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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/34—Alcohols
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

• the present invention relates to hair styling compositions including hair spray compositions, especially hair spray compositions having improved removeability from hair as defined by hair stiffness and flaking values. These spray compositions provide good style retention characteristics without being stiff or sticky.
• These compositions comprise a silicone containing adhesive copolymer and a solvent for the copolymer selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof.
• the spray compositions when dried, exhibit a cohesive strength of greater than about 0.5 kgf/rnm ⁇ , and a total energy absorption per unit volume of greater than about 0.55 kgfmm/mm- .
• the compositions, when dried, also preferably exhibit an impact strength of greater than about 7000 ergs.
• the desire to have the hair retain a particular style or shape is widely held.
• the most common methodology for accomplishing this is by spraying a composition, typically from a mechanical pump spray device or from a pressurized aerosol canister, to the hair.
• Such compositions provide temporary setting benefits and can usually be removed by water or by shampooing.
• the materials used in hair spray compositions are generally resins, gums, and adhesive polymers.
• the present invention provides hair spray compositions having good style retention without being stiff or sticky.
• the resulting hair styles obtained from using these compositions hold up well under the common stress conditions and other factors as mentioned above.
• such compositions provide the benefit of allowing the user to restyle the hair without the need for reapplication of spray product.
• the spray compositions of the present invention leave the hair both feeling and looking natural. Also, these products do not have the disadvantage of causing the hair to quickly resoil.
• VOC hair spray compositions having reduced volatile organic compound (i.e. "VOC") levels.
• VOC hair sprays typically have 80% or less of VOCs, whereas conventional VOC hair sprays have greater than about 80% of VOCs.
• the hair spray compositions of the present invention can be formulated as reduced VOC hair sprays.
• the preferred hair spray compositions of the present invention have an improved removeability from hair during shampooing, wherein the removeability is defined in terms of hair stiffness and hair flaking values ranging from 0 to about 3.5 (0 to 4 scale) These hair stiffness and flaking values are indirect measures of hair spray removeability. Each of these values are determined in accordance with the methodology defined herein.
• the present invention relates to hair styling compositions, especially hair spray compositions, comprising:
• a solvent for said copolymer selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof, wherein said hair spray composition, when dried, has a cohesive strength of greater than about 0.5 kgf/mm ⁇ and a total energy absorption per unit volume of greater than about 0.55 kgfmm/mnM
• the hair spray compositions also prefreferably have improved removeability, wherein removeability is defined by a hair stiffness value of from 0 to about 3.5 and a hair flaking value of from 0 to 3.5 (0 to 4 scale)
• the present invention relates to hair spray compositions wherein the hair spray composition, when dried, has an impact strength of greater than about 7000 ergs.
• the present invention relates to a method of styling and/or holding hair comprising the step of applying to the hair an effective amount of a composition comprising,
• a solvent for said copolymer selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof, wherein said hair spray composition, when dried, has a cohesive strength of greater than about 0.5 kgf/mm ⁇ and a total energy absorption per unit volume of greater than about 0.55 kgfmm/mm ⁇ .
• Fig. 1 illustrates an overhead view of a dumbbell-shaped planar dried hair spray film sample useful for measuring the physical properties such as the cohesive strength and total energy absorption per unit volume as described herein.
• Fig. 2 illustrates a cross-sectional view, showing the thickness of the dumbbell- shaped dried film illustrated in Fig. 1.
• the present invention can comprise, consist of, or consist essentially of any of the required or optional ingredients and/or limitations described herein.
• compositions or components thereof so described are suitable for use in contact with human hair and the scalp and skin without undue toxicity, incompatibility, instability, allergic response, and the like.
• kgf is a standard physical term denoting a kilogram of force subjected to gravitational acceleration, i.e. 9.82 m/s ⁇ .
• compositions of the present invention comprise from about 0.1 % to about 30%), preferably from about 0.5%> to about 20%, and more preferably from about 0.5% to about 10%), by weight of the composition, of a silicone-containing adhesive copolymer.
• adheresive is meant that when applied as a solution to a surface and dried, e.g., the hair fibers, the copolymer forms films or welds. Such a film or weld will have adhesive and cohesive strength, as is understood by those skilled in the art.
• silicone-containing is meant that the copolymers contain one or more alkyl or aryl siloxane moieties, as defined further in the specification.
• the copolymers of the present invention are selected from the group consisting of silicone grafted copolymers, silicone block copolymers, sulfur-linked silicone containing copolymers, sulfur-linked silicone block copolymers, and mixtures thereof.
• silicone grafted copolymers is familiar to one of ordinary skill in polymer science and is used herein to describe the copolymers which result by adding or “grafting” polymeric silicone moieties (i.e. "grafts") onto another polymeric moiety commonly referred to as the "backbone".
• the backbone typically has a higher molecular weight than the grafts.
• silicone grafted copolymers can be described as polymers having pendant polymeric silicone side chains, and as being formed from the "grafting” or incorporation of polymeric silicone side chains onto or into a polymer backbone.
• the polymer backbone can be a homopolymer or a copolymer.
• the graft copolymers are derived from a variety of monomer units.
• these copolymers can comprise grafts derived from nonsilicone-containing macromonomers, e.g., macromonomers formed by the polymerization of acrylates, methacrylates, and other ethylenic moieties.
• macromonomers can be selected to have either high (>25°C) or low Tg ( ⁇ 25°C) values.
• Tg means glass transition temperature, which is familiar to one of ordinary skill in polymer science.
• block copolymers is familiar to one of ordinary skill in polymer science and is used herein to describe copolymers having sequentially arranged moieties or blocks which are further composed of smaller repeating units.
• the block copolymers herein comprise silicone blocks and nonsilicone blocks.
• the block copolymers can be represented by the following structures: A-B structures, containing two block segments; A-B-A, containing three block segments, and -(A-B) n -, wherein n is an integer of 2 or greater, containing multiple blocks.
• sulfur-linked as used herein in the terms “sulfur-linked silicone grafted copolymer” and “sulfur-linked silicone block copolymer” means a silicone grafted or block copolymer containing a sulfur linkage (i.e. -S-), a disulfide linkage (i.e. -S-S-), or a sulfhydryl group (i.e.-SH).
• copolymers, or salts thereof, of the present invention are soluble or dispersible in a solvent selected from the group consisting of water, ethanol, n- propanol, isopropanol, and mixtures thereof, at a concentration of at least about 0.1 mg/mL, preferably at least about 0.5 mg/mL, and more preferably at least about 1 mg/mL, at about 73 °F.
• the copolymers of the present invention have a weight average molecular weight, in grams/mole, of at least about 10,000. There is no upper limit for molecular weight except that which limits applicability of the invention for practical reasons, such as viscosity, processing, aesthetic characteristics, spreadability, formulation compatibility, etc.
• the weight average molecular weight is generally less than about 5,000,000, more generally less than about 2,500,000, and typically less than about 1,500,000.
• the weight average molecular weight is from about 10,000 to about 5,000,000, more preferably from about 20,000 to about 1,000,000, even more preferably from about 30,000 to about 500,000, and most preferably from about 50,000 to about 300,000.
• silicone containing adhesive copolymers are useful in the present invention, provided the physical parameters of the dried hair spray film and the solubility or dispersibility requirements and the molecular weight requirements of the copolymer are met.
• the silicone-grafted copolymers of the present invention are formed from the random copolymerization of vinyl monomer units and polysiloxane-containing macromonomer units containing a polymeric portion and a vinyl moiety copolymerizable with vinyl monomer units.
• the siloxane polymeric portion of the macromonomer units forms the polysiloxane side chains of the copolymer.
• the vinyl monomer units and the vinyl moiety portion of the macromonomer units form the backbone.
• the vinyl monomer and the polysiloxane- containing macromonomer can be selected form a wide variety of structures as long as the copolymer has the required properties described herein.
• the copolymer may have one or more polysiloxane side chains grafted to the backbone.
• the compositions of the present invention can include, in addition to the copolymer, low levels of the corresponding copolymers having no polysiloxane side chains grafted to the backbone.
• synthetic graft copolymerization processes may produce a mixture of polymer molecules containing none, one, or more than one polysiloxane side chains covalently bonded to and pendant from the polymeric backbone. From knowledge of the amount and number average molecular weight of side chains in a polymer sample, and the number average molecular weight of the polymer sample, it is possible to calculate the average number of polysiloxane side chains per polymer backbone.
• the grafted copolymers should satisfy the following three criteria:
• the copolymer phase when dried the copolymer phase-separates into a discontinuous phase which includes the grafted polymeric side chain portion and a continuous phase which includes the non-side chain portion; (2) the polymeric side chain portion is covalently bonded to the backbone portion; and
• the number average molecular weight of the polymeric side chain portion is from about 1000 to about 50,000.
• phase separation property provides a specific orientation of the copolymer which results in the desired combination of tactile feel, film-forming or adhesive benefits, and the ability to dry quickly and completely.
• the phase-separating nature of the compositions of the present invention may be determined as follows.
• the copolymer is cast as a solid film out of a solvent as described below. This film is then sectioned and examined by transmission electron microscopy. Microphase separation is demonstrated by the observation of inclusions in the continuous phase. These inclusions should have the proper size to match the size of the side chains (typically a few hundred nm or less) and the proper density to match the amount of side chain present. This behavior is well documented in the literature for polymers with this structure. See, for example, S. D. Smith, Ph.D. Thesis, University of Virginia, 1987, and references cited therein, said thesis incorporated by reference herein.
• the copolymers of the present invention are prepared by the polymerization combination of vinyl monomers and polysiloxane macromonomers.
• the copolymers can be synthesized by free radical polymerization of the monomers and macromonomers.
• the general principles of free radical polymerization methods are well understood. See, for example, Odian, "Principles of Polymerization", 3rd edition, John Wiley & Sons, 1991, pp. 198-334.
• the desired vinyl monomers and polysiloxane macromonomers are all placed in a reactor, along with a sufficient amount of a mutual solvent so that when the reaction is complete the viscosity of the reaction is reasonable. Undesired terminators, especially oxygen, are removed as needed.
• the initiator is introduced and the reaction brought to the temperature needed for initiation to occur, assuming thermal initiators are used. Alternatively, redox or radiation initiation can 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 then removed, usually by evaporation or by precipitating the copolymer by addition of a nonsolvent.
• the copolymer can be further purified, as desired.
• the copolymer can 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 when 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 can 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.
• the copolymers are prepared by the polymerization combination of vinyl monomers and polysiloxane 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 copolymers can be optimized for various physical properties and for compatibility with other ingredients commonly used in hair care applications.
• the silicone copolymers of the present invention comprise from about 50%) to about 98%, preferably from about 60%> to about 95%, and more preferably from about 70% to about 90%) by weight of the vinyl monomer units.
• the vinyl monomer unit is selected from copolymerizable monomers, preferably ethylenically unsaturated monomers. Either a single type of vinyl monomer unit or combinations of two or more vinyl monomer units can be utilized. The vinyl monomers are selected to meet the requirements of the copolymer.
• copolymerizable is meant that the vinyl monomer can be reacted with or polymerized with the polysiloxane 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.
• ethyleneically 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.
• the monomer units can be derived from hydrophilic monomers (typically polar monomers), or mixtures of such hydrophilic monomers with hydrophobic monomers (typically low polarity monomers), provided that the solubility characteristics of the overall copolymer is achieved.
• hydrophilic monomers means monomers which form homopolymers which are substantially water soluble
• hydrophobic monomers means monomers which form substantially water insoluble homopolymers.
• Nonlimiting classes of monomers useful herein include monomers selected from the group consisting of 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
• Such monomers include acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine, vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (such as that produced by the hydrolysis of vinyl acetate after polymerization), vinyl caprolactam, methacrylic acid esters of Cj-Ci g alcohols, such as methanol, ethanol, methoxy
• Preferred monomers include acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, acrylic or methacrylic acid esters of Cj-Ci g alcohols, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2- methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, salts of any acids and amines listed above, and mixtures thereof.
• 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 copolymer of polysiloxane macromonomer units.
• the polysiloxane macromonomer units are copolymerizable with the vinyl monomers, said macromonomers preferably having a vinyl moiety. Either a single type of macromonomer unit or combinations or two or more macromonomer units can be utilized herein.
• the macromonomers are selected to meet the requirements of the copolymer.
• copolymerizable is meant that the macromonomers can be reacted with or polymerized with the vinyl monomers in a polymerization reaction using one or more conventional synthetic techniques, as described above.
• polysiloxane macromonomers that are useful herein contain a polymeric portion and a copolymerizable moiety which is preferably an ethylenically unsaturated moiety.
• the preferred macromonomers are those that are endcapped with the vinyl moiety.
• endcapped as used herein is meant that the vinyl moiety is at or near a terminal position of the macromonomer.
• the macromonomers can be synthesized utilizing a variety of standard synthetic procedures familiar to the polymer chemist of ordinary skill in the art. Furthermore, these macromonomers can be synthesized starting from commercially available polymers. Typically, the weight average molecular weight of the macromonomer is from about 1000 to about 50,000.
• Polysiloxane macromonomers are exemplified by the general formula: X(Y) n Si(R) 3 _ m Z m wherein X is a vinyl group copolymerizable with the vinyl monomer units; Y is a divalent linking group; each R is independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, styryl, phenyl, C1-C6 alkyl or alkoxy-substituted phenyl; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 1000, is essentially unreactive under copolymerization conditions, and is pendant from the vinyl polymeric backbone described above; n is 0 or 1; and m is an integer from 1 to 3.
• the polysiloxane macromonomer has a weight average molecular weight from about 1000 to about 50,000
• the polysiloxane macromonomer has a formula selected from the following formulas:
• s is an integer from 0 to 6; preferably 0, 1, or 2; more preferably 0 or 1; m is an integer from 1 to 3, preferably 1; p is 0 or 1; q is an integer from 2 to 6; each Ri is independently selected form the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, phenyl, C1-C6 alkyl or alkoxy-substituted phenyl, preferably C1-C6 alkyl, or C1-C6 alkyl or alkoxy-substituted phenyl, more preferably C1-C6 alkyl, even more preferably methyl, R ⁇ is independently selected form the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, phenyl, C1-C6 alkyl or alkoxy-substituted phen
• R3 wherein R3 is hydrogen or -COOH, preferably R ⁇ is hydrogen; R ⁇ is hydrogen, methyl or -CH 2 COOH, preferably R4 is methyl; Z is
• R ⁇ , R6. and R? are independently selected from hydrogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, styryl, phenyl, C1-C6 alkyl or alkoxy- substituted phenyl, hydrogen or hydroxyl, preferably R ⁇ , R6, and R ⁇ are C1-C6 alkyls; more preferably methyl; and r is an integer of from about 14 to about 700, preferably about 60 to about 400, and more preferably about 100 to about 170. Silicone Block Copolymers
• silicone block copolymers comprising repeating block units of polysiloxanes.
• silicone-containing block copolymers are found in U.S. Patent No. 5,523,365, to Geek et al., issued June 4, 1996; U.S. Patent 4,689,289, to Crivello, issued August 25, 1987; U.S. Patent 4,584,356, to Crivello, issued April 22, 1986; Macromolecular Design, Concept & Practice, Ed: M.K. Mishra, Polymer Frontiers International, Inc., Hopewell Jet., NY (1994), and Block Copolymers, A. Noshay and J.E. McGrath, Academic Press, NY (1977), which are all incorporated by reference herein in their entirety.
• the silicone-containing block copolymers of the present invention can be described by the formulas A-B, A-B-A, and -(A-B) n - wherein n is an integer of 2 or greater.
• A-B represents a diblock structure
• A-B-A represents a triblock structure
• - (A-B) n - represents a multiblock structure.
• the silicone block portion, A can be represented by the following polymeric structure
• each R is independently selected from the group consisting of hydrogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkylamino, styryl, phenyl, C1-C6 alkyl or alkoxy-substituted phenyl, preferably wherein R is methyl.
• m is an integer of about 10 or greater
• m is an integer of about 40 or greater, more preferably of about 60 or greater, and most preferably of about 100 or greater.
• the nonsilicone block, B comprises monomers selected from the vinyl monomers as described above for the silicone grafted copolymers.
• the block copolymers can comprise mixtures of diblocks, triblocks, and higher multiblock combinations as well as small amounts of homopolymers.
• Sulfur-Linked Silicone Containing Copolymers And Sulfur-Linked Silicone Block Copolymers can comprise mixtures of diblocks, triblocks, and higher multiblock combinations as well as small amounts of homopolymers.
• sulfur-linked silicone containing and block copolymers are also useful herein.
• sulfur-linked means that these containing and block copolymers contain a sulfur linkage (i.e. -S-), a disulfide linkage (i.e. -S-S-), or a sulfhydryl group (i.e.-SH).
• G6 represents monovalent moieties which can independently by the same or different selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and — ZSA;
• G 2 comprises A
• G4 comprises A
• R ⁇ represents monovalent moieties which can independently be the same or different and are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl.
• R ⁇ represents monovalent moieties which can independently be the same or different selected from the group consisting of C ⁇ .A alkyl and hydroxyl for reasons of commercial availability. Most preferably, R ⁇ is methyl.
• R 2 can independently be the same or different and represents divalent linking groups. Suitable divalent linking groups include but are not limited to the following: C] to C10 alkylene, arylene, alkarylene, and alkoxyalkylene. Preferably, R 2 is selected from the group consisting of
• R 2 is selected from the group consisting of — CH 2 — , 1,3 -propylene, and
• R4 is selected from the group consisting of — CH 2 — , 1,3-propylene, and x is an integer of 0-3; y is an integer of 5 or greater; preferably y is an integer ranging from about 14 to about 700, preferably from about 100 to about 170; q is an integer of 0-3; wherein at least one of the following is true: q is an integer of at least 1 ; x is an integer of at least 1 ;
• G5 comprises at least one — ZSA moiety
• G5 comprises at least one — ZSA moiety.
• A is a vinyl polymeric segment formed from polymerized free radically polymerizable monomers. The selection of A is typically based upon the intended uses of the composition, and the properties the copolymer must possess in order to accomplish its intended purpose. If A comprises a block in the case of block copolymers, a polymer having AB and ABA architecture will be obtained depending upon whether a mercapto functional group — SH is attached to one or both terminal silicon atoms of the mercapto functional silicone compounds, respectively.
• the weight ratio of vinyl polymer block or segment, to silicone segment of the copolymer can vary.
• the preferred copolymers are those wherein the weight ratio of vinyl polymer segment to silicone segment ranges from about 98:2 to 50:50, in order that the copolymer possesses properties inherent to each of the different polymeric segments while retaining the overall polymer's solubility.
• polymers which have acidic functionalities are usually used in at least partially neutralized form to promote solubility/dispersibility of the polymer.
• use of the neutralized form aids in the ability of the dried hair spray compositions to be removed from the hair by shampooing.
• neutralized it is preferred that from about 10%> to 100%, more preferably from about 20%> to about 90%, and even more preferably from about 40% to about 85%, of the acidic monomers of the copolymer be neutralized.
• Any conventionally used base including organic or inorganic (metallic or other) bases, can be used for neutralization of the polymers.
• Metallic bases are particularly useful in the present compositions.
• Hydroxides where the cation is ammonium, an alkali metal or an alkaline earth metal, are suitable neutralizers for use in the present hair spray compositions.
• Preferred neutralizing agents for use in hair spray compositions of the present invention are potassium hydroxide and sodium hydroxide.
• Polymers having basic functionalities, e.g., amino groups, are preferably at least partially neutralized with an acid, e.g., hydrochloric acid.
• Neutralization can be accomplished by techniques well known in the art, and before or after polymerization of the monomers comprising the graft copolymer.
• Nonlimiting examples of preferred polymers of the present invention include those selected from the group consisting of poly[(t-butylacrylate-co-n-butylacrylate-co- acrylic acid)-graft-poly(dimethylsiloxane)], poly[(t-butylacrylate-co-2-methoxyethyl acrylate-co-acrylic acid)-graft-poly(dimethylsiloxane)], poly(t ⁇ butylacrylate-co-acrylic acid)-graft-[poly(isobutylene); poly(dimethylsiloxane)], poly(4-t-butylstyrene-co- methacrylic acid)-graft-[(poly(isobutylene); poly(dimethysiloxane)], poly[(t- butylstyrene-co-methacrylic acid)]-graft-[poly(2-ethylhexyl methacrylate), poly(dimethyl
• Nonlimiting examples of preferred polymers of the present invention include those selected from the group consisting of poly [(t-butylacrylate-co-2-methoxy ethyl acrylate-co-methacrylic acid)]-graft-[poly(n-propyl methacrylate-co-methacrylic acid); poly(dimethylsiloxane)], poly[(t-butylacrylate-co-n-butylacrylate-co-acrylic acid)- graft-poly(dimethylsiloxane)] , [poly (dimethyl siloxane)-block-poly(t-butylacrylate-co- n-butylacrylate-co-acrylic acid-co-methacrylic acid)] n , [poly (dimethyl siloxane)-block- poly(t-butylacrylate-co-n-butylacrylate-co-acrylic acid-co-methacrylic acid)] n , [poly (
• poly(dimethyl siloxane)-block-polv(t-butylacrylate-co-n-butylacrylate-co-acrylic acid- co-methacrylic acid)1 n having a weight average molecular weight of about 100,000, comprising about 62% t-butylacrylate, 11%> acrylic acid, 10% methacrylic acid, 17% poly(dimethylsiloxane) macroazoinitiator with a molecular weight of about 10,000.
• poly(isobutylene);polv(dimethylsiloxane)l having a weight average molecular weight of about 200,000, comprising about 40% t-butylacrylate, 20% n-butylacrylate, 20% acrylic acid, 10% poly(dimethylsiloxane) macromonomer with a molecular weight of about 10,000, and 10% poly(isobutylene) macromonomer with a molecular weight of about 4,000.
• compositions of the present invention comprise from about 70% to about 99.9%, preferably from about 75%) to about 98%, and more preferably from about 85%) to about 98%), by weight of the composition, of a solvent for the copolymer.
• the solvent is selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof.
• the water content of the compositions is generally in the range of from about 0.5% to about 99%), preferably from about 5%> to about 50%>, by weight of the total composition.
• the alcohol solvents are generally present in the range of from 0.5%> to about 99%>, preferably from about 50% to about 95%>, by weight of the total composition.
• hair spray compositions which contain reduced levels of volatile organic compounds such as solvents.
• volatile organic compounds such as solvents.
• VOCs volatile organic compounds
• a reduced volatile organic compound hair spray composition of the present invention contains no more than 80%> volatile organic compounds.
• the hair spray compositions of the present invention when dried, have specific physical properties as defined by the cohesive strength and total energy absorption per unit area.
• the dried hair spray compositions also exhibit specific impact strength properties.
• the hair spray compositions also preferably have an improved removeability as defined in terms of hair stiffness and flaking values.
• Cohesion is the strength of the bonds formed within a sample, e.g., a dried hair spray composition.
• the cohesive strength which is designated as kgf/mm ⁇ (kilograms of force per square millimeter) is the maximum unit stress a material will withstand when being subjected to displacement in tension. Stress is the ratio of measured load (kg X f) to the original cross-sectional area (mm ⁇ ) of the sample.
• the cohesive strength of dried hair spray compositions of the current invention are determined using the following method. This method is based on ASTM Designation: D 638-91, Standard Test Method for Tensile Properties of Plastics. Published January 1992, herein incorporated by reference in its entirety.
• the following test method to measure cohesive strength is similar to the ASTM standard, however, several modifications are made to better represent the tensile properties of the dried hair spray films. The measurements are made at about 73 °F and about 50%> relative humidity.
• the test method, described herein specifically uses a modified dumbbell shape with a thickness equal to about 0.4 mm., and uses an Instron Model Mini-55 (available from Instron Corp., Canton, MA) as the testing machine for applying the force to the polymer film samples.
• a dried film sample is prepared by drying an amount of the hair spray composition (i.e., the silicone-containing adhesive copolymer and solvent selected from the group consisting of water, ethanol, n-propanol, isopropanol, and mixtures thereof, and any additional optional components) in a flat-bottomed aluminum mold coated with PFA (perfluoroalkoxy) Teflon®.
• the copolymer film is dried at about 73°F and about 50%) relative humidity until film has attained a "constant weight".
• Constant weight is meant that there is less than a 1% weight fluctuation in the sample over a period of 24 hours.
• the drying film should be kept in an area protected from air currents, which could result in non-uniform drying and formation of air bubbles.
• the copolymer film is cut into a dumbbell shape for testing.
• the sample should be substantially free of defects, i.e. cracks, chips, tears, etc.
• Figures 1 and 2 illustrate the planar dumbbell shaped film to be used in the tensile testing described herein for the cohesive strength and the total energy absorption per unit volume.
• Figure 1 illustrates an overhead view of the dumbbell shaped sample.
• Figure 2 illustrates a cross section through the dumbbell shaped sample.
• the length of the narrow, 3 mm., section of the dumbbell, 3, is about 13 mm.
• the gauge length of the narrow section, 2 is the initial film length used in the determination of the strain of the sample.
• the transition sections between the wide ends and the narrow section of the film are about 6.5 mm. in length (i.e.
• the end portions of the narrow, center portion should be smoothly curved to avoid any stress points in the sample.
• the curve of the transition section should have a radius, 7, of from about 0.5 in. to about 5 inches, and should join tangentially to the narrow section.
• the dumbbell shaped samples are further equilibrated to a "constant weight".
• Constant weight is meant that over a selected 4 day period, there is no more than 0.2%> average weight gain or loss, relative to the dumbbell's measured weight 4 days previous and no more than ⁇ 0.2% weight drift should be observed between two consecutive measurements in the four day period of time. The dumbbell should be tested within a 7 day period of reaching this constant weight.
• the samples are tested on a calibrated Instron Model Mini-55 tensile tester. Before mounting the sample into the Instron, the length, 3, width, 1, and thickness, 8, of the narrow section of the dumbbell shaped sample are measured to the nearest micron with a calibrated micrometer. The dimensional measurements are required by the Instron for force per unit area calculations. The wide ends of the dumbbell samples are clamped into the Instron and pulled at a crosshead rate of 5 mm. per minute. The Instron tester measures the overall forces (e.g., kgf) applied to the film. These forces are spread over the cross sectional area of the narrow section of the film. The cohesive strength of the copolymer is the maximum unit force measured by the Instron divided by the cross sectional area of the narrow portion of the film.
• the overall forces e.g., kgf
• the dried hair spray compositions of the present invention have a cohesive strength of greater than about 0.5 kgf/mm ⁇ , preferably greater than about 0.6 kgf/mm ⁇ , and more preferably greater than about 0.7 kgf/mm ⁇ .
• Total Energy Absorption Per Unit Volume e.g., kgfmm/mm ⁇
• the total energy absorption per unit volume which is designated as kgfmm/mm ⁇ (kilograms of force millimeters per millimeter cubed), is the ratio of the total energy required to reach the autobreak point (in kgf X mm) to the original volume of the sample (mm ⁇ ).
• the total energy required to reach the break point is calculated using standard techniques by determining the area under a load versus displacement curve for the sample.
• the total energy absorption per unit volume is also known as "toughness" by those skilled in the art of polymer science and materials testing.
• the measurements are made at about 73 °F and about 50%> relative humidity.
• the dried hair spray compositions of the present invention have a total energy absorption per unit volume of greater than about 0.55 kgfmm/mm- , preferably greater than about 0.75 kgfmm/mm->, more preferably greater than about 1.10 kgfmm/mm->, more preferably greater than about 1.60 kgfmm/mnM and most preferably greater than about 2.15 kgfmm mm ⁇ .
• Impact strength is the mean-failure energy (mass X gravity X height) required to produce sample failure, e.g., in a dried hair spray composition.
• the sample failure is characterized by a crack or split created by the impact of the falling weight that can be seen by the naked eye under normal laboratory lighting conditions.
• the impact strength of the dried hair spray compositions of the current invention are determined using the following method. This method is based on ASTM Designation: D 5420-93, Standard Test Method for Impact Resistance of Flat, Rigid Plastic Specimen by Means of a Striker Impacted by a Falling Weight (Gardner Impact), Published 1995, herein incorporated by reference in its entirety, however, several modifications are made to better represent the impact properties of the dried film. The measurements are made at about 73 °F and about 50%> relative humidity.
• the test method specifically uses rectangular shaped samples with a thickness equal to about 0.4 mm, and uses a GCA/Precision Scientific Penetrometer modified to drop a blunt faced probe to a distance of 70 mm and equipped with a Precision Scientific solenoid controller for GCA Penetrometer, a blunt faced cylindrical probe with a surface area of 8 mm ⁇ (OK M&T Corp. - part # WSU30), and a ruler which measures in 1 mm increments.
• the samples are prepared using the film drying method described above in the cohesive strength measurements.
• the copolymer film is cut into the rectangular shape, e.g. 10 mm X 20 mm.
• the thickness of the sample is 0.4 mm.
• the film thickness of various test samples should be maintained within ⁇ 15%> of 0.4 mm.
• the following measurement process is used. Turn on the solenoid operated probe release controller.
• the controller should begin to cycle on and off as indicated by a red light. Be sure the probe face is flush with the impact surface so that the sharp edge of the probe does not strike the film. Place a film sample on the Impact Tester over the target area. Direct the metric ruler gently on the film sample. Direct the lightening source across the surface of the sample such that the light source is in the same plane as the surface of the film. Small fractures in the film will reflect light and be easily detected.
• a suggested distance progression is: 1 mm, 3 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, and further 5 mm increments up to 70 mm.
• the first step in the measurement of impact energy is to find the range of probe height necessary to fracture the film. Start at 1 mm for the first step. Continue to move up according to the suggested distance progression until a fracture is observed. When a fracture is observed make a note of it and move to a new sample.
• the second step in determining impact energy is to set a new sample and start drop at an observed fracture point in the range procedure. Set a new film sample and move the probe to the next lowest setting. If the film fractures, record result and repeat previous step. If the film does not fracture, set a new sample and move to the next distance. Continue to set new samples and increase the drop distance until the film fractures. Continue the procedure until 5 fractures are observed. Calculate the amount of work energy, i.e. the fracture strength using the following formula:
• W amount of work energy in ergs
• m mass of probe (59.53 g) (The probe is removable and can be replaced with one of different mass or impact surface area).
• g gravitational constant (980.665 cm/sec ⁇ )
• h average distance probe travels to impact (cm).
• the dried hair spray compositions of the present invention have an impact strength of greater than about 7000 ergs, preferably greater than about 20,000 ergs, and more preferably greater than about 50,000 ergs.
• the adhesive copolymers herein have improved removeability when used in the preferred hairspray embodiments of the present invention.
• removeability means that the adhesive copolymers are more easily removed from the hair or other applied surface during shampooing.
• removeability is determined indirectly by evaluating hair stiffness and the appearance of observable white flakes after treating the hair in accordance with the removeability methodology described hereinafter. It has been found that the removeability of a hair spray formulation after shampooing correlates with the resulting stiffness/softness of the hair and the appearance/nonappearance of white flakes on the hair after a series of shampooing cycles.
• the hair spray compositions of the present invention have high removeability e.g., reduced stiffness and reduced white flaking.
• the term "removeability" as used herein therefore refers to hair stiffness values (0-4 scale) and white flaking values (0-4 scale) as measured in accordance with the methodology described hereinafter.
• the removeability of the hair spray compositions is defined as a combination of hair stiffness values and hair flaking values, wherein the hair spray compositions provide hair flaking values ranging from 0 to about 3.5, preferably from 0 to about 2.5, more preferably from 0 to about 2.0, and hair stiffness values ranging from 0 to about 3.5, preferably from 0 to about 2.5, more preferably from 0 to about 2.0.
• Removeability of the hairspray composition of the present invention is determined in accordance with the following methodology.
• the methodology simulates multiple application and multi-cycle application of hairspray compositions so as to indirectly determine how readily and effectively such hairspray compositions are removed from hair.
• the methodology described herein provides a means of evaluating hair switches blindly treated with hairspray embodiments of the present invention.
• the method by which each hair switch is treated with the hairspray embodiments, and the method by which each treated hair switch is then evaluated for removeability are described in detail below.
• Two trained panelists each evaluate identically treated hair switches or sets of hair switches for stiffness and the appearance of white flakes. The panelists then individually assign each of the treated hair switches with a numerical score (0 to 4 scale) for hair stiffness and a numerical score for flaking (0 to 4 scale). The order in which the hair switches are treated with different hair spray embodiments is randomized and conducted round robin. Two identical sets of switches are prepared as described below for each panelist so that each has a fresh set of switches to evaluate. Before evaluating the blindly treated hair switches, each panelist also evaluates (not blinded) an untreated hair switch as a zero reference for hair stiffness and flaking.
• Each panelist also evaluates a control treated hair switch as a flaking reference (score 4.0) and another control treated hair switch as a hair stiffness reference (score 4.0).
• the hair stiffness values as defined herein are determined by averaging the hair stiffness scores provided by the two panelist.
• the hair flaking values as defined herein are determined by averaging the hair flaking scores provided by the two panelists.
• the hair switches are treated with either an aerosol or non-aerosol hair spray embodiment of the present invention in accordance with the following steps.
• the hair stiffness reference and the flaking reference are also prepared in accordance with the following steps, except that each is treated with the corresponding hair spray formulations as described hereinafter in Tables 2 and 3.
• step 3 on the opposite side of the switch.
• a panelist then evaluates the treated switch by feeling it between their first and second fingers of their dominant hand and between their thumb and other fingers for stiffness and resistance to bending, and then assigns to the treated switch a hair stiffness score (0 to 4 scale).
• the value of the assigned score is relative to the hair stiffness reference score (4) and the untreated reference score (0).
• the panelist then combs the evaluated switch in accordance with the procedure set forth in Step 14 above, and then visually evaluates the combed switch for white flakes, coating, and white haze and assings it a hair flaking score (0 to 4 scale).
• the value of the assigned score is relative to the hair flaking reference score (4) and the untreated reference score (0).
• Each of the formulations described in Tables 1 -3 are prepared by conventional formulation and mixing techniques.
• compositions of the present invention can also comprise a wide variety of optional ingredients that are suitable for application to human hair.
• compositions hereof can optionally contain a plasticizer for the copolymer.
• a plasticizer for the copolymer Any plasticizer suitable for use in hair care products or for topical application to the hair or skin can be used.
• plasticizers are known in the art. These include glycerin, diisobutyl adipate, butyl stearate, propylene glycol, tri-C 2 -Cg alkyl citrates, including triethyl citrate and tri-propyl, -butyl, -pentyl, etc., analogs of triethyl citrate. Triethyl citrate is preferred.
• Plasticizers are typically used at levels of from about 0.01% to about 10%, by weight of the composition, preferably from about 0.05% to about 3%, more preferably from about 0.05% to about 1%.
• the weight ratio of graft copolymer to the plasticizer is from about 1 :1 to about 40:1, preferably from about 2:1 to about 30:1, more preferably from about 3:1 to about 25:1.
• the compositions of the present invention can contain an effective amount of a non-surface active ionic strength modifier system for reducing the viscosity of the hair spray composition.
• the ionic strength modifiers will be present in the present compositions at a level of at least about 0.01%, by weight of the composition. The upper limit is dependent upon the maximum amount of the ionic strength modifiers that can be present in the particular compositions hereof such that the hair setting resin remains solubilized or dispersed.
• the resin will eventually fall out of solution, or otherwise no longer remain solubilized or dispersed in the hydrophilic liquid carrier.
• the upper limit of the ionic strength modifier system level will vary depending upon the particular ionic strength modifiers, liquid vehicle, resin, and other ingredients present in the composition. Thus, for example, the maximum amount of the ionic strength modifiers that can be used will tend to be lower for compositions with liquid vehicles containing less water, compared to compositions with more water.
• the compositions will comprise about 4%, by weight, or less of the ionic strength modifiers, more generally about 2% or less, and typically about 1%) or less.
• the compositions hereof will comprise from about 0.01% to about 0.5%), more preferably from about 0.0 l%o to about 0.1 %>, of the ionic strength modifier system.
• the ionic strength modifier system comprises monomeric ions of the type which are products of acid-base reactions.
• basic and acidic ions OH " and H do not constitute part of the ionic strength modifier system hereof, although they may be present in the composition.
• the ions hereof are incorporated into the composition in a form such that they can exist in the composition as free ions, i.e., in dissociated form. It is not necessary that all of the ions added exist in the composition as free ions, but must be at least partially soluble or dissociated in the composition.
• the ionic strength modifiers can be incorporated into the hair styling compositions, for example, by addition of soluble salts, or by addition of mixtures of acids and bases, or by a combination thereof. It is a necessary aspect of the invention that both anions and cations of the ionic strength modifier system be included in the composition.
• Suitable cations for use include, for example, alkali metals, such as lithium, sodium, and potassium, and alkaline-earth metals, such as magnesium, calcium, and strontium.
• Preferred of the divalent cations is magnesium.
• Preferred monovalent metal ions are lithium, sodium, and potassium, particularly sodium and potassium.
• Suitable means of addition to the compositions hereof include, for example, addition as bases, e.g., hydroxides, sodium hydroxide and potassium hydroxide, and such as salts that are soluble in the liquid carrier, e.g. salts of monomeric anions such as those described below.
• Suitable cations include organic ions, such as quaternary ammonium ions and cationic amines, such as ammonium mono-, di-, and triethanolamines, triethylamine, morpholine, aminomethylpropanol (AMP), aminoethylpropanediol, etc.
• Ammonium and the amines are preferably provided in the forms of salts, such as hydrochloride salts.
• Monomeric anions that can be used include halogen ions, such as chloride, fluoride, bromide, and iodide, particularly chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosulfate, toluene sulfonate, xylene sulfonate, citrate, nitrate, bicarbonate, adipate, succinate, saccharinate, benzoate, lactate, borate, isethionate, tartrate, and other monomeric anions that can exist in dissociated form in the hair styling composition.
• halogen ions such as chloride, fluoride, bromide, and iodide, particularly chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosulfate, toluen
• the anions can be added to the compositions hereof, for example, in the form of acids or salts which are at least partially soluble in the liquid vehicle, e.g., sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc.
• acids or salts which are at least partially soluble in the liquid vehicle, e.g., sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc.
• such salts are entirely soluble in the vehicle.
• ionic strength modifiers are especially useful in reduced volatile organic solvent compositions.
• compositions can also contain various hydrophobic volatile solvents such as cyclomethicone and volatile hydrocarbons such as isododecane and isohexadecane.
• compositions can contain a wide variety of other optional ingredients, including among them any of the types of ingredients known in the art for use in hair care compositions, especially hair setting compositions such as especially hair spray compositions and hair setting tonics.
• hair setting compositions such as especially hair spray compositions and hair setting tonics.
• other adjuvants collectively can comprise from about 0.05% to about 5%> by weight and preferably from about 0.1 % to about 3%, by weight.
• Such conventional optional adjuvants include, but are not limited to, surfactants (which may be anionic, cationic, amphoteric, or zwitterionic and which include fluorinated surfactants and silicone copolyols), propellants, hair conditioning agents (e.g., silicone fluids, fatty esters, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc.); emollients; lubricants and penetrants such as various lanolin compounds; protein hydrolysates and other protein derivatives; ethylene adducts and polyoxyethylene cholesterol; dyes, tints, bleaches, reducing agents and other colorants; pH adjusting agents; sunscreens; preservatives; thickening agents (e.g. polymeric thickeners, such as xanthan gum); and perfume.
• surfactants which may be anionic, cationic, amphoteric, or zwitterionic and which include fluorinated surfactants and silicone copolyols
• the hair spray compositions of the present invention can be dispensed as sprayed or atomized products from containers which are pump spray dispensers or aerosol canisters.
• containers which are pump spray dispensers or aerosol canisters.
• Such containers are well known to those skilled in the art and are commercially available from a variety of manufacturers, including American National Can Corp. and Continental Can Corp.
• a propellant which consists of one or more of the conventionally- known aerosol propellants can be used to propel the compositions.
• a suitable propellant for use can be generally any liquifiable gas conventionally used for aerosol containers.
• Suitable propellants for use are volatile hydrocarbon propellants which can include liquified lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and isobutane.
• Other suitable propellants are hydrofluorocarbons such as 1,2- difluoroethane (Hydrofluorocarbon 152 A) supplied as Dymel 152A by DuPont.
• Other examples of propellants are dimethylether, nitrogen, carbon dioxide, nitrous oxide, and atmospheric gas.
• the hydrocarbons, particularly isobutane, used singly or admixed with other hydrocarbons are preferred.
• the aerosol propellant may be mixed with the present hair spray compositions and the amount of propellant to be mixed is governed by normal factors well known in the aerosol art. Generally, for liquifiable propellants, the level of propellant is from about 10% to about 60% by weight of the total composition, preferably from about 15% to about 50%) by weight of the total composition.
• pressurized aerosol dispensers can be used where the propellant is separated from contact with the hair spray composition such as a two compartment can of the type sold under the tradename SEPRO from American National Can Corp.
• suitable aerosol dispensers are those characterized by the propellant being compressed air which can be filled into the dispenser by means of a pump or equivalent device prior to use.
• Such dispensers are described in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both incorporated by reference herein, and in U.S. Serial No. 07/839,648, Gosselin et al., filed February 21, 1992, also incorporated by reference herein.
• Compressed air aerosol containers suitable for use are also currently marketed by The Procter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY® hair sprays.
• Conventional nonaerosol pump spray dispensers i.e., atomizers, can also be used.
• hair styling compositions include tonics and lotions, which are typically dispensed in a conventional bottle or tube, and applied directly to the hair or first dispensed to the hand and then to the hair.
• the hair styling compositions of the present invention can be made using conventional formulation and mixing techniques.
• the silicone-containing adhesive copolymer and the solvent are mixed to provide a homogeneous mixture. Any other ingredients are then added and mixed to yield the final composition. If the polymer is neutralized, the neutralizer is preferably added prior to addition of other ingredients.
• the composition is packaged in conventional mechanical pump spray devices, or alternatively, in the case of aerosol sprays products, the composition is packaged in conventional aerosol canisters along with an appropriate propellant system.
• compositions of the present invention are used in conventional ways to provide the hair care benefits of the present invention. Such methods generally involve application of an effective amount of the product to dry, slightly damp, or wet hair before and/or after the hair is dried and arranged to a desired style.
• Application of the product is normally effected by spraying or atomizing the product using an appropriate device, e.g. a mechanical pump spray, a pressurized aerosol container, or other appropriate means.
• the composition is then dried or allowed to dry.
• effective amount is meant an amount sufficient to provide the hair hold and style benefits desired. In general, from about 0.5g to about 30g of product is applied to the hair, depending upon the particular product formulation, dispenser type, length of hair, and type of hair style.
• Examples 1-4 Syntheses of macromonomers and copolymers.
• tetrahydrofuran IL
• trimethylsilylmethacrylate lOOg, 0.632 mole
• n-propylmethacrylate lOOg, 0.780 mole
• IL tetrahydrofuran
• diphenylhexyllithium 0.0275 moles
• vinylbenzoyl chloride 8.33 mL, 0.05 mole
• the solution is then warmed to ambient temperature and H O (lOmL) is added and stirred for 0.25 hours to deprotect the acid groups.
• the macromonomer which has a weight average molecular weight of about 6000, is obtained by precipitating the resulting solution in hexanes, collecting precipitate, and drying under vacuum.
• the polymer is precipitated from the solution by adding one part solution to 15 parts water.
• the resultant polymer is then redissolved in acetone. This procedure is repeated six times, with the final polymer being placed in a vacuum oven for heated drying.
• Copolymer 6 4.00 5.00 6.00 4.00 — — — — —
• compositions are prepared as described above, by first mixing the polymer with the ethanol, neutralizing the polymer with sodium or potassium hydroxide, then adding sequentially (as applicable) with mixing, isododecane, plasticizer, perfume, and water. If sodium benzoate is used, it is added after water addition. Most preferably a premix of water and sodium benzoate is made and then added after the main water addition. Propellants for aerosol compositions are charged to conventional aerosol containers after the remainder of the prepared composition has been added.
• the hair spray embodiments of the present invention described in Examples 5- 18 have high removeability from hair, and when evaluated by the removeability methodology described herein, provide a hair stiffness value of less than 2.0 and a hair flaking value of less than 2.0.

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