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`USt](}5977{)36A
`
`United States Patent
`
`[19]
`
`[11] Patent Number:
`
`5,977,036
`
`Guskey
`
`[451 Date of Patent:
`
`*Nov. 2, 1999
`
`[S4]
`
`STYLING SHAMPOO COMPOSITIONS
`
`[75]
`
`Inventor: Susan Marie Guskey, Montgomery,
`Ohio
`
`['73] Assignec: The Procter & Gamble Company,
`Cincinnati, Ohio
`
`[* I Notice:
`
`This patent issued on a continued pros-
`ecution application tiled under 37 CFR
`l,53{d), and is subject to the twenty year
`patent
`term provisions of 35 U.S.C.
`154-(a)(2).
`
`[21] Appl. No.: 09.r’0l'r',596
`
`[22
`
`Filed:
`
`Feb. 3, 1998
`
`Int. Cl.“ ............................ .. A6 [K ‘#075; A61K "Hit
`[51]
`
`[52| U.S. Ci.
`..... ..
`5101121; 510022; 510E123;
`510E124, . 107125; 5107127: 5103128; 51019166;
`Sl(It47S; 424l7"0.l; 424,v'7{J.t1; 424.t'z'0.l2;
`424-f7(|.15; 4241’7U.16;4241"?0.1‘); 42490.21;
`424;'7(I.24; 424170.28; 4247'7(I.3}
`Field of Search ................................... .. 510.3119, 121,
`51117122, 12:1, 124, 125, 127, 128, 466.
`475; 4247701, 7o.11, 70.12, 70.15, 70.16,
`70.19, 70.2], 70.24, 70.28. 70.3}
`
`[58]
`
`[56]
`
`References Cited
`U.S. 1"/\'l'l_iN'I' DOCUMENTS
`
`5,5'i3,?(J9
`5,658,552
`5_,Tlf),92(l
`
`1l;"l99t') Wells .................................... .. 5lU1’l22
`SE19‘)? Bolieh, Jr. et al.
`.
`. 4241'?£I.l2
`
`.................... .. 5lEI7'25‘.J
`2;'l9‘.u‘8 Glenn, Jr. et al.
`
`Prirrmry Ex(1rm'ner—Margaret ljinsmann
`Attorrrey, Agem‘, or FirmfiSlephen '1". Murphy; Tara M.
`Rosnell; William J. Winter
`
`[57]
`
`ABSTR/\C'I'
`
`Disclosed are hair styling shampoo compositions which
`comprise from about 5% to about 50% by weight of a
`surfactant selected from the group consisting of anionic
`surfactants, aswillerionic or amphotcric surfactants having an
`attached group that is anionic at the pll ofthe composition,
`and combinations thereof; from about 0.025% to about 3%
`by weight of an organic cationic polymer having at cationic
`charge density of from about 0.2 meqfgm to about 7 mcqfgm
`and a molecular weight of from about 5,000 to about 1.0
`million; from about 0.1% to about 10% by weight of a
`water-insoluble hair styling polymer; from about 0.1% to
`about 10% by weight of a water-insoluble volatile solvent;
`and from about 0.[)0:':»‘r".'<. to about 2.0% by weight a crystal-
`line hydroxyl-containing stabilizing agent; and from about
`26.5% to about 94.9% by weight water. The composition
`provides improved spreading efiticiency of the styling poly-
`mer onto hair, thus providing improved styling perfonnanee
`from the shampoo composition.
`
`S_.22l,53t’|
`
`ti,-“i993 Jarlchitraponvej el al.
`
`............ .. 424,."'1t'fJ
`
`28 Claims, No Drawings
`
`P&G Exhibit 2002
`P&G Exhibit 2002
`Conopco v. P&G
`Conopco v. P&G
`IPR2014-00628
`
`|PR2014-00628
`
`

`
`5,977,036
`
`1
`STYLING SHAMPOO COMl’OSl'l‘IONS
`
`FIELD OF THE INVENTION
`
`invention relates to hair styling shampoo
`The present
`compositions which provide: improved styling performance.
`More particularly, the present
`invention relates to styling
`shampoo compositions which contain a water insoluble hair
`styling polymer, water insoluble carrier for the hair styling
`polymer, a cationic deposition polymer and select stability
`agents to improve the styling performance and the feel of the
`hair.
`
`BACKGROUND OF THE INVENTION
`
`Many hair shampoo compositions provide acceptable
`cleaning but provide little or no styling benefits, e.g. body,
`hold, stilfness. To realize such benefits, separate cleaning
`and styling products are often used.
`Recently, hair shampoo compositions have been devel-
`oped which can provide cleaning and styling performance
`from a single product. Many of these products contain
`styling polymers in a compatible shampoo base. To prepare
`such products, styling polymers can be dissolved in an
`organic solvent and then incorporated into the shampoo
`base. The organic solvent
`thereafter helps disperse the
`styling polymer in the shampoo composition, and also helps
`enhance spreading of the styling polymer onto hair such that
`the polymer sets and forms welds between hair fibers. The
`enhanced spreading of the styling polymer onto the hair
`results in improved styling performance from the shampoo
`composition.
`Another method for further improving polymer deposi-
`tion from a shampoo involves the use of cationic deposition
`polymers. These cationic deposition polymers improve the
`deposition efiiciency of the styling polymers, which in turn
`also improves styling performance. The improved deposi-
`tion from the cationic polymer can also allow for reduction
`of the amount of styling polymer fonrtulated into the sham-
`poo composition, thus reducing raw material costs. Cationic
`deposition polymers, however, can cause compatibility
`problems with other materials in the formulation, especially
`when used at higher concentrations or at relatively higlt
`cationic charge densities. Moreover, excessive amounts of
`such deposition polymers can result in undesirably coated or
`oily wet hair feel, and can cause the hair when dry to feel
`dirty and have less body, less fullness.
`It has now been found that these water-insoluble styling
`polymers in volatile carriers can be rendered more elfective,
`and the build-up issues associated with cationic deposition
`polymers can be avoided, when these components are used
`in combination with select stabilizers. It is believed that the
`select stabilizers enhance the deposition eficiency of the
`hair styling polymer over conventional stabilizers, allowing
`for more formulation freedom to either lower the cationic
`deposition polymer usage level, or to incorporate new cat-
`ionic deposition polymers with improved bu ild-up profiles.
`Moreover, incorporation of these select stabilizers results in
`significant improvements to the hair feel while delivering
`the desired styling polymer deposit morphology, or
`character, to the hair for optimal style achievement perfor-
`mance from the styling shampoo.
`In view of the foregoing, it is therefore an object of the
`present invention to provide a styling shampoo composition
`with improved styling performance. It is a further object of
`the present invention to improve the storage stability of the
`styling shampoo and the feel of the hair after repeated use of
`the styling shampoo by using select stabilizing agents in
`
`I0
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`combination with a water-insoluble styling polymer, a vola-
`tile carrier for the styling polymer, and a cationic deposition
`polymer.
`
`SUMMARY OF THE INVENTION
`
`The present invention is directed to hair styling shampoo
`compositions which comprise from about 5% to about 50%
`by weight of a surfactant selected from the group consisting
`of anionic surfactants, zwitterionic or amphoteric
`surfactants, and combinations thereof; from about 0.025% to
`about 3% by weight of an organic cationic polymer having
`a cationic charge density of from about 0.2 meqtgm to about
`7 meqfgm and a molecular weight of from about 5,000 to
`about 10 million; from about 0.1% to about 10% by weight
`of a water-insoluble hair styling polymer; from about 0.1%
`to about 10% by weight of volatile water insoluble solvent
`which is a carrier for the styling polymer previously having
`a boiling point of less than about 300° C. and a water
`solubility at 25° C. of preferably less than about 0.2% by
`weight; and from about 0.005% to about 2.0% by weight of
`a crystalline hydroxyl-containing stabilizing agent; and from
`about 25.0% to about 94.8% by weight of water.
`It has been found that the shampoo composition of the
`present
`invention provides improved styling performance
`coupled with improved feel of the hair after styling relative
`to previous styling shampoo compositions. It has also been
`found that the select stabilizing agent, when used in com-
`bination with the cationic deposition polymer, water-
`insoluble styling polymer, water-insoluble volatile carrier
`for the styling polymer, surfactant. and water, provides for
`enhanced deposition elficiency of the styling polymer over
`conventional stabilizers without being limited by theory, it is
`believed that these select stabilizers can be used at signifi-
`cantly lower levels than conventional stabilizers to achieve
`storage stability. Additionally, less of the stabilizer is solu-
`biliaed into the surfactant micelle,
`thus resulting in less
`interference with coacervate formation between the cationic
`deposition polymer and the surfactants. As a result,
`less
`cationic depmition polymer
`is required to achieve the
`desired styling polymer deposition level and the resulting
`coacervate delivers conditioned feel to the hair without an
`unacceptable coated character and without build-up after
`repeated usage of the styling shampoo.
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The shampoo compositions of the present invention can
`comprise, consist of, or consist essentially of the essential
`elements and limitations of the invention described herein,
`as well any of the additional or optional
`ingredients,
`components, or limitations described herein.
`As used herein, the term “water-insoluble” refers to any
`material that has a solubility in water at 25° C. of less than
`about 0.5%, preferably less than about 0.3%, even more
`preferably less than about 0.2% by weight.
`All percentages, pans and ratios are based on the total
`weight of the shampoo 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 carriers or by-products that
`may be included in commercially available materials, unless
`otherwise specified.
`The styling shampoo compositions of the present
`invention, including the essential and some optional com-
`ponents thereof, are described in detail hereinafter.
`
`Detersive Surfactant Component
`The styling shampoo compositions of the present inven-
`tion comprise an detersive surfactant component to provide
`
`

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`5,977,036
`
`3
`cleaning perfonnance to the composition. The detersive
`surfactant component in turn comprises anionic detersive
`surfactant, zwitterionie or amphoteric detersive surfactant,
`or a combination thereof. Such surfactants should be physi-
`cally and chemically compatible with the essential compo-
`nents described herein, or should not otherwise unduly
`impair product stability, aesthetics or performance.
`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 sullicient
`to provide the desired cleaning and lather performance, and
`generally range from about 5% to about 50%, preferably
`from about 8% to about 30%, more preferably from about
`109510 about 25%, even more preferably from about 12% to
`about 22%, by weight of the composition.
`Preferred anionic surfactants suitable for use in the sham-
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`ill
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`poo compositions are the alkyl and alkyl ether sulfates.
`These materials have the respective formulae ROSO_.,M and
`R0(C3H,,0),.SO3M, wherein R is alkyl or alkenyl of from
`about 8 to about 18 carbon atoms, x is an integer having a
`value of from 1 to 10, and M is a cation such as ammonium,
`atkanolamines, such as triethanolamine, monovalent metals,
`such as sodium and potassium, and polyvalent metal cations, *
`such as magnesium, and calcium. Solubility of the surfactant
`will depend upon the particular anionic detersive surfactants
`and cations chosen.
`
`Preferably, R has from about 8 to about l8 carbon atoms,
`more preferably from about 10 to about to carbon atoms,
`even more preferably from about 12 to about 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 about
`8 to about 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 about 0 and about
`
`10, preferably from about 2 to about 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.
`
`Specific non limiting examples of alkyl ether sulfates
`which may be used in the shampoo compositions of the
`present invention include sodium and ammonium salts of
`coconut alkyl triethylene glycol ether sulfate, tallow alkyl
`triethylene glycol ether sulfate, and tallow alkyl hexa-
`oxyethylene sulfate. I-Iighly preferred alkyl ether sulfates are
`those comprising a mixture of individual compounds,
`wherein the compounds in the mixture have an average alkyl
`chain length of from about 10 to about to carbon atoms and
`an average degree of ethoxylation of from about 1 to about
`4 moles ot' ethylene oxide.
`Other suitable anionic detersive surfactants are the water-
`
`soluble salts of organic, sulfuric acid reaction products
`conforming to the formula [R1—S03—M] where R]
`is a
`straight or branched chain, saturated, aliphatic hydrocarbon
`radical having from about 8 to about 24, preferably about It]
`to about 18, carbon atoms; and M is a cation described
`hereinbefore. Non limiting examples of such detersive sur-
`factants are the salts of an organic sulfuric acid reaction
`product of a hydrocarbon of the methane series, including
`iso-, neo, and n-paraffins, having from about 8 to about 24
`carbon atoms. preferably about 12 to about [8 carbon atoms
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`and a sulfonating agent, e.g., S03, I-I:SO_,, obtained accord-
`ing to known sulfonation methods, including bleaching and
`hydrolysis. Preferred are alkali metal and ammonium sul-
`fonated Cw to C13 n-paralfins.
`Still other suitable anionic detersive surfactants are the
`reaction products of fatty acids estcrified with isethionie 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 ofmethyl
`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. Pat. Nos. 2,486,921; 2,486,
`922; and 2,396,278, which descriptions are incorporated
`herein by reference.
`Other anionic detersive surfactants suitable for use in the
`shampoo compositions are the succinnates, examples of
`which include disodium N-octadecylsulfosuccinnate; diso-
`dium lauryl sulfosuccinate; diammonium lauryl sulfosucci-
`nate;
`tetrasodium N-( 1 ,2-dicarboxyethyl]-N-
`octadecylsulfosuccinnate; diamyl ester of sodium
`sulfosuceinic acid; dihexyl ester of sodium sulfosuccinic
`acid; and dioctyl esters of sodium sulfosuccinic acid.
`Other suitable anionic detersive surfactants include olefin
`sulfonates having about 10 to about 24 carbon atoms. In this
`context, the term “olefin sullonates" refers to compounds
`which can be produced by the sulfonation of alpha-oleftns
`by means of uncomplexed sulfur trioxide, followed by
`neutralization of the acid reaction mixture in conditions such
`that any sulfones which have been formed in the reaction are
`hydrolyzed to give the corresponding hydroxy-
`alkanesulfonates. The sulfur
`trioxide can be liquid or
`gaseous, and is usually, but not necessarily, diluted by inert
`diluents,
`for example by liquid 80:, chlorinated
`hydrocarbons, etc., when used in the liquid form, or by air,
`nitrogen, gaseous S03, etc., when used in the gaseous form.
`The alphawolefins from which the olefin sulfonates are
`derived are mono-olefins having from about 10 to about 24
`carbon atoms, preferably from about 12 to about 16 carbon
`atoms. Preferably, they are straight chain oleli ns. In addition
`to the true alkene sulfonates and a proportion of hydroxy-
`alkanesulfonates,
`the olefin suifonales can contain minor
`amounts of other materials, such as alkene disulfonates
`depending upon the reaction conditions, proportion of
`reactants, the nature of the starting oleftns and impurities in
`the olefin stock and side reactions during the sulfonation
`process. A non limiting example of such an alpha-olelin
`sulfonate mixture is described in U.S. Pat. No. 3,332,880,
`which description is incorporated herein by reference.
`Another class of anionic detersive surfactants suitable for
`use in the shampoo compositions are the beta-alkyloxy
`alkane sulfonates. These surfactants conform to the formula
`
`where R” is a straight chain alkyl group having from about
`6 to about 2:3 carbon atoms, R: is a lower alkyl group having
`from about 1 to about 3 carbon atoms, preferably 1 carbon
`atom, and M is a water-soluble cation as described herein-
`before.
`Preferred anionic detersive surfactants for use in the
`shampoo compositions include ammonium lauryl sulfate,
`ammonium laureth sulfate, triethylamine lauryl sulfate, tri-
`ethylamine laureth sulfate, triethanolamine lauryl sulfate.
`
`

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`5,977,036
`
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`triethanolamine laureth sulfate, monoethanolamine lauryl
`sulfate, monoethanolamine lauretb sulfate, diethanolarnine
`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 saroosine, cocoyl sarcosine, ammonium
`cocoyl sulfate, ammonium lauroyl sulfate, sodium oocoyl
`sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,
`potassium lauryl sulfate, triethanolamine lauryl sulfate, tri-
`ethanolamine lauryl sulfate, monoethanolamine cocoyl
`sulfate, monoethanolamine lauryl sulfate, sodium tridccyl
`benzene sulfonate, sodium dodceyl benzene sulfonate, and
`combinations thereof.
`Suitable amphoteric or zwitterionie detersive surfactants
`for use in the shampoo composition herein include those
`which are known for use in hair care or other personal care
`cleansing. Concentration of such amphoteric detersive sur-
`factants preferably ranges from about 0.5% to about 20%,
`preferably from about 1% to about 10%, by weight of the
`composition. Non limiting examples of suitable zwitterionic
`or amphoteric surfactants are described in US. Pat. Nos.
`5,104,646 (Boliclt Jr. el al.), 5,106,609 {Bolich Jr. et al.),
`which descriptions are incorporated herein by reference.
`Amphoteric detersive surfactants suitable for use in the _
`shampoo composition are well known in the art, and include
`those surfactanfs broadly described as derivatives of all-
`phatic 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. Preferred amphoteric (letersive surfactants for
`use in the present
`invention include cocoamphoacetate,
`cocoamphodiacetate,
`lauroamphoacetale,
`lauroamphodiacetate, and mixtures thereof.
`Zwitterionic detersive surfactants suitable for use in the
`shampoo composition are well known in the art, and include
`those surfactanfs broadly described as derivatives of ali-
`phatic quaternary ammonium, phosphonium, and sulfonium
`compounds, in which the aliphatic radicals can be straight or
`branched chain, and wherein one of the aliphatic substitu-
`ents 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.
`The shampoo compositions of the present invention may
`further comprise additional surfactants for use in combina-
`tion with the anionic detersive surfactant component
`described hereinbcfore. Suitable optional surfactants include
`nonionic surfactants. 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 oth-
`erwise unduly impair product performance, aesthetics or
`stability. The concentration of the optional additional sur-
`factants in the shampoo composition may vary with the
`cleansing or lather performance desired, the optional sur-
`factant selected, the desired product concentration, the pres-
`ence of other components in the composition, and other
`[actors well known in the art.
`Non limiting examples of other anionic, zwitterionic,
`amphoteric or optional additional surfactants suitable for use
`in the shampoo compositions are described in
`McCrttclreon’s_, Erriufsrfiers and Dctergem‘s_, 1989 Arrmml,
`published by M. C. Publishing Co.. and U.S. Pat. Nos.
`
`45
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`3,929,678, 2,658,072; 2,438,091; 2,528,378, which descrip-
`tions are incorporated herein by reference.
`
`Cationic Deposition Polymer
`
`The shampoo compositions of the present invention com-
`prise an organic cationic polymer as a deposition aid for the
`styling polymer component described hereinafter. The con-
`centration of the cationic polymer in the shampoo compo-
`sition ranges from about 0.025% to about 3%, preferably
`from about 0.05% to about 0.5%, more preferably from
`about 0.1% to about 0.25%, by weight of the shampoo
`composition.
`The cationic polymer for use in the shampoo composition
`of the present
`invention contains cationic nitrogen-
`containing moieties such as quaternary ammonium or cat-
`ionic protonated amino moieties. The cationic protonated
`amines can be primary, secondary, or
`tertiary amines
`(preferably secondary or tertiary), depending upon the par-
`ticular species and the selected pll of the styling shampoo
`composition. The average molecular weight of the cationic
`polymer is between about
`[0 million and about 5,000,
`preferably at least about 100,000, more preferably at least
`about 200,000, but preferably not more than about 2 million,
`more preferably not more than about 1.5 million. The
`polymers also have a cationic charge density ranging from
`about 0.2 meqfgm to about 7 meqfgm, preferably at least
`about 0.4 meqlgm, more preferably at least about 0.6 meqi’
`gm, but also preferably less than about 5 meqlgm, more
`preferably less than about 2 meqlgm, at the pH of intended
`use of the shampoo composition, which pH will generally
`range from about pH 3 to about pH 9, preferably between
`about pH 4 and about pH 1''.
`Any anionic counterions can be use in amociation with
`the cationic polymers 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 coun-
`terions include halides (e.g., chlorine, fluorine, bromine,
`iodine), sulfate and methylsulfate.
`The cationic nitrogen-containing moiety of the cationic
`polymer is generally present as a substituent on all, or more
`typically on some, of the monomer units thereof. Thus, the
`cationic polymer for use in the shampoo composition
`includes homopolymers, copolymers,
`let-polymers, and so
`forth, of quaternary ammonium or cationic amine-
`substituted monomer units, optionally in combination with
`non-cationic monomers referred to herein as spacer mono-
`mers. Non limiting examples of such polymers are described
`in the CTT*l Cosmetic lrrgrediertt Dictionary, 3rd edition,
`edited by Estrin, Crosley, and Haynes, (The Cosmetic.
`Toiletry, and Fragrance Association, [nc., Washington, D.(_‘.
`(1982)), which description is i.ncorporated herein by refer-
`EDCC.
`
`Non limiting examples of suitable cationic polymers
`include copolymers of vinyl monomers having cationic
`protonated amine or quaternary ammonium functionalities
`with water soluble spacer monomers such as acrylamide,
`methacrylamide, alkyl and dialkyl aerylamides, alkyl and
`dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate,
`vinyl caprolactone or vinyl pyrrolidone. The alkyl and
`Clialkyl substituted monomers preferably have from C 1 to C,
`al.kyl groups, more preferably from C‘, to C3 alkyl groups.
`Other suitable spacer monomers include vinyl esters. vinyl
`
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`5,977,036
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`alcohol (made by hydrolysis of polyvinyl acetate), maleic
`anhydride, propylene glycol, and ethylene glycol.
`Suitable cationic protonated amino and quaternary ammo-
`nium monomers, for inclusion in the cationic polymers of
`the shampoo composition herein, include vinyl compounds
`substituted with dialkylaminoalkyl acrylate, dialkylami-
`noalkyl methacrylate, monoalkylaminoalkyl acrylate,
`monoalkylaminoalkyl mcthacrylate, trialkyl methacryloxy—
`alkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt,
`diallyl quaternary ammonium salts, and vinyl quaternary
`ammonium monomers having cyclic cationic nitrogen-
`containing rings such as pyridinium, imidamlium, and quat-
`ernized pyrrolidone, e.g., alkyl vinyl
`imidazolium, alkyl
`vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl
`portions of these monomers are preferably lower alkyls such
`as the C,, C: or C3 alkyls.
`Suitable amine-substituted vinyl monomers for use herein
`include diall-rylarninoalkyl acrylate, diall-tylaminoalkyl
`methacrylate, dialkylaminoalkyl acrylamide, and dia1ky-
`laminoalkyl methacrylamide, wherein the alkyl groups are
`preferably C,—C, hydrocarbyls, more preferably C,—C3,
`alkyls.
`Other suitable cationic polymers for use in the shampoo
`composition include copolymers of 1-vinyl-2-pyrrolidone
`and l—vinyl—3~methylimidazolium salt (e.g., chloride salt)
`(referred to in the industry by the Cosmetic, Toiletry, and _
`Fragrance Association, “C'I'l"A”, as Polyquaternium-16),
`such as those commercially available from BASF Wyan-
`dotte Corp. (Parsippany, N.J., U.S.A.) under the LUVI-
`QUAT tradenarne {e.g., LUVIQUAT FC 370); copolymers
`of I-vinyl-2-pyrrolidone and dimethylaminoethyl rnethacry-
`late (referred to in the industry by CTFA as l’olyquatcrnium—
`11) such as those commercially available from ISP Corpo-
`ration (Wayne, N.J., U.S.A.) under
`the GAFQUAT
`tradename (e.g., GAFQUAT 755N); cationic diallyl qu aler-
`nary ammonium-containing polymers,
`including,
`for
`example, dirnethyldiallylammonium chloride homopolymer
`and copolymers of acrylamide and dimethyldiallylamrno-
`nium chloride,
`referred to in the industry (CT!-‘A) as
`Polyquaternium 6 and Polyquaternium 7, respectively; and
`mineral acid salts of amino-alkyl esters of homopolymers
`and copolymers of unsaturated carboxylic acids having from
`3 to 5 carbon atoms, as described in US. Pat. No. 4,009,256,
`which description is incorporated herein by reference.
`Other suitable cationic polymers for use in the shampoo
`composition include polysaccharide polymers, such as cat-
`ionic cellulose derivatives and cationic starch derivatives.
`Suitable cationic polysaccharide polymers include those
`which conform to the formula
`
`35
`
`40
`
`45
`
`Tl
`A—0—('R— l|\"'— R"X'J
`R.‘
`
`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 as described in hereinbefore.
`Preferred cationic cellulose polymers are those polymers
`available from Amerchol Corp. (Edison, NJ., USA) in their
`
`50
`
`55
`
`60
`
`65
`
`8
`Polymer JR and LR series of polymers, as salts of hydroxy-
`ethyl cellulose reacted with trimethyl ammonium substituted
`epoxide, referred to in the industry (CTPA) as Polyquater-
`nium I0. Another
`type of preferred cationic cellulose
`includes the polymeric quaternary ammonium salts of
`hydroxyethyl cellulose reacted with lauryl dimethyl
`ammonium-substituted epoxide, referred to in the industry
`(CTFA) as Polyquaternium 24. These materials are available
`from Arnerchol Corp. (Edison, N.J., USA) under the trade
`name Polymer LM-200.
`Other suitable cationic polymers include cationic guar
`gum derivatives, such as guar hydroxypropyltrimonium
`chloride. specific examples of which include the Jaguar
`series commercially available from Rhone-Poulenc Incor-
`porated. Other suitable cationic polymers include quaternary
`nitrogen—containing cellulose ethers, some examples of
`which are described in U.S. Pat. No. 3,962,418, which
`description is incorporated herein by reference herein. Other
`suitable cationic polymers include copolymers of etherified
`cellulose, guar and starch, some examples of which are
`described in U.S. Pat. No. 3,958,581, which description is
`incorporated herein by reference.
`The cationic polymers herein are either soluble in the
`shampoo composition, or preferably are soluble in a com-
`plex coacervate 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 in the shampoo composition.
`Coacervate formation is dependent upon a variety of
`criteria such as molecular weight, component concentration,
`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, pll, and temperature. Coacervate systems and
`the effect of these parameters have been described,
`for
`example, by J. Caelles, et al., “Anionic and Cationic Com-
`pounds in Mixed Systems", Cosmetics & To£ietrie.s, Vol.
`106, April 1991, pp 49-54, C. J. van Oss, “Coacervation,
`Complex—Coacervat ion and Flocculation", J. Dispersion
`Science and Tecltnology, Vol. 9 (5,6), 1988-89, pp 561-573,
`and D. J. Burgess, "Practical Analysis of Complex Coacer-
`vate Systems", J. ofCo."l.or'd and InterfnceScirmce_, Vol. 140,
`No. l, November 1990, pp 227-238, which descriptions are
`incorporated herein by reference.
`the
`It
`is believed to be particularly advantageous for
`cationic polymer to be present in the shampoo composition
`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.
`If not
`already a coaeervate in the shampoo composition, the cat-
`ionic polymer will preferably exist in a complex coacervate
`form in the shampoo upon dilution with water.
`Techniques for analysis of formation of complex coacerw
`vates 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 com-
`position.
`
`Styling Polymer
`The shampoo compositions of the present invention com-
`prise a water-insoluble hair styling polymer, concentrations
`
`

`
`5,977,036
`
`9
`of which range from about 0. 1% to about 10%, preferably
`from about 0.3% to about 7%, more preferably from about
`0.5% to about 5%, by weight of the composition. These
`styling polymers provide the shampoo composition of the
`present invention with hair styling performance by provid-
`ing polymeric deposits on the hair after application from a
`shampoo composition. The polymer deposited on the hair
`has adhesive and cohesive strength and delivers styling
`primarily by forming welds between hair libers upon drying,
`as is understood by those skilled in the art.
`including
`Many such polymers are known in the art,
`water-insoluble organic polymers and water-insoluble
`silicone-grafted polymers, all of which are suitable for use
`in the shampoo composition herein provided that they also
`have the requisite features or characteristics described he re-
`inafter. Such polymers can be made by conventional or
`otherwise known polymerization techniques well known in
`the art, an example of which includes. free radical polymer-
`ization.
`
`10
`
`15
`
`10
`ethylenically unsaturated monomers, cellulosic chains or
`other carbohydrate-derived polymeric chains. The backbone
`may comprise ether groups, ester groups, amide groups,
`urethanes, combinations thereof, and the like.
`The organic styling polymers may further comprise one