Europllsches
`Patentamt
`European
`Patent Office
`Office europeen
`des brevets
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`EP 1 513 485 81
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`EUROPEAN PATENT SPECIFICATION
`
`(45) Date of publication and mention
`of the grant of the patent:
`04.05.2011 Bulletin 2011/18
`
`(21) Application number: 03736954.3
`
`(22) Date of filing: 10.06.2003
`
`(51) lnt Cl.:
`A61Q 5/02(2oo6.o1J
`
`A61K 8/06(2oo6.o1J
`
`(86) International application number:
`PCT/US2003/018157
`
`(87) International publication number:
`WO 2003/105793 (24.12.2003 Gazette 2003/52)
`
`(54) COMPOSITION CONTAINING A CATIONIC POLYMER WITH A HIGH CHARGE DENSITY AND A
`CONDITIONING AGENT
`
`ZUSAMMENSETZUNGEN AUS KATIONISCHEN POLYMEREN MIT HOHER LADUNGSDICHTE
`UND KONDITIONIERUNGSMITIEL
`
`COMPOSITION CONTENANT UN POLYMERE CATIONIQUE PRESENTANT UNE DENSITE DE
`CHARGE ELEVEE ET UN AGENT DE TONIFICATION CAPILLAIRE
`
`(84) Designated Contracting States:
`AT BE BG CH CY CZ DE DK EE ES Fl FR GB GR
`HU IE IT Ll LU MC NL PT RO SE Sl SK TR
`
`• JOHNSON, Eric, Scott
`Hamilton, OH 45011 (US)
`
`(30) Priority: 18.06.2002 US 389634 P
`
`(43) Date of publication of application:
`16.03.2005 Bulletin 2005/11
`
`(73) Proprietor: THE PROCTER & GAMBLE COMPANY
`Cincinnati, OH 45202 (US)
`
`(72) Inventors:
`• GEARY, Nicholas, William
`Cincinnati, OH 45242 (US)
`
`(74) Representative: Hampton, Matthew John et al
`Hoyng Monegier LLP
`Rembrandt Tower, 31st Floor
`Amstelplein 1
`1096 HA Amsterdam (NL)
`
`(56) References cited:
`WO-A-95/09599 WO-A-03/032935
`US-A- 5 720 964 US-A- 5 756 436
`US-A- 5 977 038
`
`Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
`Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
`Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
`paid. (Art. 99(1) European Patent Convention).
`
`Printed by Jouve, 75001 PARIS (FR)
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`Description
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`EP 1 513 485 81
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`[0001] The present invention relates to a hair cleansing shampoo comprising cationic polymers with a high charge
`density and a conditioning agent. More specifically, it relates to a shampoo containing cationic polysaccharide polymers
`having a high charge density and a nano-emulsified conditioning agent.
`
`BACKGROUND
`
`[0002] Human hair becomes soiled due to its contact with the surrounding atmosphere and, to a greater extent, from
`sebum secreted by the head. The build-up of the sebum causes the hair to have a dirty feel and an unattractive appearance.
`The soiling of the hair necessitates it being shampooed with frequent regularity.
`[0003] Shampooing the hair cleans by removing excess soil and sebum. However, the shampooing process has
`disadvantages in that the hair is left in a wet, tangled and generally unmanageable state. Shampooing can also result
`in the hair becoming dry or "frizzy", and a loss of luster, due to removal of natural oils or other hair moisturizing materials.
`After shampooing, the hair can also suffer from a loss of "softness" perceived by the user upon drying. The hair can also
`suffer from increased levels of static upon drying after shampooing. This can interfere with combing and can result in
`fly-away hair. A variety of approaches have been developed to alleviate the after-shampoo problems. These range from
`the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses.
`Hair rinses are generally liquid in nature and must be applied in a separate step following the shampooing, left on the
`hair for a length of time, and rinsed with fresh water. This, of course, is time consuming and is not as convenient as
`shampoos containing both cleaning and hair conditioning ingredients. Therefore, it is desirable to have a shampoo
`capable of depositing conditioning aids.
`[0004] Depositing materials such as conditioning aids from a shampoo composition can be difficult Deposition must
`be balanced against other factors such as cleansing properties of the shampoo, "feel" of the shampoo during use, and
`hair feel post-shampoo. Current polymers used as deposition aids are not always effective at depositing materials while
`maintaining the balance described above.
`[0005] Silicone fluids suitable for use in the personal cleansing compositions have been disclosed in several patents
`dating back to the early 1970's, for example U.S. Pal No. 2,826,551, U.S. Pat. No. 3,964,500, U.S. Pat. No. 4,364,837,
`U.S. Pat. No. 4,788,006, GB Pat. No. 849,433, and Silicon Compounds, Petrarch Systems, Inc. (1984), all of which
`teach the use of silicone fluids.
`[0006] The use of cationic polymers within personal cleansing applications has also been disclosed. Of particular
`interest to this application is the use of cationic polymers to aid in the deposition of conditioning actives such as silicones.
`U.S. patent 4,364,837 (Pader 1982) teaches the use of both cationic polymers and silicones in a shampoo composition.
`In the patent, a preferred hair grooming agent system is a mixture of silicone and a cationic cellulose, and the most
`preferred hair grooming agent is a mixture of polydimethylsiloxane and polymer JR. This patent further teaches the use
`of cationic celluloses, cationic guars, such as Jaguar C-17 in combination with silicone.
`[0007] U.S. Pat. No. 3,964,500 (Drakoff 1976) also teaches the combination of a cationic cellulose polymer, specifically
`polymer JR, and silicone, Further, Drakoff teaches the former (termed a hair bodying resin in the application) to enhance
`the deposition of the latter. Specifically, this reference teaches that the hair bodying resin precipitates upon dilution of
`the shampoo composition and application of the hair whereupon the resin coacervates with the siloxane and the coac(cid:173)
`ervate deposits on the hair strands. This proposed mechanism for the formation of a coacervate precipitant that forms
`upon rinsing is now known to occur between the cationic polymer and surfactant. This phase separated complex is
`known in the art as a coacervate or floc, the former term being first used by H.G. Bungenberg De Jong in 1929 and
`literally means to "heap together". Without being bound by theory, it is believed the precipitated coacervate has a tendency
`to both deposit itself and aid in the deposition of suspended droplets or particles.
`It remains, therefore, highly desirable to have a rinse-off composition, preferably a cleansing composition,
`[0008]
`capable of containing and effectively depositing and retaining conditioning aids on the surface treated therewith. It has
`now been discovered that select cationic polymers, when used in the cleansing compositions of the present invention,
`can surprisingly enhance the deposition and retention of conditioning benefit agents on the surfaces treated therewith.
`
`SUMMARY
`
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`[0009] The present invention is directed to a shampoo composition comprising:
`
`a) from 4 to 50 weight percent of a detersive surfactant comprising anionic surfactant and betaines
`b) at least 0.05 weight percent of a cationic polymer,
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`EP 1 513 485 81
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`i) wherein said cationic polymer has a molecular weight from 10,000 to 1 0,000,000; and
`ii) wherein said cationic polymer has a charge density from 1.4 meq/g to 7 meq/g;
`
`c) at least 0.05 weight percent of a conditioning agent material having a volume average diameter of less than 1.0
`microns; and
`d) at least 20.0 weight percent of an aqueous carrier.
`
`[001 0] The present invention is further directed to a cosmetic method of using the shampoo composition.
`[0011] These and other features, aspects, and advantages of the present invention will become evident to those skilled
`in the art from a reading of the present disclosure.
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`[0012] While the specification concludes with claims that particularly point out and distinctly claim the invention, it is
`believed the present invention will be better understood from the following description.
`[0013] One embodiment of the present invention concerns the surprising discovery that compositions combining
`certain high charge density cationic polymers in combination with surfactants, forms, upon rinsing, a preferred micro(cid:173)
`scopically-phase separate coacervate suspended in an aqueous surfactant phase. In use, the dispersed, coacervate
`phase provides improved conditioning agent deposition versus that previously known in the art. A further embodiment
`of the present invention concerns the surprising discovery that particular charge density cationic polymers yield yet
`higher levels of conditioning agent deposition. The following table exemplifies several of the highly preferred polymers
`and their charge density and also contains the same information for "non preferred" cationic polymers previously dis(cid:173)
`closed. A further embodiment of the present invention concerns the surprising discovery that compositions combining
`the certain high charge density cationic polymers are particularly effective at aiding in the deposition of the conditioning
`agent when the condition agent is below 1 micron, more preferably below 0.3 microns and even more preferably below
`0.1 microns. We herein define nanoemulsions as conditioning agent materials with a volume average diameter of less
`than 1 micron.
`[0014] As noted, the use of cationic polymers to aid in the deposition of silicones -without regard to particle size -was
`taught by Pader (1982) and Drakoff (1976) -the latter specifically teaching Polymer JR400 and the former teaching
`Polymer JR and cationic Guars. The first reference to very small silicone particles and or microemulsions occurred in
`the 1980's when this class of silicones was commercialised by the silicone industry. The Toray silicone company in
`European patent 0268982 (Priority date of Nov 1986, JP 274799/86) teach the use of dimethlpolysiloxane microemulsions
`with a preferred particle size of less than 0.15 microns in combination with a cationic polymer, specifically Merquat 550,
`in a shampoo context. Gee at al. teach the combination of surfactants, cationic polymers and an aqueous siloxane
`35 microemulsion in a hair fixative preparation Gee et al., specifically teach the use of Jaguar 400.
`[0015] Birtwistle in European pat. No. 0529883A 1 also teach the use of silicones with a particles size less then 0.15
`microns with cationic deposition polymers, specifically teaching the use of Jaguar C-13S, Jaguar C-15, Jaguar C-17,
`Jaguar C-162, JR400 and JR30M. These cationic polymers all have low charge densities, while the preferred cationic
`polymers of the present invention have high charge densities.
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`Charge Density Meq/gm
`
`Jaguar C17 (1)
`
`JR400 (2)
`
`Jaguar C-13S (3)
`
`Jaguar C 162 (4)
`
`Polyquaternium 10 JR30M (5)
`
`Guar Hydroxypropyl trimonium chloride (6)
`
`Guar Hydroxypropyl trimonium chloride (7)
`
`Guar Hydroxypropyl trimonium chloride (8)
`
`Guar Hydroxypropyl trimonium chloride (9)
`
`Polyquaternium 10 (1 0)
`
`Polyquaternium 10 (11)
`
`0.9
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`1.25
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`0.5
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`0.3
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`1.25
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`2.40
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`2.10
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`2.10
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`1.57
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`1.97
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`2.38
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`Taught in US 4.364,837
`
`Taught in US 4,364,837
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`Taught in EP 0529883
`
`Taught in EP 0529883
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`Taught in EP 0529883
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`Highly Preferred
`
`Preferred
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`Preferred
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`Preferred
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`Highly Preferred
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`Highly preferred
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`(continued)
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`Charge Density Meq/gm
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`Polyquaternium 10 (12)
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`Polyquaternium 10 (13)
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`Polyquaternium 10 (14)
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`2.39
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`1.79
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`2.74
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`Highly Preferred
`
`Preferred
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`Preferred
`
`1. Guar Hydroxypropyl trimonium chloride Jaguar C17 available from Rhodia and having a charge
`density of 0.9 meq/gm and a molecular weight of 2,200,000
`2. Polyquaternium 10 Polymer JR400 available from Amerchoi/Dow Chemical and having a
`charge density of 1.25 meq/gm and a molecular weight of 400,000
`3. Guar Hydroxypropyl trimonium chloride Polymer Jaguar C-13S available from Rhodia and
`having a charge density pf 0.5 meq/gm and a molecular weight of 2,200,000.
`4. Guar Hydroxypropyl trimonium chloride Polymer Jaguar C162 available from Rhodia and
`having a charge density of 0.3 meq/gm
`5. Polyquaternium 10 - Polymer JR30M available from Amerchoi/Dow Chemical and having a
`charge density of 1.25 meq/gm and a molecular weight of 1 ,800,000
`6. Guar having a molecular weight of about 600,000, and having a charge density of about 2.40
`meq/g, available from Aqualon.
`7. Guar having a molecular weight of about 400,000, and having a charge density of about 2.10
`meq/g, available from Aqualon.
`8. Guar having a molecular weight of about 1,1 00,000, and having a charge density of about
`2.10 meq/g, available from Aqualon.
`9. Guar having a molecular weight of about 400,000, and having a charge density of about 1.57
`meq/g, available from Aqualon.
`10. Polymer KG30M available from Amerchoi/Dow with a charge density of 1.97 meq/gm and a
`molecular weight of 2,000,000
`11. Cationic cellulose polymer available from Amerchoi/Dowwith a charge density of 2.38 meq/gm
`and a molecular weight of 2,000,000
`12. Cationic cellulose polymer available from Amerchoi/Dowwith a charge density of 2.39 meq/gm
`and a molecular weight of 400,000
`13. Cationic cellulose polymer available from Amerchoi/Dowwith a charge density of 1. 79 meq/gm
`and a molecular weight of 2,000,000
`14. Cationic cellulose polymeravailablefrom Amerchoi/Dowwith a charge density of 2.74 meq/gm
`and a molecular weight of 450,000
`
`[0016] The shampoo compositions of the present invention include detersive surfactant, a cationic polymer, a nanoe(cid:173)
`mulsified conditioning agent, and an aqueous carrier. Each of these essential components, as well as preferred or
`optional components, are described in detail hereinafter.
`[0017] All percentages, parts and ratios are based upon the total weight of the compositions of the present invention,
`unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and,
`therefore, do not include solvents or by-products that may be included in commercially available materials, unless
`otherwise specified.
`[0018] All molecular weights as used herein are weight average molecular weights expressed as grams/mole, unless
`otherwise specified.
`[0019] The term "nanoemulsion", as used herein, is an emulsion made with a conditioning agent material, with a
`volume average diameter of less than 1 micron. The emulsion may or may not be chemically stable. It may be formed
`mechanically or via the use of appropriate surfactants.
`[0020] The term "charge density", as used herein, refers to the ratio of the number of positive charges on a polymer
`to the molecular weight of said polymer.
`[0021] Herein, "comprising" means that other steps and other ingredients which do not affect the end result can be
`added. This term encompasses the terms "consisting of" and "consisting essentially of". The compositions and methods/
`processes of the present invention can comprise, consist of, and consist essentially of the essential elements and
`limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps,
`or limitations described herein.
`[0022] The term "polymer" as used herein shall include materials whether made by polymerization of one type of
`monomer or made by two (i.e., copolymers) or more types of monomers.
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`[0023] The term "suitable for application to human hair" as used herein, means that the 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.
`[0024] The term "water soluble" as used herein, means that the polymer is soluble in water in the present composition.
`In general, the polymer should be soluble at 25° Cat a concentration of 0.1% by weight of the water solvent, preferably
`at 1%, more preferably at 5%, even more preferably at 15%.
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`A. Detersive Surfactant
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`[0025] The personal cleansing composition useful in the present invention includes a surfactant selected from a group
`consisting of anionic, cationic, nonionic, amphoteric, and zwitterionic surfactants and mixtures thereof. The surfactant
`system of the present invention is preferably present in the personal cleansing compositions at a level of from 4% to
`50%, more preferable from 4% to 40%, still more preferably from 4% to 30%, even more preferably from 5% to 20%
`and even more preferably from 6% to 16%. It should be recognized, however, that the concentration of the surfactant
`system may vary with the cleaning or lather performance desired, the surfactants incorporated into the surfactant system,
`the desired product concentration, the presence of other components in the composition, and other factors well known
`in the art.
`[0026] Suitable anionic detersive surfactant components for use in the shampoo composition herein include those
`which are known for use in hair care or other personal care cleansing compositions. The concentration of the anionic
`surfactant component in the shampoo composition should be sufficient to provide the desired cleaning and lather per(cid:173)
`formance, and generally range from 5% to 50%, preferably from 8% to 30%, more preferably from 1 0% to 25%, even
`more preferably from 12% to 18%, by weight of the composition.
`[0027] Preferred anionic surfactants suitable for use in the shampoo compositions are the alkyl and alkyl ether sulfates.
`These materials have the respective formulae ROS03M and RO(C2H40)xS03M, wherein R is alkyl or alkenyl of from
`about 8 to about 18 carbon atoms, xis an integer having a value of from 1 to 10, and M is a cation such as ammonium,
`alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal
`cations, such as magnesium, and calcium.
`[0028] Preferably, R has from 8 to 18 carbon atoms, more preferably from 1 0 to 16 carbon atoms, even more preferably
`from 12 to 14 carbon atoms, in both the alkyl and alkyl ether sulfates. The alkyl ether sulfates are typically made as
`condensation products of ethylene oxide and monohydric alcohols having from 8 to 24 carbon atoms. The alcohols can
`be synthetic or they can be derived from fats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol and straight chain
`alcohols derived from coconut oil or palm kernel oil are preferred. Such alcohols are reacted with between 0 and 10,
`preferably from 2 to 5, more preferably about 3, molar proportions of ethylene oxide, and the resulting mixture of molecular
`species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
`[0029] Other suitable anionic detersive surfactants are the water-soluble salts of organic, sulfuric acid reaction products
`conforming to the formula [RLS03-M] where R1 is a straight or branched chain, saturated, aliphatic hydrocarbon radical
`having from 8 to 24, preferably 10 to 18, carbon atoms; and M is a cation described hereinbefore.
`[0030] Still other suitable anionic detersive surfactants are the reaction products of fatty acids esterified with isethionic
`acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil or palm
`kernel oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are
`derived from coconut oil or palm kernel oil. Other similar anionic surfactants are described in U.S. Patent 2,486,921;
`U.S. Patent 2,486,922; and U.S. Patent 2,396,278, U.S. Patent 3,332,880 and U.S. Patent 5,756,436 (Royce et al.).
`[0031] Preferred anionic detersive surfactants for use in the shampoo compositions include ammonium lauryl sulfate,
`ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, tri-
`ethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl
`sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate,
`potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarco(cid:173)
`sine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl
`sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,
`50 monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl
`benzene sulfonate, and combinations thereof.
`[0032] Suitable amphoteric or zwitterionic detersive surfactants for use in the shampoo composition herein include
`those which are known for use in hair care or other personal care cleansing composition, and which contain a group
`that is anionic at the pH of the shampoo composition. Concentration of such amphoteric detersive surfactants preferably
`ranges from 0.5% to 20%, preferably from 1% to 10%, by weight of the composition. Non limiting examples of suitable
`zwitterionic or amphoteric surfactants are described in U.S. Patents 5,104,646 (Bolich Jr. et al.), U.S. Patent 5,106,609
`(Bolich Jr. et al.).
`[0033] Amphoteric detersive surfactants suitable for use in the shampoo composition are well known in the art, and
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`include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic
`radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about
`18 carbon atoms and one contains an anionic water solubilizing group such as carboxy, sulfonate, sulfate, phosphate,
`or phosphonate.
`[0034] Zwitterionic detersive surfactants suitable for use in the shampoo composition are well known in the art, and
`include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sul(cid:173)
`fonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic
`substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy,
`sulfonate, sulfate, phosphate or phosphonate. Zwitterionics such as betaines are preferred.
`[0035] Cationic surfactants are also useful in compositions of the present invention and typically contain amino or
`quaternary ammonium hydrophilic moieties 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 : M.C.
`Publishing Co., McCutcheon's. Detergents & Emulsifiers, (North American edition 1989); Schwartz, et al., Surface Active
`Agents, Their Chemistry and Technology. New York: lnterscience Publishers, 1949; U.S. Patent 3,155,591, Hilfer, issued
`November 3, 1964; U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975; U.S. Patent 3,959,461, Bailey
`et al., issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983. If included in the compositions
`of the present invention, the cationic surfactant must not interfere with the in-use performance and end-benefits of the
`personal cleansing composition.
`[0036] The shampoo compositions of the present invention may further comprise additional surfactants for use in
`combination with the anionic detersive surfactant component described hereinbefore. Suitable optional surfactants in(cid:173)
`clude non ionic surfactants, cationic surfactants, and combinations thereof. Any such surfactant known in the art for use
`in hair or personal care products may be used, provided that the optional additional surfactant is also chemically and
`physically compatible with the essential components of the shampoo composition, or does not otherwise unduly impair
`product performance, aesthetics or stability. The concentration of the optional additional surfactants in the shampoo
`composition may vary with the cleansing or lather performance desired, the optional surfactant selected, the desired
`product concentration, the presence of other components in the composition, and other factors well known in the art.
`[0037] Non limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for
`use in the shampoo compositions are described in McCutcheon's. Emulsifiers and Detergents, 1989 Annual, published
`by M. C. Publishing Co., and U.S. Patent3,929,678, U.S. Patent2,658,072; U.S. Patent2,438,091; U.S. Patent2,528,378.
`
`B. Cationic Polymer
`
`[0038] The composition of the present invention includes a cationic deposition polymer of sufficiently high cationic
`charge density to effectively enhance deposition of the nanoemulsion conditioning agent described herein. Suitable
`cationic polymers will have cationic charge densities of at least 1.4 meq/gm, preferably at least 1.6 meq/gm, more
`preferably at least 1.8 meq/gm, even more preferably at least 20 meq/gm, but also preferably less than 7 meq/gm, more
`preferably less than 5 meq/gm, still more preferably less than 4.0 meq/gm at the pH of intended use of the shampoo
`composition, which pH will generally range from pH 3 to pH 9, preferably between pH 4 and pH 8. The average molecular
`weight of such suitable cationic polymers will generally be between 10,000 and 10 million, preferably between 50,000
`and 5 million, more preferably between 100,000 and 3 million.
`[0039] The "cationic charge density" of a polymer, as that term is used herein, refers to the ratio of the number of
`positive charges on a polymer to the molecular weight of said polymer. The cationic charge density multiplied by the
`polymer molecular weight determines the number of positively charged sites on a given polymer chain. Charge Density
`is further defined as the number of mili-equivalents of charge (quaternary nitrogen) per gram (meq/g) of polymer. For
`cationic cellulose (described hereinafter) this is calculated from the %N value determined by Kjeldahl nitrogen determi(cid:173)
`nation. The cationic celluloses %N values were reported from Dow/ Amerchol and the meq/g was calculated by the
`inventors. Cationic guars (described hereinafter) measure degree of substitution, the number of hydroxyl groups sub(cid:173)
`stituted with cationic groups on a particular sugar moiety (maximum of three per sugar). Degree of substitution is used
`to account for the equivalents of N per sugar moiety, which then leads to the mili-equivalents of charge per gram of
`polymer. The cationic guar degree of substitution was determined by Aqualon/ Hercules and the meq/g was calculated
`by the inventors.
`[0040] The concentration of the cationic polymer in the shampoo composition ranges from 0.05% to 3%, preferably
`from 0.075% to 2.0%, more preferably from 0.1% to 1.0%, by weight of the shampoo composition. The weight ratio of
`cationic polymer to a conditioning agent (described hereinafter) in the shampoo compositions is preferably from 4:1 to
`1 :40, more preferably from 2:1 to 1 :20, still more preferably from 1:1 to 1:5.
`[0041] The cationic polymers herein are either soluble in the shampoo composition or are soluble in a complex coac(cid:173)
`ervate phase in the shampoo composition formed by the cationic polymer and the anionic detersive surfactant component
`described hereinbefore. Complex coacervates of the cationic polymer can also be formed with other charged materials
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`EP 1 513 485 81
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`in the shampoo composition.
`[0042] Coacervate formation is dependent upon a variety of criteria such as molecular weight, component concentra(cid:173)
`tion, and ratio of interacting ionic components, ionic strength (including modification of ionic strength, for example, by
`addition of salts), charge density of the cationic and anionic components, pH, and temperature. Coacervate systems
`and the effect of these parameters have been described, for example, by J. Caelles, et al., "Anionic and Cationic
`Compounds in Mixed Systems", Cosmetics & Toiletries, Vol. 106, April 1991, pp 49-54, C. J. van Oss, "Coacervation,
`Complex-Coacervation and Flocculation", J. Dispersion Science and Technology, Vol. 9 (5,6), 1988-89, pp 561-573,
`and D. J. Burgess, "Practical Analysis of Complex Coacervate Systems", J. of Colloid and Interface Science, Vol. 140,
`No. 1, November 1990, pp 227-238.
`It is believed to be particularly advantageous for the cationic polymer to be present in the shampoo composition
`[0043]
`in a coacervate phase, or to form a coacervate phase upon application or rinsing of the shampoo to or from the hair.
`Complex coacervates are believed to more readily deposit on the hair. Thus, in general, it is preferred that the cationic
`polymer exist in the shampoo composition as a coacervate phase or form a coacervate phase upon dilution.
`[0044] Techniques for analysis of formation of complex coacervates are known in the art. For example, microscopic
`analyses of the shampoo compositions, at any chosen stage of dilution, can be utilized to identify whether a coacervate
`phase has formed. Such coacervate phase will be identifiable as an additional emulsified phase in the composition. The
`use of dyes can aid in distinguishing the coacervate phase from other insoluble phases dispersed in the shampoo
`composition.
`In the compositions of the present invention, it is believed that the tendency for high charge density cationic
`[0045]
`polymers to form relatively large coacervates of sizes ranging from 20 microns to 500 microns which are capable of
`effectively binding or flocculating with the particle and enhancing delivery to hair contributes to the superior deposition
`efficiency. Additionally, coacervates which have a cohesive character as evidenced by large, structured floes which
`retain a substantial amount of the particle component on dilution and resist deflocculation on exposure to shear enhance
`the deposition and retention of particles on hair.
`[0046] A particular preferred class of cationic polymers are polysaccharide polymers. These can be further divided
`into polyanhydroglucose polymers and cationic guar derivatives.
`
`1. Cationic Polyanhydroglucose Polymer
`
`[0047] Cationic polymers useful in the present invention are polyanhydroglucose polymers, such as cationic cellulose
`derivatives and cationic starch derivatives. Suitable cationic polyanhydroglucose polymers include those which conform
`to the Formula 1:
`
`wherein A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual; R is an alkylene
`oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1, R2, and R3 independently are alkyl,
`aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the
`total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably being
`about 20 or less; and X is an anionic counterion. Any anionic counterions can be use in association with the cationic
`polymers of the present invention so long as the polymers remain soluble in water, in the shampoo composition, or in
`a coacervate phase of the shampoo composition, and so long as the counterions are physically and chemically compatible
`with the essential components of the shampoo composition or do not otherwise unduly impair product performance,
`stability or aesthetics. Non limiting examples of such counterions include halides (e.g., chlorine, fluorine, bromine, iodine),
`sulfate and methylsulfate, and mixtures thereof. The degree of cationic substitution in these polysaccharide polymers
`is typically from 0.01-1 cationic groups per anhydroglucose unit.
`[0048] Preferred cationic cellulose polymers salts of hydroxyethyl cellulose reacted with trimethyl ammonium substi(cid:173)
`tuted epoxide, referred to in the industry (CTFA) as Polyquaternium 10 and available from Amerchol Corp. (Edison, N.J.,
`USA) as Polymer KG 30M with a charge density of 1.9 and a molecular weight of- 1.25 million.
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`2. Cationic Guar Derivative
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`[0049] Another class of