PCT
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`wo 97/26854
`
`WORLD INTELLECTUAL PROPERTY ORGANIZATION
`International Bureau
`
`(51) International Patent Classification 6 :
`A61K 7/06~ 7/50
`
`Al
`
`(11) International Publication Number:
`
`(43) International Publication Date:
`
`31 July 1997 (31.07.97)
`
`(21) International Application Number:
`
`PCT/US97/00081
`
`(22) International Filing Date:
`
`6 January 1997 (06.01.97)
`
`(30) Priority Data:
`08/593,727
`
`27 January 1996 (27.01.96)
`
`us
`
`THE PROCTER & GAMBLE COMPANY
`(71) Applicant:
`[US/US]; One Procter & Gamble Plaza, Cincinnati, OH
`45202 (US).
`
`(72) Inventors: KALLA, Karen, Kay; 653 Rushton Road, Cincin(cid:173)
`nati, OH 45226 (US). HUNT, Julie, Marie; 6187 Shawna
`Court, Middletown, OH 45044 (US).
`
`(74) Agents: REED, T., David et al.; The Procter & Gamble
`Company, 5299 Spring Grove Avenue, Cincinnati, OH
`45217 (US).
`
`(81) Designated States: AL, AM, AT, AU, AZ, BA, BB, BG, BR,
`BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE,
`HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS,
`LT. LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL,
`PT, RO, RU, SD, SE, SG, SI, SK, TJ, TM, TR, TT, UA,
`UG, UZ, VN, ARIPO patent (KE, LS, MW, SD, SZ, UG),
`Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European patent (AT, BE, CH, DE, DK, ES, FI, FR, GB,
`GR, IE, IT, LU, MC, NL, PT, SE), OAPI patent (BF, BJ,
`CF, CG, CI, CM, GA, GN, ML, MR. NE, SN, TD, TG).
`
`Published
`With international search report.
`Before the expiration of the time limit for amending the
`claims and to be republished in the event of the receipt of
`amendments.
`
`{54) Title: SHAMPOO COMPOSITIONS WITH IMPROVED DEPOSITION OF ANTIMICROBIAL AGENTS
`
`(57) Abstract
`
`Disclosed are antidandruff shampoo compositions with improved deposition of antimicrobial agents, which compositions comprise
`(a) from about 7 % to about 30 % by weight of a detersive surfactant selected from the group consisting of anionic surfactant, amphoteric
`surfactant, zwitterionic surfactant, and combinations thereof; (b) from about 0.1 o/o to about lO % by weight of an antimicrobial agent; (c)
`from about 0.5 % to about to o/o by weight of a suspending agent; (d) from about 0.01 % to about 1.0 % by weight of a cationic guar
`polymer having a charge density of from about 0.01 meq/g to about 3 meq/gm; and (e) from about 40 %to about 92 o/o by weight of water;
`wherein at least about 50 % by weight of the cationic guar polymer is in coacervate form, said coacervate comprising detersive surfactant
`and cationic guar polymer.
`
`1
`
`

`

`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the Per on the front pages of pamphlets publishing international
`applications under the Per.
`
`AM
`AT
`AU
`BB
`BE
`BF
`BG
`BJ
`BR
`BY
`CA
`CF
`CG
`CH
`CI
`CM
`CN
`cs
`cz
`DE
`DK
`EE
`ES
`Fl
`FR
`GA
`
`Annenia
`Austria
`Australia
`Barbado&
`Belgium
`Burkina Faso
`Bulgaria
`Benin
`Braz.il
`Belarus
`Canada
`Central African Republic
`Congo
`Switzerland
`COte d'lvoire
`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
`Lu.ernbourg
`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
`Me•ico
`Niger
`Netherlands
`Norway
`New Zealand
`Poland
`Ponugal
`Romania
`Russian Federation
`Sudan
`Sweden
`Singapore
`Slovenia
`Slovakia
`Senegal
`Swaziland
`Chad
`Togo
`Tajikistan
`Trinidad and Tobago
`Ulcraine
`Uganda
`United States of America
`Uzbekistan
`VietNam
`
`2
`
`

`

`W097/26854
`
`PCT/US97/00081
`
`SHAMPOO COMPOSITIONS WITH IMPROVED
`DEPOSITION OF ANTIMICROBIAL AGENTS
`
`FIELD OF THE INVENTION
`invention
`relates
`to
`shampoo compositions contammg
`The present
`In particular, the present
`antimicrobial agents which provide antidandruff activity.
`invention
`relates
`to shampoo compositions containing antimicrobial agents,
`preferably particulate antimicrobial agents, in combination with a cationic guar
`polymer as an antimicrobial agent deposition aid.
`
`BACKGROUND OF THE INVENTION
`Various anti-dandruff shampoo compositions are commercially available or
`otherwise known in the shampoo art. These compositions typically comprise
`particulate, crystalline antimicrobial agents dispersed and suspended throughout the
`composition. Antimicrobial agents used for this purpose include sulfur, selenium
`sulfide and heavy metal salts of pyridinethione. During the shampooing process,
`these antimicrobial agents deposit on the scalp to provide anti-dandruff activity.
`Many anti-dandruff shampoos, however, do no provide
`sufficient
`antimicrobial agent deposition during the shampooing process. Without such
`deposition, the antimicrobial agents simply rinse away during shampooing and
`In addition, the detersive
`therefore provide little or no anti-dandruff activity.
`surfactants in these shampoo compositions which are designed to remove oil, grease,
`dirt, and particulate matter will also carry away particulate antimicrobial agents
`during rinsing, thus further decreasing deposition and anti-dandruff activity.
`Deposition of particulate antimicrobial agents is especially difficult in anti(cid:173)
`dandruff shampoo compositions containing crystalline suspending agents. These
`suspending agents help disperse and suspend particulate antimicrobial agents in the
`shampoo composition. These suspending agents, however, adversely affect lathering
`performance. It has therefore become conventional practice to enhance the lathering
`performance of these shampoos by increasing detersive surfactant concentrations or
`by adding foam boosters, both of which further decrease deposition of particulate
`antimicrobial agents from the shampoo compositions.
`It has now been found that select cationic deposition polymers are especially
`effective in providing enhanced deposition of antimicrobial agents, especially
`particulate antimicrobial agents, from a shampoo composition. The select polymers
`
`3
`
`

`

`wo 97/26854
`
`PCTIUS97 /00081
`
`2
`
`are cationic derivatives of guar gum which have been found to be most effective
`when used in combination with crystalline suspending agents and high levels of
`anionic, amphoteric or zwitterionic surfactant
`in an anti-dandruff shampoo
`composition.
`It is therefore an object of the present invention to provide an anti-dandruff
`shampoo composition with improved deposition of antimicrobial agents, especially
`particulate antimicrobial agents, and further to provide for such improved deposition
`in the presence of crystalline suspending agents and high concentrations of detersive
`surfactant. It is yet another object of the present invention to provide anti-dandruff
`shampoo compositions with excellent
`anti-dandruff activity
`and
`reduced
`concentration of antimicrobial agents.
`
`SUMMARY OF THE INVENTION
`The present invention is directed to high lathering, anti-dandruff shampoo
`compositions with improved deposition of antimicrobial agents, which compositions
`comprise (a) from about 7% to about 30% by weight of a detersive surfactant
`selected from the group consisting of anionic surfactant, amphoteric surfactant,
`zwitterionic surfactant, and combinations thereof; (b) from about 0.1% to about 10%
`by weight of an antimicrobial agent; (c) from about 0.5% to about 10% by weight of
`a suspending agent; (d) from about 0.01% to about 1.0% by weight of a cationic
`guar polymer having a charge density offrom about 0.1 to about 3meq/gm, and (e)
`from about 40% to about 92% by weight of water; wherein at least about 50% by
`weight of the cationic guar polymer is in coacervate form, said coacervate comprising
`detersive surfactant and cationic guar polymer.
`
`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.
`All percentages, parts and ratios are based upon 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.
`
`4
`
`

`

`W097/26854
`
`PCTIUS97/00081
`
`3
`
`Detersive Surfactant
`The shampoo compositions of the present invention compnse a detersive
`surfactant selected from the group consisting of anionic surfactants, amphoteric
`surfactants, zwitterionic surfactants, and combinations thereof The shampoo
`compositions preferably comprise an anionic surfactant. The detersive surfactant
`provides the shampoo compositions with cleaning performance.
`
`Anionic surfactant
`The detersive surfactant component of the shampoo compositions Js
`preferably an anionic surfactant. Concentrations of anionic surfactant can range from
`about 7% to about 30%, preferably from about I 0% to about 25%, more preferably
`from about 12% to about 22%, by weight of the shampoo compositions.
`Anionic surfactants for use in the shampoo compositions include 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 30
`carbon atoms, x is an integer from 1 to 10, and M is a hydrogen, alkali metal (e.g.,
`lithium, sodium, potassium), alkali earth metal (e.g., beryllium, magnesium, calcium,
`strontium, barium) ammonium or substituted ammonium.
`Preferably, R has from about 10 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 or tallow, or
`can be synthetic. Laury! alcohol and straight chain alcohols derived from coconut oil
`are preferred. Such alcohols are reacted with between about 0 and about 10, 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 may be used in the shampoo·
`compositions of the present invention 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 combination of individual compounds, the combination having an
`average alkyl chain length of from about 10 to about 16 carbon atoms and an average
`degree of ethoxylation of from about l to about 4 moles of ethylene oxide.
`Other suitable anionic surfactants are the water-soluble salts of organic,
`sulfuric acid reaction products of the general formula [ R 1-S03 -M J where R 1 is
`
`5
`
`

`

`wo 97/26854
`
`PCT/US97/00081
`
`4
`
`selected from the group consisting of a straight or branched chain, saturated aliphatic
`hydrocarbon radicals having from about 8 to about 24, preferably about 10 to about
`18, carbon atoms; and M hydrogen, alkali metal (e.g., lithium, sodium, potassium),
`alkali earth metal
`(e.g., beryllium, magnesium, calcium, strontium, barium)
`ammonium or substituted ammonium. Examples of such surfactants are the salts of
`an organic sulfuric acid reaction product of a 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., S03,
`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 from coconut oil; sodium or potassium salts of
`fatty acid amides of methyl tauride in which the fatty acids, for example, are derived
`from coconut 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, which descriptions
`are incorporated herein by reference.
`Other anionic surfactants suitable for use in the shampoo compositions are
`the succinnates, examples of which include disodium N-octadecylsulfosucciMate;
`lauryl sulfosuccinate; diammonium Iaury) sulfosuccinate; tetrasodium
`disodium
`N-( 1 ,2-dicarboxyethyl)-N-octadecylsulfosucciMate;
`diamyl
`ester of
`sodium
`sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of
`sodium sulfosuccinic acid.
`Other suitable anionic surfactants include olefin sulfonates having about 10 to
`about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean
`compounds which can be produced by the sulfonation of alpha-olefins 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 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 olefin sulfonates are derived from
`mono-olefins having from about 12 to about 24 carbon atoms, preferably from about
`14 to about 16 carbon atoms. Straight chain olefins are preferred.
`sulfonates and a proportion of
`In addition
`to
`the
`true alkene
`hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other
`
`6
`
`

`

`wo 97/26854
`
`PCT/US97/0008l
`
`5
`
`materials, such as alkene disulfonates depending upon the reaction conditions,
`proportion of reactants, the nature of the starting olefins and impurities in the olefin
`stock and side reactions during the sulfonation process.
`A specific alpha-olefin sulfonate mixture of the above type is described more
`fully in the U.S. Patent 3,332,880, which description is incorporated herein by
`reference.
`the shampoo
`in
`Another class of anionic surfactants suitable for use
`compositions are the beta-alkyloxy alkane sulfonates. These compounds can be
`represented by the formula:
`
`OR2 H
`
`R1-b-b-sO;,M
`I
`I
`H H
`
`where R 1 is a straight chain alkyl group having from about 6 to about 20 carbon
`atoms, R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon
`atoms, and M hydrogen, alkali metal (e.g., lithium, sodium, potassium), alkali earth
`metal (e.g., beryllium, magnesium, calcium, strontium, barium) ammonium or
`substituted ammonium.
`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.
`Preferred anionic surfactants for use in the shampoo compositions include
`ammonium Iaury! sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, tri(cid:173)
`ethylamine laureth sulfate, triethanolamine Iaury! sulfate, triethanolamine laureth
`Iaury)
`sulfate, monoethanolamine
`laureth sulfate,
`sulfate, monoethanolamine
`diethanolamine Iaury! 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 sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl
`sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,
`potassium Iaury! sulfate, monoethanolamine cocoyl sulfate, monoethanolamine Iaury)
`sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate and
`combinations thereof
`
`Amphoteric and zwitterionic surfactants
`The detersive surfactant component of the shampoo compositions may
`comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such
`
`7
`
`

`

`W097/26854
`
`PCTIUS97/00081
`
`6
`
`surfactants can range from about 0.5% to about 20%, preferably from about I% to
`about I 0%, by weight of the shampoo compositions
`Amphoteric surfactants for use in the shampoo compositions include the
`derivatives of aliphatic secondary and tertiary arnines in which the aliphatic radical is
`straight or branched and one of the aliphatic substituents contains from about 8 to
`about 18 carbon atoms and one contains an anionic water solubilizing group, e.g.,
`carboxy, sulfonate, sulfate, phosphate, or phosphonate.
`Zwitterionic surfactants for use in the shampoo compositions include the
`derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium
`compounds, in which the aliphatic radicals are straight or branched, and wherein one
`of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one
`contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phos(cid:173)
`phonate. These compounds can be represented by the formula:
`(R3Jx
`I.
`2
`R -Y -CH:z-R4-Z
`
`where R 2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to
`about 18 carbon atoms, from 0 to about I 0 ethylene oxide moieties and from 0 to
`about I glyceryl moiety; Y is selected from the group consisting of nitrogen,
`phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group
`containing about I to about 3 carbon atoms; X is I when Y is a sulfur atom, and 2
`when Y is a nitrogen or phosphorus atom; R 4 is an alkylene or hydroxyalkylene of
`from about I to about 4 carbon atoms and Z is a radical selected from the group
`consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
`Examples of amphoteric and zwitterionic surfactants also include sultaines
`and amidosultaines. Sultaines and amidosultaines can be used as foam enhancing
`surfactants that are mild to the eye in partial replacement of anionic surfactants.
`Sultaines,
`including
`amidosultaines,
`include
`for
`example,
`cocodimethylpropylsultaine,
`stearyldimethylpropylsultaine,
`lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the arnidosultaines
`such as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine,
`laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like.
`Preferred are
`amidohydroxysultaines such as the C 12-C 18 hydrocarbyl ami do propyl hydroxy(cid:173)
`sultaines, especially C 12-C 14 hydrocarbyl amide propyl hydroxysultaines, e.g.,
`laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other
`sultaines are described in U.S. Patent 3,950,417, which descriptions are incor(cid:173)
`porated herein by reference.
`
`8
`
`

`

`wo 97/26854
`
`PCTIUS97/00081
`
`7
`
`surfactants are the aminoalkanoates of the
`the
`formula
`iminodialkanoates of
`the
`
`Other suitable amphoteric
`formula
`R-NH(CH2)nCOOM,
`R-N[(CH2)mCOOM]2
`and mixtures thereof; wherein n and m are integers from 1 to 4, R is Cg - C22
`alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium
`or alkanolammonium.
`Examples of suitable aminoalkanoates include n-alkylamino-propionates
`and n-alkyliminodipropionates, specific examples of which include N-lauryl(cid:173)
`-beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic
`acid or salts thereof, and mixtures thereof
`Other suitable amphoteric surfactants include those represented by the
`formula:
`
`where R 1 is alkyl or alkenyl having from about 8 to about 22 carbon atoms,
`is hydrogen or
`preferably from about 12 to about 16 carbon atoms; R2
`CH2C02M; R3 is CH2CH20H or CH2CH20CH2CH2COOM; R4 is hydrogen,
`CH2CH20H, or CH2CH20CH2CH2COOM; Z is C02M or CH2C02M; n is the
`integer 2 or 3, preferably 2; M is a hydrogen, alkali metal (e.g., lithium, sodium,
`potassium), alkali earth metal (e.g., beryllium, magnesium, calcium, strontium,
`barium) ammonium or substituted ammonium.
`This type of surfactant is sometimes classified as an imidazoline-type amphoteric
`surfactant, although it does not necessarily have to be derived, directly or
`indirectly, through an imidazoline intermediate.
`Suitable materials of this type are marketed under the trade name
`MIRANOL and are understood to comprise a complex mixture of species, and
`can exist in protonated and non-protonated species depending upon pH with
`respect to species that can have a hydrogen at R 2. All such variations and species
`are meant to be encompassed by the above formula.
`Examples of surfactants of the above formula are monocarboxylates and
`of
`these
`materials
`include
`dicarboxylates.
`Examples
`cocoamphocarboxypropionic
`acid,
`cocoamphocarboxypropionate,
`cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and
`cocoamphoacetate.
`Commercial amphoteric surfactants include those sold under the trade
`names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P.,
`
`9
`
`

`

`wo 97/26854
`
`PCT/US97 /00081
`
`8
`
`MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC
`2Cffi (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC
`CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C
`(Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals)
`in
`the shampoo
`Betaine surfactants (zwitterionic) suitable for use
`compositions are those represented by the formula:
`
`0
`II
`
`R4
`I
`
`C-N-(C~
`
`Rs
`
`n
`
`where R 1 is COOM or CH(OH)CH2S03M;
`R2 is lower alkyl or hydroxyalkyl;
`R3 is lower alkyl or hydroxyalkyl;
`R4 is a member selected from the group consisting ofhydrogen and lower alkyl;
`R 5 is higher alkyl or alkenyl;
`Y is lower alkyl, preferably methyl;
`m is an integer from 2 to 7, preferably from 2 to 3;
`n is the integer 1 or 0; and
`M is a hydrogen, alkali metal, alkali earth metal, ammoruum or substituted
`ammomum.
`As used in this context, the term "lower alkyl" or "hydroxyalkyl" means straight
`or branch chained, saturated, aliphatic hydrocarbon radicals and substituted
`hydrocarbon radicals having from one to about three carbon atoms such as, for
`example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the
`like. The term "higher alkyl or alkenyl" means straight or branch chained satu(cid:173)
`rated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic
`hydrocarbon radicals having from about eight to about 20 carbon atoms such as,
`for example, lauryl, cetyl, stearyl, oleyl, and the like. It should be understood that
`the term "higher alkyl or alkenyl" includes mixtures of radicals which may contain
`one or more intermediate linkages such as ether or polyether linkages or
`non-functional substitutents such as hydroxyl or halogen radicals wherein the
`radical remains ofhydrophobic character.
`Examples of suitable surfactant betaines of the above formula wherein n is
`include
`the alkylbetaines such as cocodimethylcarboxymethylbetaine,
`zero
`lauryldimethylcarboxymethylbetaine, Iaury! dimethyl-alpha-carboxyethylbetaine,
`cetyldimethylcarboxymethylbetaine,
`lauryl-bis-(2-hydroxyethyl)carboxymethyl-
`
`10
`
`

`

`W097/268S4
`
`PCTIUS97/00081
`
`9
`
`oleyl(cid:173)
`stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine,
`betaine,
`dimethyl-gamma-carboxypropylbetaine,
`Iauryl-bis-(2-hydroxypropyl)-
`alpha-carboxyethylbetaine,
`etc.
`Suitable
`sulfobetaines
`include
`cocodimethylsulfopropyl-
`stearyldimethylsulfopropylbetaine,
`betaine,
`lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine.
`Suitable amido betaines and amidosulfo betaines for use in the shampoo
`the
`amidocarboxybetaines,
`such
`as
`compositions
`includ~
`cocoamidodimethylcarboxymethylbetaine,
`laurylamidodi-
`methylcarboxymethylbetaine,
`cetylarnidodimethylcarboxymethylbetaine,
`laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine,
`cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. Amido sulfobetaines
`include
`cocoamidodimethylsulfopropylbetaine,
`and
`Iaury!-
`stearylamidodimethylsulfopropylbetaine,
`amido-bis-(2-hydroxyethyl)-sulfopropylbetaine.
`
`and
`
`Highly solubilizing surfactants
`The shampoo compositions of the present invention are preferably free of
`highly solubilizing surfactants such as N-acyl amino acid surfactants. As used in this
`context, "substantially free" means that the shampoo compositions preferably contain
`no more than about 1%, more preferably no more than about 0.5%, even more
`preferably no more than about 0.25%, most preferably essentially zero percent, of
`highly solubilizing surfactants by weight of the shampoo compositions.
`Less preferably, the shampoo compositions may comprise N-acyl amino acid
`surfactants as a secondary optional surfactant or as the detersive surfactant
`component ofthe shampoo compositions.
`N-acyl amino acid surfactants are well known surfactants for use in a variety
`of products. A description of these surfactants and their synthesis can be found, for
`example, in Anionic Suractants. Part II. Surfactant Science Series. Vol. III, edited by
`Warner M. Linfield, Marcel Dekker, Inc. (New York and Basel), pp 581-617 (1976),
`which description is incorporated herein by reference.
`Suitable N-acyl amino acid surfactants for use in the shampoo compositions
`herein include N-acyl hydrocarbyl acids and salts thereof, which can be represented
`by the formula:
`
`11
`
`

`

`wo 97/26854
`
`PCT/US97/0008l
`
`10
`
`'t 1-
`
`0 R2
`ll
`R1-C-N R3j COOM
`n
`wherein R I is a alkyl or alkenyl radical having from about 8 to about 24 carbon
`atoms, preferably from about 12 to about 18 carbons atoms; R 2 is hydrogen, alkyl
`having from about I to about 4 carbon atoms, phenyl, or CH2COOM, preferably
`alkyl having from about 1 to about 4 carbon atoms, more preferably alkyl having
`from about 1 to about 2 carbon atoms; R3 is (CR4)2 or alkoxy having from about 1
`or about 2 carbon atoms, wherein each R4 is independently hydrogen or alkyl having
`from about 1 to about 6 carbon atoms or alkylester thereof; n is an integer from 1 to
`l or 2; and M a hydrogen, alkali metal (e.g., lithium, sodium,
`4, preferably
`potassium), alkali earth metal (e.g., beryllium, magnesium, calcium, strontium,
`barium) ammonium or substituted ammonium. Especially preferred are N-acyl
`sarcosinates and acids thereof, examples of which include lauroyl sarcosinate,
`myristoyl sarcosinate, cocoyl sarcosinate, and oleoyl sarcosinate, preferably as
`sodium or potassium salts.
`It has been found
`the highly solubilizing surfactants described
`that
`hereinabove, when used in combination with the guar cationic polymers described
`hereinafter, are less effective in providing improved deposition of the antimicrobial
`agent of the shampoo compositions herein. It has also been found that, by increasing
`the cationic charge density of the guar cationic polymer in the presence of these
`highly solubilizing surfactant, the less effective antimicrobial agent deposition can be
`improved substantially. In the presence of the highly solubilizing surfactants in the
`shampoo compositions herein, therefore, the cationic guar polymer should have a
`cationic charge density offrom about 0.9meq/g to about 4meq/g, preferably between
`about 1.0 and 3meq/g.
`
`Antimicrobial Agent
`The shampoo compositions of the present invention comprise a safe and
`effective amount of an antimicrobial agent. The antimicrobial agent provides the
`shampoo compositions with antimicrobial activity. The antimicrobial agent is
`preferably a crystalline particulate that is insoluble in, and dispersed throughout, the
`Effective concentrations of such antimicrobial agents
`shampoo compositions.
`generally range from about 0.1% to about 5%, more preferably from about 0.3% to
`about 5%, by weight of the shampoo compositions. Suitable antimicrobial agents
`include sulfur, octopirox, selenium sulfide, and pyridinethione salts.
`Selenium sulfide is a preferred particulate antimicrobial agent for use in the
`shampoo compositions, effective concentrations of which range from about 0.1% to
`
`12
`
`

`

`wo 97/26854
`
`PCT/US97/00081
`
`11
`
`about 5.0%, preferably from about 0.3% to about 2.5%, more preferably from about
`0.5% to about 1.5%, by weight of the shampoo compositions. Selenium sulfide is
`generally regarded as a compound having one mole of selenium and two moles of
`sulfur, although it may also be a cyclic structure, SexSy, wherein x + y = 8. Average
`panicle diameters for the selenium sulfide (selenium disulfide) are less than l5um,
`preferably less than I 0 urn, as measured by forward laser light scattering device, e.g.,
`Malvern 3600 instrument. Selenium sulfide compounds are well known in the
`shampoo an, and are described, for example in U.S. Patent 2,694,668; U.S. Patent
`3, 152,046; U.S. Patent 4,089,945; and U.S. Patent 4,885, 107, which descriptions are
`incorporated herein by reference.
`l-hydroxy-2-pyridinethione
`Pyridinethione antimicrobial agents, especially
`salts, are highly preferred particulate antimicrobial agents for use in the shampoo
`compositions, concentrations of which range from about 0.1% to about 3%,
`preferably about 0.3% to about 2%, by weight of the shampoo compositions.
`Preferred pyridinethione salts are those formed from heavy metals such as zinc, tin,
`cadmium, magnesium, aluminum and zirconium. Zinc salts are most preferred,
`especially the zinc salt of l-hydroxy-2-pyridinethione (zinc pyridinethione, ZPT).
`Other cations such as sodium may also be suitable. Particularly preferred are l(cid:173)
`hydroxy-2-pyridinethione salts in platelet particle form, wherein the particles have an
`average size of up to about 20 microns, preferably up to about 8 microns, most
`preferably up to about 5 microns.
`Pyridinethione antimicrobial agents are well known in the shampoo an, and
`are described, for example, in U.S. Patent 2,809,971; U.S. Patent 3,236,733; U.S.
`Patent 3,753,196; U.S. Patent 3,761,418; U.S. Patent 4,345,080; U.S. Patent
`4,323,683; U.S. Patent 4,379, 753; and U.S. Patent 4,470,982, which descriptions are
`incorporated herein by reference.
`Sulfur may also be used as the particulate antimicrobial agent in the shampoo
`compositions herein. Effective concentrations of the particulate sulfur are generally
`from about 1% to about 5%, more preferably from about 2% to about 5%, by weight
`of the compositions.
`the
`Octopirox and related salts and derivatives may also be used as
`antimicrobial agent in the shampoo compositions. Such antimicrobial agents are
`soluble in the shampoo composition and, therefore, do not disperse throughout the
`composition as crystalline particulates as do the other antimicrobial agents described
`hereinbefore.
`
`13
`
`

`

`wo 97/26854
`
`PCTIUS97/00081
`
`12
`
`Suspending or Thickening Agent
`The shampoo compositions ofthe present invention comprise a suspending or
`thickening agent to help maintain dispersion of particulate antimicrobial agents
`throughout the composition. Any known suspending or thickening agent may be
`used in the shampoo compositions, provided that it is physically and chemically
`compatible with the essential components of the shampoo composition described
`herein, or does not otherwise unduly impair product stability, aesthetics or
`performance.
`Crystalline suspending agents are preferred for suspending the particulate
`antimicrobial agent in the shampoo compositions. The selected suspending agent, at
`the selected concentration, should help maintain the suspension for at a period of at
`least one month, preferably at least three months, more preferably at least about
`twenty-four months, at ambient temperatures. In general, effective concentrations of
`the crystalline suspending agent range from about 0. 5% to about 1 0%, preferably
`from about 0.5% to about 5%, more preferably about 1% to about 4%, most
`preferably about 1% to about 3%, by weight of the shampoo composition.
`In general, concentrations of the crystalline suspending agent should be
`minimized to achieve only the desired property.
`Preferred crystalline suspending agents are acyl derivatives and amine oxides,
`especially