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WO2000028948A1 - Compositions cosmetiques - Google Patents

Compositions cosmetiques Download PDF

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Publication number
WO2000028948A1
WO2000028948A1 PCT/US1998/024131 US9824131W WO0028948A1 WO 2000028948 A1 WO2000028948 A1 WO 2000028948A1 US 9824131 W US9824131 W US 9824131W WO 0028948 A1 WO0028948 A1 WO 0028948A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
poly
methacrylate
unsaturated
methacrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1998/024131
Other languages
English (en)
Inventor
Christopher Todd Morrissey
Edward Dewey Smith, Iii
Sanjeev Midha
Timothy Roy Nijakowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PCT/US1998/024131 priority Critical patent/WO2000028948A1/fr
Priority to AU13161/99A priority patent/AU1316199A/en
Publication of WO2000028948A1 publication Critical patent/WO2000028948A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings

Definitions

  • the present invention relates to compositions useful as cosmetic or therapeutic agents.
  • the compositions are particularly useful as nail polishes, and are especially useful as topcoat compositions.
  • Cosmetic compositions refer to products generally recognized as being formulated for beautifying or grooming the skin (especially the face), lips, eyes or nails.
  • cosmetic compositions such as lotions, creams, emulsions, packs, make-up (e.g., foundations, lipsticks, nail polish, eye shadows and the like) are used to improve one's outward appearance.
  • make-up e.g., foundations, lipsticks, nail polish, eye shadows and the like
  • nail polishes to cosmetically enhance their nails or protect the nails from everyday conditions and stressors.
  • these nail polish compositions are deficient in many respects, including their inability to provide long wear.
  • Nail polishes which are known or currently available often exhibit deterioration, particularly in the form of chipping or peeling, in as few as one or two days. Such poor wear often forces consumers to remove their nail polish soon after original application and reapply additional nail polish to the nails. Consumers may also attempt to correct the unsightly appearance of the deteriorating nail polish by "touching-up" the areas of the nail which exhibit the deterioration, a practice which actually impairs the overall look of the nail polish.
  • consumers may choose to do nothing about the deterioration and allow, for example, chipping and peeling to progress, resulting in nails which are not only minimally protected from the environment but are unsightly as well.
  • nail polish compositions which are promoted as having long wear, and / or resistance to chipping. While some nail polish compositions provide better wear than others, a need remains for nail polish compositions having improved wear properties.
  • the present inventors have surprisingly discovered that the present compositions provide excellent long wear properties including, for example in the case of nail polishes, chip-resistance and superior hardness. These compositions have preferred toughness properties for deflecting environmental stressors which contribute to wear. The compositions exhibit long wear at a superior level not provided by the nail polishes which are presently known and used.
  • the present invention relates to cosmetic compositions having improved wear, preferably comprising:
  • each of the grafts exhibits a T g of from about 50 °C to about 200 °C, and wherein the average molecular weight of each of the grafts is greater than about 1000; and (b) from about 50% to about 99.9%, based on the weight of the composition, of a suitable carrier.
  • the carrier comprises from about 10% to about 98%, based on the weight of the composition, of a volatile organic diluent.
  • compositions are suitable for use in a variety of cosmetic applications, such as facial moisturizers or other treatments, foundations, lipsticks, mascaras, nail polishes and the like, and provide improved wear.
  • cosmetic applications such as facial moisturizers or other treatments, foundations, lipsticks, mascaras, nail polishes and the like, and provide improved wear.
  • the compositions are in the form of a nail polish which, when applied to nails, exhibit excellent long wear properties.
  • the present invention also relates to films formed from the compositions, kits comprising the compositions, and methods of treating the skin, lips, nails or eyelashes comprising application of the composition to the substrate.
  • the essential components of the present invention are described herein below. Also included are non-limiting descriptions of various optional and preferred components useful in the compositions of the present invention.
  • the present invention can comprise, consist of, or consist essentially of any of the required or optional components and / or limitations described herein.
  • compositions of the present invention are suitable for topical application.
  • suitable for topical application means that the compositions are suitable for use in contact with skin, lips, nails, and/or eyelids without undue toxicity, incompatibility, instability, allergic response, and the like.
  • the compositions are nail polishes which are accordingly suitable for use in contact with the nails.
  • nail polish as well known in the art describes a composition which is to be applied to the nails and which forms a durable film and provides benefits to the nail, such as aesthetic (e.g., color, shine), therapeutic, or prophylactic benefits.
  • a nail polish may consist of the compositions described herein, as well as systems/kits comprising such compositions.
  • the present compositions may be formulated for analogous topical application to other mammals or non-mammals. COMPOSITIONS OF THE PRESENT INVENTION
  • the compositions of the present invention are beneficial to long wear because they provide films which deflect environmental stressors by virtue of their hardness, toughness, durability, rigidity, and/or resistance to chipping.
  • the present compositions comprise a film-forming graft copolymer.
  • the graft copolymer tends to contribute to the wear benefits of the present invention. For example, the beauty benefits provided by a composition tend to last longer, and/or the composition as applied tends to last longer, relative to a composition not containing the graft copolymer of the present invention.
  • the term "film-forming” means that the copolymer to which it refers forms an adherent continuum from a composition when applied to a substrate. See, e.g.. Polymer Colloids. Robert M. Fitch, ed., New York: Plenum Press, pp. 173- 183 (1971).
  • the term "graft” in reference to a polymer, especially herein a copolymer, is familiar to one of ordinary skill in the art.
  • the term “graft” describes copolymers that have "grafted" polymeric side chain moieties ("grafts”) covalently bonded to another portion of the polymer which is referred to as the "backbone".
  • graft copolymers can be described as polymers having pendant polymeric side chains, and as being formed from the "grafting” or covalent bonding of polymeric side chains onto a backbone.
  • compositions of the present invention preferably comprise at least about 0.1%, by weight of the composition, of the film forming graft copolymer. More preferred compositions comprise from about 1% to about 50%, preferably from about 2% to about 40%, more preferably from about 5% to about 30%, and most preferably from about 10% to about 25%, by weight of the composition, of the film- forming graft copolymer.
  • the graft copolymers of the present invention have a weight average molecular weight of at least about 20,000. There is no upper limit for molecular weight except that which limits applicability of the invention for practical reasons such as, for example, processing, aesthetic characteristics, and ease of formulation. Generally, the weight average molecular weight is less than about 10,000,000, more generally less than about 5,000,000, and typically less than about 3,000,000. Preferably, the weight average molecular weight is from about 50,000 to about 2,000,000, more preferably from about 75,000 to about 1,000,000, and most preferably from about 80,000 to about 750,000.
  • the graft copolymers of the present invention exhibit one or more glass transition temperatures (T g ).
  • Preferred copolymers have at least two distinct immiscible phases, wherein the essential, hydrophilic polymeric side chains are closely associated with each other and exist in one phase and the polymeric backbone of the copolymer remains in a second separate phase.
  • the copolymer may exhibit at least two distinct T g values, namely one T g value for the backbone and one T g value for the side chains, if the temperature separation between each of the T g values involved is large enough.
  • the graft copolymer optionally comprises one or more other side chains, e.g., polysiloxane side chains according to one embodiment of the invention
  • the copolymer may also exhibit one or more third T g 's corresponding to the other side chains. Whether such additional T g values are observable depends upon a number of factors including, but not limited to, the number of side chains on the graft copolymer, the temperature separation between each of the T g values involved, and in the case of polysiloxane side chains, the percent silicone in the graft copolymer.
  • the essential backbone and side chains of the graft copolymer are derived from monomers.
  • the side chains comprise at least one type of hydrophilic monomer, and optionally one or more types of hydrophobic monomers.
  • the backbone may be derived from hydrophilic monomers, hydrophobic monomers, or mixtures thereof.
  • Suitable monomers are selected such that the overall copolymer is soluble or dispersible in the carrier of choice.
  • the selection of suitable monomers for a given carrier of choice can be readily made by those skilled in the art. In general, one skilled in the art chooses monomers which form homopolymers that are soluble or dispersible in the carrier of choice, and uses a majority of those in the graft copolymer.
  • soluble means that the material so described (e.g., the copolymer) is soluble in a designated carrier (e.g., the carrier of choice) at 25°C at a concentration of at least about 20 mg/mL, more preferably at least about 50 mg/mL, and most preferably at least about 100 mg/mL.
  • a designated carrier e.g., the carrier of choice
  • dispenser is meant that the material so described forms a stable, uniform suspension (without the addition of further materials such as emulsifiers; includes latexes and pseudolatexes) when combined with the designated carrier at 25°C at a concentration of at least about 20 mg/mL, more preferably at least about 50 mg/mL, and most preferably at least about 100 mg/mL.
  • hydrophilic means that the material so described is soluble or dispersible in water, lower alcohols (Ci - C 4 ), or mixtures of water and lower alcohols.
  • hydrophobic means that the material so described is not soluble or dispersible in water, lower alcohols (Ci - C ), or mixtures of water and lower alcohols.
  • hydrophilic or hydrophobic refers to the property of a homopolymer of the monomer.
  • the graft copolymers can be nonionic, ionic (anionic or cationic), amphoteric, or zwitterionic.
  • Graft polymers suitable for use herein include those described in commonly assigned, copending U.S. Patent Application Serial Nos. 08/854,513 (Attorney's Docket 6629); 08/854,698 (Attorney's Docket 6630); both filed May 12, 1997; and 08/854,070 (Attorney's Docket 6637) and 08/858,071 (Attorney's Docket 6638); both filed May 16, 1997; all filed in the names of Midha and Nijakowski; and incorporated herein by reference in their entirety.
  • the backbones of the graft copolymers comprise from about 50% to about
  • the backbone exhibits a T g of from about 0 °C to about 50 °C, preferably from about 0 °C to about 45 °C, more preferably from about 0 °C to about 35 °C, and most preferably from about 0 °C to about 25 °C.
  • the backbone vinyl monomer units are derived from copolymerizable monomers (including macromonomers such as described herein, infra), preferably ethylenically unsaturated monomers.
  • the term "copolymerizable” means that the monomer may be reacted with or polymerized with other monomers or macromonomers in a polymerization reaction using one or more conventional synthetic techniques, such as ionic, emulsion, dispersion, Ziegler-Natta, free radical, group transfer or step growth polymerization.
  • ethylenically unsaturated is used herein to mean a material that contains at least one polymerizable carbon- carbon double bond, which can be mono-, di-, tri- or tetra-substituted.
  • Preferred monomers include unsaturated alcohols, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides, alcohol esters of unsaturated monocarboxylic acids, alcohol esters of unsaturated dicarboxylic acids, alcohol esters of unsaturated anhydrides, alkoxylated esters of unsaturated monocarboxylic acids, alkoxylated esters of unsaturated dicarboxylic acids, alkoxylated esters of unsaturated anhydrides, aminoalkyl esters of unsaturated monocarboxylic acids, aminoalkyl esters of unsaturated dicarboxylic acids, aminoalkyl esters of unsaturated anhydrides, amides of unsaturated monocarboxylic acids, amides of unsaturated dicarboxylic acids, amides of unsaturated anhydrides, salts of unsaturated monocarboxylic acids, salts of unsaturated dicarboxylic acids, salts of unsaturated anhydrides, unsaturated
  • More preferred monomers are selected from the group consisting of acrylic acid, methacrylic acid, N,N-dimethylacrylamide, N,N- dialkylaminoalkyl(meth)acrylate, N,N-dialkylaminoalkyl(meth)acrylamide, N,N- dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, Cj-Cj alkyl esters of acrylic or methacrylic acid, styrene, a- methylstyrene, /-butylstyrene, 4-hydroxystyrene, 4-acetoxystryrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl toluene, 2-methoxyethyl acrylate, w-butyl methacrylate, / ' s ⁇ -butyl methacrylate, t-butyl acryl
  • Typical counterions for the salts of anionic monomers include inorganic, (alkali, alkaline earth metals, or transition metals) or organic (ammonium or alkylammonium including mono, di, tri and tetraalkyl) cations and the like, provided that the overall solubility or dispersibility of the polymer in the carrier is not adversely affected.
  • Typical counterions for the salts of cationic monomers include halides, sulfates, sulfonates, phosphates, nitrates, and the like, provided that the overall solubility or dispersibility of the polymer in the carrier is not adversely affected.
  • the most preferred monomers are selected from the group consisting of acrylic acid, methacrylic acid, 2-methoxyethyl acrylate, N,N-dimethylaminoethyl methacrylate, w-butyl methacrylate, w ⁇ -butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and mixtures thereof.
  • the copolymers of the present invention comprise from about 2% to about 50%, preferably from about 5% to about 40%, and more preferably from about 10% to about 30%, by weight of the graft copolymer, of hydrophilic side chains.
  • the weight average molecular weight of the side chains is from about 1000 to about 50,000.
  • the hydrophilic side chains exhibit a T g of from about 50 °C to about 200 °C, preferably from about 60 °C to about 150 °C, and most preferably from about 70 °C to about 110 °C.
  • a preferred method for copolymer preparation utilizes one or more types of macromonomers to provide the side chain grafts.
  • the macromonomers that are useful herein contain a polymeric portion and a moiety which is copolymerizable with the vinyl monomers comprising the backbone. That is, the macromonomers can be reacted with or polymerized with the vinyl monomers of the backbone in a polymerization reaction using one or more conventional synthetic techniques such as described herein.
  • the copolymerizable moiety is preferably an ethylenically unsaturated moiety.
  • Preferred macromonomers are endcapped with a vinyl moiety which is copolymerizable with the backbone monomer units. As used herein, the term "endcapped" means that the vinyl moiety is at or near a terminal position of the macromonomer.
  • the macromonomers may be synthesized utilizing a variety of standard synthetic procedures known to one of ordinary skill in the art. Furthermore, these macromonomers may be synthesized starting from commercially-available starting materials.
  • Preferred macromonomers are polyacrylate, polymethacrylate, polyoxazolines, polypyridines, or copolymers thereof.
  • Suitable macromonomers include those exemplified by the general formula:
  • I is an optionally present initiator
  • n is an integer from 0 to 1
  • W is a monomer unit
  • m is an integer of from about 10 to about 2000
  • E is an endcapping group.
  • I can be derived from a chemical initiator or solvent used in the synthesis of the macromonomer.
  • initiators from which I may be derived include hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, C ⁇ -
  • C20 carbocations C1-C20 carbanions, C1-C20 carbon radicals, C1-C20 aliphatic and aromatic alkoxy anions, ammonium ion, and substituted ammonium ions (e.g., C1-
  • C20 alkyl and C1-C20 alkoxy substituted may also be derived from any useful solvent including, for example, water, methanol, ethanol, propanol, /s ⁇ -propanol, acetone, hexane, dichloromethane, chloroform, benzene, toluene, and mixtures thereof.
  • W is derived from monomers selected from the group consisting of hydrophilic monomers, and mixtures of hydrophilic monomers with hydrophobic monomers, provided that the overall macromonomer is hydrophilic.
  • W is a monomer selected from the group consisting of oxazolines, N-alkyloxazolines, alkylene glycols, N-vinylpyrrolidones, N- allylpyrrolidones, vinylpyridines, allylpyridines, vinylcaprolactams, allylcaprolactams, vinylimidazoles, allylimidaoles, vinylfurans, allylfurans, vinyltetrahydrofurans, allyltetrahydrofurans, vinylaminobenzenes, vinylaminomethylbenzenes, vinylaminoethylbenzenes, N,N-dialkylacrylamides, N,N-dialkyl(alkyl)acrylamides, acrylic acid, methacrylic acid, phenyl
  • More preferable monomers include acrylic acid, methacrylic acid, 7-propyl methacrylate, / ' .r ⁇ -butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, / ' so-propyl methacrylate, methylmethacrylate, styrene, oxazoline, 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, vinylpyridine, and mixtures thereof.
  • the most preferable monomers include acrylic acid, methacrylic acid, «-propyl methacrylate, iso-butyl methacrylate, w ⁇ -propyl methacrylate, methylmethacrylate, 2-ethyl-2-oxazoline, vinylpyridines, and mixtures thereof.
  • the graft copolymers may further comprise one or more polysiloxane macromonomers, preferably exemplified by the general formula:
  • X is a vinyl group copolymerizable with the backbone vinyl monomers
  • Y is a divalent linking group
  • each R is independently selected from hydrogen, hydroxyl, Ci -Cg alkyl, C1 -C6 alkoxy, C2-Cg alkylamino, phenyl, C]-C6 alkyl, and alkoxy- substituted phenyl
  • Z is a polysiloxane moiety having an average molecular weight of at least about 1000 and is essentially unreactive under copolymerization conditions
  • n is an integer from 0 to 1
  • m is an integer from 1 to 3.
  • the polysiloxane macromonomer has an average molecular weight from about 1000 to about 50,000, preferably from about 5,000 to about 30,000, and more preferably from about 8,000 to about 25,000.
  • the polysiloxane macromonomer has a structure selected from one of the following three structures:
  • each R ⁇ is independently selected from hydrogen, hydroxyl, Ci-C ⁇ alkyl, Ci-C ⁇ alkoxy, C 2 -C 6 alkylamino, phenyl, Ci-C ⁇ alkyl phenyl, and Ci-C ⁇ alkoxy-substituted phenyl, preferably C ⁇ -C 6 alkyl, Ci-C ⁇ alkyl phenyl, and Cj-C ⁇ alkoxy-substituted phenyl, more preferably Ci-C ⁇ alkyl, even more preferably methyl, R ⁇ is selected from Ci-C ⁇ alkyl and Ci-C ⁇ alkyl substituted phenyl, preferably methyl, n is an integer from 0 to 4, preferably 0 to 1, more preferably 0, X is:
  • R ⁇ is selected from hydrogen and -COOH, preferably hydrogen
  • R ⁇ is selected from hydrogen, methyl
  • -CH2COOH preferably methyl
  • Z is:
  • Nonlimiting examples of graft copolymers for use in the present invention are:
  • the graft copolymers may be synthesized by a variety of techniques known to one skilled in the art. These include attaching preformed grafts to preformed backbones ("grafting onto"), polymerizing grafts from preformed backbones ("grafting from”), and copolymerizing monomers with macromonomers.
  • the backbones and grafts can be polymerized by a variety of techniques including radical, cationic, anionic, Ziegler-Natta, group transfer polymerization, step growth polymerization, or combinations thereof.
  • the polymerizations can optionally be "living” or "living-like” polymerizations such as are known to those skilled in the art.
  • the copolymers are synthesized by free radical polymerization of the backbone monomers with side chain macromonomers, or the polymerization of grafts from existing backbones ("grafting from”).
  • free radical polymerization methods are well known to one skilled in the art. See, e.g.. Odian, "Principles of Polymerization", 3rd ed., John Wiley & Sons, pp. 198-334 (1991).
  • the desired vinyl monomers and macromonomers are placed in a reactor, along with a sufficient amount of a solvent so that when the reaction is complete the viscosity of the reaction is reasonable.
  • Undesired terminators are removed as needed, for example, by evacuation or by purging with an inert gas.
  • the initiator is introduced and the reaction is brought to the temperature needed for initiation to occur, wherein thermal initiators are used. Alternatively, redox or radiation initiation may be used.
  • the polymerization is allowed to proceed as long as needed for a high level of conversion to be achieved, typically from a few hours to a few days.
  • the solvent is removed, typically by evaporation or by precipitating the copolymer.
  • the copolymer may be further purified, as desired.
  • the copolymer may be made by a semi- continuous or continuous process.
  • the semi-continuous process two or more additions of monomers or macromonomers are made during the polymerization reaction. This is advantageous wherein the copolymer is made of several monomers which react during the polymerization at different rates.
  • the proportions of monomers added to the reaction at the separate points of addition may be adjusted by one of ordinary skill in the art such that the polymers of the final product have a more uniform structure. In other words, the polymers of the final product will have a more consistent monomer content distribution for each of the monomer types charged to the reaction.
  • copolymers according to the above method are prepared by the polymerization combination of vinyl monomers and macromonomers.
  • the copolymer composition is characterized by the amount of each monomer charged to the polymerization reaction vessel, or alternatively, used in a continuous or semi- continuous process.
  • the grafts are polymerized from existing backbones.
  • a particularly preferred synthetic method involves two essential reaction steps.
  • the polymeric backbone of the graft polymer is first prepared. This is accomplished by reacting copolymerizable monomers to form a polymeric backbone containing a plurality of organic halide moieties covalently bonded to and pendant from the polymeric backbone, and includes those polymers which conform generally to the formula
  • A is a monomer unit having an organic halide moiety "C” attached which is covalently bonded to and pendant from the “A” monomer unit
  • B is a monomer unit that is copolymerizable with the "A” monomer unit
  • a is a positive integer having a value of 2 or greater, preferably a value of from about 2 to about 30
  • "b” is a positive integer having a value of at least about 4, preferably a value of from about 10 to about 2000.
  • the organic halide moiety "C” includes any linear, branched or cyclic (aromatic or otherwise) carbon structure, whether substituted or unsubstituted, which also contain a halogen atom (CI, Br or I).
  • the "A" monomer unit with the attached organic halide moiety "C” is preferably selected from the group of allyl monomers, vinyl acetate monomers, acid halide monomers, styryl monomers, or combination thereof, and more preferably selected from the monomer units characterized by the following general structures (Groups I-V): (I)
  • H 7 C CH-0 — R J — X
  • R is methyl or hydrogen
  • X is a halogen atom (CI, Br, I)
  • R and R ⁇ are each independently selected from methyl, hydrogen or methoxy
  • R- is an alkyl group having from 1 to 8 carbon atoms.
  • the first reaction step involves any conventional or otherwise known polymerization techniques such as ionic, Ziegler-Natta, free radical, group transfer or step growth polymerization, or combinations thereof.
  • the first reaction step preferably involves conventional free radical polymerization techniques.
  • the reaction mixture is heated to about 120°C for about 15 minutes to consume or react any remaining free radical initiator, and thereafter the reaction mixture is cooled or allowed to cool to room temperature to allow the reaction to self terminate before addition of ingredients to start the second reaction step.
  • the polymeric backbone described hereinabove is reacted with one or more copolymerizable monomers in the presence of a catalytic amount of a transition metal salt, preferably a Cu(I) salt and preferably complexed to a suitable ligand.
  • the organic halide moieties act as initiators in the presence of the copolymerizable monomers and the catalyst, resulting in the grafting of the monomers onto the polymeric backbone by atom transfer free radical polymerization, the monomers forming a plurality of polymeric side chains covalently bonded to and pendant from the backbone.
  • the polymeric side chains form on the polymeric backbone without the need to use copolymerizable macromonomers to achieve the pendant polymeric graft chains.
  • Suitable monomers in the second reaction step include those described herein above in regard to the macromonomer.
  • the catalyst for the second reaction step is a transition metal salt, preferably a Cu(I) salt such as Cu(I) halide salts (CI, F, Br, I) and which is preferably complexed to a ligand which is suitable for solubilizing the Cu(I) salt in the reaction mixture, wherein the reaction mixture of the second reaction step comprises dissolved or partially dissolved polymer, unreacted monomer, solvent and catalyst.
  • a transition metal salt preferably a Cu(I) salt such as Cu(I) halide salts (CI, F, Br, I) and which is preferably complexed to a ligand which is suitable for solubilizing the Cu(I) salt in the reaction mixture, wherein the reaction mixture of the second reaction step comprises dissolved or partially dissolved polymer, unreacted monomer, solvent and catalyst.
  • Preferred ligands for use in solubilizing the Cu(I) salts in the reaction mixture are aprotic bidendates such as diphosphates, 2,2' bipyridyl, C1-C20 alkyl substituted bipyridyl (4,4'-di-5-nonyl-2,2'-bipyridine, 4,4'-di-t-butylbi ⁇ yridine, 4,4'-dihe ⁇ tyl-2,2'-bi ⁇ yridine) and combinations thereof.
  • aprotic bidendates such as diphosphates, 2,2' bipyridyl, C1-C20 alkyl substituted bipyridyl (4,4'-di-5-nonyl-2,2'-bipyridine, 4,4'-di-t-butylbi ⁇ yridine, 4,4'-dihe ⁇ tyl-2,2'-bi ⁇ yridine) and combinations thereof.
  • copolymers of the present invention can be used alone or with low levels of the corresponding copolymers having no side chains grafted to the backbone.
  • synthetic graft copolymerization processes may produce a mixture of polymer molecules containing none, one, or more than one side chains covalently bonded to and pendant from the polymeric backbone. From knowledge of the amount and average molecular weight of side chains in a polymer sample, and the average molecular weight of the polymer sample, it is possible to calculate the average number of side chains per polymer backbone. ⁇ ) CARRIERS OF THE PRESENT INVENTION
  • compositions of the present invention comprise a carrier, or vehicle, which is suitable for topical application, as a support for the graft copolymer.
  • carriers are well-known to one of ordinary skill in the art, and include one or more compatible liquid diluents or vehicles which are suitable for topical application.
  • the carrier may optionally also contain one or more compatible solid filler diluents or vehicles which are suitable for topical application.
  • the carrier may comprise one or more active or inactive materials, including but not limited to optional components described below.
  • the graft copolymers herein are soluble or dispersible in (dissolved or dispersed in) at least one liquid diluent. In single phase systems, the copolymer is soluble or dispersible in the liquid diluent component mixture. In multiple phase systems, e.g., emulsions, the copolymer is soluble or dispersible in at least one liquid diluent.
  • compositions of the present invention generally comprise from about 50% to about 99.9% of the carrier by weight of the composition.
  • the amount of carrier varies depending on the cosmetic application desired.
  • the compositions preferably comprise from about 60% to about 98%, more preferably from about 70% to about 95%, also preferably from about 75% to about 90%, carrier by weight of the composition.
  • preferred compositions comprise 74% to about 99.7%, more preferably from about 79% to about 99%, carrier by weight of the composition.
  • Suitable liquid diluents may be hydrophilic, hydrophobic, or a combination thereof.
  • the diluents may be organic, inorganic, or a mixture thereof.
  • the liquid diluent may be volatile, non-volatile, or a mixture thereof.
  • Preferred liquid diluents comprise a volatile diluent.
  • volatile it is meant that the diluent exhibits a significant vapor pressure at ambient conditions (e.g., 1 atmosphere, 25 °C), as is understood by those in the art, and has a boiling point at one atmosphere of 260 °C or less.
  • Preferred volatile organic diluents have a boiling point of from about 50 °C to about 140 °C, and more preferably from about 56 °C to about 125 °C, at atmospheric pressure.
  • Volatile diluents include water, alcohols, esters, ketones, ethers, aromatic hydrocarbons, aliphatic hydrocarbons and siloxanes.
  • Preferred alcohols, esters, ketones, and ethers are Ci to about Cio, more preferably d to C .
  • Preferred aromatic hydrocarbons and aliphatic hydrocarbons are C O to about C ⁇ 8 .
  • preferred organic diluents are selected from Ci to about Cio (preferably Ci to C 4 ) alcohols, esters, ketones, and mixtures thereof; more preferably such alcohols, esters and mixtures thereof.
  • Preferred alcohols are monohydric.
  • the most preferred monohydric alcohols are selected from ethanol, /s ⁇ -propanol, «-propanol, and butanol.
  • the most preferred esters are selected from ethyl acetate and butyl acetate.
  • Preferred aliphatic hydrocarbons are branched chain hydrocarbons, preferably characterized by a boiling point of at least about 105°C, more preferably at least about 110°C, even more preferably at least about 125°C, most preferably at least about 150°C.
  • the boiling point is also generally about 260°C or less, preferably about 200°C or less.
  • the branched chain hydrocarbon diluents are preferably selected from the group consisting of C10-C14 branched chain hydrocarbons, and mixtures thereof, more preferably C ⁇ ⁇ -C]3 branched chain hydrocarbons, most preferably C ⁇ 2 branched chain hydrocarbons. Saturated hydrocarbons are preferred, although it is not intended to exclude unsaturated hydrocarbons.
  • Suitable branched chain hydrocarbons include isoparaffins of the above chain sizes.
  • Isoparaffins are commercially available from Exxon Chemical Co., USA. Examples include Isopar G (CJQ-C I ] isoparaffins), Isopar H and K (Ci i -Cj2 isoparaffins),
  • Isopar L C11-C13 isoparaffins. Most preferred are Cj2 branched chain hydrocarbons, especially isododecane. Isododecane is commercially available from Preperse, Inc. (South Plainfield, NJ, USA) as PermethylTM 99 A.
  • Preferred siloxanes are phenyl pentamethyl disiloxane, phenylethyl pentamethyl disiloxane, hexamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, cyclomethicones (including octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane), and mixtures thereof. Most preferred are cyclomethicones, more preferably octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane.
  • organic liquid diluents examples include benzyl alcohol, amyl acetate, propyl acetate, acetone, heptane, ⁇ r ⁇ -butyl acetate, / ' s ⁇ -propyl acetate, toluene, methyl acetate, /s ⁇ -butanol, «-amyl alcohol, «-butyl alcohol, hexane, and methyl ethyl ketone.
  • compositions herein more preferably comprise one, two, or three, and most preferably one or two, different organic diluents.
  • the liquid diluents preferably consist of water, one or more liquid, volatile organic diluents suitable for topical application, or a mixture of water and one or more such organic diluents.
  • the most preferred organic diluents are selected from so-propanol, w-propanol, ethanol, ethyl acetate, butyl acetate, and acetone.
  • the liquid diluent component is hydrophobic.
  • the liquid diluent component of mascaras of the present invention may be hydrophobic, e.g., where water-proofness is desired, or alternatively hydrophilic or a combination thereof (e.g., emulsions and single phase mixtures).
  • the liquid diluent component of skin care compositions, including wrinkle reducing compositions, foundations and the like, may be hydrophobic, hydrophilic, or a combination thereof ( emulsions and single phase mixtures).
  • the liquid diluent is non-aqueous, comprises one or more hydrophilic, organic, volatile liquid diluents, and optionally one or more hydrophobic liquid diluents.
  • the graft copolymer in such nail polishes is preferably soluble or dispersible in the hydrophilic, organic liquid diluent component, and insoluble and non-dispersible in water.
  • the nail polish composition preferably comprises from about 10% to about 98%, more preferably from about 10% to about 90%, even more preferably from about 50% to about 90%, and most preferably from about 75% to about 90%, by weight of the composition, of one or more volatile organic liquid diluents.
  • the carrier can be formulated in a number of ways, including but not limited to solutions, latexes, pseudolatexes and emulsions (in emulsion technology, a composition comprising a "dispersed phase” and a "continuous phase;” the dispersed phase existing as small particles or droplets that are suspended in and surrounded by a continuous phase).
  • suitable emulsions include oil-in-water, water-in- oil, water-in-oil-in-water, oil-in-water-in-oil, and oil-in-water-in-silicone emulsions.
  • Preferred compositions for applications to the skin, e.g., foundations, moisturizers and the like, comprise an oil-in-water emulsion.
  • compositions of the present invention thus contain, in a suitable carrier, the graft copolymers described herein, for as wide a range of applications as encountered, for example, in the field of cosmetics, including skin care, make-up (e.g., color cosmetics), in which utilization of the graft copolymers is desired.
  • the compositions of the present invention can be formulated into a wide variety of product types, including creams, lotions, milks, mousses, masks, gels, oils, tonics, serums, sprays, and lacquers.
  • Preferred compositions are formulated into lotions, creams, gels, sprays, aerosols and lacquers.
  • product forms may be used for a number of applications, including, but not limited to, hand and body lotions, cold creams, facial moisturizers, anti-acne preparations, wrinkle-reducing preparations, topical analgesics, make-ups including foundations, lipsticks, mascaras, eyeliners, eyeshadows, nail polishes and the like.
  • Any additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art.
  • such products and their formulations to which the graft copolymers of the present invention may be added are those described in Harry's Cosmeticology. 7 th Ed., R.G. Harry, J.B. Wilkinson and R.J. Moore, Chemical Pub. Co.
  • Nonlimiting examples of mascara compositions to which the present invention is applicable are also described in copending, commonly assigned U.S. Patent Application Serial Nos. 08/951,285 (Alwatarri et al.), filed October 16, 1997, (Attorney's Docket 6345C); 08/757,538 (Bartholomey et al.), filed November 27, 1996 (Attorney's Docket 6397); and 09/121,138 (Alwatarri et al.), filed July 23, 1998 (Attorney's Docket 5654C2); and in PCT Application Nos. US96/04154, published October 31, 1996; US97/19786, published May 7, 1998; and US97/21890, published June 4, 1998; each incorporated herein by reference in its entirety.
  • Nonlimiting examples of lipstick compositions to which the present invention is applicable are also described in U.S. Patent No. 5,593,662 (Deckner et al.), issued on January 14, 1997; and PCT Application Nos. US93/08684 and US 93/08683, both published March 31, 1994; all incorporated herein by reference in their entirety.
  • Nonlimiting examples of foundation compositions to which the present invention is applicable are also described in copending, commonly assigned U.S. Patent Application Serial No. 08/430,961 (Canter et al.), filed April 28, 1995 (Attorney's Docket 5655); and in PCT Application No. US96/04302, published October 31 , 1996, incorporated herein by reference in their entirety.
  • compositions of the present invention are formulated as an aerosol and applied to the skin as a spray-on product, a propellant is preferably added to the composition.
  • suitable propellants include chlorofluorinated lower molecular weight hydrocarbons.
  • a more complete disclosure of propellants useful herein can be found in the above-referenced Cosmetics. Science and Technology(Vol. 2, pp. 443-465).
  • compositions of the present invention may contain a variety of other ingredients such as are conventionally used in a given product type, provided that the advantageous properties that are intrinsic to the compositions are not, or not substantially altered by the optional component. These optional components should be suitable for topical application.
  • CTFA Cosmetic Ingredient Handbook, Second Edition (1992) describes a wide variety of nonlimiting cosmetic and pharmaceutical ingredients commonly used in the skin care industry, which are suitable for use in the compositions of the present invention. Examples of these ingredient classes include: abrasives, absorbents, aesthetic components such as fragrances, pigments, colorings/colorants, essential oils, skin sensates, astringents, etc.
  • anti-acne agents e.g., resorcinol, sulfur, salicylic acid, erythromycin, zinc, etc.
  • anti-caking agents e.g., antifoaming agents
  • antimicrobial agents e.g., iodopropyl butylcarbamate
  • antioxidants binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers or materials, e.g., polymers, for aiding the film-forming properties and substantivity of the composition (e.g., copolymer of eicosene and vinyl pyrrolidone), humectants, opacifying agents, pH adjusters, propel
  • compositions of the present invention may contain one or more of such optional components.
  • the components herein can be categorized by the benefit they provide or by their postulated mode of action, however, it is to be understood that they can in some instances provide more than one benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit the component to the particular application or applications listed.
  • the nail polish compositions of the present invention may comprise a variety of optional components to enhance their performance as a nail polish.
  • optional components for example, antifoams, buffers, chelating agents, coalescents, dispersing agents, dyes, epoxies, fillers, pigments, preservatives, resins, therapeutic and prophylactic agents, thickeners, wax additives, wetting agents, secondary film formers, plasticizers and the like can be included in the compositions herein.
  • Preferred nail polish compositions comprise a plasticizer and pigment.
  • Such optional components may be dispersed, solubilized, or otherwise mixed in the carrier and / or the liquid diluent of the compositions. These components may be added to the compositions herein provided they do not substantially hinder the wear properties, particularly the adhesion, of the compositions. Non-limiting examples of such optional components are given below. a) Pigments or Dyes
  • Pigments and other suitable coloring agents may be incorporated into the present compositions.
  • Suitable pigments include inorganic or organic pigments known as, for example, the FD&C and D&C colors, lakes, and iron oxides. Such pigments are disclosed in the C.T.F.A. Cosmetic Ingredient Handbook. First Edition, 1988.
  • Organic pigments include, for example, D and C Red, Nos. 10, 11, 12, and 13, D and C Red No. 7, D and C Red Nos. 5 and 6, D and C Red Nos. 30 and 34, lacquers such as D and C Yellow No. 5 and D and C Red No. 2, and guanine.
  • Inorganic pigments include, for example, titanium dioxide, bismuth oxychloride, brown iron oxide, and the red iron oxides. Preferably from 0% to about 5%, by weight of the composition, of a pigment or dye are used in the present nail polish compositions.
  • Plasticizers for example, titanium dioxide, bismuth oxychloride, brown iron oxide, and the red iron oxides
  • plasticizers cause a composition to become more easily deformed.
  • One or more plasticizers may optionally be added to the present compositions.
  • Suitable plasticizers include those disclosed in WO 97/00664, Chen et al. assigned to Eastman Chemical Co.
  • Suitable plasticizers include phthalates, nonionic surfactant polymers, and polyesters.
  • Preferred plasticizers include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl tartrate, dibutyl tartrate, diethyl phosphate, dibutyl phosphate, polyester sebacates, such as Paraplex
  • polyester adipates such as Paraplex G-50® (CP. Hall) and tetraethylene glycol di-2-ethylhexoate, available as Tegmer® (CP. Hall).
  • the most preferred plasticizers include dibutyl phthalate, Paraplex G-25®, Paraplex G-50®, and Tegmer®.
  • the nail polish compositions preferably comprise from 0% to about 10%, more preferably from about 0% to about 5%, by weight of the composition, of a plasticizer. c) Preservatives
  • compositions may optionally be added to the present compositions to prevent, inhibit, or retard microbial growth in the composition.
  • the compositions comprise a preservative wherein the composition comprises less than about 40% of one or more organic solvents.
  • Preferred preservatives include methyl paraben, ethyl paraben, propyl paraben, benzyl alcohol, benzoic acid, benzoates (preferably sodium benzoate), sorbates (preferably potassium sorbate), sodium dehydroacetate, l-(3-chloroallyl)-3,5,7-triaza-l-azoniaadamantane chloride (which may be obtained commercially as Quaternium-15® from Dow Chemical Co., Midland, MI), a mixture of 95% l,3-dimethylol-5,5-dimethyl hydantoin and 5% 3-iodo-2-propynyl butyl carbamate (which mixture is commercially available as Glydant Plus® from Lonza, Inc
  • the most preferred preservatives include methyl paraben, ethyl paraben, propyl paraben, benzyl alcohol, benzoic acid, benzoates (preferably sodium benzoate), sorbates (preferably potassium sorbate), and sodium dehydroacetate.
  • the nail polish compositions preferably comprise from 0% to about 10%, more preferably from 0% to about 5%, and most preferably from 0% to about 1%, by weight of the composition, of a preservative.
  • Resins including, for example, epoxies and polyacrylics, may optionally be added.
  • suitable resins include Polytex E75® (commercially available from Estron Chemical, Inc., Calvert City, KY) and Acryloid B66® (commercially available from Rohm and Haas, Philadelphia, PA).
  • the nail polish compositions preferably comprise from 0% to about 15%, more preferably from about 0.5% to about 10%, by weight of the composition, of a resin. e) Slip Aids
  • Slip aids may optionally be added to improve surface friction, water resistance, abrasion resistance, and mechanical properties.
  • Slip aids which may be used include wax additives including, for example, animal, fossil, vegetable, mineral, or synthetic waxes.
  • Preferred wax additives include beeswax, carob, candelilla, ozocerite, polyethylene waxes, paraffin waxes, polypropylene waxes, polytetrafluoroethylene (commercially available as Teflon ® from DuPont, Wilmington, DE), nylons, and polyamides.
  • preferred wax additives include, but are not limited to, Jonwax ® 26 (commercially available from S.C.
  • slip aids include materials containing silicone such as copolymers of polyether and polysiloxane.
  • slip aids include, for example, Glide 450 and Abil B-8830 (both of which are commercially available from Goldschmidt Chemical, Hopewell, VA).
  • the present nail polish compositions preferably comprise from 0% to about
  • Therapeutic and Prophylactic Agents such as, for example, vitamins, proteins, anti-fungal and anti-microbial agents, and sunscreens (including UV-A, UV- B, and broad spectrum solar filters) may optionally be added to the present nail polish compositions for the further care and protection of the nails.
  • Thickeners Thickeners may optionally be added to the present compositions to achieve desired rheology and application properties.
  • Preferred thickeners include solution polymers (e.g., hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and other conventional cellulosic polymers), associative thickeners (e.g. , hydrophobically modified cellulosic polymers, nonionic urethanes, and alkali swellable urethanes) including Aculyn ® 44 (commercially available from Rohm & Haas, Philadelphia, PA), clays (e.g., laponite and hydrophilic montmorillonite (commercially available as Bentone ® from Rheox, Hightstown, NJ)), and natural rubbers and gums (e.g., guar gum, quaternized guar gum sold under the name Jaguar ® C-13-S by Rhone-Poulenc, Shelton, CT, hydroxypropyl guar gum, gum arabic, carob gum, carrageenan, and xanthan gum).
  • solution polymers e
  • the present nail polish compositions preferably comprise from 0% to about 10%, more preferably from about 0.1% to about 10%, and even more preferably from about 0.1% to about 5% of a thickener, by weight of the composition.
  • Secondary Film Formers The present nail polish compositions may contain one or more other polymeric film formers, provided that they do not substantially impair the benefits of the graft copolymer, especially through visible macrophase separation.
  • the film-forming polymers herein can be selected from nonionic, ionic (anionic or cationic), and amphoteric (including zwitterionic) polymers.
  • Anionic polymers are preferred for water-borne compositions.
  • Suitable film-forming polymers include any such as are known in the art, such as cellulosic polymers, polyacryls, polymethacryls, styrene-acryl copolymers, polystyrenes, polysiloxanes, polyesters, urethanes, urethane-acryl copolymers, siloxane-urethane copolymers, silicone-acryl copolymers, silicone grafted polymers, silicone block copolymers, polyolefins, vinyl esters, vinyl ethers, and mixtures thereof.
  • Preferred compositions comprise polyacryls, polymethacryls, styrene-acryl copolymers, vinyl esters and cellulosic polymers.
  • the film-forming cellulosic polymers may be selected from polymers derived from cellulose such as are known in the art, including but not limited to cellulose esters.
  • Preferred cellulosic polymers are nitrocellulose, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate. Nitrocellulose polymers are more preferred.
  • Exemplary nitrocellulose polymers are nitrocellulose RS types (nitrogen content of 11.5-12.2%) of Hercules, such as nitrocellulose - RS Vi second, - RS second, - RS 1/8 second, - RS 1/16 second or the like.
  • a "polyacryl” includes polyacrylates, polyacrylics, or polyacrylamides
  • polymethacryl includes polymethacrylates, polymethacrylics, or polymethacrylamides
  • Styrene-acryl copolymers include copolymers of styrene with acrylate, acrylic, acrylamide, methacrylate, methacrylic, and/or methacrylamide monomers. Examples of preferred polyacryls, polymethacryls, and styrene-acryl copolymers include Gelva ® 2497 (commercially available from Monsanto Co., St.
  • Preferred vinyl esters are vinyl butyrate polymers and vinyl acetate polymers.
  • the graft copolymers can be made according to the methods disclosed herein above.
  • the compositions of the present invention can be made using conventional formulation and mixing techniques.
  • the compositions of the present invention include those comprising each of the essential components in addition to any optional components, as well as those prepared by a process of combining, in any order, the above described essential components as well as any optional components.
  • the present compositions are applied to the skin, lips, eyelashes, eyelids, nails, or like topical substrate in any suitable manner such as known in the art.
  • the nail polish compositions can be applied to nails using any suitable applicator such as are known in the art, e.g., a standard brush-applicator as is commonly utilized in the art.
  • Sufficient liquid diluent is then removed from the applied composition (through evaporation of volatiles, most preferably at ambient pressures and temperatures), to form a substantially dry layer or film, that is, the film or layer feels dry, smooth, or not tacky when it is touched with a human fingertip.
  • the present nail polish compositions may be used as the sole nail polish composition, or in conjunction with other nail polishes or treatments.
  • Other nail polish/treatment compositions may be used in conjunction with the present compositions to provide additional benefits, such as aesthetic benefits (e.g., color, shine) and / or additional performance benefits (e.g., further wear improvements).
  • the compositions may be applied in combination with, on top of, or underneath other cosmetic or skin care products.
  • topcoat compositions are particularly useful as topcoat compositions, in conjunction with a basecoat and optionally a midcoat composition.
  • a “topcoat composition” is a composition which is suitable for application to a nail to form a topcoat, which is the most distal layer of nail polish relative to layers of one or more different nail polishes which have been previously applied to the nails.
  • the topcoat composition is more preferably applied contiguously to one (basecoat) or two (basecoat and midcoat) different, previously applied layers, most preferably two different layers.
  • basecoat composition is a composition which is suitable for application to a nail to form a basecoat, which is the most proximal layer of nail polish relative to layers of different nail polish which are subsequently applied to the nails.
  • the basecoat compositions comprise a film-forming polymer, a volatile liquid diluent, and, optionally, other components suitable for nail polishes such as described herein.
  • Preferred optional components for basecoat compositions are selected from plasticizers, pigments, and dyes.
  • a “midcoat composition” is a composition which is suitable for application to a nail to form a midcoat, which is a layer of nail polish between a basecoat and a topcoat.
  • the midcoat compositions comprise a film-forming polymer, a volatile liquid diluent, and, optionally, other components suitable for nail polishes such as described herein.
  • Preferred optional components for midcoat compositions are selected from plasticizers, pigments, and dyes.
  • the midcoat compositions preferably comprise from about 10% to about 25%, more preferably from about 10% to about 18% of a film-forming polymer, from about 60% to about 85%, more preferably from about 60% to about 80% of a volatile organic diluent (such as described herein above), and preferably 0% to about 13%, more preferably from about 5% to about 13%, and most preferably from about 6% to about 12% of a plasticizer, by weight of the composition.
  • Film-forming polymers comprising the midcoat compositions are preferably selected from cellulosic polymers, polyurethanes, polyacryls, polymethacryls, polysiloxanes, and mixtures thereof.
  • More preferred film-forming polymers are polyacryls and cellulosic polymers, with cellulosic polymers being the most preferred.
  • Preferred polyacryls for the midcoat compositions are those which are hydrophobic and / or exhibit a glass-transition temperature (T g ) of from about -10 °C to about +30 °C. Wherein the polyacryl has a T g higher than about +30 °C, the midcoat composition preferably comprises a plasticizer.
  • Exemplary compositions suitable for use as midcoat compositions are commercially available such as, for example, those marketed by the Procter & Gamble Company under the Max Factor ® or Cover Girl ® trade names.
  • Suitable basecoat or midcoat compositions include those basecoats and midcoats disclosed in commonly assigned, copending U.S. Patent Application Serial Nos. 09/070,960 (Ellingson et al.), 09/071,424 (Ellingson et al.), 09/071,098 (Ellingson et al.), 09/071,097 (Smith, III et al.), 09/071,273 (Ellingson et al.), 09/071,423 (Ellingson et al.), and 09/071,099 (Ellingson et al.), corresponding to Attorney's Docket 7140, 7141, 7142, 7143, 7144, 7145 and 7146, each filed on May 1, 1998, and each incorporated herein by reference in their entirety.
  • Preferred basecoats and midcoats are as follows (in the examples herein below, all polymer component percentages are expressed in weight percent of solid polymer (based on the total composition)).
  • Basecoat formula BC 2 is particularly preferred.
  • An alternatively preferred basecoat is a conventional nail polish composition such as Max Factor ® International, marketed by the Procter & Gamble Company (comprising butyl acetate, ethyl acetate, nitrocellulose, toluenesulphonamide formaldehyde resin, dibutyl phthalate, toluene, / ' s ⁇ -propanol, camphor, benzophenone, stearalkonium hectorite, and polyester resin).
  • copolymer of polypropylene glycol, isophorone diisocyanate, and 2,2-dimethylolpropionic acid having the International Nomenclature Cosmetic Ingredient name "PPG-17/PPG-34 IPDI/DMPA Copolymer", BF Goodrich, Cleveland, OH
  • Preferred midcoats for use with the above basecoat formulas BC 6 - BC 9 are as described above. Particularly preferred is a conventional polish such as the above- described Max Factor ® International.
  • the present invention includes a method of coating nails with a nail polish film, wherein the film comprises one or more layers of different nail polishes. In one embodiment, the method comprises the steps of:
  • Another embodiment of the present invention is a method comprising the steps of: (i) applying a basecoat composition contiguously to the nail, wherein the basecoat composition comprises a film-forming polymer and a carrier suitable for application to nails comprising a volatile liquid diluent;
  • Vinylphenyl-terminated Poly(»-propyl methacrylate-co-methacrylic acid) macromonomer In a flask under slight argon pressure (8 psi) is added tetrahydrofuran (THF) (1 L), trimethylsilylmethacrylate (100 g, 0.63 mole), and n- propylmethacrylate (100 g, 0.78 mole). The solution is cooled to -80 °C and initiated with diphenylhexyllithium (0.0275 mole) (prepared by adding 1 : 1 mole ratio of sec- butyl lithium and 1, 1-diphenyl ethylene in THF) for chain propagation via anionic polymerization mechanism.
  • THF tetrahydrofuran
  • butyl acetate Into an argon purged round-bottomed-flask equipped with mechanical stirring and a reflux condenser, is added butyl acetate (IL), trimethylsilylmethacrylate (18.4g, 0.1 16 mole), t-butylacrylate (27.2g, 0.212 mole), 2-methoxyethyl acrylate (31.4g, 0.241 mole), and chloromethyl styrene (0.4g, 0.003 mole).
  • AIBN azobisisobutyronitrile
  • the resulting solution is then heated to 100°C and allowed to cool.
  • butyl acetate IL
  • trimethylsilyl methacrylate (18.4g, 0.116 mole
  • t-butylacrylate (27.2g, 0.212 mole)
  • 2-methoxyethyl acrylate (26.4g, 0.203 mole)
  • polydimethylsiloxane macromonomer molecular weight 10,000
  • chloromethyl styrene 0.4g, 0.003 mole
  • the solution is heated to 60°C then initiated with AIBN (l .Og, 0.006 mole) and allowed to undergo free radical polymerization for 10 hours.
  • the resulting solution is then heated to 100°C then allowed to cool.
  • trimethylsilylmethacrylate 22. Og, 0.139 mole
  • styrene (18.0g, 0.173mole
  • 2,2'-dipyridyl 1.g, 0.009 mole
  • Cu(I)Cl 0.3g, 0.003 mole
  • the solution is heated to 120°C with stirring for 6h.
  • the solution is then cooled to ambient temperature and catalyst is removed via vacuum filtration. Filtrate is diluted with acetone (200 ml) and water (10 ml) and stirred for 2 hours.
  • the resulting solution is precipitated into hexanes and the graft polymer collected and dried.
  • compositions of Examples 6-8 are representative nail polishes of the present invention: acid)-graft-poly (w-propyl methacrylate-co-methacrylic acid) " Poly(/-butyl acrylate-co-2-methoxyethyl acrylate-co-acrylic acid)- graft-[poly (w-propyl methacrylate-co-methacrylic acid) poly(dimethylsiloxane)] This product is prepared by mixing all the ingredients until dispersed.
  • the following is a facial wrinkle remover composition representative of the present invention.
  • the following is a lipstick composition representative of the present invention.

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Abstract

L'invention se rapporte à des compositions cosmétiques comportant (a) 0,1 % environ à 50 % environ, par rapport au poids de la composition, d'un copolymère greffé feuillogène possédant (i) un squelette doté d'une température de transition vitreuse Tg comprise entre 0 °C environ et 50 °C environ et (ii) un ou plusieurs greffons hydrophiles attachés audit squelette, chacun desdits greffons ayant une température Tg comprise entre 50 °C environ et 200 °C environ et présentant un poids moléculaire moyen supérieur à 1000 environ et (b) 50 % environ à 99.9 % environ, par rapport au poids de la composition, d'un excipient approprié. Ces compositions sont dotées de bonnes propriétés d'usage et peuvent être utilisées dans une variété d'applications cosmétiques, du type produits hydratants pour le visage, fonds de teint, rouges à lèvres, mascaras, vernis à ongles et analogues. Dans une réalisation préférée, les compositions se présentent sous la forme d'un vernis à ongles qui, lorsqu'il est appliqué, présente d'excellentes caractéristiques de longévité.
PCT/US1998/024131 1998-11-12 1998-11-12 Compositions cosmetiques Ceased WO2000028948A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004028493A2 (fr) 2002-09-26 2004-04-08 L'oréal Composition de revetement des fibres keratiniques ayant un extrait sec eleve comprenant un polymere sequence
WO2004055082A3 (fr) * 2002-12-12 2004-09-10 Oreal Composition cosmetique comprenant une dispersion de particules d'un polymere ethylenique greffe non silicone dans une phase grasse liquide
WO2007020203A1 (fr) * 2005-08-19 2007-02-22 Basf Se Copolymeres anioniques, ampholytiques destines a des compositions faiblement volatiles
CN100360110C (zh) * 2002-09-26 2008-01-09 莱雅公司 包含嵌段聚合物的唇膏
US20180325789A1 (en) * 2015-11-09 2018-11-15 Three Bond Co., Ltd. Photocurable composition to be used on fingernails or artificial nails, and method for coating by using same

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JP2006507364A (ja) * 2002-09-26 2006-03-02 ロレアル 配列決定ポリマーを含む光沢液体組成物
WO2004028485A3 (fr) * 2002-09-26 2004-07-08 Oreal Composition brillante et non transfert comprenant un polymere sequence
WO2004028491A3 (fr) * 2002-09-26 2004-07-08 Oreal Composition cosmetique non transfert comprenant un polymere sequence
WO2004028492A3 (fr) * 2002-09-26 2004-07-08 Oreal Composition de revetement des fibres keratiniques comprenant un polymere sequence
WO2004028489A3 (fr) * 2002-09-26 2004-07-08 Oreal Rouge a levres comprenant un polymere sequence
WO2004028493A3 (fr) * 2002-09-26 2004-07-08 Oreal Composition de revetement des fibres keratiniques ayant un extrait sec eleve comprenant un polymere sequence
US9017704B2 (en) 2002-09-26 2015-04-28 L'oreal Composition comprising a block polymer and a film-forming agent
JP2006503921A (ja) * 2002-09-26 2006-02-02 ロレアル ブロックポリマーを含む光沢のある耐移り性組成物
JP2006507366A (ja) * 2002-09-26 2006-03-02 ロレアル 配列ポリマーを含む耐移行性化粧品組成物
JP2006503922A (ja) * 2002-09-26 2006-02-02 ロレアル 配列されたポリマーとゲル化剤を含む組成物
JP2006510734A (ja) * 2002-09-26 2006-03-30 ロレアル 配列ポリマーを含む高度乾燥抽出物を含む、ケラチン繊維被膜組成物
JP2006507367A (ja) * 2002-09-26 2006-03-02 ロレアル ブロックポリマーおよび皮膜形成剤を含む組成物
WO2004028493A2 (fr) 2002-09-26 2004-04-08 L'oréal Composition de revetement des fibres keratiniques ayant un extrait sec eleve comprenant un polymere sequence
US8992903B2 (en) 2002-09-26 2015-03-31 L'oreal Composition comprising at least one block polymer and at least one gelling agent
CN100360110C (zh) * 2002-09-26 2008-01-09 莱雅公司 包含嵌段聚合物的唇膏
US7794695B2 (en) 2002-12-12 2010-09-14 L'oreal S.A. Non-transfer cosmetic composition comprising a dispersion of particles of a silicon-free grafted ethylene polymer in a liquid fatty phase
WO2004055082A3 (fr) * 2002-12-12 2004-09-10 Oreal Composition cosmetique comprenant une dispersion de particules d'un polymere ethylenique greffe non silicone dans une phase grasse liquide
WO2007020203A1 (fr) * 2005-08-19 2007-02-22 Basf Se Copolymeres anioniques, ampholytiques destines a des compositions faiblement volatiles
US20180325789A1 (en) * 2015-11-09 2018-11-15 Three Bond Co., Ltd. Photocurable composition to be used on fingernails or artificial nails, and method for coating by using same
US10500144B2 (en) * 2015-11-09 2019-12-10 Three Bond Co., Ltd. Photocurable composition to be used on fingernails or artificial nails, and method for coating by using same

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