FR3119323A1 - COMPOSITIONS COMPRISING A STYRENE BLOCK COPOLYMER, A NON-POLAR OIL AND A POLAR OIL - Google Patents

Abstract

COMPOSITIONS COMPRISING A STYRENATED BLOCK COPOLYMER, A NON-POLAR OIL AND A POLAR OIL The present invention relates to compositions for application to the lips. The compositions include at least about 8% by weight of a thermoplastic block copolymer comprising styrene blocks; at least one non-polar oil and at least one polar oil having a molecular weight less than 650 g/mole. The ratio of the concentrations by weight of the at least one nonpolar oil to the concentration by weight of the at least one polar oil having a molecular weight less than 650 g/mole is at least about 1:1. Figure for abstract: NIL

Description

COMPOSITIONS COMPRISING A STYRENE BLOCK COPOLYMER, A NON-POLAR OIL AND A POLAR OIL

FIELD OF THE INVENTION

The present invention relates to compositions including thermoplastic block copolymers and, in particular, to compositions including thermoplastic block copolymers, non-polar oils and polar oils.

CONTEXT DISCUSSION

Various compositions are known to be applied to human lips for cosmetic purposes. For example, lipstick and lip gloss compositions are typically formulated to possess color, sheen or gloss characteristics upon application. Lip gloss compositions, in particular, are sought after for providing high gloss and shine. However, the inventors have found that conventional lip gloss compositions generally do not provide a perception of volume, which is a desirable attribute for the consumer. Approaches to bulking include the use of irritants such as capsaicin and vasodilators such as niacin and nicotinic acid derivatives. These ingredients do not give cosmetic volume to the lips and generally do not always constitute the most satisfactory solution for the consumer. The inventors have also recognized that conventional products do not simultaneously provide the ability to form a thick layer on the lips, long-term durability and self-leveling films which give high gloss and conceal lip lines.

The inventors have now identified compositions which make it possible to overcome one or more of the drawbacks mentioned above.

The present invention relates to compositions for application to the lips. The compositions include at least about 8% by weight of a thermoplastic block copolymer comprising styrenated blocks. The compositions further comprise at least one nonpolar oil and at least one polar oil having a molecular weight of less than 650 g/mol. The at least one nonpolar oil and the at least one polar oil having a molecular weight of less than 650 g/mole are present such that the ratio between the concentrations by weight of the at least one nonpolar oil and the concentration by weight of the at least one polar oil having a molecular weight of less than 650 g/mole is at least about 1:1. The compositions have a zero shear viscosity at 32°C in the range of 15 Pa s to 90 Pa s, a critical shear rate of about 10 s ^-1 to about 250 s ^-1 at any temperature between 32 °C and 37°C, and a normal stress of about 50 Pa to about 10,000 Pa at any temperature between 32°C and 37°C.

According to certain embodiments, these compositions have a concentration by weight of the thermoplastic block copolymer comprising styrenated blocks of approximately 8% to approximately 15%, a concentration by weight of at least one nonpolar oil of approximately 20% to approximately 75%, and a concentration by weight of at least one polar oil having a molecular weight of less than 650 g/mole of about 1% to about 50%.

According to certain other embodiments, the concentration by weight of the thermoplastic block copolymer comprising styrenated blocks is from about 8% to about 15%, the concentration by weight of the at least one non-polar oil, such as a polyolefin, is from about 30% to about 65%, the concentration by weight of the at least one polar oil, such as a fatty ester, having a molecular weight of less than 650 g/mole, is from about 2% to about 30% , and the ratio between the concentration by weight of the at least one nonpolar oil and the concentration by weight of the at least one polar oil having a molecular weight of less than 650 g/mole is from about 1:1 to about 14: 1 (such as about 3:1 to about 14:1); and the composition further comprises from about 5% to about 30% additional fatty compounds.

In other aspects, the present invention also relates to methods of improving the appearance of the lips by applying compositions of the present invention to the lips in an amount sufficient to improve the appearance of the lips.

It should be understood that the above general description and the following detailed description are both exemplary and explanatory only and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "at least one" means one or more and therefore includes individual components as well as mixtures/combinations.

All concentrations/percentages given are by weight unless otherwise specified. Numerical ranges include bounds and are meant to include all combinations and sub-combinations. For example, from about 5%, 10% or 15% to about 20%, 50% or 60% means about 5% to about 20%, about 5% to about 50%, about 5% to about 60%, about 10% to about 20%, about 10% to about 50%, about 10% to about 60%, about 15% to about 20%, about 15% to about 50%, or about 15% to about 60%.

Except in working examples, or where otherwise indicated, all numbers expressing amounts of ingredients and/or reaction conditions are to be understood as being modified in all cases by the term "about", i.e. that is to say within the limits of 10% of the number indicated, such as within the limits of approximately 5%, such as within the limits of 1% or 2% of the number indicated.

The term "active base" as used herein means considering only the particular component of the ingredient (e.g., in a composition) and ignoring other chemically unrelated components that may also be present. in the same raw material source of that particular component.

The term "polymer" as used herein means a compound which is composed of two or more monomers.

"Substantially free" as used herein means that although it is preferred that no amount of the specific component be present in the composition, it is possible to have very small amounts in the compositions of the invention provided that these amounts do not markedly affect at least one, preferably most, of the beneficial properties of the conditioning compositions of the invention. In some embodiments, "substantially free of" means less than about 2% of the identified ingredient, such as less than about 1%, such as less than about 0.5%, such as less than about 0.1 % of ingredient. In certain embodiments, the compositions of the present invention are anhydrous, that is, substantially free of water.

"Substituted", as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups, hydroxyalkyl groups and polysiloxane groups. The substituent(s) may be further substituted.

"Volatile" as used herein means having a flash point below about 50°C.

The compositions and methods of the present invention may include, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in the personal care products, in particular lip products.

Copolymer sequence thermoplastic comprising sequences styrene e s

The block copolymers of the present invention are characterized by the presence of at least one "hard" segment and at least one "soft" segment. Besides their compositional nature, the hard and soft segments of the block copolymers of the present invention can be defined according to their respective glass transition temperatures, T _g . The hard segment may have a T _g of 50°C or more, while the soft segment may have a T _g of 20°C or less. The T _g of the hard sequence can range from 50°C to 150°C. The T _g of the pout sequence can range from -150°C to 20°C.

Block copolymers useful in the compositions of the present invention can be thermoplastic elastomers. Thermoplastic elastomer hard segments typically include vinyl monomers in varying amounts. Examples of suitable vinyl monomers include, but are not limited to, styrene as well as other optional monomers including methacrylate, acrylate, vinyl ester, vinyl ether, vinyl acetate and others.

The soft segments of the thermoplastic elastomer include olefin polymers and/or copolymers which may be saturated, unsaturated, or combinations thereof. Suitable olefin copolymers can include, but are not limited to, ethylene/propylene copolymers, ethylene/butylene copolymers, propylene/butylene copolymers, polybutylene, polyisoprene, polymers of butanes and hydrogenated isoprenes, and mixtures thereof.

Thermoplastic elastomers useful in the present invention are block copolymers, for example di-block, tri-block, multi-block, radial block and star copolymers, and mixtures thereof. A di-block thermoplastic elastomer is generally defined as an A-B type or a hard segment (A) followed by a soft segment (B) in sequence. A tri-block is generally defined as an A-B-A type copolymer or a ratio of a hard segment, a soft segment and a hard segment. Multiblock, radial block, or star block thermoplastic elastomers usually contain any combination of hard and soft segments, provided the elastomers possess both hard and soft characteristics.

In some embodiments, the thermoplastic elastomer of the present invention may be selected from the KRATON class of rubbers (Kraton Corporation of Houston, Texas) or similar thermoplastic elastomers. KRATON rubbers are thermoplastic elastomers in which the polymer chains comprise a di-block, tri-block, multi-block or radial or star configuration or many mixtures thereof. Tri-block KRATON rubbers have polystyrene (hard) segments attached to each end of a rubber (soft) segment, while diblock KRATON rubbers have a polystyrene (hard) segment attached to a rubber (soft) segment . The radial or star configuration of the KRATON can be a four-point star or another multi-point rubber star with a polystyrene segment attached to each end of a rubber segment. The configuration of each of the KRATON rubbers forms separate domains of polystyrene and rubber.

Each KRATON rubber molecule would comprise sequenced segments of styrene monomer units and rubber monomer and/or co-monomer units. The most common structure of KRATON triblock copolymer is the linear A-B-A block of styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylenepropylene-styrene or styrene-ethylenebutylene-styrene type. The KRATON diblock is preferably of the AB type, such as styrene-ethylenepropylene, styrene-ethylenebutylene, styrene-butadiene or styrene-isoprene. The configuration of KRATON rubber is well known in the art and any block copolymer elastomer having a similar configuration is within the practice of the invention. Other block copolymers are sold under the Septon brand (which stands for elastomers known as SEEPS, sold by Kurary, Co., Ltd) and those sold by ExxonMobil Chemical under the VECTOR brand.

Other thermoplastic elastomers useful in the present invention include block copolymer elastomers comprising styrene-butylene/ethylene-styrene copolymer (tri-block), ethylene/propylene-styrene copolymer (radial or star block) or a mixture or a combination of the two. (Some manufacturers refer to block copolymers as hydrogenated block copolymers, for example hydrogenated styrene-butylene/ethylene-styrene (tri-block) copolymer).

The compositions of the present invention include at least one block copolymer, for example diblock, triblock, multiblock, or radial block copolymers, and mixtures thereof. The at least one block copolymer comprises at least one styrene block and may further comprise at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene, or a mixture thereof. this.

Diblock copolymers which may be mentioned include, but are not limited to, styrene/ethylene-propylene copolymers (comprising a block of styrene and a block obtained from ethylene and propylene), styrene/ethylene-propylene copolymers butylene, styrene-ethylene/butadiene copolymers, styrene/butadiene copolymers and styrene/isoprene copolymers.

In certain notable embodiments, the block copolymer includes styrene blocks and one or more blocks selected from: butadiene blocks, isoprene blocks and ethylene-butylene blocks. In other embodiments, the block copolymer includes (1) styrene blocks and butadiene blocks; or (2) styrene blocks and ethylene-butadiene blocks; or (3) styrene and isoprene blocks.

Triblock copolymers which may be mentioned include, but are not limited to, styrene/ethylene-propylene/styrene copolymers, styrene/ethylene-butylene/styrene copolymers, styrene/ethylene-butadiene/styrene copolymers, styrene/isoprene/styrene and styrene/butadiene/styrene copolymers. For example, triblock polymers sold under the names KRATON G1650, KRATON G1652, KRATON D1101, KRATON D1102 and KRATON, commercially available from Kraton Polymers.

For example, a blend of a diblock copolymer and a triblock copolymer can be used as the block copolymer. According to at least one embodiment, the diblock copolymer and the triblock copolymer can be chosen from block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene. In one embodiment, the block copolymer comprises from about 50% to about 90% triblock and from about 10% to about 50% diblock.

Examples of suitable block copolymers include Kraton's G series such as Kraton G1701 (INCI name for hydrogenated styrene/isoprene copolymer) and KRATON G1657 (HYDROGENATED STYRENE/BUTADIENE COPOLYMER). KRATON G1657 (styrene-ethylene/butylene-styrene triblock and styrene-ethylene-butylene diblock at 30%); INCI: HYDROGENATED STYRENE/BUTADIENE COPOLYMER; a mixture of 70% styrene-ethylene-butylene triblock) is particularly noteworthy.

It is preferred that the styrene content of the block copolymer be less than 30% by weight, preferably less than 25% by weight, and more preferably less than 20% by weight, and more preferably from about 5% to about 15% , based on the weight of the block copolymer. This is due to the tendency of block copolymers with a styrene content greater than 30% by weight to harden/gel in conventional support systems.

The inventors have found that the thermoplastic block copolymer comprising styrenated blocks can desirably be present in the cosmetic composition in an amount ranging, for example, from approximately 5%, 6%, 8%, 10% or 12% to approximately 12%, 14%, 15%, 18%, 20% or 25% by weight. In certain notable embodiments, the thermoplastic block copolymer comprising styrenated blocks is present in a concentration of at least about 8%, such as from about 8% to about 15%, such as from about 10% to about 15%.

In certain embodiments, the thermoplastic block copolymer comprising styrenated blocks can represent from about 10%, 15% or 20% by weight to about 20%, 40%, 60%, 80%, 90% or 100% by weight of all the polymers of the composition.

The compositions of the present invention include non-polar oils and polar oils. By "oils" herein is meant compounds suitable for cosmetic use, having a melting point below about 30°C and generally insoluble in water, and include a hydrophobic moiety, such as that meeting one or more of following three criteria: (a) has a carbon chain of at least six carbons in which none of the six carbons is a carbonyl or has a hydrophilic moiety (defined below) directly attached to it; (b) has two or more alkylsiloxy groups; or (c) has two or more oxypropylene groups in sequence. The hydrophobic moiety can include linear, cyclic, aromatic, saturated or unsaturated groups. While in some embodiments the oil may include fatty acids or fatty alcohols, in some other embodiments the oil is in some embodiments non-amphiphilic and as such in this embodiment does not include hydrophilic moieties, such as anionic, cationic, zwitterionic, or nonionic groups, which are polar, including sulfate, sulfonate, carboxylate, phosphate, phosphonate, ammonium moieties, including mono-, di-, and trialkylammonium, pyridinium, imidazolinium, amidinium, poly(ethyleneiminium), ammonioalkylsulfonate, ammonioalkylcarboxylate, amphoacetate and poly(ethyleneoxy)sulfonyl moieties. In some embodiments, the oil does not include hydroxyl moieties.

The cosmetic oil is a solvent for the thermoplastic block copolymer and is therefore capable of dissolving at least portions of the thermoplastic block copolymer when mixed in the proportions described herein.

Non-polar oil

The compositions of the present invention include at least one non-polar oil. Without wishing to be bound by theory, it is believed that the non-polar oil functions to solvate the flexible "rubber" intermediate blocks of the thermoplastic block copolymer.

By "non-polar oil" is meant a hydrocarbon oil. “Hydrocarbon” means an oil whose molecules contain only hydrogen and carbon (without heteroatoms) and can be linear or branched. In some embodiments, the non-polar oil has a partition coefficient (logP) value greater than 15, such as greater than about 20. In certain other embodiments, the non-polar oil is selected from an alkane, an olefin (alkene) such as a polyolefin, and combinations thereof. Suitable alkanes include, for example, C ₁₀ -C ₂₀ alkanes, such as C ₁₂ -C ₁₆ alkanes such as isoheaxadecane or isododecane; or isoparaffins.

According to some embodiments, the non-polar oil is an olefin such as a polyolefin. Suitable polyolefins include oligomeric or polymeric compounds such as squalene, hydrogenated polyisobutene, hydrogenated polydecene, hydrogenated poly(6-14)olefin and polybutenes having a molecular weight below about 650.

According to certain embodiments, the non-polar oil is present in a concentration by weight ranging from approximately 15%, 20%, 25%, 30%, 35%, 40% or 45% to approximately 60%, 65%, 75% or 80% by weight.

Polar oils

The compositions of the present invention include at least one polar oil. Without wishing to be bound by theory, it is believed that the polar oil functions to solvate both the soft "rubber" middle blocks of the thermoplastic block copolymer as well as the hard styrenated blocks, thus reducing the viscosity.

By "polar oil" is meant an oil comprising a polar functional group such as an ester group. Further, the inventors have found that the polar oil should have a molecular weight of less than about 650 g/mole, such as less than about 500 g/mole, such as about 150 g/mole to about 650 g/mole, such as from about 150 g/mole to about 500 g/mole. Thus, another term used for these compounds herein is "medium molecular weight polar oils". In some embodiments, the polar oil has a partition coefficient (logP) value of less than or equal to about 20, such as less than about 17, such as less than about 15. Without wishing to be bound by theory, we believe that the moderate molecular weights allow for better solvation of the styrene and rubber blocks, resulting in reduced viscosity.

The at least one polar oil can be chosen from a fatty ester. Suitable fatty esters include vegetable oils (glyceryl esters of fatty acids, monoglycerides, diglycerides, triglycerides) and synthetic esters.

Specific non-limiting examples of these polar oils include, without limitation, isodecyl neopentanoate (logP=6.00), diethylhexyl malate (logP=6.61), isopropyl myristate (logP=7.43 ), isopropyl palmitate (logP=8.49), tricaprylin (logP=9.33), isopropyl isostearate (logP=9.37); isostearyl neopentanoate (logP=10.25); octyldodecyl neopentanoate (logP=11.32); ethylhexyl palmitate (logP=11.34); ethylhexyl stearate (logP=12.40) and cetyl palmitate (logP=15.59); tridecyl trimellitate (logP=16.54); and diisostearyl malate (logP=16.87).

The polar oil can be present in the composition in a concentration of about 1%, 2%, 3%, 5% or 10% to about 15%, 25%, 30% or 50% by weight.

The inventors have found that the at least one nonpolar oil and the at least one polar oil having a molecular weight of less than 650 g/mole must be present in concentrations by weight such that the ratio between the concentration by weight of the at least a nonpolar oil and the concentration by weight of the at least one polar oil having a molecular weight of less than 650 g/mole is at least about 1:1. In some embodiments, this ratio is from about 1:1, 2:1, 3:1, 4:1, or 5:1 to about 6:1, 7:1, 8:1, 9:1, 10 :1, 11:1, 12:1, 13:1 or 14:1. In some notable embodiments, this ratio is from about 1:1 to about 14:1. According to certain other embodiments, this ratio is from about 3:1 to about 14:1.

According to certain other embodiments, the inventors have found that when the concentration by weight of thermoplastic block copolymer comprising styrenated blocks in the composition is high, for example greater than 10%, such as at least approximately 12%, such as about 12% to about 15%, it may be desirable to select one, several, or all of certain specific design criteria for the composition. For example, in this situation, it may be desirable (a) to use a ratio between the concentration by weight of the at least one non-polar oil and the concentration by weight of the at least one polar oil having a molecular weight less than 650 g/mole, which is from about 1:1 or 2:1 or 3:1 to about 4:1, 5:1, 6:1, 7:1 or 8:1; (b) selecting the polar oil having a molecular weight of less than 650 g/mole to have a relatively low logP, such as less than about 11, such as from about 5.6 or 7 to about 8.9, 10 or 11; and/or (c) selecting the non-polar oil to have a molecular weight less than about 400 or to include hydrogenated polyisobutene.

Additional fatty compounds

According to embodiments, the composition can include additional fatty compounds. Suitable additional fatty compounds include additional polar oils, such as those having molecular weights greater than 650 g/mole ("high molecular weight polar oil") such as one of various vegetable oils and vegetable-derived fatty compounds such as, for example, coconut oil, jojoba oil, grapeseed oil, and certain liquid esters such as pentaerythrityl tetraisostearate, and the like.

Other suitable additional fatty compounds include fatty compounds which are not liquid at ambient temperature and pressure, such as solid fatty compounds, including waxes. By solid fatty compounds is meant lipophilic fatty compounds which are solid at ambient temperature (approximately 25° C.) and at atmospheric pressure (760 mm Hg, ie 10 5 Pa). By waxes is meant solid fatty compounds which undergo a reversible solid/liquid change of state and whose melting point is greater than 30°C and, in certain embodiments, greater than approximately 55°C up to approximately 120°C or even as high as about 200°C.

Examples of waxes include waxes of animal origin, waxes of vegetable origin, waxes of mineral origin and waxes of synthetic origin. Examples of waxes of animal origin include beeswaxes, lanolin waxes and Chinese insect waxes. Examples of vegetable waxes include rice waxes, carnauba wax, candelilla wax, ouricuri wax, cork fiber waxes, sugar cane waxes, Japan waxes, Sumac wax and cotton wax. Examples of waxes of mineral origin include paraffins, microcrystalline waxes, lignite waxes and ozokerites. Examples of waxes of synthetic origin include polyolefin waxes, for example polyethylene waxes (low molecular weight linear polyethylene waxes), waxes obtained by Fischer-Tropsch synthesis, waxy copolymers and their esters, and waxes silicon and fluoro. Other examples of solid fatty compounds include esters such as, for example, Butyrosperum parkii (shea) butter (logP ~21 to 29); other vegetable/nut cosmetic butters; BIS-diglyceryl polyacyladipate-2, and others. In some embodiments, the additional fatty compounds have a molecular weight greater than 650 g/mole, such as from about 800 g/mole to about 2000 g/mole.

In some embodiments, the additional fatty compounds include both a high molecular weight polar oil and a solid fatty compound. If present, the amount of additional fatty compounds present in the composition is about 5%, 10%, 12%, 15% to about 20%, 25%, 30% or 50% by weight. If present, the waxes may be present in concentrations less than about 10%, such as less than about 5%, such as about 0.1% to about 5%.

Other cosmetic ingredients

According to embodiments, the composition may include other cosmetic ingredients such as additional polymers, particulate colorants, fragrances, preservatives and/or silicones. The total concentration by weight of the additional ingredients may range from about 0%, 0.1%, 1%, 2%, 3% or 4% to about 8%, 10%, 15%, 25% or 30%, 50 %.

Suitable additional polymers include certain polymers which may not be considered oils and/or certain polymers which do not solvate the soft rubber intermediate blocks of the thermoplastic block copolymer comprising styrenated blocks. In some embodiments, the additional polymers include low molecular weight resins, such as low molecular weight hydrocarbon resins. Examples of suitable low molecular weight resins include hydrocarbon-based resins selected from olefin polymers, which may be classified, depending on the type of monomer they contain, as indene polymers, pentadiene resins, cyclopentadiene dimer resins and terpene resins. Other examples of additional polymers include polybutenes having a molecular weight greater than about 650.

The indene polymers may be chosen from polymers resulting from the polymerization in a major proportion of indene monomer and in a minor proportion of monomers chosen from styrene, methylindene and methylstyrene, and mixtures thereof. These polymers may optionally be hydrogenated and may have a molecular weight ranging from 200 to 1500 g/mole.

According to at least one embodiment, the indene hydrocarbon-based polymer is a block copolymer obtained from indene and styrene or a derivative of styrene. According to at least one embodiment, the resin is chosen from indene resins, such as the hydrogenated styrene/methylstyrene/indene copolymers sold under the name "Regalite" by the company Eastman Chemical, such as REGALITE R 1100, REGALITE R 1090 , REGALITE R-7100, REGALITE R 1010 HYDROCARBON RESIN and REGALITE R 1125 HYDROCARBON RESIN, as well as those sold under the references Escorez 7105 by Exxon Chem. , Nevchem 100 and Nevex 100 by Neville Chem, Norsolene S105 by Sartomer, Picco 6100 by Hercules and Resinall by Resinall Corp.

Whereas in some embodiments one or more hydrocarbon resins are present in a total amount between about 0.5%, 1%, 2% or 3% and about 3%, 5% or 10%. In certain other notable embodiments, the compositions of the present invention include less than about 10% of such low molecular weight hydrocarbon resins, such as substantially free of such low molecular weight hydrocarbon resins.

In certain other embodiments, the ratio between the concentrations by weight in the composition of the thermoplastic block copolymer and the low molecular weight hydrocarbon resin is not less than 2:1, such as not less than 3:1, such as not less than at 4:1, as not less than 5:1.

According to certain embodiments of the present invention, additional ingredients may include at least one colorant (coloring agent). According to this embodiment, the at least one colorant is preferably chosen from pigments, tints, such as liposoluble colorants, pearlescent pigments and pearlescent agents.

Representative oil-soluble dyes that can be used in accordance with the present invention include Sudan Red, DC Red 17, DC Green 6, β-Carotene, Soybean Oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, Annatto and Quinoline Yellow.

The pearlescent pigments which can be used according to the present invention can be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and pearlescent pigments based on bismuth oxychloride.

The pigments, which can be used according to the present invention, can be chosen from white, colored, inorganic, organic, polymeric, non-polymeric, coated and uncoated pigments. Representative examples of inorganic pigments include titanium dioxide, optionally surface treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Representative examples of organic pigments include carbon black, D & C type pigments, and cochineal carmine, barium, strontium, calcium and aluminum lakes. In some embodiments, the colorant is present in an amount sufficient for an observer to identify the composition as having a "red" color, e.g., red, reddish-brown, pink, or the like.

If present, it is preferred that the amount of colorant present in the composition be less than 20%, such as less than 10%, preferably 5% or less by weight of the total weight of the composition. In some embodiments, the compositions are substantially free of colorants.

According to certain embodiments of the invention, the compositions can include particles such as inorganic particles. "Inorganic particle" means any finely divided material that is predominantly inorganic (including inorganic particles having an organic or silicon-based coating), including titanium dioxide, talc, mica, silica, silylates silica, perlite, kaolin, hectorite, as well as bismuth oxychloride, zinc oxide, among others. The inorganic pigment may or may not be coated.

If present, the amount of particles present in the composition is less than 20%, such as less than 10%, preferably 5% or less by weight of the total weight of the composition, including all ranges and sub- ranges between these such as, for example, 1% to 10%.

Although the "additional fatty compounds" listed above may provide cosmetic benefit to the compositions of the present invention, in some embodiments the compositions of the present invention are substantially free of silicone oils or other silicones, which tend not to be compatible with the ingredients used in the compositions of the present invention. Silicone oils include, for example, dimethicone, cyclopentasiloxane and volatile silicones such as linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6 cSt and having from 2 to 7 silicon atoms; these silicones being optionally substituted by alkyl or alkoxy groups of 1 to 10 carbon atoms. Examples include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

According to certain other embodiments, in order to avoid compatibility problems, the compositions of the present invention may be substantially free of silicone polymers, silicone gums and resins, such as those which are solid at room temperature and which include repeating Si-O-Si units and various hydrocarbon functional groups or other organic functional groups.

Silicone resins or siloxysilicate resins include those of the general formula [(R) ₃ SiO] _x (SiO _4/2 ) _y where R is an alkyl group preferably comprising 1 to 8 carbon atoms. A non-limiting example of a siloxysilicate is trimethylsiloxysilicate, which can be represented by the following formula:

[(CH ₃ ) ₃ SiO] _x (SiO _4/2 ) _y . In the formulas above, x and y are preferably between numbers such as 10 and 150, 25 and 125, 35 and 100, and 50 and 80.

Silicone gums can, for example, correspond to the formula:

in which :

R ₇ , R ₈ , R ₁₁ and R ₁₂ are identical or different, and are each chosen from alkyl radicals containing from 1 to 6 carbon atoms,

R ₉ and R ₁₀ are identical or different, and are each chosen from alkyl radicals containing from 1 to 6 carbon atoms and aryl radicals,

X is chosen from alkyl radicals containing from 1 to 6 carbon atoms, a hydroxyl radical and a vinyl radical,

n and p are preferably chosen so as to give the silicone gum a viscosity of 25,000 cSt to 20,000,000 cSt,

With respect to desirable attributes of the composition, the inventors have found it highly desirable that the compositions exhibit a particular blend of properties not taught in the prior art. These properties: zero shear viscosity, shear thinning ratio and high shear viscosity are described below.

ZERO SHEAR VISCOSITY

The inventors have found that in order to form a thick layer of viscous product on the lips which does not run or escape from the lip, it is desirable that the compositions of the present invention have a zero shear viscosity at 32° C. at least about 15 Pa s, such as about 15 Pa s to about 90 Pa s, such as about 15 Pa s to about 80 Pa s, such as about 15 Pa s to about 60 Pa s.

To measure zero shear viscosity (ZSV), approximately 1 gram of a composition is first deposited onto the bottom plate of a rheometer such as a Discovery HR-3 hybrid rheometer from TA Instruments equipped with a Peltier stage. thermocouple (TA Instruments, New Castle, Delaware) set at the desired temperature, for example 32°C. A 40 mm flat parallel plate is used as the rheology probe with a 1000 μm gap between the bottom plate and the probe. Each sample is first equilibrated at 32°C for 120 seconds and then a shear rate experiment is performed. The duration of the experiment is 10 minutes, the shear rate varies from 0.001 to 1000/s, with 5 data points recorded during each decade. After the experiment, a zero-shear viscosity is determined from a logarithmic (viscosity) plot against a logarithmic (shear rate) plot, by linearly adjusting the initial plateau region to intersect the y-axis . This value represents the viscosity of each formula in an undisturbed situation.

CRITICAL SHEAR RATE

The inventors have found that to hold the product on the lips, particularly when performing everyday functions such as speaking, it is desirable that the compositions of the present invention have a critical shear rate of about 10 s ^-1 to about 250 s ^{- 1} , such as from about 10 s ^-1 to about 225 s ^-1 , such as from about 10 s ^-1 to about 100 s ^{- 1} , at any temperature between 32°C and 37 °C, as when measured at 32°C. The critical shear rate (CTR) is determined using the same experiment as described above for ZSV, for example using a rheometer such as a Discovery HR-3 hybrid rheometer from TA Instruments fitted with a Peltier stage. thermocouple (TA Instruments, New Castle, Delaware) set at 32°C, using parallel plate geometry with 1000 µm spacing. The sample is loaded onto the stage and brought to equilibrium at 32°C for 2 min, followed by a 600 s sweep measuring the shear viscosity (Pa s) and rotational stress (Pa) as a function of the applied shear rate. The CSR is found by fitting the SV curve with intersecting linear lines and taking the starting point, or point of intersection.

NORMAL STRESS

The inventors have found that in order to obtain a portable thick film which gives a feeling of thickness, it is desirable that the compositions of the present invention have a normal stress (NS) measured at 800 s ^-1 , which is approximately 50 Pa at approximately 10,000 Pa at any temperature between 25°C and 37°C, as when measured at 32°C. According to certain other embodiments, the NS is about 50 Pa to about 1000 Pa, such as about 50 Pa to about 500 Pa when measured under these conditions.

To determine NS, the sample is placed in the rheometer as above, equilibrated at 32°C for 120 seconds, using a parallel plate geometry with a 1000 micron gap. Rotational stress is measured as a function of the applied shear rate. The duration of the experiment is 10 minutes, the shear rate varies from 0.001 to 1000/s, with five data points recorded during each decade. If the sample exhibits normal stress during the measurement, the rheometer (Discovery HR-3 hybrid) will allow the user to record this normal stress. In this case, the normal stress at 800 s ^-1 is noted. A positive normal stress indicates that the sample, during flow, exerts a force that attempts to separate the parallel plates of the rheometer. This is more often seen with some samples that include higher molecular weight polymers.

The compositions of the present invention can be applied to the human body. In some embodiments, the compositions can be applied to the lips to provide the appearance of increased labial volume and/or to provide lip treatment, care or conditioning. For example, the composition can be spread on the user's lips. The spreading process usually reduces the composition to a thin layer that adheres to the lips and covers them. This can be done using a device or an applicator. The user can spread the composition on the upper and lower lips covering most or, preferably, all of the user's upper and lower lips.

The present invention also relates to methods of improving the appearance of the lips by applying compositions of the present invention to the lips in an amount sufficient to improve the appearance of the lips.

The compositions of the present invention can be made by any of a variety of methods, such as heating the oil to, for example, about 90°C and mixing under high shear while slowly adding the thermoplastic styrene block copolymer. Once the oil/block copolymer mixture is homogeneous, other optional ingredients can be added, such as one at a time.

Although the numerical ranges and parameters showing the general scope of the invention are approximations, the numerical values presented in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without therefore limiting its scope.

Example I - VS compositions comparative and test results

Four commercial products were tested for ZSV, CSR and NS at 32°C. Commercial products were: MAC Lipglass (light tone) available from Estée Lauder Companies, Dior Lip Maximizer (pink tone) available from Christian Dior SE; Maybelline Lifter Gloss available from L'Oréal SA, and Lancôme L'Absolu Rôsy Plump available from L'Oréal SA, and Buxom Full-On Plumping Lip Polish (light pearl tone) available from Shiseido Americas. These products are shown respectively as Comp. 1, 2, 3, 4 and 5 of Table 1 below. No measurable CSR could be determined for Comp 1 and Comp 5, both of which exhibited near-Newtonian behavior for all measured shear rates. No CSR was observed in any of the samples at 800 s ^-1 .

Property Comp 1 Comp 2 Comp 3 Comp 4 Comp 5 ZSV ( ^Pa.s ) 7.4 53.4 648 265.5 9.3 CSR (s ^-1 ) -- 0.03 0.01 0.03 ---

The results indicate that Comp. 1 had a lower than desirable ZSV and no observed NS at 800 s ^-1 ; the Comp. 2 had a CSR below the desirable value and no observed NS; the Comp. 3 had higher ZSV and lower CSR than desirable and no NS observed at 800 s ^-1 ; the Comp. 4 had higher ZSV and lower CSR than the desirable observed NS at 800 s ^{- 1} . Comp. 5 had a lower ZSV than the desirable observed NS at 800 s ^-1 .

Example II - Other compositions and results of trials

Six compositions were prepared and tested for ZSV at 32°C. The compositions are arranged in pairs, each member of a pair having either 10% and a ratio of non-polar oil to polar oil of average molecular weight of 14:1; ie 15% thermoplastic block copolymer (KRATON) and a ratio between polar oil and non-polar oil of average molecular weight of 3:1. The first pair (A1 and A2) included hydrogenated polydecene as the non-polar oil (a C ₁₀ polyolefin) and isopropyl myristate (low logP, high polarity) as the polar oil having a molecular weight below about 650 g/mole . The second pair (B1 and B2) included a hydrogenated C ₆ -C ₁₄ polyolefin as the non-polar oil and tridecyl trimellitate (high logP, low polarity) as the polar oil having a molecular weight less than about 650 g/mole. The third pair (C1 and C2) included hydrogenated polyisiobutene as the non-polar oil (a C ₄ polyolefin) and octyldodecyl neopentanoate (moderate logP, moderate polarity) as the polar oil having a molecular weight less than about 650 g/mole .

The weight concentrations of the ingredients are shown in Table 2, below, along with the values for ZSV.

INGREDIENT Example A1 Example A2 Example B1 Example B2 Ex.C1 Example C2 KRATON G1657 10% 15% 10% 15% 10% 15% Hydrogenated polydecene
(non-polar oil) 84% 63.75% Hydrogenated C ₆ -C ₁₄ olefin
(non-polar oil) 84% 63.75% hydrogenated polyisobutene
(non-polar oil) 84% 63.75% Isopropyl myristate (polar oil) 6% 21.25% Tridecyl trimellilate (polar oil) 6% 21.25% Octyldodecyl Neopentanoate
(polar oil) 6% 21.25% ZSV (Pa.s) 509 40 2,114 693 8.1 33

Several things can be observed about the data in Table 2. First, when comparing within pairs, whereas increasing KRATON independent of other variables generally increases ZSV (this independent effect is not shown here) , decreasing the ratio of non-polar oil to average molecular weight polar oil tends to counteract this effect and cause the ZSV to drop.

Second, samples C1 and C2 have lower ZSV than corresponding samples of equal amounts of KRATON. This seems to suggest that given the lower carbon chain nonpolar polyolefin, hydrogenated polyisobutene induces lower ZSV compared to higher carbon chain and/or higher molecular weight polyolefins, possibly due to effects reduced entanglement with the thermoplastic block copolymer.

Third, samples B1 and B2 have a higher ZSV than corresponding samples of equal amounts of KRATON. This seems to suggest that the high logP polar oil (lower polarity than other polar oils tested) used in these samples does not plasticize the block copolymer as well as other lower logP polar oils, so it is less to even bring down the ZSV.

Example III- Inventive Compositions, Other Comparative Compositions and Results of trials

Eight compositions (six inventive, two comparative) were prepared and tested for ZSV, CSR and NS at 32°C.

The weight concentrations of the ingredients are shown in Table 2 below, along with values for ZSV, CSR and NS.

INGREDIENT INV. 1 REV 2 REV 3 REV 4 REV 5 REV 6 CPM 1 CMP 2 KRATON G1657 10% 10% 15% 10% 8% 10% 15% 15% Hydrogenated polydecene
(non-polar oil) 53.2% 55.3 Squalene 48.8% Hydrogenated C ₆ -C ₁₄ olefin (non-polar oil)
39.2% hydrogenated polyisobutene
(non-polar oil) 53.3% 52.3% 39.2 44.5% Isopropyl myristate
(polar oil) 13.1 4.0 3.5% Tridecyl trimellitate (polar oil) 14.8% 13.1% Octyldodecyl neopentanoate (polar oil) 4% 4% 4% Other cosmetic ingredients 32.7% 33.7% 32.7% 32.7% 32.7% 32.7% 32.7% 32.7% ZSV (Pa.s) 17.1 25.4 22.3 73.8 27.4 11.2 1,427 866 CSR (s ^-1 ) 56.8 55.8 69.3 37.0 96.6 216 4.0 2.73 NS (Pa) 300 290 67.8 9,807 3,304 360.4 28,345 27,620

With respect to "other cosmetic ingredients", all samples were otherwise identical in that they all included low molecular weight hydrocarbon resin (5%), inorganic particles (2%), and preservatives ( <1%). All samples also included 25% additional fatty compounds, including the specific compounds: BIS-diglyceryl polyacyladipate-2, polybutene (MW of 920), shea butter; and pentaerythrityl tetraisostearate - molecular weight between 800 and 2000). The only exception was that INV 2 contained 26% more fatty compounds and included polyethylene wax. For all samples, the ratio between the concentrations by weight in the composition of the thermoplastic block copolymer and the low molecular weight hydrocarbon resin was not less than 2:1.

From the above data, it can be seen that CMP1 and CMP 2 exhibited a higher than desirable ZSV, a lower than desirable CSR, and a higher than desirable NF. It can also be generally seen that to achieve acceptable CSR and normal strength, for high Kraton levels, it is best to select one, more or all of the following criteria: lower carbon chain non-polar oils such as hydrogenated polyisobutene, lower logP polar oils such as isopropyl myristate, and/or a lower ratio of non-polar oils to polar oils.

Inventive Examples INV 1 through INV 6 were evaluated for their ability to form a thick layer on the lips, their long-term durability, and self-leveling films which provide high gloss and conceal lip lines. It was surprising to find that these samples performed well for all of these attributes, whereas CMP 1 and CMP 2 lacked the ability to smear on the lips.

Claims (10)

Composition for application to the lips, comprising:
from about 8% by weight to about 15% by weight of a thermoplastic block copolymer comprising styrenated blocks;
at least one non-polar polyolefin oil; And
at least one polar fatty ester oil having a molecular weight of less than 650 g/mole, wherein the at least one nonpolar polyolefin oil and the at least one polar fatty ester oil are present in concentrations by weight such that a ratio between the concentration by weight of the at least one nonpolar polyolefin oil and the concentration by weight of the at least one polar fatty ester oil having a molecular weight of less than 650 g/mole is at least about 1:1, wherein the composition has a zero shear viscosity at 32°C in a range of 15 Pa s to 90 Pa s, wherein the composition has a critical shear rate which is about 10 s ^-1 to about 250 s ^-1 at any temperature between 32°C and 37°C, and wherein the composition has a normal stress of about 50 Pa to about 10,000 Pa at any temperature between 32°C and 37 °C. Composition according to Claim 1, in which the ratio between the concentration by weight of the at least one non-polar polyolefin oil and the concentration by weight of the at least one polar fatty ester oil having a molecular weight of less than 650 g/ mole is about 1:1 to about 14:1. A composition according to any preceding claim, wherein the concentration by weight of the at least one polyolefin non-polar oil is from about 20% to about 75%, and the concentration by weight of the at least one polar oil of The fatty ester having a molecular weight of less than 650 g/mole is from about 1% to about 50%. A composition according to any preceding claim, wherein the concentration by weight of the at least one polyolefin non-polar oil is from about 30% to about 65%, and the concentration by weight of the at least one polar oil of fatty ester having a molecular weight of less than 650 g/mole is from about 2% to about 30%, and wherein the composition further comprises from about 5% to about 30% additional fatty compounds. A composition according to any preceding claim, further comprising at least one additional fatty compound having a molecular weight greater than 650 g/mole in a concentration by weight of from about 5% to about 50%. Composition according to any one of the preceding claims, in which the thermoplastic block copolymer comprising styrenated blocks is chosen from a hydrogenated styrene/butadiene copolymer and a hydrogenated styrene/isoprene copolymer. A composition according to any preceding claim, wherein the composition further comprises from 0.1% to about 25% by weight of one or more other cosmetic ingredients selected from particles, additional polymers, colorants, preservatives, flavors and combinations thereof. Composition according to one of the preceding claims, in which the composition is anhydrous. A composition according to any preceding claim, further comprising a low molecular weight hydrocarbon resin, wherein the thermoplastic block copolymer and the low molecular weight hydrocarbon resin are present in a ratio between the concentrations by weight of the thermoplastic block copolymer comprising styrenated blocks, and the low molecular weight hydrocarbon resin which is not less than 2:1. A method for improving the appearance of the lips comprising applying a composition to the lips in an amount sufficient to improve the appearance of the lips, wherein the composition comprises:
from about 8% by weight to about 15% by weight of a thermoplastic block copolymer comprising styrenated blocks;
at least one non-polar polyolefin oil; And
at least one polar fatty ester oil having a molecular weight of less than 650 g/mole, wherein the at least one nonpolar polyolefin oil and the at least one polar fatty ester oil are present in concentrations by weight such that a ratio between the concentration by weight of the at least one nonpolar oil and the concentration by weight of the at least one polar oil having a molecular weight of less than 650 g/mole is at least about 1:1, in wherein the composition has a zero shear viscosity at 32°C in a range of 15 Pa s to 90 Pa s, wherein the composition has a critical shear rate which is from about 10 s ^-1 to about 250 s ^-1 at any temperature between 32°C and 37°C, and wherein the composition has a normal stress of about 50 Pa to about 10,000 Pa at any temperature between 32°C and 37°C.