+

WO1993003704A1 - Compositions d'atomisation des cheveux avec polymere ionique de mise en forme - Google Patents

Compositions d'atomisation des cheveux avec polymere ionique de mise en forme Download PDF

Info

Publication number
WO1993003704A1
WO1993003704A1 PCT/US1992/006975 US9206975W WO9303704A1 WO 1993003704 A1 WO1993003704 A1 WO 1993003704A1 US 9206975 W US9206975 W US 9206975W WO 9303704 A1 WO9303704 A1 WO 9303704A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
hair
ionic
liquid
hair styling
Prior art date
Application number
PCT/US1992/006975
Other languages
English (en)
Inventor
Marjorie Mossman Peffly
Nelson James Holzschuh
Peter Marte Torgerson
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to FI940771A priority Critical patent/FI940771A0/fi
Priority to SK192-94A priority patent/SK19294A3/sk
Priority to EP92918839A priority patent/EP0600008A1/fr
Priority to JP5504558A priority patent/JPH06509807A/ja
Priority to CS94352A priority patent/CZ35294A3/cs
Priority to BR9206388A priority patent/BR9206388A/pt
Publication of WO1993003704A1 publication Critical patent/WO1993003704A1/fr
Priority to NO940538A priority patent/NO940538L/no

Links

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
    • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23—Sulfur; Selenium; Tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
    • A61K8/70—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine containing perfluoro groups, e.g. perfluoroethers
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • 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
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
    • 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
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
    • 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
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5428—Polymers characterized by specific structures/properties characterized by the charge amphoteric or zwitterionic

Definitions

  • HAIR SPRAY COMPOSITIONS WITF IONIC STYLING POLYMER
  • this invention relates to hair spray compositions containing high molecular weight hair styling polymer and having improved sprayability.
  • compositions to provide the setting benefits are generally applied in the form of mousses, gels, lotions or sprays.
  • 25 retention is typically achieved by the use of resins, such as AMPHOMER, supplied by National Starch, and GANTREZ SP 225, sup ⁇ plied by GAF. As used in commercially sold hair spray products, these resins generally have a weight average molecular weight of from about 40,000 to about 150,000. When such resins are incor-
  • such formulations tend to have spray quality characterized by reduced spray pattern diameter, increased incidence of wet, drippy centers, and a tendency toward larger droplet size or streaming upon spraying, as opposed to a fine mist.
  • This can result in overly heavy concentrations of hair spray in regions of the hair, causing the hair to be too stiff in those regions, whereas other areas may have too little hair spray applied and, consequently, have poor style retention and hold.
  • silicone macromer-containing polymers can provide good style retention benefits to the hair while also providing improved hair feel.
  • silicone macromer-containing polymers can impart a tactile sense of softness and conditioning to the hair relative to conventional, non-silicone-containing resins.
  • Silicone macromer-containing hair styling polymers and formulations containing them are disclosed, for example, in EPO Application
  • these silicone macromer-containing hair styling polymers can provide good overall hair styling performance with a desirable hair conditioning effect, they are preferably used in hair spray at relatively high molecular weights, compared to most commercial products (although they can also be used at more conventional hair spray resin molecular weights (eg., about 50,000 to about 150,000 weight average molecular weight). Furthermore, they are difficult to formulate into a hair spray composition with g 0 od sprayability characteristics.
  • volatile organic solvents e.g., ethanol, propanol, etc.
  • the present invention provides improved sprayability hair spray compositions with high molecular weight hair styling poly- ers that can provide excellent hair styling/hold benefits upon spray application to the hair.
  • sprayability of high molecular weight polymers can be improved through the use of ionic strength modifier systems consisting essentially of mixtures of non-surface active anions and cations. It is an essential aspect of the invention that the hair styling polymer also be of an ionic character.
  • the present invention relates to a liquid hair styling composition useful for spray application to hair which comprises:
  • liquid vehicle selected from the group consisting of water, C ⁇ -C 6 , preferably C 2 -C 4 , monohydric alcohols, and mixtures thereof;
  • the high molecular weight hair styling polymer can be any of the conventional classes of hair styling or hair setting polymers in the art, i.e., polymers free of silicone portions.
  • the high molecular weight polymer is a silicone macromer-containing hair setting polymer that can provide hair styling and hold benefits while also providing improved softness to the hair relative to non-silicone-containing polymers.
  • reduced volatile organic solvent hairspray compositions having improved hair feel comprising silicone-containing hair setting polymer, an effective amount of an ionic strength modifier system for reducing viscosity of the compositions, as described above, and a liquid vehicle which comprises a mixture of water with one or more C ⁇ Cg, preferably C 2 -C 4 , monohydric alcohols, wherein said composition comprises at least about 10%, by weight, water.
  • compositions of the present invention contain an effec ⁇ tive amount of a high molecular weight hair styling polymer to impart styling benefits upon application to hair.
  • hair styling polymer means any polymer, natural or synthetic, that can provide hair setting benefits. Polymers of this type are well known in the art.
  • the level of hair styling polymer used will be at least about 0.1%, by weight, of the co po- ° sition. Typically, it will be present at a level of from about 0.1% to about 15%, preferably from about 0.5% to about 8%.
  • the hair styling polymers hereof also are of ionic character.
  • ionic hair styling polymer or the term “ionic character” in reference to hair styling polymers or monomers of 5 which such hair styling polymers are comprised, means hair styling polymers that are anionic, cationic, amphoteric, zwitterionic, or otherwise can exist in the liquid vehicle of the hair styling composition in dissociated form.
  • any type of ionic hair styling polymer which is soluble or dispersible in the liquid carrier can be used in the present invention.
  • a wide variety of such types of hair styling polymers are known in the art.
  • the ionic hair styling polymers hereof can be homopolymers, copolymers, terpoly ers, etc.
  • the term "polymer” shall encompass all of such types of polymeric materials.
  • the polymers hereof must comprise monomers of an ionic character.
  • monomeric units present in the polymers may be referred to as the monomers from which they can be derived.
  • the ionic monomers can be derived from polymerizable ionic starting monomers, or from polymerizable nonionic monomers which are modified subsequent to polymerization to be of ionic character. Also included are corresponding salts, acids and bases of the monomers exemplified. Examples of anionic monomers include:
  • unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, itaconic acid, fu aric acid, and crotonic acid;
  • a phosphoric acid group such as acid phosphooxyethyl acrylate and methacrylate, 3-chloro-2-acid phos- phooxypropyl acrylate and methacrylate, and the like.
  • cationic monomers include:
  • ( eth)acrylamide and a dialkylalkanolamine having C 1 -C 4 alkyl groups such as dimethylaminoethyl ( eth)acrylate, diethyla ino- ethyl ( eth)acrylate, dimethylaminopropyl (meth)acrylate, or dimethylaminopropyl (meth)acrylamide; and
  • the cationic unsaturated monomers include amine derivatives of allyl compounds such as diallyldimethylammonium chloride and the like.
  • cationic unsaturated monomers can be polymerized in cationic form, or as an alternative they can be polymerized in the form of their precursors, which are then modified to be cationic, for example, by a quaternizing agent (e.g. ethyl monochloro ⁇ acetate, dimethyl sulfate, etc.).
  • a quaternizing agent e.g. ethyl monochloro ⁇ acetate, dimethyl sulfate, etc.
  • amphoteric monomers examples include zwitterionized derivatives of the aforementioned amine derivatives of ( eth)- acrylic acids or the amine derivatives of (meth)acrylamide such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acryl- amide by a halogenated fatty acid salt such as potassium mono ⁇ chloroacetate, sodium monobromopropionate, aminomethylpropanol salt of monochloroacetic acid, triethanolamine salts of mono- chloroacetic acid and the like; and amine derivatives of (meth)- acrylic acid or (meth)acryla ide, as discussed above, modified with propanesultone.
  • a halogenated fatty acid salt such as potassium mono ⁇ chloroacetate, sodium monobromopropionate, aminomethylpropanol salt of monochloroacetic acid, triethanolamine salts of mono- chloroacetic acid and the like
  • amphoteric monomers like the aforementioned cationic monomers, can be polymerized in amphoteric form or, as an alterna- tive, they can also be polymerized in the form of their pre ⁇ cursors, which are then converted into the amphoteric state.
  • Preferred ionic monomers include acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternized dimethyl- aminoethyl methacrylate, maleic acid, maleic anhydride half esters, crotonic acid, itaconic acid, diallyldimethyl ammonium chloride, polar vinyl heterocyclics such as vinyl imidazole, vinyl pyridine, styrene sulfonate, and mixtures thereof.
  • Especially preferred ionic monomers include acrylic acid, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, and mixtures thereof.
  • Salts of acid and amine monomers listed above can also be used, e.g., sodium, potassium, or other alkali or alkaline earth metal salts.
  • the polymers hereof should contain at least about 1%, by weight, ionic monomer, preferably at least about 2%, more pre ⁇ ferably at least about 5%.
  • the hair styling polymers hereof can also contain nonionic monomers including, both high polarity monomers and low polarity monomers.
  • the ionic polymers hereof will generally comprise from about 1% to 100% ionic monomers and from 0% to about 99% nonionic monomers, preferably from about 2% to about 75% ionic monomers and from about 25% to about 98% nonionic monomers, more preferably from about 5% to about 50% ionic monomers and from about 50% to about 95% nonionic monomers.
  • Representative examples of low polarity nonionic monomers are acrylic or methacrylic acid esters of C !
  • -C 24 alcohols such as methanol, ethanol , 1-propanol, 2-propanol, 1-butanol, 2-methyl-l- propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol , 1-methyl-1-butanol , 3-methyl-l-butanol, 1-methyl-l-pentanol, 2-methyl-l-pentanol , 3-methyl -1-pentanol , t-butanol, cyclohexanol , 2-ethyl-l-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6- methyl-1-heptanol, 2-ethyl-l-hexanol, 3,5-dimethyl-l-hexanol, 3,5,5-trimethyl-l-hexanol , 1-decanol, 1-dodecanol, 1-he
  • nonionic monomers include acrylate and methacrylate derivatives such as allyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, and methacrylate, oleyl acrylate and methacryl te, benzyl acrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate, ethylene glycol di-acrylate and -methacrylate, 1,3-butyleneglycol di-acrylate and -methacrylate, diacetonacryl- amide, isobornyl (meth)acrylate, and the like.
  • acrylate and methacrylate derivatives such as allyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, and methacrylate, oleyl acrylate and methacryl te, benzyl acrylate and methacrylate, tetrahydrofurfuryl acrylate and methacryl
  • Preferred nonionic monomers include n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl meth- acrylate, t-butylacrylate, t-butylmethacrylate, and mixtures thereof.
  • Representative polar nonionic monomers include acrylamide, N,N-dimethylacrylamide, methacrylamide, N-t-butyl acrylamide, methacrylonitrile, acrylamide, acrylate alcohols (e.g. C 2 -C 6 acrylate alcohols such as hydroxyethyl acrylate and hydroxyproxyl acrylate), methacrylate, and hydroxypropyl methacrylate, vinyl pyrrolidone, vinyl ethers, such as methyl vinyl ether, acyl lactones, vinyl pyridine, allyl alcohols, vinyl alcohols and vinyl caprolactam.
  • acrylamide N,N-dimethylacrylamide
  • methacrylamide N-t-butyl acrylamide
  • methacrylonitrile acrylamide
  • acrylate alcohols e.g. C 2 -C 6 acrylate alcohols such as hydroxyethyl acrylate and hydroxyproxyl acrylate
  • methacrylate e.g. C 2
  • anionic hair spray polymers are copolymers of vinyl acetate and crotonic acid, terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate; and copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50% esterified with a saturated aliphatic alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol ; and acrylic copolymers and terpolymers containing acrylic acid or methacrylic acid as the anionic radical containing moiety such as copolymers with methacrylic acid, butyl acrylate, ethyl methacrylate, etc.
  • Another example of an acrylic polymer which can be employed in the compositions of the present invention is a polymer of tertiary-butyl acrylamide, acrylic acid, and ethyl
  • an amphoteric polymer which can be used in the present invention is Octylacrylamide/Acrylates/Butylaminoethyl Methacrylate Copolymer, described generally in U.S. Pat. No. 4,192,861 as being a polymer of N-tert-octyl acrylamide, methyl methacrylate, hydroxypropyl methacrylate, acrylic acid and t-butyl aminoethyl methacrylate, of appropriate molecular weight for purposes hereof.
  • Examples of cationic hair spray polymers are copolymers of amino-functional acrylate monomers such as lower alkyla ino alkyl acrylate or methacrylate monomers such as dimethyl aminoethyl- methacrylate with compatible monomers such as N-vinylpyrrolidone or alkyl ethacrylates such as methyl methacrylate and ethyl methacrylate and alkyl acrylates such as methyl acrylate and butyl acrylate.
  • Cationic polymers containing N-vinylpyrrolidone are commercially available from GAF Corp.
  • Still other organic, ionic hair styling polymers include carboxymethyl cellulose, copolymers of PVA and crotonic acid, copolymers of PVA and maleic anhydride, sodium polystyrene sul ⁇ fonate, PVP/ethylmethacrylate/methacrylic acid terpolymer, vinyl acetate/crotonic acid/vinyl neodecanoate copolymer, octylacryl- amide/acrylates copolymer, monoethyl ester of poly(methyl vinyl ether-maleic acid), and octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers. Mixtures of polymers may also be used. Silicone-Containinq Hair Styling Polymers
  • Preferred ionic hair styling polymers are silicone-containing polymers.
  • Ionic silicone macromer-containing polymers are de ⁇ scribed, for example, in EPO Application 90307528.1, published as EPO Application 0 408 311 A2 on January 11, 1991, Hayama, et al . , U.S. Patent 5,061,481, issued October 29, 1991, Suzuki et al . , U.S. Patent 5,106,609, Bolich et al . , issued April 21, 1992, U.S. Patent 5,100,658, Bolich et al . , issued March 31, 1992, U.S. Patent 5,100,657, Ansher-Jackson, et al . , issued March 31, 1992, U.S.
  • Examples of useful polymers and how they are made are also (*equivalent to EP 0412704 and 0412707, published 13 February 1991) described in detail in U.S. Patent 4,693,935, Mazurek, issued September 15, 1987, U.S. Patent 4,728,571, Clemens et al., issued March 1, 1988, both of which are incorporated herein by reference.
  • Preferred ionic silicone macromer-containing polymers com ⁇ prise an organic polymeric backbone, preferably a vinyl backbone, having a Tg above about -20'C (more preferably above about 20'C) and, grafted to the backbone, a siloxane macromer having a weight average molecular weight of preferably at least about 500 preferably from about 1,000 to about 100,000, more preferably from about 2,000 to about 50,000, most preferably about 5,000 to about 20,000.
  • silicone-containing polymers also include block copolymers prefer ⁇ ably containing up to about 50% (more preferably from about 10% to about 40%) by weight of one or more siloxane blocks and one or more non-silicone blocks (such as acrylates or vinyls).
  • the silicone macromer-containing polymers preferred for use herein are such that when formulated into the finished hair care composition, and dried, the polymer phase separates into a dis ⁇ continuous phase which includes the silicone portion and a con ⁇ tinuous phase which includes the organic portion.
  • the silicone macromer-containing ionic hair styling polymers generally comprise nonionic silicone-containing monomers together with ionic monomers as described above, and can also contain non-silicone-containing nonionic monomers, also described above.
  • the silicone-containing monomers also can be ionically charged and, as such, contribute, in part or in whole, to the overall charge density of the polymer.
  • the silicone-containing hair styling polymers hereof will generally comprise about 0.01% to about 50% of silicone-containing monomer, preferably from about 0.5% to about 40%, more preferably from about 2% to about 25%.
  • the silicone-containing monomer will generally have the formula: X(Y)nSi(R)3-mZm wherein X is a vinyl group copolymerizable with the other monomers of the polymer; Y is a divalent linking group; R is a hydrogen, lower alkyl (eg. C j -C 4 ), aryl , alkaryl, alkylamino, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, and is pendant from the organic polymeric backbone; n is 0 or 1; and m is an integer from 1 to 3. Of course, Z should be essentially unreactive under polymerization conditions.
  • the silicone-containing monomer preferably has a weight average molecular weight of at least about 500, preferably from about 1,000 to about 100,000, more preferably from about 2,000 to about 50,000, most preferably from about 5,000 to about 20,000. Preferably, it is of the formula:
  • R is hydrogen or -C00H (preferably R 2 is hydrogen); R 3 is hydro ⁇ gen, methyl or -CH 2 C00H (preferably R 3 is methyl); Z is R 5
  • the silicone-containing monomers of the ionic polymers hereof can be polymerized in a silicone-containing monomer form. Alter ⁇ natively, they can be polymerized in the form of their non-sili- cone containing precursor, and a silicone group can then be added.
  • carboxylate-containing monomers such as acrylic acid
  • a silicone-contain ⁇ ing compound with a terminal epoxy group can be polymerized and then reacted with a silicone-contain ⁇ ing compound with a terminal epoxy group.
  • the result will, in general, be a silicone-containing monomer in the polymer having an equivalent structure to the formula X(Y)nSi(R)3-mZm, described above, and is intended to be encompassed herein.
  • the preferred silicone-containing polymers useful in the present invention generally comprise from 0% to about 98% (prefer ⁇ ably from about 5% to about 98%, more preferably from about 50% to about 90%) of nonionic monomer, from 1% to about 98% (preferably from about 15% to about 80%) of ionic monomer, with from about 0.1% to about 50% (preferably from about 0.5% to about 40%, most preferably from about 2% to about 25%) of the monomers being silicone-containing monomer.
  • the combination of the non-si!icone- containing monomers preferably is from about 50% to about 99% (more preferably about 60% to about 99%, most preferably from about 75% to about 95%) of the polymer.
  • Exemplary silicone-containing polymers for use in the present invention include the following:
  • ionic hair styling polymers including both silicone- containing and non-silicone containing polymers, having car- boxylate or other acidic functionalities will preferably be utilized in at least partially neutralized form in the com ⁇ positions hereof to promote solubility or dispersibility of the polymer in the vehicle.
  • use of the neutralized form aids in shampoo removability of the hair spray compositions. In general, it is preferred that from about 10% to 100%, more preferably from about 20% to about 90%, even more preferably from about 40% to about 85%, of the acidic monomers of the polymer be neutralized.
  • Hydroxides of alkali metal and alkaline earth metal are suitable neutralizers for use in the present hair spray compositions. It will be recognized by those skilled in the art that various of the cations supplied neutralizing the polymer will also contribute to the ionic strength modifier system, as described herein.
  • Preferred neutralizing agents for use in hair spray com ⁇ positions of the present invention are potassium hydroxide and sodium hydroxide.
  • Suitable neutralizing agents which may be included in the hair spray compositions of the present invention include amines, especially amino alcohols such as 2-amino-2- methyl-l,3-propanediol (AMPD), 2-amine-2-ethyl-l,3-propanediol (AEPD), 2-amino-2-methyl-l-propanol (AMP), 2-amino-l-butanol (AB), onethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), moniospropanolamine (MIPA), diisopropanol-amine (DIPA), triisopropanolamine (TIPA) and dimethyl steramine (DMS).
  • Par ⁇ ticularly useful for neutralization are mixtures of amines and metallic bases.
  • Polymers having basic functionalities, e.g., amino groups, are preferably at least partially neutralized with an acid, e.g., hydrogen chloride.
  • the hair spray compositions of the present invention also include a liquid vehicle.
  • a liquid vehicle can comprise any of those conven ⁇ tionally used in resin hair spray formulations.
  • the liquid vehicle is present in the hair spray compositions at from about 80% to about 99%, preferably from about 85% to about 99%. More preferably, the liquid vehicle is present at from about 90% to about 98% of the total composition.
  • Organic solvents suitable for use in the liquid vehicle of the present compositions are Ci-Ce alkanols, carbitol, acetone and mixtures thereof.
  • Cj-Cs alkanols preferred for use in the present compositions are C 2 -C 4 monohydric alcohols such as ethanol, isopropanol and mixtures thereof.
  • Water is also a preferred solvent for use in the liquid vehicle of the present hair spray compositions.
  • the liquid vehicle for the present compositions is selected from the group consisting of C ⁇ Cg alkanols, water, carbitol, acetone and mixtures thereof. More preferably, the liquid vehicle of the present composition is selected from the group consisting of water and C 2 -C 4 monohydric alcohols such as ethanol and isopropanol, and mixtures thereof.
  • water may be absent from the liquid vehicle or may comprise all of the liquid vehicle.
  • the liquid vehicle is a mixture of water and organic solvents.
  • 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 organic 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.
  • the hair setting resin is of particularly high weight average molecular weight, i.e. weight average molecular weight above about 300,000, especially above about 500,000. It has been found that surprisingly effective hair spray performance can be obtained using these high molecular weight resins in combination with ionic strength modifier system.
  • This invention is especially effective at providing the resins with characteristics in hair spray compositions such that they can be sprayed with good spray quality, especially with respect to silicone macromer-containing hair setting resins, which are preferably used at relatively high molecular weights.
  • a low volatile organic solvent hairspray composition which comprises a silicone macromer-containing ionic hair setting resin, an ionic strength modifier system as described herein, and a liquid vehicle.
  • a reduced volatile organic solvent hair spray composi ⁇ tion of the present invention comprises no more than 80% volatile organic solvents (which include, for purposes hereof, volatile silicone fluids and excludes water).
  • the hair spray compositions can comprise no more than about 65%, 55%, 50%, or other levels of volatile organic solvents, as may be chosen by product formulators.
  • the hair spray compositions comprise at least 10%, by weight, of water.
  • the weight average molecular weight of the silicone macromer-containing hair setting resins can be of any level suitable for providing effective hair styling. Typically, it will be at least about 50,000, more typically at least about 70,000, preferably at least about 100,000.
  • volatile organic solvents means solvents which have at least one carbon atom and exhibit a vapor pressure of greater than 0.1 mm Hg at 20'C.
  • the weight average molecular weight of the resin is from about 70,000 to about 1,000,000, most preferably from about 100,000 to about 750,000.
  • the reduced volatile organic solvent compositions hereof will comprise up to about 90%, preferably up to about 70%, more preferably up to about 60%, even more preferably up to about 50% water; and from about 10% to about 80%, preferably from about 20% to about 80%, more preferably from about 40% to about 80%, of volatile organic solvents. It is also specifically contemplated that the compositions can be limited to no more than other maximum limits on volatile organic solvents, eg., no more than about 75%, 65%, or 55%, etc.
  • the weight average molecular weight of the styling polymer is limited only by practical concerns. Generally, it will be below about 10,000,000, preferably below about 3,000,000, more preferably below about
  • compositions of the present invention include, as an essential element, an effective amount of an ionic strength modifier system for reducing the viscosity of the hair styling composition, relative to the same composition absent the ionic strength modifiers.
  • the present compositions will comprise at least about 0.01%, by weight, of the ionic strength modifier.
  • the upper limit of the ionic strength modifier system level will vary depending upon the particular ionic strength modifiers, liquid vehicle, hair styling polymer, and other ingredients present in the composition.
  • 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 com ⁇ positions 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 0.01% to about 0.1%, of the ionic strength modifier system.
  • the ionic strength modifier system comprises a mixture of monomeric cations and anions.
  • the ions of the ionic strength modifier system hereof are non-surface active, i.e. they do not significantly reduce surface tension.
  • non-surface active shall mean the ions, which at a 0.5% aqueous solution concentration, reduce surface tension by no more than 5.0 dynes/cm 2 .
  • the ions of the ionic strength modifier system hereof will be characterized by having, at maximum, four or less carbon atoms per charge, preferably two or less carbon atoms, in any aliphatic chain or straight or branched organic hetero- chain.
  • 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 com- position 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 they must be at least partially soluble or dis ⁇ sociated 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, eg., hydroxides, sodium hydroxide and potassium hydroxide, and such as salts that are soluble in the liquid carrier, eg. salts of monomeric anions such as those described below.
  • Suitable cations include organic ions, such as quater- nary ammonium ions and cationic amines, such as ammonium mono-, di-, and tri-ethanolamines, triethylamine, morpholine, amino- ethylpropanol (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, ni ⁇ trate, bicarbonate, adipate, succinate, saccharinate, benzoate, lactate, borate, isethionate, tartrate, and other monomeric anions that can exist in dissociated form in the hair styling composi ⁇ tion.
  • halogen ions such as chloride, fluoride, bromide, and iodide, particularly chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosul
  • the anions can be added to the compositions hereof, for example, in the form of acids or salts which are at least par ⁇ tially soluble in the liquid vehicle, eg., sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc.
  • acids or salts which are at least par ⁇ tially soluble in the liquid vehicle, eg., sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc.
  • such salts are entirely soluble in the vehicle.
  • compositions hereof have a water-equivalent pH of about 10 or less, preferably from about 3 to about 10, more preferably from about 5 to about 10.
  • water-equivalent pH shall correspond to the pH of a composition containing all of the components of the composition, except that any non-aqueous coponent of the carrier is replaced by an equal weight of double reverse osmosis (DRO) water.
  • DRO double reverse osmosis
  • a preferred reduced volatile organic solvent hairspray composition of the present invention contains from about .01% to about 2% of a fluorosurfactant; from about 0.1% to about 15% of an ionic resin, including those having a weight average molecular weight of 300,000 and above, as well as those below 300,000, and also including those having silicone macromer portions as well as those without; an ionic strength modifier system as described herein, and a liquid vehicle comprising about 10% to about 45%, by weight of the composition water and about 50% to about 80%, by weight of the composition, of an organic solvent, preferably selected from the group consisting of ethanol, isopropanol and mixtures thereof.
  • the level of ionic strength modifier system used in general, is given above. It is to be recognized, however, that the par ⁇ ticular level of ionic strength modifier system which must be used to achieve an improvement in hair spray performance, or to achieve optimum performance, for a particular hair spray composition can vary depending upon a variety of factors, including the particular type of resin chosen and its molecular weight, and level in the composition, the specific ionic strength modifier system, the level of water and the type and level of volatile organic solvent, and the presence of optional components in the system. In gene- ral , higher levels of ionic strength modifier system may be needed to achieve a performance benefit as resin molecular weight and/or water levels are reduced. In general, the compositions hereof should contain at least an effective amount of the ionic strength modifier system provide an improvement in hair feel for a given level of hair hold performance or for improved spray quality (?).
  • compositions hereof can optionally contain other materials to improve sprayability of the compositions.
  • ionic surfactants in combination with the non-surface active anions and cations of the ionic strength modifier system hereof.
  • surfactants may be advantageously incorporated into the compositions hereof. These include anionic, cationic, amphoteric, and zwitterionic surfactants, and further include both fluorinated surfactants, as described below, and nonfluorinated surfactants.
  • Anionic surfactants include, for example: alkyl and alkenyl sulfates; alkyl and alkenyl ethoxylated sulfates; (preferably having an average degree of ethoxylation of 1 to 10), succinamate surfactants, such as alkylsulfosuccinamates and dialkyl esters of sulfosuccinic acid; neutralized fatty acid esters of isethionic acid; and alkyl and alkenyl sulfonates, including, for example, olefin sulfonates and beta-alkoxy alkane sulfonates.
  • alkyl and alkenyl sulfates and alkyl and alkenyl ethoxylated sulfates such as the sodium and ammonium salts of C ⁇ 2 -C 18 sulfates and ethoxylated sulfates with a degree of ethoxylation of from 1 to about 6, preferably from 1 to about 4, e.g., lauryl sulfate and laureth (3.0) sulfate.
  • Amphoteric surfactants include those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, N-alkyl- taurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S.
  • Patent 2,658,072 N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent 2,528,378.
  • Others include alkyl, preferably C6-C22 and most preferably C8-C12, amphoglycinates; alkyl, preferably C6-C22 and most preferably C8-C12, amphopropionates; and mixtures thereof.
  • Suitable zwitterionic surfactants for use in the present compositions can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phos- phonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the ali ⁇ phatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula for these compounds is:
  • R2 ... ⁇ (+) ... CH 2 --- R 4 --- Z(-)
  • R 2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety
  • Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms
  • R 3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms
  • x is 1 when Y is sulfur or phosphorus, 1 or 2 when Y is nitrogen
  • R 4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms
  • Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • Classes of zwitterionics include alkyl amino sulfonates, alkyl betaines, and alkyl amido betaines.
  • Cationic surfactants useful in compositions of the present invention contain amino or quaternary ammonium hydrophilic moi- eties which are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M. C. Publishing Co., McCut- cheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al . , Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Pat. No.
  • quaternary ammonium-containing cationic surfactant materials useful herein are those of the general formula:
  • R j is an a ip atic group o rom 1 to 22 carbon atoms, or an aromatic, aryl or alkylaryl group having from 12 to 22 carbon atoms
  • R 2 is an aliphatic group having from 1 to 22 carbon atoms
  • 3 and R 4 are each alkyl groups having from 1 to 3 carbon atoms
  • X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsulfate radicals.
  • the aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amido groups.
  • Other quaternary ammonium salts useful herein are diquaternary ammonium salts.
  • Preferred quaternary ammonium salts include dialkyldimethyl- ammonium chlorides, wherein in the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acid. (Tallow fatty acids give rise to quaternary compounds wherein R x and R 2 have predominately from 16 to 18 carbon atoms.)
  • Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactants for use herein.
  • the alkyl groups of such amines preferably have from 12 to 22 carbon atoms, and may be substituted or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred.
  • Such amines useful herein, include stearamido propyl dimethyl amine, diethyl amino ethyl steara ide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and arachidyl- behenylamine.
  • Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued June 23, 1981 (incorporated by reference herein).
  • Suitable cationic surfactant salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts.
  • Nonionic surfactants can also be included in the compositions hereof.
  • the nonionic surfactants have an average HLB (Hydrophile-Lipophile Balance) of less than or equal to about 7.
  • HLB Hydrophile Balance
  • Methods of determining HLB are well known in the art and any of such methods may be used for HLB determination. A description of the HLB System and methods for HLB determination are described in "The HLB System: a time saving guide to emulsifier selection, " ICI Americas Inc.; Wilmington, Delaware; 1976.
  • Nonionic surfactants include polyethylene oxide condensates of alkyl phenols (preferably C 6 -C 12 alkyl, with a degree of ethoxylation of about 1 to about 6), condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, condensation products of aliphatic alcohols with ethylene oxide, long chain (i.e., typically C 12 -C 22 ) tertiary amine oxides, long chain tertiary phosphine oxides, dialkyl sulfoxides containing one long chain alkyl or hydroxy alkyl radical and one short chain (preferably C ! -C 3 ) radical, silicone copolyols, and Ci-C alkanol amides of acids having a C 8 -C 22 acyl moiety.
  • alkyl phenols preferably C 6 -C 12 alkyl, with a degree of ethoxylation of about 1 to about 6
  • Fluorosurfactants i.e., fluorinated surfactants
  • fluorinated surfactants can be linear or branched alkyl, alkenyl or alkylaryl fluorohydrocarbons having a chain length of prefer ⁇ ably 3 to 18 carbon atoms and being fully or partially fluori- nated.
  • the hydrophilic moiety can be, for example, sulfate, phosphate, phosphonate, sulfonate, amine, amine salts, quaternary ammonium, carboxylate, and any combination thereof.
  • Ionic fluorosurfactants useful in the present compositions include perfluorinated compounds represented by the formula
  • Z is a water solubilizing group of either organic or in ⁇ organic character
  • x is an integer which is generally from 2 to 17, particularly from 7 to 11
  • y is an integer from 0 to 4
  • said compounds may be cationic, anionic, amphoteric or zwit ⁇ terionic, depending upon the nature of the grouping or groupings encompassed by Z.
  • the Z groups may be or may comprise sulfate, sulfonate, carboxylate, amine salt, quaternary ammonium, phos- phate, phosphonate, and combinations thereof.
  • the perfluorinated compounds are known in the art. These compounds are described in U.S.
  • a preferred fluorinated alkyl quaternary ammonium iodide is FLUORAD FC-135 supplied by Minnesota Mining & Manufacturing (St. Paul, Minnesota, USA; 3M) .
  • Preferred anionic fluorosurfactants are mixed mono- and bis-perfluoroalkyl phosphates, ammonium salts; mixed mono- and bis-fluoroalkyl phosphate, ammonium salts, complexed with ali ⁇ phatic quaternary methosulfates; perfluoroalkyl sulfonic acid, ammonium salts; mixed telomer phosphate diethanolamine salts; amine perfluoroalkyl sulfonates; ammonium perfluoroalkyl sul ⁇ fonates; potassium perfluoroalkyl sulfonates; potassium fluori- nated alkyl carboxylates; ammonium perfluoroalkyl sulfonates; and ammonium perfluoroalkyl carboxylates.
  • Amphoteric fluorosurfactants preferred for use in the present compositions are fluorinated alkyl amphoteric surfactants avail ⁇ able commercially as FLUORAD FC-100 from 3M.
  • mixtures of amphoteric or zwitterionic fluoro- surfactants with anionic fluorosurfactants or mixtures of anionic and cationic fluorosurfactants are used.
  • fluorosurfactants is especially desirable in reduced volatile organic solvent compositions, and most especially those with silicone macromer-containing polymers.
  • Surfactants are preferably included in the compositions at a level of from about 0.01% to about 2%, more preferably from about 0.01% to about 1.5%, most preferably from about 0.01% to about 1%.
  • Plasticizer The performance of the hair styling polymers can be improved through the optional incorporation of a nonvolatile plasticizer into the composition.
  • the plasticizer will generally be present in the compositions at a plasticizer: styling polymer weight ratio of about 1:20: to about 1:1, preferably from about 1:15 to about 1:2.
  • nonvolatile in regard to plasticizers means that the plasticizer exhibits essentially no vapor pressure at atmospheric pressure and 25'C.
  • the polymer-liquid vehicle solution should not suffer from substantial plasticizer weight loss while the volatile carrier is evaporating, since this may excessively reduce plasticization of the polymer during use.
  • the plasticizers for use herein should generally have boiling points of about 250 * C or higher.
  • Plasticizers are well known in the art and are generally described in Kirk-Othmer Encyclopedia of Chemical Technology. second edition, Volume 15, pp. 720-789 (John Wiley & Sons, Inc. New York, 1968) under the topic heading "Plasticizers", and by J. Kern Sears and Joseph R. Darby in the text The Technology of Plasticizers (John Wiley & Sons, Inc., New York, 1982), both incorporated herein by reference. See especially in the Appendix of Sears/Darby Table A.9 at pages 983-1063 where a wide variety of plasticizers are disclosed. Plasticizers include both cyclic and acyclic nonvolatile materials.
  • Suitable categories of nonvolatile plasticizers include adipates, phthalates, isophthalates, azelates, stearates, citrates, tri ellitates, silicone copolyols, iso C 14 -C 22 alcohols, methyl alkyl silicones, carbonates, sebacates, isobutgrates, oleates, phosphates, myristates, ricinoleates, pelargonates, valerates, oleates, camphor, and castor oil, and silicone co ⁇ polyols.
  • adipate plasticizers include adipic acid deriva- tives such as diisobutyl adipate, bis(2-ethylhexyl) adipate, diisodecyl adipate, bis(2-butoxyethyl) adipate, and di-n-hexyl adipate.
  • phthalate plasticizers include phthalic acid derivatives such as dibutyl phthalate, butyl octyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, bis(2-ethylhexyl) phthalate, n-octyl n-decyl phthalate, di-n-hexyl phthalate, isooctyl isodecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butyl cyclohexyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, isodecyl benzyl phthalate, and bis(2-butoxyethyl) phthalate.
  • phthalic acid derivatives such as dibutyl phthalate, butyl octyl phthalate, di-n-
  • Isophthalate plasticizers include bis(2-ethylhexyl) iso- phthalate.
  • azelate plasticizers include azelaic acid deri ⁇ vatives such as di(2-ethylhexyl) azelate, and bis(2-ethylhexyl) azelate.
  • stearate plasticizers include stearic acid derivatives such as n-butyl stearate, butyl acetoxystearate, and butoxyethyl stearate.
  • citrate plasticizers include citric acid deriva- tives such as acetyl tri-n-butyl citrate, tri-n-butyl citrate, and acetyl tri-2-ethylhexyl citrate.
  • trimellitate plasticizers include tri-(2-ethyl- hexyl) trimellitate, and triisooctyl trimellitate.
  • plasticizers include dibutyl carbonate, butyl oleate, n-butyl, butyrate, isobutyl butyrate, isopropyl butyrate, dibutyl carbonate, ethyl palmitate, isooctyl palmitate, methyl ricinoleate, butyl ricinoleate, diisooctyl sebacate, triisobutyl phosphate, isodecy pelargonate, ethyl valerate, isocetyl alcohol, octododecanol , isopropyl myristate, isostearyl alcohol and methyl alkyl silicones having C 2 -C 20 alkyl and from 1 to about 500 siloxane monomer units, silicone copolyols, eg ⁇ di ethicone copolyol .
  • Hair spray compositions of the present invention can be dispensed from containers which are aerosol dispensers or pump spray dispensers. Such dispensers, i.e., 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 propel1ants may 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 pro- pellants which can include liquified lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and isobutane.
  • Other suit ⁇ able propellants are hydrofluorocarbons such as 1,2-difluoroethane (Hydrofluorocarbon 152A) supplied as Dymel 152A by DuPont.
  • Other examples of propellants are dimethylether, nitrogen, carbon dioxide, nitrous oxide and atmospheric gas.
  • hydrocarbons particularly isobutane, used singly or admixed with other hydrocarbons are preferred.
  • the aerosol propellant may be mixed with the present compo ⁇ sitions 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 A erical 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.
  • Compressed air aerosol containers suitable for use are also currently marketed by The Procter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY ® hair sprays.
  • the hair spray formulations of the present invention can optionally contain a variety of other hair spray adjuvants as are known in the art.
  • the compositions will comprise from about 0.05% to 5%, by weight, preferably from about 0.1% to 3%, by weight, of adjuvants.
  • Hair spray adjuvants include: silicones; emollients; lubricants and penetrants such as various lanolin compounds; protein hydrolysates and other protein derivatives; ethylene adducts and polyoxyethylene cholesterol; dyes, tints and other colorants; sunscreens; and perfume.
  • the hair spray compositions of the present invention are used in conventional ways to provide the hair styling/holding benefits of the present invention. Such method generally involves spraying an. effective amount of the product to dry or damp hair before or after the hair is styled, or both.
  • effective amount is meant an amount sufficient to provide the hair volume and style benefits desired considering the length and texture of the hair.
  • Example I weight average molecular weight of about 150,000.
  • Examples II-VI weight average molecular weight of about 1.7 million;
  • Examples VII-XIV weight average molecular weight of about 800,000;
  • Examples XV-XVI weight average molecular weight of about 1.2 million.
  • the hair spray formulations are prepared by forming a premix of the polymer in isopropanol, and then adding the ethanol.
  • the polymer is added directly to the ethanol.
  • a magnetic or air driven stirrer is used to mix the ingredients until the polymer is dissolved, typically about 1 to 2 hours.
  • the neutralizing agent KOH or AMP, or both
  • Adjuvants may also be added to the compositions, including, for example, perfume or fragrance.
  • the hair spray compositions prepared are especially suitable for pump spray application.
  • the compositions will characterized by good sprayability character ⁇ istics and hair styling performance
  • Example XVII A hair spray composition, of the present invention, which is suitable for pump spray dispensers, is prepared as follows:
  • Example XVIII A hair spray composition, of the present invention, which is suitable for pump spray dispensers, is prepared as follows: Ingredient Weight %
  • Example XIX A hair spray composition of the present invention, which is suitable for pump spray dispensers, is prepared as follows: Ingredient Weight % Ethanol, 200 proof 78.8
  • a hair spray composition, of the present invention which is suitable for pump spray dispensers, is prepared as follows:
  • Example XXIII 60% t-butyl acrylate/20% acrylic acid/20% silicone macromer, having a weight average molecular weight of about 860,000 (Example XXIII), and 1.5 million (Example XXIV); and 1.7 million (Example XXV).
  • Example XXIII 60% t-butyl acrylate/20% acrylic acid/20% silicone macromer, having a weight average molecular weight of about 860,000
  • Example XXIV 1.5 million
  • Example XXV 1.7 million
  • a hair spray concentrate composition, of the present inven ⁇ tion, which is suitable for aerosol dispensers, is prepared as follows:
  • N,N dimethylacrylamide/70% isobutylmethacrylate/15% acrylic acid having a weight average molecular weight of about 1.2 million.
  • 15% N,N dimethylacrylamide/60% isobutylmethacrylate/15% acrylic acid/10% PDMS macromer (weight average molecular weight of about 10,000), having a weight average molecular weight of about 1.2 million).
  • hexane extraction After drying the resin from its reaction solvent hexane extraction of the reaction product can be performed by adding an excess of hexane to the reaction product and heating to near the Tg of the non-silicone portion of the polymer. The mixture is held at this temperature with stirring for about 30 minutes and cooled to-room temperature. The hexane is removed by vacuum suction. Two more hexane extraction cycles are preferably conducted in the same manner as above. After the third cycle, residual hexane remaining with the product is removed by distillation and vacuum drying.
  • Low molecular weight polysiloxane-containing monomer and polymer about 1 hour is solubilized by the supercritical carbon dioxide and transported away from the remaining polymer via a transfer line, which is maintained at identical temperature and pressure as the extraction vessel.
  • the extracted materials are collected in an extraction vessel. Following extraction, the system is depressurized and dry, extracted polymer is recovered from the extraction vessel.
  • the resin can be purified by removing unreacted silicone-containing monomer and silicone macromer-grafted polymer with viscosities at 25 * C of about 10,000,000 centistokes and less. This can be done, for the example, by hexane extraction. After drying the resin from its reaction solvent, hexane extraction of the reaction product can be performed by adding an excess of hexane to the reaction product and heating to near the Tg of the non-silicone portion of the polymer. The mixture is held at this temperature with stirring for about 30 minutes and cooled to room temperature. The hexane is removed by vacuum suction. Two more hexane extraction cycles are preferably conducted in the same manner as above. After the third cycle, residual hexane remaining with the product is removed by distillation and vacuum drying.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La composition liquide de mise en forme des cheveux appropriée comme atomiseur pour cheveux comprend: (a) un polymère ionique pour la mise en forme des cheveux ayant un poids moléculaire moyen d'au moins 300.000 environ; (b) un véhicule liquide sélectionné dans le groupe comprenant de l'eau, des alcools monohydriques en C1-C6, et leurs mélanges; (c) une quantité efficace d'un système modificateur de la force ionique permettant de réduire la viscosité de la composition, ce système consistant essentiellement en un mélange d'anions et de cations non-tensioactifs, ces cations et ces anions étant au moins partiellement solubles dans l'excipient liquide; ladite composition possède un pH d'environ 10 ou moins. Un autre aspect de cette invention concerne des compositions de solvant organique volatil d'atomisation des cheveux qui confère aux cheveux un toucher plus agréable et qui comprend un polymère de fixation des cheveux contenant de la silicone, une quantité efficace d'un système de modification de la force ionique pour réduire la viscosité des compositions, comme indiqué ci-dessus, et un véhicule liquide qui comprend un mélange d'eau avec un ou plusieurs alcools monohydriques en C1-C6, ladite composition comprennant au moins 10 % environ en poids d'eau.
PCT/US1992/006975 1991-08-19 1992-08-18 Compositions d'atomisation des cheveux avec polymere ionique de mise en forme WO1993003704A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
FI940771A FI940771A0 (fi) 1991-08-19 1992-08-18 Hiussumutekoostumuksia joissa on ionista muotoilupolymeeria
SK192-94A SK19294A3 (en) 1991-08-19 1992-08-18 Hair-styling aerosol compositions with contains of ionic polymers
EP92918839A EP0600008A1 (fr) 1991-08-19 1992-08-18 Compositions d'atomisation des cheveux avec polymere ionique de mise en forme
JP5504558A JPH06509807A (ja) 1991-08-19 1992-08-18 イオン性スタイリングポリマーを含有したヘアスプレー組成物
CS94352A CZ35294A3 (en) 1991-08-19 1992-08-18 Hair aerosol preparations containing ionic polymers forming the hair style
BR9206388A BR9206388A (pt) 1991-08-19 1992-08-18 Composições de spray para cabelos com polímero de encorpamento iônico
NO940538A NO940538L (no) 1991-08-19 1994-02-16 Hårspray-blandinger med ionisk formgivnings-polymer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US74716491A 1991-08-19 1991-08-19
US747,164 1991-08-19
US88397592A 1992-05-15 1992-05-15
US883,975 1992-05-15

Publications (1)

Publication Number Publication Date
WO1993003704A1 true WO1993003704A1 (fr) 1993-03-04

Family

ID=27114702

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006975 WO1993003704A1 (fr) 1991-08-19 1992-08-18 Compositions d'atomisation des cheveux avec polymere ionique de mise en forme

Country Status (15)

Country Link
EP (1) EP0600008A1 (fr)
JP (1) JPH06509807A (fr)
CN (1) CN1071331A (fr)
AU (1) AU2502892A (fr)
BR (1) BR9206388A (fr)
CA (1) CA2115154A1 (fr)
CZ (1) CZ35294A3 (fr)
FI (1) FI940771A0 (fr)
HU (1) HUT67488A (fr)
MA (1) MA22628A1 (fr)
MX (1) MX9204802A (fr)
NZ (1) NZ243996A (fr)
PT (1) PT100791A (fr)
SK (1) SK19294A3 (fr)
WO (1) WO1993003704A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004518A1 (fr) * 1993-08-05 1995-02-16 The Procter & Gamble Company Compositions de coiffage contenant un polymere greffe silicone et une faible concentration d'un solvant d'hydrocarbure volatil
WO1995009600A1 (fr) * 1993-10-01 1995-04-13 The Procter & Gamble Company Compositions de soins capillaires contenant des alcools gras a bas point de fusion et des epaississants polymeres reticules
FR2739284A1 (fr) * 1995-09-29 1997-04-04 Oreal Composition pour le traitement des matieres keratiniques comprenant au moins un polymere silicone greffe et au moins un amide a chaine grasse et utilisations
WO1997025963A1 (fr) * 1996-01-16 1997-07-24 The Procter & Gamble Company Composition capillaire revitalisante
WO1997025964A1 (fr) * 1996-01-12 1997-07-24 The Procter & Gamble Company Compositions capillaires revitalisantes
WO1999022700A1 (fr) * 1997-11-05 1999-05-14 The Procter & Gamble Company Compositions de soins personnels appropriees a la coiffure
WO1999017711A3 (fr) * 1997-10-03 1999-06-03 Unilever Plc Compositions de fixatif capillaire autophobes
WO1999048462A3 (fr) * 1998-03-24 1999-12-16 Unilever Plc Procede de nettoyage de surfaces d'aluminium
EP0943312A3 (fr) * 1998-02-11 2000-03-08 Wella Aktiengesellschaft Produits pour soins capillaires avec des acides fluorés et des polymères
US6350439B1 (en) 1995-10-18 2002-02-26 L'oreal Aqueous lacquer packaged in an aerosol device and including at least one silicone graft polymer for treating keratinous materials, and uses thereof
US6368606B1 (en) 1995-10-18 2002-04-09 L'oreal Cosmetic composition for the treatment of keratinous materials comprising at least a grafted silicone polymer and at least an aqueous dispersion of insoluble particles of non ionic or cationic polymer
RU2203102C2 (ru) * 1999-09-16 2003-04-27 Л'Ореаль Аэрозольное устройство, содержащее композицию для волос, включающую по крайней мере один сополимер силикона и акрилата
WO2005030917A1 (fr) 2003-09-29 2005-04-07 Ethena Healthcare Inc. Compositions sous forme de mousse et de gel a teneur elevee en alcool
EP1972329A3 (fr) * 2003-03-24 2009-02-18 Unilever PLC Compositions de traitement capillaire contenant un adhésif de silicone sensible à la pression
US8034324B2 (en) 2003-03-24 2011-10-11 Conopco, Inc. Hair treatment compositions
US20130344017A1 (en) * 2011-02-09 2013-12-26 Lalitesh Chandra Hair treatment composition
US20130344006A1 (en) * 2011-02-09 2013-12-26 Akinwole Oladiran Akinpelu Hair treatment compositions
WO2017176403A1 (fr) * 2016-04-08 2017-10-12 Empire Technology Development Llc Procédé et composition pour l'atténuation de daggin sur les cheveux

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU65373A1 (fr) * 1972-05-17 1973-11-23
US3958581A (en) * 1972-05-17 1976-05-25 L'oreal Cosmetic composition containing a cationic polymer and divalent metal salt for strengthening the hair
FR2355497A1 (fr) * 1976-06-21 1978-01-20 Unilever Nv Shampooing conditionnant pour cheveux
EP0059428A2 (fr) * 1981-03-03 1982-09-08 Kao Soap Company, Ltd. Compositions pour le traitement des cheveux
GB2098226A (en) * 1981-05-08 1982-11-17 Oreal Composition intended for the treatment of keratin fibres based on a cationic polymer and ananionic polymer containing vinylsulphonic groups
EP0101920A1 (fr) * 1982-07-27 1984-03-07 Kao Corporation Composition détergente liquide
EP0370338A1 (fr) * 1988-11-16 1990-05-30 National Starch and Chemical Investment Holding Corporation Compositions pour fixer la chevelure contenant des bétaines alpha-aminométhylène-phosphonate
EP0408311A2 (fr) * 1989-07-12 1991-01-16 Mitsubishi Chemical Corporation Polymères pour des produits de traitement des cheveux
EP0412704A2 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Compositions pour traiter et fixer la chevelure
EP0412710A2 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Système de véhicule pour compositions cosmétiques
EP0412707A1 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Compositions pour le conditionnement et la mise en forme des cheveux

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU65373A1 (fr) * 1972-05-17 1973-11-23
US3958581A (en) * 1972-05-17 1976-05-25 L'oreal Cosmetic composition containing a cationic polymer and divalent metal salt for strengthening the hair
FR2355497A1 (fr) * 1976-06-21 1978-01-20 Unilever Nv Shampooing conditionnant pour cheveux
EP0059428A2 (fr) * 1981-03-03 1982-09-08 Kao Soap Company, Ltd. Compositions pour le traitement des cheveux
GB2098226A (en) * 1981-05-08 1982-11-17 Oreal Composition intended for the treatment of keratin fibres based on a cationic polymer and ananionic polymer containing vinylsulphonic groups
EP0101920A1 (fr) * 1982-07-27 1984-03-07 Kao Corporation Composition détergente liquide
EP0370338A1 (fr) * 1988-11-16 1990-05-30 National Starch and Chemical Investment Holding Corporation Compositions pour fixer la chevelure contenant des bétaines alpha-aminométhylène-phosphonate
EP0408311A2 (fr) * 1989-07-12 1991-01-16 Mitsubishi Chemical Corporation Polymères pour des produits de traitement des cheveux
EP0412704A2 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Compositions pour traiter et fixer la chevelure
EP0412710A2 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Système de véhicule pour compositions cosmétiques
EP0412707A1 (fr) * 1989-08-07 1991-02-13 The Procter & Gamble Company Compositions pour le conditionnement et la mise en forme des cheveux

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR27820A (tr) * 1993-08-05 1995-08-29 Procter & Gamble Bir silikon asili polimeri ve düsük seviyede bir ucucu hidrokarbon cözücü maddeyi ihtiva eden saca stil verme bilesimleri.
WO1995004518A1 (fr) * 1993-08-05 1995-02-16 The Procter & Gamble Company Compositions de coiffage contenant un polymere greffe silicone et une faible concentration d'un solvant d'hydrocarbure volatil
WO1995009600A1 (fr) * 1993-10-01 1995-04-13 The Procter & Gamble Company Compositions de soins capillaires contenant des alcools gras a bas point de fusion et des epaississants polymeres reticules
FR2739284A1 (fr) * 1995-09-29 1997-04-04 Oreal Composition pour le traitement des matieres keratiniques comprenant au moins un polymere silicone greffe et au moins un amide a chaine grasse et utilisations
WO1997012587A1 (fr) * 1995-09-29 1997-04-10 L'oreal Composition pour le traitement des matieres keratiniques comprenant au moins un polymere silicone greffe et au moins un amide a chaine grasse et utilisations
US6165444A (en) * 1995-09-29 2000-12-26 L'oreal Composition for treating keratinous material, including at least one silicone-grafted polymer and at least one fatty-chain amide, and uses thereof
US6440404B1 (en) 1995-10-18 2002-08-27 L'oreal S.A. Aqueous lacquer for treating keratin substances, packaged in an aerosol device and comprising at least one grafted silicone polymer, and uses thereof
US6368606B1 (en) 1995-10-18 2002-04-09 L'oreal Cosmetic composition for the treatment of keratinous materials comprising at least a grafted silicone polymer and at least an aqueous dispersion of insoluble particles of non ionic or cationic polymer
US6350439B1 (en) 1995-10-18 2002-02-26 L'oreal Aqueous lacquer packaged in an aerosol device and including at least one silicone graft polymer for treating keratinous materials, and uses thereof
WO1997025964A1 (fr) * 1996-01-12 1997-07-24 The Procter & Gamble Company Compositions capillaires revitalisantes
CN1090014C (zh) * 1996-01-12 2002-09-04 普罗克特和甘保尔公司 头发护理组合物
KR100287807B1 (ko) * 1996-01-12 2001-05-02 데이비드 엠 모이어 모발컨디셔닝조성물
CN1090013C (zh) * 1996-01-16 2002-09-04 普罗克特和甘保尔公司 头发调理组合物
WO1997025963A1 (fr) * 1996-01-16 1997-07-24 The Procter & Gamble Company Composition capillaire revitalisante
WO1999017711A3 (fr) * 1997-10-03 1999-06-03 Unilever Plc Compositions de fixatif capillaire autophobes
US6319489B1 (en) 1997-10-03 2001-11-20 Helene Curtis, Inc. Autophobic hairspray compositions
WO1999022700A1 (fr) * 1997-11-05 1999-05-14 The Procter & Gamble Company Compositions de soins personnels appropriees a la coiffure
US6264929B1 (en) 1998-02-11 2001-07-24 Wella Aktiengesellschaft Hair treatment compositions containing fluorinated acids and polymers
EP0943312A3 (fr) * 1998-02-11 2000-03-08 Wella Aktiengesellschaft Produits pour soins capillaires avec des acides fluorés et des polymères
US6350433B1 (en) 1998-03-24 2002-02-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Autophobic hair spray composition comprising film forming resin, propellant, and autophobic hair spray additive
AU735095B2 (en) * 1998-03-24 2001-06-28 Unilever Plc Aerosol hairspray composition
WO1999048462A3 (fr) * 1998-03-24 1999-12-16 Unilever Plc Procede de nettoyage de surfaces d'aluminium
RU2203102C2 (ru) * 1999-09-16 2003-04-27 Л'Ореаль Аэрозольное устройство, содержащее композицию для волос, включающую по крайней мере один сополимер силикона и акрилата
US8034324B2 (en) 2003-03-24 2011-10-11 Conopco, Inc. Hair treatment compositions
EP1972329A3 (fr) * 2003-03-24 2009-02-18 Unilever PLC Compositions de traitement capillaire contenant un adhésif de silicone sensible à la pression
US7850952B2 (en) 2003-03-24 2010-12-14 Conopco, Inc. Hair treatment compositions
EP1668105A4 (fr) * 2003-09-29 2010-03-03 Deb Worldwide Healthcare Inc Compositions sous forme de mousse et de gel a teneur elevee en alcool
WO2005030917A1 (fr) 2003-09-29 2005-04-07 Ethena Healthcare Inc. Compositions sous forme de mousse et de gel a teneur elevee en alcool
EP3428257A1 (fr) * 2003-09-29 2019-01-16 Deb IP Limited Compositions sous forme de mousse et de gel à teneur élevée en alcool
US20130344017A1 (en) * 2011-02-09 2013-12-26 Lalitesh Chandra Hair treatment composition
US20130344006A1 (en) * 2011-02-09 2013-12-26 Akinwole Oladiran Akinpelu Hair treatment compositions
US9186313B2 (en) * 2011-02-09 2015-11-17 Conopco, Inc. Hair treatment composition
WO2017176403A1 (fr) * 2016-04-08 2017-10-12 Empire Technology Development Llc Procédé et composition pour l'atténuation de daggin sur les cheveux

Also Published As

Publication number Publication date
FI940771L (fi) 1994-02-18
CZ35294A3 (en) 1994-07-13
EP0600008A1 (fr) 1994-06-08
BR9206388A (pt) 1994-12-27
HUT67488A (en) 1995-04-28
AU2502892A (en) 1993-03-16
NZ243996A (en) 1995-06-27
PT100791A (pt) 1993-09-30
MX9204802A (es) 1993-04-01
JPH06509807A (ja) 1994-11-02
CN1071331A (zh) 1993-04-28
HU9400475D0 (en) 1994-06-28
SK19294A3 (en) 1994-12-07
FI940771A0 (fi) 1994-02-18
CA2115154A1 (fr) 1993-03-04
MA22628A1 (fr) 1993-04-01

Similar Documents

Publication Publication Date Title
US5565193A (en) Hair styling compositions containing a silicone grafted polymer and low level of a volatile hydrocarbon solvent
EP0600032B1 (fr) Compositions de laque capillaire
WO1993003704A1 (fr) Compositions d'atomisation des cheveux avec polymere ionique de mise en forme
US6248316B1 (en) Hair styling compositions containing non-silicone and silicone grafted polymers and low level of a volatile hydration solvent
WO1995000108A1 (fr) Compositions cosmetiques pour les cheveux
EP1019013B2 (fr) Compositions de fixatif capillaire autophobes
US5811109A (en) Hair cosmetic compositions
AU671598B2 (en) Hair spray compositions containing fluorosurfactant
WO1995000106A1 (fr) Compositions cosmetiques pour les cheveux
CA2329235A1 (fr) Compositions de laque anhydre en aerosol renfermant des copolymeres a greffe de silicone

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MG MN MW NO PL RO RU SD

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL SE BF BJ CF CG CI CM GA GN ML MR SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1992918839

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2115154

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 19294

Country of ref document: SK

Ref document number: PV1994-352

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 940771

Country of ref document: FI

WWP Wipo information: published in national office

Ref document number: 1992918839

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV1994-352

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: PV1994-352

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: 1992918839

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1992918839

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载