PCT
`WORLD INTELLECfUAL PROPERTY ORGANIZATION
`International Bureau
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`wo 97114406
`
`(11) International Publication Number:
`
`(51) International Patent Classification 6 :
`A61K 7/50
`
`A2
`
`(43) International Publication Date:
`
`24 April 1997 (24.04.97)
`
`(21) International Application Number:
`
`PCT/US96116536
`
`(22) International Filing Date:
`
`16 October 1996 (16.10.96)
`
`(81) Designated States: BR, CN, JP, MX, European patent (AT,
`BE, CH, DE, DK, ES, Fl, FR, GB, GR, IE, IT, LU, MC,
`NL, PT, SE).
`
`(30) Priority Data:
`08/543,668
`
`16 October 1995 (16.10.95)
`
`US
`
`Published
`Without international search report and to be republished
`upon receipt of that report.
`
`THE PROCTER & GAMBLE COMPANY
`(71) Applicant:
`[US/US]; One Procter & Gamble Plaza, Cincinnati, OH
`45202 (US).
`
`(72) Inventors: UCHIYAMA, Hirotaka; 5-8-17-3B, Nishiokamoto,
`Higashinada-ku, Kobe 658 (JP). SAKO, Takashi; 1-15-
`7-103, Sumiyoshi Honmachi, Higashinada-ku, Kobe 658
`(JP). OKUYAMA, Yoshinari; 3-12-13-306, Sumiyoshi
`Honmachi, Higashinada-ku, Kobe 658 (JP).
`
`(74) Agents: REED, T., David et al.; The Procter & Gamble
`Company, 5299 Spring Grove Avenue, Cincinnati, OH
`45217 (US).
`
`(54) Title: CONDITIONING SHAMPOO COMPOSITIONS HAVING IMPROVED STABILITY
`
`(57) Abstract
`
`The present invention relates to conditioning shampoo compositions having improved stability and conditioning benefits. These
`compositions comprise a detersive anionic surfactant, other than anionic amino acid derivative surfactants; a stabilizing surfactant selected
`from the group consisting of anionic amino acid derivative surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof; a
`fatty compound selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures
`thereof; a hair conditioning agent selected from the group consisting of nonvolatile dispersed silicone conditioning agents, hydrocarbon
`conditioning agents, water soluble cationic polymeric conditioning agents, and mixtures thereof; and water. The present invention also
`relates to methods for cleansing and conditioning the hair.
`
`1
`
`

`

`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the PCT on the front pages of pamphlets publishing international
`applications under the PCT.
`
`AM
`AT
`AU
`BB
`BE
`BF
`BG
`BJ
`BR
`BY
`CA
`CF
`CG
`CH
`Cl
`CM
`CN
`cs
`cz
`DE
`DK
`EE
`ES
`Fl
`FR
`GA
`
`Annenia
`Austria
`Australia
`Barbados
`Belgium
`Burkina Faso
`Bulgaria
`Benin
`Brazil
`Belarus
`Canada
`Central African Republic
`Congo
`Switzerland
`COte d'Ivoire
`Cameroon
`China
`Czechoslovakia
`Czech Republic
`Gennany
`Denmark
`Estonia
`Spain
`Finland
`France
`Gabon
`
`GB
`GE
`GN
`GR
`HU
`IE
`IT
`JP
`KE
`KG
`KP
`
`KR
`KZ
`Ll
`LK
`LR
`LT
`LU
`LV
`MC
`MD
`MG
`ML
`MN
`MR
`
`United Kingdom
`Georgia
`Guinea
`Greece
`Hungary
`Ireland
`Italy
`Japan
`Kenya
`Kyrgystan
`Democratic People's Republic
`of Korea
`Republic of Korea
`Kazakhstan
`Liechtenstein
`Sri Lanka
`Liberia
`Lithuania
`Luxembourg
`Latvia
`Monaco
`Republic of Moldova
`Madagascar
`Mali
`Mongolia
`Mauritania
`
`MW
`MX
`NE
`NL
`NO
`NZ
`PL
`PT
`RO
`RU
`SD
`SE
`SG
`Sl
`SK
`SN
`sz
`TD
`TG
`TJ
`TT
`UA
`UG
`us
`uz
`VN
`
`Malawi
`Mexico
`Niger
`Netherlands
`Norway
`New Zealand
`Poland
`Portugal
`Romania
`Russian Federation
`Sudan
`Sweden
`Singapore
`Slovenia
`Slovakia
`Senegal
`Swaziland
`Chad
`Togo
`Tajikistan
`Trinidad and Tobago
`Ukraine
`Uganda
`United States of America
`Uzbekistan
`VietNam
`
`2
`
`

`

`wo 97/14406
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`PCT /US96/16536
`
`-1-
`
`5
`
`1 0
`
`CONDITIONING SHAMPOO COMPOSITIONS HAVING IMPROVED STABILITY
`
`FIELD OF THE INVENTION
`
`The present invention relates to conditioning shampoo compositions having improved
`
`stability. These compositions are useful for both cleansing and conditioning the hair. These
`
`compositions comprise a detersive anionic surfactant, other than anionic amino acid derivative
`
`surfactants; a stabilizing surfactant selected from the group consisting of anionic amino acid
`
`15
`
`derivative surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof; a fatty
`
`compound selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives,
`
`fatty acid derivatives, and mixtures thereof; a hair conditioning agent selected from the group
`
`consisting of nonvolatile dispersed silicone conditioning agents, hydrocarbon conditioning agents,
`
`water soluble cationic polymeric conditioning agents, and mixtures thereof; and water. The present
`
`20
`
`invention also relates to methods for cleansing and conditioning the hair.
`
`BACKGROUND OF THE INVENTION
`
`Human hair becomes soiled due to its contact with the surrounding environment and from
`
`the sebum secreted by the scalp. The soiling of hair causes it to have a dirty feel and an unattractive
`
`appearance. The soiling of the hair necessitates shampooing with frequent regularity.
`
`25
`
`Shampooing cleans the hair by removing excess soil and sebum. However, shampooing can
`
`leave the hair in a wet, tangled, and generally unmanageable state. Once the hair dries, it is often left
`
`in a dry, rough, lusterless, or frizzy condition due to removal of the hair's natural oils and other
`
`natural conditioning and moisturizing components. The hair can further be left with increased levels
`
`of static upon drying, which can interfere with combing and results in a condition commonly referred
`
`30
`
`to as "fly-away hair."
`
`A variety of approaches have been developed to alleviate these after-shampoo problems.
`
`These approaches range from post-shampoo application of hair conditioners such as leave-in and
`
`rinse-off products, to hair conditioning shampoos which attempt to both cleanse and condition the
`
`hair from a single product. Hair conditioners are typically applied in a separate step following
`
`35
`
`shampooing. The hair conditioners are either rinsed-off or left-in, depending upon the type of
`
`product used. Hair conditioners, however, have the disadvantage of requiring a separate and
`
`3
`
`

`

`wo 97/14406
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`PCT IUS96/16536
`
`2
`
`inconvenient treatment step. Conditioning shampoos. i.e. shampoos which both cleanse and
`
`condition the hair, are highly desirable products because they are convenient for consumers to use.
`
`In order to provide hair conditioning benefits in a cleansing shampoo base. a wide variety of
`
`conditioning actives have been proposed. However, many of these actives have the disadvantage of
`
`5
`
`leaving the hair feeling soiled or coated, of interfering with the cleansing efficacy of the shampoo, or
`
`of yielding a resultant shampoo with poor shelf stability.
`
`It has surprisingly been found
`
`in the present invention that highly stable shampoo
`
`compositions can be achieved utilizing a stabilizing surfactant system comprising a surfactant
`
`selected from the group consisting of anionic amino acid derivative surfactants, amphoteric
`
`10
`
`surfactants. cationic surfactants, and mixtures thereof. This stabilizing surfactant system is used in
`
`the present invention in combination with a detersive anionic surfactant, certain fatty compounds,
`
`and certain hair conditioning agents, to provide compositions having improved wet hair conditioning
`
`benefits such as smoothness and ease of combing compared to conventional conditioning shampoos.
`
`These compositions also provide improved dry hair conditioning benefits such as leaving the hair
`
`15
`
`feeling soft, smooth, and moistened. These dry hair benefits can also provide hair that looks shiny.
`
`It
`
`is therefore an object of the present invention to provide conditioning shampoo
`
`compositions, i.e. compositions which both cleanse and condition the hair from a single product.
`
`It is another object of the present invention to provide compositions which are stable.
`
`It is another object of the present invention to provide compositions which do not leave the
`
`20
`
`hair feeling coated, heavy, or soiled.
`
`It is another object of the present invention to provide compositions which provide
`
`improved wet hair conditioning benefits such as smoothness and ease of combing.
`
`It is another object of the present invention to provide compositions which provide
`
`improved dry hair conditioning benefits such as leaving the hair feeling soft, smooth, moist and
`
`25
`
`looking shiny.
`
`It is another object of the present invention to provide methods for cleansing and
`
`conditioning the hair utilizing a single composition.
`
`These and other objects will become readily apparent from the detailed description which
`
`follows.
`
`30
`
`35
`
`SUMMARY OF THE INVENTION
`
`The present invention relates to a hair conditioning shampoo composition comprising:
`
`(a)
`
`from about 5% to about 50% by weight of a detersive anionic surfactant, other
`
`than anionic amino acid derivative surfactants;
`
`(b)
`
`from about 0.05% to about 20% of a stabilizing surfactant selected from the group
`
`consisting of anionic amino acid derivative surfactants, amphoteric surfactants,
`
`cationic surfactants, and mixtures thereof,
`
`4
`
`

`

`wo 97/14406
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`PCT /US96/16536
`
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`
`(c)
`
`from about 0.01% to about 10% by weight of a fany compound selected from the
`
`group consisting of fany alcohols, fany acids, fany alcohol derivatives, fany acid
`
`derivatives, and mixtures thereof;
`
`(d)
`
`from about 0.05% to about 20% by weight of a hair conditioning agent selected
`
`5
`
`from the group consisting of nonvolatile dispersed silicone conditioning agents.
`
`hydrocarbon conditioning agents, water soluble cationic polymeric conditioning
`
`agents, and mixtures thereof; and
`
`(e)
`
`from about 20% to about 94.89% by weight water.
`
`The present invention also relates to methods for cleansing and conditioning the hair
`
`10
`
`utilizing these compositions.
`
`Unless otherwise indicated, all percentages and ratios used herein are by weight and based
`
`upon the total composition, and all measurements are made at 25°C or room temperature.
`
`The invention hereof can comprise, consist of. or consist essentially of the essential
`
`elements and limitations of the invention described herein, as well any of the additional ingredients.
`
`components, or limitations described herein. All documents referred to herein are incorporated by
`
`reference herein in their entirety.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`The compositions of the present invention comprise the following essential as well as
`
`optional components.
`
`The compositions of the present invention are highly stable compositions. Stability is
`
`defined herein to include both physical and chemical stability as such phenomena can be related and
`
`15
`
`20
`
`overlapping.
`
`Detersive Anionic Surfactant
`
`The compositions of the present invention comprise a detersive anionic surfactant, which is
`
`25
`
`selected from anionic surfactants other than anionic amino acid derivative surfactants, as defmed
`
`herein, below. Without being limited by theory, the purpose of the detersive anionic surfactant is to
`
`provide cleansing performance to the composition. The term detersive surfactant, as used herein, is
`
`intended to distinguish these surfactants from surfactants which are primarily emulsifying
`
`surfactants, i.e. surfactants which provide an emulsifying benefit and which have low cleansing
`
`30
`
`performance. It is recognized that most surfactants have both detersive and emulsifying properties.
`
`It is not intended to exclude anionic emulsifying surfactants from the present invention. provided the
`
`surfactant also possesses sufficient detersive properties to be useful herein.
`
`The detersive anionic surfactant will generally comprise from about 5% to about 50%,
`
`preferably from about 8% to about 30%, and more preferably from about 8% to about 25%, by
`
`35
`
`weight of the composition.
`
`Detersive anionic surfactants useful herein include alkyl and alkyl ether sulfates. These
`
`materials have the respective formulae ROS0
`
`M and RO(C
`
`3
`
`H
`4
`
`2
`
`0\S0
`
`3
`
`M, wherein R is alkyl or
`
`5
`
`

`

`W097/14406
`
`PCT IUS96/16536
`
`4
`
`alkenyl of from about 8 to about 30 carbon atoms. x is l to about I 0, and M is hydrogen or a cation
`
`such as ammonium. alkanolammonium (e.g., triethanolammonium). a monovalent metal cation (e.g.,
`
`sodium and potassium), or a polyvalent metal cation (e.g., magnesium and calcium). Preferably, M
`
`should be chosen such that the anionic surfactant component is water soluble. The anionic surfactant
`
`5
`
`or surfactants should be chosen such that the Krafft temperature is about I5°C or less, preferably
`
`about I 0°C or less, and more preferably about ooc or less.
`
`It is also preferred that the anionic
`
`surfactant be soluble in the composition hereof.
`
`Krafft temperature refers to the point at which solubility of an ionic surfactant becomes
`
`determined by crystal Janice energy and heat of hydration, and corresponds to a point at which
`
`I 0
`
`solubility undergoes a sharp, discontinuous increase with increasing temperature. Each type of
`
`surfactant will have its own characteristic Krafft temperature. Krafft temperature for ionic
`
`surfactants is, in general, well known and understood in the art. See, for example, Myers, Drew,
`
`Surfactant Science and Technology. pp. 82-85, VCH Publishers. Inc. (New York, New York. USA),
`
`1988 (ISBN 0-89573-399-0), which is incorporated by reference herein in its entirety.
`
`15
`
`In the alkyl and alkyl ether sulfates described above, preferably R has from about 12 to
`
`about 18 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 derived from fats, e.g., coconut oil, palm oil,
`
`tallow, or the like, or the alcohols can be synthetic. Laury! alcohol and straight chain alcohols
`
`20
`
`derived from coconut oil and palm oil are preferred herein. Such alcohols are reacted with I to about
`
`I 0, and especially 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 examples of alkyl ether sulfates which can be used in the present inventidn are
`
`sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene
`
`glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether sulfates
`
`are those comprising a mixture of individual compounds, said mixture having an average alkyl chain
`
`length of from about 12 to about 16 carbon atoms and an average degree of ethoxy lation of from I to
`
`about 4 moles of ethylene oxide. Such a mixture also comprises from 0% to about 20% by weight
`
`25
`
`30
`
`35
`
`c
`
`_
`12
`13
`to about 20% by weight of c
`
`compounds; from about 60% to about 100% by weight ofc
`
`_
`_
`14
`16
`15
`compounds; from about 3% to about 30% by weight of
`
`compounds, from 0%
`
`_
`_
`17
`19
`18
`compounds having a degree of ethoxylation of 0; from about 45% to about 90% by weight of
`
`compounds having a degree of ethoxylation of from I to about 4; from about I 0% to about 25% by
`
`weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from about
`
`0.1% to about 15% by weight of compounds having a degree of ethoxylation greater than about 8.
`
`Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid
`
`reaction products of the general formula [R 1-S03-M] where R 1 is selected from the group consisting
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`5
`
`of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about
`
`24, preferably about I 0 to about 18, carbon atoms; and M is as previously described above in this
`
`section. Examples of such surfactants are the salts of an organic sulfuric acid reaction product of a
`
`5
`
`hydrocarbon of the methane series, including iso-, neo-, and n-paraffins. having about 8 to about 24
`carbon atoms. preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g .. so3,
`H2S04. obtained according to known sulfonation methods, including bleaching and hydrolysis.
`
`Preferred are alkali metal and ammonium sulfonated C 10-18 n-paraffins.
`
`Still other suitable anionic 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
`
`10
`
`from coconut or palm oil; or sodium or potassium salts of fatty acid am ides of methyl tauride in
`
`which the fatty acids, for example, are derived from coconut oil. Other similar anionic surfactants
`
`are described in U.S. Patents 2,486,921. 2.486.922, and 2.396,278, which are incoproated by
`
`reference herein in their entirety.
`
`Still other useful surfactants are those that are derived from taurine, which is also known as
`
`15
`
`2-aminoethanesulfonic acid. An example of such an acid is N-acyi-N-methyl taurate.
`
`Other anionic surfactants suitable for use in the shampoo compositions are the succinates.
`
`examples of which include disodium N-octadecylsulfosuccinate; disodium Iaury! sulfosuccinate;
`
`diammonium Iaury! sulfosuccinate; tetrasodium N-( 1,2-dicarboxyethyi)-N-octadecylsulfosuccinate;
`
`the diamyl ester of sodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinic acid; and the
`
`20
`
`dioctyl ester of sodium sulfosuccinic acid.
`
`Other suitable anionic surfactants include olefin sulfonates having about I 0 to about 24
`
`carbon atoms. The term "olefm sulfonates" is used herein to mean compounds which can be
`
`produced by the sulfonation of alpha-olefms by means of uncomplexed sulfur trioxide, followed by
`
`neutralization of the acid reaction mixture in conditions such that any sulfones which have been
`
`25
`
`formed in the reaction are hydrolyzed to give the corresponding hydroxyalkanesulfonates. The
`
`sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents,
`
`for example by liquid S02, chlorinated hydrocarbons, etc., when used in the liquid form, or by air,
`
`nitrogen, gaseous S02, etc., when used in the gaseous form.
`
`The alpha-olefins from which the olefm sulfonates are derived are mono-olefins having
`
`30
`
`about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they
`
`are straight chain olefms.
`
`In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the
`
`olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates
`
`depending upon the reaction conditions, proportion of reactants, the nature of the starting olefms and
`
`35
`
`impurities in the olefm stock and side reactions during the sulfonation process. A specific
`
`alpha-olefin sulfonate mixture of the above type is described more fully in U.S. Patent 3,332,880, to
`
`Pflaumer and Kessler, issued July 25, 1967, which is incorporated by reference herein in its entirety.
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`Another class of anionic surfactants suitable for use in the shampoo compositions are the
`
`beta-alkyloxy alkane sulfonates. These compounds have the following formula:
`
`OR2 H
`
`R'++SO,M
`
`H H
`
`where R I is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower
`
`5
`
`alkyl group having from about I. preferred, to about 3 carbon atoms, and M is as hereinbefore
`
`10
`
`15
`
`20
`
`25
`
`described.
`
`Many other anionic 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
`
`in U.S. Patent 3,929,678, which descriptions are incorporated herein by reference in their entirety.
`
`Preferred anionic surfactants for use in the shampoo compositions include ammonium Iaury!
`
`sulfate, ammonium laureth sulfate, triethylamine Iaury! sulfate, triethylamine laureth sulfate,
`
`triethanolamine Iaury! sulfate, triethanolamine laureth sulfate, monoethanolamine Iaury! sulfate.
`
`monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate,
`
`lauric monoglyceride sodium sulfate, sodium Iaury! sulfate, sodium laureth sulfate, potassium Iaury!
`
`sulfate, potassium laureth sulfate, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium
`
`cocoyl sulfate, sodium
`
`lauroyl sulfate, potassium cocoyl sulfate, potassium
`
`Iaury! sulfate,
`
`triethanolamine Iaury! sulfate, triethanolamine Iaury! sulfate, monoethanolamine cocoyl sulfate,
`
`monoethanolamine lauryl sulfate, sodium N-lauroyi-N-methyl taurate, sodium tridecyl benzene sul(cid:173)
`
`fonate, and sodium dodecyl benzene sulfonate. Preferred for use herein are detersive anionic
`
`surfactants selected from the group consisting of ammonium laureth-3 sulfate, sodium alureth-3
`
`sulfate, ammonium Iaury! sulfate, sodium lauryl sulfate. and mixtures therelf.
`
`Stabilizing Surfactants
`
`The compositions of the present invention comprise from about 0.05% to about 20%.
`
`preferably from about 0.1% to about 10%, and more preferably from about 0.5% to about 10% of a
`
`stabilizing surfactant selected from the group consisting of amphoteric surfactants, anionic amino
`
`acid derivative surfactants, cationic surfactants, and mixtures thereof.
`
`By stabilizing surfactant is meant a surfactant that provides enhanced stability of the
`
`shampoo compositions, whereby the products are resistant to separation. Without being limited by
`
`theory, it is believed that these surfactants help to disperse and/or dissolve the fatty compounds in the
`
`30
`
`aqueous shampoo base.
`
`The stabilizing surfactant component, and in particular the anionic amino acid derivative
`
`surfactants, described herein are defmed to be excluded from the anionic detersive surfactant
`
`component, as described above.
`
`Amphoteric Surfactants
`
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`The stabilizing surfactant component of the present invention can comprise an amphoteric
`
`surfactant.
`
`The tenn "amphoteric surfactant," as used herein, is also intended to encompass
`
`zwitterionic surfactants, which are well known to fonnulators skilled in the art as a subset of
`
`amphoteric surfactants. A wide variety of amphoteric surfactants can be used in the compositions of
`
`5
`
`the present invention. Particularly useful are those which are broadly described as derivatives of
`
`aliphatic secondary and tertiary amines, preferably wherein the nitrogen is in a cationic state, in
`
`which the aliphatic radicals can be straight or branched chain and wherein one of the radicals
`
`contains an ionizable water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or
`
`phosphonate.
`
`10
`
`15
`
`Non limiting examples of amphoteric surfactants useful in the compositions of the present
`
`invention are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition
`
`( 1986), published by allured Publishing Corporation; and McCutcheon's, Functional Materials,
`
`North American Edition ( 1992); both of which are incorporated by reference herein in their entirety.
`
`Preferred amphoteric or zwinerionic surfactants are
`
`the betaines. sultaines, and
`
`hydroxysultaines. Examples of betaines include the higher alkyl betaines, such as coco dimethyl
`
`carboxymethyl betaine, Iaury! dimethyl carboxymethyl betaine, Iaury! dimethyl alphacarboxyethyl
`
`betaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine (available as Lonzaine 16SP
`
`from Lonza Corp.),
`
`Iaury! bis-(2-hydroxyethyl) carboxymethyl betaine,
`
`stearyl bis-(2-
`
`hydroxypropyl) carboxymethyl betaine, oleyl d-methyl gamma-carboxypropyl betaine, Iaury! bis-(2-
`
`20
`
`hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl sulfopropyl betaine, stearyl dimethyl
`
`sulfopropyl betaine, stearyl betaine, Iaury! dimethyl sulfoethyl betaine, Iaury! bis-(2-hydroxyethyl)
`
`sulfopropyl betaine, and amidobetaines and amidosulfobetaines (wherein the RCONH(CH
`
`)
`3
`2
`is attached to the nitrogen atom of the betaine), oleyl betaine (available as amphoteric Velvetex
`
`radical
`
`OLB-50 from Henkel), and cocamidopropyl betaine (available as Velvetex BK-35 and BA-35 fr'om
`
`25
`
`Henkel).
`
`Examples of sultaines and hydroxysultaines include materials such as cocarnidopropyl
`
`hydroxysultaine (available as Mirataine CBS from Rhone Poulenc).
`
`Preferred for use herein are amphoteric surfactants having the following structure:
`
`0
`R2
`+I
`II
`R1-(C-NH-(CH2) )-N-R4-X
`m n
`1
`R3
`
`30
`
`wherein R I is unsubstituted, saturated or unsaturated, straight or branched chain alkyl having from
`
`about 9 to about 22 carbon atoms. Preferred R 1 has from about I I to about 18 carbon atoms; more
`
`preferably from about 12 to about 18 carbon atoms; more preferably still from about 14 to about 18
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`carbon atoms; m is an integer from I to about 3, more preferably from about 2 to about 3, and more
`
`preferably about 3; n is either 0 or I, preferably I; R2 and R3 are independently selected from the
`
`group consisting of alkyl having from I to about 3 carbon atoms, unsubstituted or mono-substituted
`
`with hydroxy, preferred R2 and R3 are CH3; X is selected from the group consisting of C02, S03
`
`5
`
`and S04; R4 is selected from the group consisting of saturated or unsaturated, straight or branched
`chain alkyl, unsubstituted or monosubstituted with hydroxy, having from 1 to about 5 carbon atoms.
`When X is C02, R4 preferably has I or 3 carbon atoms, more preferably 1 carbon atom. When X is
`S03 or so4, R4 preferably has from about 2 to about 4 carbon atoms, more preferably 3 carbon
`atoms.
`
`10
`
`Examples of amphoteric surfactants of the present invention include the following
`
`compounds:
`
`Cetyl dimethyl betaine (this material also has the CTFA designation cetyl betaine)
`
`15
`
`Cocamidopropylbetaine
`
`20
`
`wherein R has from about 9 to about 13 carbon atoms
`
`Cocamidopropyl hydroxy sultaine
`
`OH
`CH3
`0
`_
`I
`+I
`II
`R-C-NH-(CH2)J-N-CH2-CH-CH2-S03
`I
`CH3
`
`wherein R has from about 9 to about 13 carbon atoms,
`
`25
`
`Stearyl dimethyl betaine, which is also known as stearyl betaine,
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`and, behenyl dimethyl betaine, which is also known as behenyl betaine,
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`9
`
`Preferred amphoteric surfactants of the present invention include cetyl dimethyl betaine,
`
`cocamidopropyl betaine, stearyl dimethyl betaine, and cocamidopropyl hydroxy sultaine. Still more
`
`preferred are cetyl dimethyl betaine, stearyl dimethyl betaine, and cocamidopropyl betaine. Most
`
`preferred is cocamidopropyl betaine.
`
`Examples of other useful
`
`amphoteric
`
`surfactants are
`
`alkyliminoacetates,
`
`and
`
`5
`
`10
`
`iminodialkanoates
`
`and
`
`aminoalkanoates
`
`of
`
`the
`
`formulas RN[(CH
`
`)m C0
`
`M]
`
`and
`
`2
`2
`2
`)m C0 2M wherein m is from I to 4, R is a Cg-C22 alkyl or alkenyl, and M is H, alkali
`
`RNH(CH
`
`2
`metal, alkaline earth metal ammonium, or alkanolammonium. Also included are imidazolinium and
`
`ammonium derivatives. Other examples of useful amphoterics include phosphates, such as
`
`cocamidopropyl PG-dimonium chloride phosphate (commercially available as Monaquat PTC, from
`
`Mona Corp.).
`
`15
`
`Amino Acid Derivative Surfactants
`
`20
`
`25
`
`30
`
`The stabilizing surfactant of the compositions of the present invention can comprise an
`
`amino acid derivative surfactant. By amino acid derivative, as defined herein, is meant a
`
`surfactant that has the basic chemical structure of an amino acid compound, i.e. that contains a
`
`structural component of one of the naturally-occurring amino acids.
`
`Common amino
`
`acids
`
`from which such surfactants are derived include glycine, N-methyl glycine which is also known
`
`as sarcosine, glutamic acid, arginine, alanine, phenylalanine, and the like. Other anionic
`
`surfactants suitable for use in the shampoo compositions are those that are derived from amino
`
`acids. Also useful herein are salts of these amino acid derived surfactants. Nonlimiting
`
`examples of such surfactants include N-acyl-L-glutamate; N-acyl-N-methyl-13-alanate; N-
`
`acylsarcosinate; N-alkylamino-propionates and N-alkyliminodipropionates specific examples of
`
`which
`
`include N-lauryl-beta-amino propionic acid or salts
`
`thereof, and N-lauryl-beta(cid:173)
`
`-imino-dipropionic acid; sodium Iaury! sarcosinate, sodium lauroyl sarcosinate, Iaury! sarcosine,
`
`cocoyl sarcosine, and mixtures thereof.
`
`Cationic Surfactants
`
`The stabilizing surfactant of the present invention can comprise a cationic surfactant.
`
`Cationic surfactants typically contain quaternary nitrogen moieties. Cationic surfactants among
`
`those useful herein are disclosed in the following documents, all of which are incorporated by
`
`reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,
`
`(North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and
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`
`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.
`
`5
`
`1983.
`
`formula:
`
`Among the cationic surfactant materials useful herein are those corresponding to the general
`
`+
`
`wherein R 1, R2, R3. and R4 are independently selected from an aliphatic group of from I to about
`
`22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or
`
`10
`
`alkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those
`
`selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate,
`
`sulfate, and alkylsulfate radicals. The aliphatic groups can contain, in addition to carbon and
`
`hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic
`
`groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. Preferred is when
`
`15
`
`R 1, R2, R3, and R4 are independently selected from Cl to about C22 alkyl. Especially preferred are
`
`cationic materials containing two long alkyl chains and two short alkyl chains or those containing
`
`one long alkyl chain and three short alkyl chains. The long alkyl chains in the compounds described
`
`in the previous sentence have from about 12 to about 22 carbon atoms, preferably from about 16 to
`
`about 22 carbon atoms, and the short alkyl chains in the compounds described in the previous
`
`20
`
`sentence have from I to about 3 carbon atoms, preferably from I to about 2 carbon atoms.
`
`Also preferred are cationic materials in which at least one of the substituents is seleded
`
`from hydroxyalkyl, preferably hydroxyethyl or hydroxy propyl, or polyoxyalkylene, preferably
`
`polyoxyethylene or polyoxypropylene wherein the total degree of ethoxylation or propoxylation in
`
`the molecule is from about 5 to about 20. Nonlimiting examples of commercially available materials
`
`25
`
`include Variquat Kl215 and 638 from Witco Chemical, Dehyquat SP from Henkel, and Atlas G265
`
`from ICI Americas.
`
`Other cationic materials include the materials having the following CTF A designations:
`
`polyquatemium-8, polyquatemium-24, polyquatemium-26, polyquatemium-27, polyquatemium-30,
`
`polyquatemium-33, polyquatemium-43, polyquatemium-52, polyquatemium-53, polyquatemium-
`
`30
`
`56,
`
`polyquatemium-60,
`
`polyquatemium-62,
`
`polyquatemium-70,
`
`polyquatemium-72,
`
`polyquatemium-75, polyquatemium-77, polyquatemium-78, polyquatemium-79, polyquatemium-
`
`80, polyquatemium-81, polyquatemium-82, polyquatemium-83, polyquatemium-84, and mixtures
`
`thereof.
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`Salts of primary. secondary and tertiary fatty amines are also suitable cationic surfactant
`
`materials. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms,
`
`and can be substituted or unsubstituted. Such amines, useful herein. include stearamido propyl
`
`dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine. dimethyl soyamine, soyamine,
`
`5
`
`myristyl amine, tridecyl amine. ethyl stearylamine, N-tallowpropane diamine. ethoxylated (with 5
`
`moles of ethylene oxide) stearylamine. dihydroxy ethyl stearylamine. and arachidylbehenylamine.
`
`Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate, and alkyl sulfate
`
`salts. Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N(cid:173)
`
`tallowpropane d