “grafting” or incorporation of polymeric side chains onto or into a polymer backbone. The polymer backbone can be a homopolymer or a copolymer. The graft copolymers are derived from a variety of monomer units.
One type of polymer that may be used as the film forming polymer is a vinyl-silicone graft or block copolymer having the formula:
wherein G5 represents monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and -ZSA;
wherein A represents a vinyl polymeric segment consisting essentially of a polymerized free radically polymerizable monomer, and Z is a divalent linking group such as C1-10 alkylene, aralkylene, arylene, and alkoxylalkylene, most preferably Z is methylene or propylene,
G6 is a monovalent moiety which can independently be the same or different selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and -ZSA;
G2 comprises A;
G4 comprises A;
R1 is a monovalent moiety which can independently be the same or different and is selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl; but preferably C1-4 alkyl or hydroxyl, and most preferably methyl.
R2 is independently the same or different and is a divalent linking group such as C1-10 alkylene, arylene, aralkylene, and alkoxyalkylene, preferably C1-3 alkylene or C7-10 aralkylene, and most preferably —CH2— or 1,3-propylene,
R3 is a monovalent moiety which is independently alkyl, aryl, aralkyl, alkoxy, alkylamino, fluoroalkyl, hydrogen, or hydroxyl, preferably C1-4 alkyl or hydroxyl, most preferably methyl;
R4 is independently the same or different and is a divalent linking group such as C1-10 alkylene, arylene, aralkylene, alkoxyalkylene, but preferably C1-3 alkylene and C7-10 alkarylene, most preferably —CH2— or 1,3-propylene,
x is an integer of 0-3;
y is an integer of 5 or greater; preferably 10 to 270, and more preferably 40-270; and
q is an integer of 0-3.
These polymers are described in U.S. Pat. No. 5,468,477, which is hereby incorporated by reference. Most preferred is poly(dimethylsiloxane)-g-poly(isobutyl methacrylate), which is manufactured by 3-M Company under the tradename VS 70 IBM. This polymer may be purchased in the dry particulate form, or as a solution where the polymer is dissolved in one or more solvents such as isododecane. Preferred is where the polymer is in dry particulate form, and as such it can be dissolved in one or more of the liquids comprising the liquid carrier. This polymer has the CTFA name Polysilicone-6.
Another type of such a polymer comprises a vinyl, methacrylic, or acrylic backbone with pendant siloxane groups and pendant fluorochemical groups. Such polymers preferably comprise repeating A, C, D and optionally B monomers wherein:
A is at least one free radically polymerizable acrylic or methacrylic ester of a 1,1,-dihydroperfluoroalkanol or analog thereof, omega-hydridofluoroalkanols, fluoroalkylsulfonamido alcohols, cyclic fluoroalkyl alcohols, and fluoroether alcohols,
B is at least one reinforcing monomer copolymerizable with A,
C is a monomer having the general formula X(Y)nSi(R)3-mZm wherein
X is a vinyl group copolymerizable with the A and B monomers,
Y is a divalent linking group which is alkylene, arylene, alkarylene, and aralkylene of 1 to 30 carbon atoms which may incorporate ester, amide, urethane, or urea groups,
n is zero or 1;
m is an integer of from 1 to 3,
R is hydrogen, C1-4 alkyl, aryl, or alkoxy,
Z is a monovalent siloxane polymeric moiety; and
D is at least one free radically polymerizable acrylate or methacrylate copolymer.
Such polymers and their manufacture are disclosed in U.S. Pat. Nos. 5,209,924 and 4,972,037, which are hereby incorporated by reference. More specifically, the preferred polymer is a combination of A, C, and D monomers wherein A is a polymerizable acrylic or methacrylic ester of a fluoroalkylsulfonamido alcohol, and where D is a methacrylic acid ester of a C1-2 straight or branched chain alcohol, and C is as defined above. Most preferred is a polymer having moieties of the general formula:
wherein each of a, b, and c has a value in the range of 1-100,000, n has a value preferably in the range of 1-1,000,000, and the terminal groups are selected from the group consisting of a C1-20 straight or branched chain alkyl, aryl, and alkoxy and the like. These polymers may be purchased from Minnesota Mining and Manufacturing Company under the tradenames “Silicone Plus” polymers. Most preferred is poly(isobutyl methacrylate-co-methyl FOSEA)-g-poly(dimethylsiloxane) which is sold under the tradename SA 70-5 IBMMF.
Another suitable silicone acrylate copolymer is a polymer having a vinyl, methacrylic, or acrylic polymeric backbone with pendant siloxane groups. Such polymers as disclosed in U.S. Pat. Nos. 4,693,935, 4,981,903, 4,981,902, and which are hereby incorporated by reference. Preferably, these polymers are comprised of A, C, and optionally B monomers wherein:
A is at least one free radically polymerizable vinyl, methacrylate, or acrylate monomer;
B, when present, is at least one reinforcing monomer copolymerizable with A,
C is a monomer having the general formula:
X(Y)nSi(R)3-mZm
wherein:
X is a vinyl group copolymerizable with the A and B monomers;
Y is a divalent linking group;
n is zero or 1;
m is an integer of from 1 to 3;
R is hydrogen, C1-10 alkyl, substituted or unsubstituted phenyl, C1-10 alkoxy; and
Z is a monovalent siloxane polymeric moiety.
Examples of A monomers are lower to intermediate methacrylic acid esters of C1-12 straight or branched chain alcohols, styrene, vinyl esters, vinyl chloride, vinylidene chloride, acryloyl monomers, and so on.
The B monomer, if present, is a polar acrylic or methacrylic monomer having at least one hydroxyl, amino, or ionic group (such as quaternary ammonium, carboxylate salt, sulfonic acid salt, and so on).
The C monomer is as above defined.
Examples of other suitable copolymers that may be used herein, and their method of manufacture, are described in detail in U.S. Pat. No. 4,693,935, Mazurek and U.S. Pat. No. 4,728,571, Clemens et al., both of which are incorporated herein by reference. Additional grafted polymers are also disclosed in EPO application 90307528.1, published as EPO application 0 408 311, U.S. Pat. No. 5,061,481, Suzuki et al., U.S. Pat. No. 5,106,609, Bolich et al., U.S. Pat. No. 5,100,658, Bolich et al., U.S. Pat. No. 5,100,657, Ansher-Jackson et al., U.S. Pat. No. 5,104,646, Bolich et al., U.S. Pat. No. 5,618,524, issued Apr. 8, 1997, all of which are incorporated by reference herein in their entirety.
(iii). Synthetic Organic Polymers
Also suitable for use as film forming polymers in the compositions are polymers made by polymerizing one or more ethylenically unsaturated monomers. The final polymer may be a homopolymer, copolymer, terpolymer, or graft or block copolymer, and may contain monomeric units such as acrylic acid, methacrylic acid or their simple esters, styrene, ethylenically unsaturated monomer units such as ethylene, propylene, butylene, etc., vinyl monomers such as vinyl chloride, styrene, and so on.
In some cases, polymers containing one or more monomers which are esters of acrylic acid or methacrylic acid, including aliphatic esters of methacrylic acid like those obtained with the esterification of methacrylic acid or acrylic acid with an aliphatic alcohol of 1 to 30, preferably 2 to 20, more preferably 2 to 8 carbon atoms. If desired, the aliphatic alcohol may have one or more hydroxy groups are particularly suitable. Also suitable are methacrylic acid or acrylic acid esters esterified with moieties containing alicyclic or bicyclic rings such as cyclohexyl or isobomyl, for example.
The ethylenically unsaturated monomer may be mono-, di-, tri-, or polyfunctional as regards the addition-polymerizable ethylenic bonds. A variety of ethylenically unsaturated monomers are suitable.
Examples of suitable monofunctional ethylenically unsaturated monomers include those of the formula:
wherein R1 is H, a C1-30 straight or branched chain alkyl, aryl, or aralkyl; R2 is a pyrrolidone, a C1-30 straight or branched chain alkyl, or a substituted or unsubstituted aromatic, alicyclic, or bicyclic ring where the substituents are C1-30 straight or branched chain alkyl, or COOM or OCOM wherein M is H, a C1-30 straight or branched chain alkyl, pyrrolidone, or a substituted or unsubstituted aromatic, alicyclic, or bicyclic ring where the substituents are C1-30 straight or branched chain alkyl which may be substituted with one or more hydroxyl groups, or [(CH2)mO]nH wherein m is 1-20, and n is 1-200.
More specific examples include the monofunctional ethylenically unsaturated monomer is of Formula I, above, wherein R1 is H or a C1-30 alkyl, and R2 is COOM or OCOM wherein M is a C1-30 straight or branched chain alkyl which may be substituted with one or more hydroxy groups.
Further examples include where R1 is H or CH3, and R2 is COOM wherein M is a C1-10 straight or branched chain alkyl which may be substituted with one or more hydroxy groups.
Di-, tri- and polyfunctional monomers, as well as oligomers, of the above monofunctional monomers may also be used to form the polymer. Suitable difinctional monomers include those having the general formula:
II.
wherein R3 and R4 are each independently H, a C1-30 straight or branched chain alkyl, aryl, or aralkyl; and X is [(CH2)xOy]z wherein x is 1-20, and y is 1-20, and z is 1-100. Particularly preferred are difunctional acrylates and methacrylates, such as the compound of Formula II above wherein R3 and R4 are CH3 and X is [(CH2)xOy]z wherein x is 1-4; and y is 1-6; and z is 1-10.
Trifunctional and polyfunctional monomers are also suitable for use in the polymerizable monomer to form the polymer used in the compositions of the invention. Examples of such monomers include acrylates and methacrylates such as trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.
The polymers can be prepared by conventional free radical polymerization techniques in which the monomer, solvent, and polymerization initiator are charged over a 1-24 hour period of time, preferably 2-8 hours, into a conventional polymerization reactor in which the constituents are heated to about 60-175° C., preferably 80-100° C. The polymers may also be made by emulsion polymerization or suspension polymerization using conventional techniques. Also anionic polymerization or Group Transfer Polymerization (GTP) is another method by which the copolymers used in the invention may be made. GTP is well known in the art and disclosed in U.S. Patent Nos. 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,598,161; 4,605,716; 4,605,716; 4,622,372; 4,656,233; 4,711,942; 4,681,918; and 4,822,859; all of which are hereby incorporated by reference.
Also suitable are polymers formed from the monomer of Formula I, above, which are cyclized, in particular, cycloalkylacrylate polymers or copolymers having the following general formulas:
wherein R1, R2, R3, and R4 are as defined above. Typically such polymers are referred to as cycloalkylacrylate polymers. Such polymers are sold by Phoenix Chemical, Inc. under the tradename Giovarez AC-5099M. Giovarez has the chemical name isododecane acrylates copolymer and the polymer is solubilized in isododecane. The monomers mentioned herein can be polymerized with various types of organic groups such as propylene glycol, isocyanates, amides, etc.
One type of organic group that can be polymerized with the above monomers includes a urethane monomer. Urethanes are generally formed by the reaction of polyhydroxy compounds with diisocyanates, as follows:
wherein x is 1-1000.
Another type of monomer that may be polymerized with the above comprise amide groups, preferably having the the following formula:
wherein X and Y are each independently linear or branched alkylene having 1-40 carbon atoms, which may be substituted with one or more amide, hydrogen, alkyl, aryl, or halogen substituents.
Another type of organic monomer may be alpha or beta pinenes, or terpenes, abietic acid, and the like.
One additional type of synthetic organic polymer that may be used in the compositions of the invention is obtained by polymerizing ethylenically unsaturated monomers which comprise vinyl ester groups either alone or in combination with other monomers including silicone monomers, other ethylenically unsaturated monomers, or organic groups such as amides, urethanes, glycols, and the like. The various types of monomers or moieties may be incorporated into the film forming polymer by way of free radical polymerization, addition polymerization, or by formation of grafts and blocks which are attached to the growing polymer chain according to processes known in the art. Typically, this type of film forming polymer comprises vinyl ester monomers having the following general formula:
wherein M is H, or a straight or branched chain C1-100 alkyl, preferably a C1-50 alkyl, more preferably a C1-45 alkyl which may be saturated or unsaturated, or substituted or unsubstituted, where the substituents include hydroxyl, ethoxy, amide or amine, halogen, alkyloxy, alkyloxycarbonyl, and the like. Preferably, M is H or a straight or branched chain alkyl having from 1 to 30 carbon atoms. The film forming polymer may be a homopolymer or copolymer having the vinyl ester monomers either alone or in combination with other ethylenically unsaturated monomers, organic groups, or silicone monomers.
Suitable other monomers that may be copolymerized with the vinyl ester monomer include those having siloxane groups, including but not limited to those of the formula:
wherein R and R′ are each independently a C1-30 straight or branched chain alkyl, phenyl, or trimethylsiloxy and n ranges from 1-1,000,000. The silicone monomers are preferably polymerized into a siloxane polymer then attached to the polymer chain by attaching a terminal organic group having olefinic unsaturation such as ethylene or propylene, to the siloxane, then reacting the unsaturated group with a suitable reactive site on the polymer to graft the siloxane chain to the polymer.
Also suitable are various types of organic groups that may be polymerized with the vinyl ester monomers including but not limited to urethane, amide, polyalkylene glycols, and the like as set forth above.
The vinyl ester monomers may also be copolymerized with other ethylenically unsaturated monomers that are not vinyl esters, including those set forth above.
(d). Natural Polymers
Also suitable for use are one or more naturally occurring polymeric materials such as resinous plant extracts including such as rosin, shellac, chitin, and the like.
7. Preservatives
The composition may contain 0.001-8%, preferably 0.01-6%, more preferably 0.05-5% by weight of the total composition of preservatives. A variety of preservatives are suitable, including such as benzoic acid, benzyl alcohol, benzylhemiformal, benzylparaben, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, butyl paraben, phenoxyethanol, methyl paraben, propyl paraben, diazolidinyl urea, calcium benzoate, calcium propionate, captan, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, chloroacetamide, chlorobutanol, p-chloro-m-cresol, chlorophene, chlorothymol, chloroxylenol, m-cresol, o-cresol, DEDM Hydantoin, DEDM Hydantoin dilaurate, dehydroacetic acid, diazolidinyl urea, dibromopropamidine diisethionate, DMDM Hydantoin, and all of those disclosed on pages 570 to 571 of the CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, which is hereby incorporated by reference.
8. Vitamins and Antioxidants
The compositions of the invention may contain vitamins and/or coenzymes, as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, more preferably 0.05-5% by weight of the total composition are suggested. Suitable vitamins include ascorbic acid and derivatives thereof, the B vitamins such as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymes such as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and derivatives thereof are suitable. Examples are Vitamin A palmitate, acetate, or other esters thereof, as well as Vitamin A in the form of beta carotene. Also suitable is Vitamin E and derivatives thereof such as Vitamin E acetate, nicotinate, or other esters thereof. In addition, Vitamins D and K are suitable.
Suitable antioxidants are ingredients that assist in preventing or retarding spoilage. Examples of antioxidants suitable for use in the compositions of the invention are potassium sulfite, sodium bisulfite, sodium erythrobate, sodium metabisulfite, sodium sulfite, propyl gallate, cysteine hydrochloride, butylated hydroxytoluene, butylated hydroxyanisole, and so on.
The compositions according to the invention may contain other ingredients in addition to those mentioned herein.
II. The Method
The invention is directed to a method for improving the moisturization and hydration of lips comprising applying to the lips a lipstick composition comprising water and at least one occlusive oil capable of forming a barrier layer on the lips after the lipstick composition has been applied to the lips.
As noted, in prior art compositions, lipsticks that contained water tended to be somewhat drying on the lips. For example, when an individual licks their lips it provides a temporary feeling of hydration and comfort. However, when this moisture evaporates from the lip surface it often causes the lips to feel even dryer than they were before. The method of the invention provides a way to hydrate lips by applying a composition containing water, but also including in the composition an occlusive oil that maintains lip hydration and moisturization by either entrapping the water present in the composition so that it remains on the lips or serving as an occlusive barrier on the lips after the water has evaporated. With respect to the method of the invention, a variety of occlusive oils may be suitable provided they are capable of forming this type of barrier on the lips, which in return requires that the oils have a certain substantial viscosity. Suggested viscosity ranges of such oils begin at about 650 centipoise at 25° C. and may range up to about 600,000 centipoise at 25° C. Suitable oils are pourable at room temperature, and include the phenyl-substituted silicone mentioned herein, as well as other natural or synthetic oils capable of performing the occlusive function. Examples of suitable occlusive oils include, but are not limited to those set forth herein.
A. High Viscosity Occlusive Oils
Other occlusive oils having the same general viscosity ranges as set forth above may be used in the compositions including but not limited to:
1. Non-Phenyl Substituted Silicones
A variety silicones, other than the phenyl-substituted silicone mentioned above, may be suitable for use as the occlusive oil in the method of the invention. Such occlusive oils include dimethicones having a viscosity ranging from about 650 to 15,000 centipoise at room temperature (25° C.), C2-14 alkyl dimethicones such as cetyl dimethicone, are examples of occlusive oils capable of providing an occlusive barrier function in the method of the invention.
2. Organic Occlusive Oils
(a). Polymeric Alpha Olefins
Also suitable as the occlusive oil in the method of the invention are various types of homopolymeric alpha olefins such as polydecene, polybutene, and hydrogenated versions thereof. Such polymeric alpha olefins have viscosities ranging from about 650 to 600,000 centipoise at room temperature. Such polymeric alpha olefins are sold under the trade name Puresyn®.
(b). Copolymers of Alpha Olefins and Ethylenically Unsaturated Monomers
Also suitable as the occlusive oil are copolymers of alpha olefins and ethylenically unsaturated monomers such as ethylene, vinyl pyrrolidone, propylene, acrylates, methacrylates, and so on. Such copolymeric materials have a viscosity in the range mentioned above.
(c). Natural Organic Oils
Also suitable are naturally derived organic oils having occlusive properties such as sesame oil, peanut oil, coconut oil, jojoba, apricot seed oil, almond oil, castor oil, and the like.
(d). Esters
Also suitable are certain carboxylic acid esters of C6-40 straight or branched chain, saturated or unsaturated fatty acids. Examples include mono-, di-, and triesters of C6-30 fatty acids and C1-45 carboxylic acids. Examples of such esters include citric acid esters such as triisostearyl citrate, trioctyldodecyl citrate,
As noted above, when the water based lipstick compositions containing the occlusive oil are applied to the lips, the occlusive oil forms a barrier layer on the lips which either entraps the water present so that it remains to hydrate the lip underneath the barrier layer formed by the oil. However, in the case where the water evaporates from the lip the occlusive oil that forms the barrier layer remains on the lip to protect the lip surface from environmental assaults. In either case, the water present in the composition provided some hydration to the lip. Any dryness was prevented by the occlusive oil that forms the barrier layer.
In the method of the invention, the composition is applied once a day, or many times a day in order to provide the desired effects. While the composition contains water, it still provides a moisturizing and hydrating effect often found with chapsticks or lip balms.
The invention will be further described in connection with the following examples which are set forth for the purposes of illustration only.
Lipstick compositions in accordance with the invention were made as follows:
The compositions were prepared by grinding the pigments in the polglyceryl-4 isosteareate/cetyl PEG/PPG 10/1 dimethicone, hexyl laurate mixture. The waxes were melted and combined with the oil ingredients. The pigment grind, sunscreens, and other oil phase components were added. The molten compositions were poured into molds and allowed to cool.
Lipstick compositions in accordance with the invention were prepared as follows: Lipstick compositions in accordance with the invention were made as follows:
The compositions were prepared by grinding the pigments in the polglyceryl-4 isosteareate/cetyl PEG/PPG 10/1 dimethicone, hexyl laurate mixture. The waxes were melted and combined with the oil ingredients. The pigment grind, sunscreens, and other oil phase components were added. The molten compositions were poured into molds and allowed to cool.
Twenty three panelists tested the lip composition of Example 1. The panelists were asked to not to use any lip products for three days prior to beginning the test. The panelists were asked to rate the condition of their lips prior to application of the product and after the three day moratorium on lip products. The panelists were then given the product for use in a two week at home use test. Panelists were asked to report on lip condition on day 1, 3, 7, and 14 of the test. The results were as follows:
The results demonstrate that lip condition improved consistently with repeated usage.
While the invention has been described in connection with the preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.