PCT
`
`worm: INTELLECTUAL PROPERTY ORGANIZATION
`International Bureau
`
`
`
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(51) International Patent Classification 6:
`
`(11) International Publication Number:
`
`W0 9736854
`
`AGIK 7’06, 7,50
`
`A1
`
`(43) International Publication Date:
`
`31 July 1997 (31.07.97)
`
`(21) International Application Number:
`
`PCTtU597i00081
`
`(22) International Filing Date:
`
`6 January 1997 (06.01.97)
`
`(30} Priority Data:
`08593.72?
`
`27 January 1996 (27.01.96)
`
`US
`
`THE PROCTER & GAMBLE COMPANY
`(71) Applicant:
`[USt‘US]; One Procter & Gamble Plaza. Cincinnati, OH
`45202 (US).
`
`(72) Inventors: KALLA. Karen. Kay; 653 Rushton Road. Cincin-
`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,
`l-IU. IL. IS. JP. ICE. KG. KP. KR. KZ. LC. LK. LR. LS,
`LT. LU. LV, MD. MG. MK. MN. MW. MX, NO. NZ. PI...
`PT. RO. RU. SD. SE. 30. SI. SK. TJ. TM. TR. “IT. UA.
`UG. UZ. VN. ARIPO patent (KE. LS, MW. SD. 82. U0).
`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 parent (BF, B].
`CF. CG. CI. CM. GA. GN. ML. MR. NE. SN. TD. 'I‘G).
`
`
`
`Published
`With internationai 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 antidandmfi' shampoo comp05itions with improved deposition of antimicrobial agents. which compositions comprise
`(a) born about 7 9b to about 30 it: 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.! 9b to about 10 % by weight of an antimicrobial agent; (c)
`from about 0.5 % to about 10 it: by weight of a suspending agent; (cl) from about 0.01 % to about 1.0 95: by weight of a cationic guar
`polymer having a charge density of from about 0.01 meqig to about 3 rneqirgm; and (e) from about 40 % to about 92 ‘i’o by weight of water.
`wherein at least about 50 9’0 by weight of the cationic guar polymer is in coacervate form. said coaeervate comprising detersive surfactant
`and cationic guar polymer.
`
`000001
`000001
`
`
`UNILEVER EXHIBIT 1060
`
`
`
`
`
`
`
`
`
` %UN T.*'.V*'.R *ZX-I i 1060
`
`
`_.
`
`I
`UNILEVER VS. PROCTOR & GAMBLE
`
` UN T.*'.V*'.R VS. BKOCIOK & GAM%T.
`
`
`
`
`IPR2013-00509
`
`
`-2PR2013—00509
`
`

`

`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.
`
`Viet Nam
`
`Malawi
`Me: 300
`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
`
`AM
`NI"
`
`Armenia
`Austria
`Auslnlia
`Barbados
`Belgium
`Barkina Faao
`Bulgaria
`Benin
`lllazil
`Belarus
`Canada
`Central African Republic
`Congo
`Swilaierlmd
`Cele d'lvoire
`Cm
`China
`Czeehoaloualtia
`Enoch Republic
`Germany
`Durant
`Kimmie
`Spain
`Finland
`France
`Gabon
`
`GI!
`GE
`GN
`GR
`HU
`IE
`IT
`JP
`ICE
`KG
`KP
`
`KR
`KZ
`Ll
`LK
`LR
`LT
`LU
`LV
`MC
`MD
`MG
`MI.
`MN
`MR
`
`United Kingdom
`
`Democratic People's Republic
`of Rum
`Republic of Korea
`Kazakhstan
`Liechtenstein
`Sri lmka
`Liberia
`Lithuania
`Luaernbourg
`Latvia
`Monaco
`Republic of Moldova
`Madagascar
`Mali
`Mongolia
`Mauritania
`
`000002
`000002
`
`2
`
`

`

`WO 97326354
`
`PCT{US97I'00081
`
`SHAMPOO COMPOSITIONS WITH IMPROVED
`
`DEPOSITION OF ANTIMICROBIAL AGENTS
`
`FIELD OF THE INVENTION
`
`The
`
`present
`
`invention
`
`relates
`
`to
`
`shampoo
`
`compositions
`
`containing
`
`antimicrobial agents which provide antidandrufi‘ activity.
`
`In particular, the present
`
`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
`
`therefore provide little or no anti-dandmff activity.
`
`In addition,
`
`the detersive
`
`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 fimher decreasing deposition and anti-dandruff activity.
`
`Deposition of particulate antimicrobial agents is especially difficult
`
`in anti-
`
`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 filrther 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
`
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`000003
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`3
`
`

`

`WO 97126854
`
`PCTIUS97100081
`
`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, amphoten'c 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 l.0% by weight of a cationic
`
`guar polymer having a charge density of from 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 catiouic 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 can‘iers or by-products that may be
`
`included in
`
`commercially available materials.
`
`000004
`000004
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`4
`
`

`

`W0 9706854
`
`FCTIUSWIIJWSI
`
`Detersive Surfactant
`
`The shampoo compositions of the present
`
`invention comprise 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.
`
`Aniouic surfactant
`
`The detersive surfactant component of the shampoo compositions
`
`is
`
`preferably an anionic surfactant Concentrations of anionic surfactant can range from
`
`about 7% to about 30%. preferably from about 10% to about 25%, more preferably
`
`from about 12% to about 22%, by weight of the shampoo compositions.
`
`AniOnic surfactants for use in the shampoo cempositions include alkyl and
`
`alkyl ether sulfates. These materials have the respective formulae ROSO3M and
`
`RO(C2H4O)XSO3M. wherein R is alkyl or alkenyl of from about 8 to about 30
`
`carbon atoms, at is an integer from 1 to 10, and M is a hydrogen. alkali metal (cg.
`
`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 l8 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. Lauryl 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 I 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 [ Rl-SO3-M ] where R;
`
`is
`
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`
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`

`

`W0 97.06354
`
`PCTJ'US971‘00031
`
`4
`
`selected from the group consisting of a straight or branched chain, saturated aliphatic
`
`hydrocarbon radicals having from about 8 to about 24, preferably ahead 10 to about
`
`18, carbon atoms; and M hydrogen, alkali metal (e.g.,
`
`lithium, sodium, potassium),
`
`alkali earth metal
`
`(cg,
`
`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-parafiins, having about 8 to about 24 carbon atoms,
`
`preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., 803,
`
`H2804, obtained according to known sulfonation methods, including bleaching and
`
`hydrolysis. Preferred are alkali metal and ammonium sulfonated C1043 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 US. Patent
`
`2,486,921; US. Patent 2,486,922; and US. 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-octadecylsulfosuccinnate;
`
`disodium lauryl
`
`sulfosuccinate; diammonium lauryl
`
`sulfosuccinate;
`
`tetrasodium
`
`N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate;
`
`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 sulfouation 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 $02, chlorinated hydrocarbons, etc, when used in the liquid
`
`form, or by air, nitrogen, gaseous 802, etc., when used in the gaseous form.
`
`The alpha—olefins
`
`from which the olefin sulfonates are derived from
`
`mono—olefins having fi'om about 12 to about 24 carbon atoms, preferably frorn about
`
`14 to about 16 carbon atoms. Straight chain olefins are preferred.
`
`In
`
`addition
`
`to
`
`the
`
`true
`
`alkene
`
`sulfonates
`
`and
`
`a
`
`proportion of
`
`hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other
`
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`6
`
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`

`W0 9786854
`
`PCTIUS9W00081
`
`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 US. Patent 3,332,880, which description is incorporated herein by
`reference.
`
`Another class of anionic surfactants
`
`suitable for use in the shampoo
`
`compositions are the beta-alkyloxy alkane sulfonates. These compounds can be
`
`represented by the formula:
`
`H
`
`R20
`Rt—i—ri—soau
`J,
`I
`
`where R1 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 (cg, 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 US. Patent 3,929,678, which descriptions are
`
`incorporated herein by reference.
`
`Preferred anionic surfactants for use in the shampoo compositions include
`
`ammonium Iauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, tri-
`
`ethylamine laureth sulfate,
`
`triethanolamine lauryl sulfate,
`
`triethanolamine laureth
`
`sulfate, monoethanolamine
`
`lauryl
`
`sulfate, monoethanolamine
`
`laureth
`
`sulfate,
`
`diethanolamine lauryl sulfate, diethanolamine laureth sulfate,
`
`lauric menoglyceride
`
`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 lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl
`
`sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate and
`
`combinations thereof.
`
`Amghoteric and zwitterionic surfactants
`
`The detersive surfactant component of the shampoo compositions may
`
`comprise an amphoteric andz’or zwitterionic surfactant. Concentrations of such
`
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`PCT{US97100081
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`6
`
`surfactants can range from about 0.5% to about 20%, preferably from abOut
`
`l% to
`
`about 10%. by weight of the shampoo compositions.
`
`Amphoteric surfactants for use in the shampoo compositions include the
`
`derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is
`
`straight or branched and one of the aliphatic substituents contains from about 8 to
`
`about 13 carbon atoms and one contains an anionic water solubilizing group, e.g.,
`
`carb0xy, 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-
`
`phonate. These compounds can be represented by the formula;
`l“
`RZ—Y'—CH2—R4—-Z'
`
`where R2 contains an alkyl, alkenyl; or hydroxy alkyl radical of from about 8 to
`
`about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to
`
`1 glyceryl moiety; Y is selected from the group consisting of nitrogen,
`about
`phosphorus, and sulfiJr atoms; R3 is an alkyl or monohydroxyalkyl group
`containing about 1 to about 3 carbcm atoms; X is I when Y is a sulfur atom. and 2
`when Y is a nitrogen or phosphorus atom; R4 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,
`
`stearyldimethylpropyisultaine,
`
`lauryl—bis-(Z-hydroxyethyl) propylsultaine and the like; and the amidosultaines
`
`Such as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine,
`
`laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like.
`
`Preferred are
`
`amidohydroxysultaines such as the Clz—Clg hydrocarbyl amidopropyl hydroxy-
`
`sultaines, especially C12'C14 hydrocarbyl amido propyl hydroxysultaines, cg,
`
`laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultainei Other
`
`sultaines are described in US. Patent 3,950,417, which descriptions are incor-
`
`porated herein by reference.
`
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`W0 97.06854
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`PCTIUS97100081
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`7
`
`Other suitable amphoten'c surfactants are the aminoalkanoates of the
`
`formula
`
`R-NH(CH2)nCOOM,
`
`the
`
`iminodiaikanoates
`
`of
`
`the
`
`formula
`
`R-N[(CH2)mCOOM]2
`
`and mixtures thereof; wherein n and m are integers from 1 to 4, R is C3 - C23
`
`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-
`
`-beta-amino propionic acid or salts thereof. and N-lauryl-beta-imino—dipmpiortic
`
`acid or salts thereof, and mixtures thereof.
`
`Other suitable amphoteric surfactants include those represented by the
`
`formula :
`
`R3
`l
`R‘COllsl-(CHZJET—CFQZ
`
`R“
`
`R2
`
`where R1 is alkyl or alkenyl having from about 8 to about 22 carbon atoms,
`preferably from about
`12 to about 16 carbon atoms; R2 is hydrogen or
`CH2C02M; R3 is CHZCHon or CHZCHZOCHQCH2COOM; R4 is hydrogen,
`
`CH2CH20H, or CH2CH20CH2CH2COOM; Z is COZM 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 R2. All such variations and species
`
`are meant to be encompassed by the above formula.
`
`Examples of surfactants of the above formula are monocarboxylates and
`
`dicarboxylates.
`
`Examples
`
`of
`
`these
`
`materials
`
`include
`
`cocoamphocarboxypropionate,
`
`cocoamphocarboxypropionic
`
`acid,
`
`cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and
`
`cocoamphoacetate.
`
`Commercial amphoteric surfactants include those sold under the trade
`
`names MIRANOL CZM CONC. N.P., MIRANOL C2M CONC. O.P.,
`
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`000009
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`9
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`W0 97.326354
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`PCTIUS97100081
`
`8
`
`MIRANOL CZM SF, MIRANOL CM SPECIAL (Miranol, Inc); ALKATERIC
`
`2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc); MONATERIC
`
`CDX~38. MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-ZC
`
`(Rewo Chemical Group); and SCI-[ERCOTERIC MS-2 (Scher Chemicals).
`
`Betaine surfactants
`
`(zwitterionic)
`
`suitable for use in
`
`the shampoo
`
`compositions are those represented by the formula:
`C]
`R“
`R?
`III
`I
`c—N-{cm -N’—Y——R1
`l.
`
`R5
`
`where R1 is COOM or CH(0H)CH2303M;
`R2 is lower alkyl or hydroxyalkyl;
`R3 is lower alkyl or hydroxyalkyl;
`R4 is a member selected from the group consisting of hydrogen and lower alkyl;
`R5 is higher alkyl or alkenyl;
`
`Y is lower alkyl, preferably methyl;
`
`m is an integer flow 2 to 7. preferably from 2 to 3',
`
`n is the integer l or 0'. and
`
`M is a hydrogen, alkali metal, alkali earth metal, ammortium or substituted
`
`ammonium.
`
`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-
`
`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 poiyether
`
`linkages or
`
`non-functional substitutents such as hydroxyl or halogen radicals wherein the
`
`radical remains of hydrophobic character.
`
`Examples of suitable surfactant betaines of the above formula wherein n is
`
`zero include
`
`the
`
`alkylbetaines
`
`such as cocodimethylcarboxymethylbetaine,
`
`lauryldimethylcarboxymethylbetaine,
`
`lauryl dimerhyl-alpha-carboxyethylbetaine.
`
`cetyldimethylcarboxymethylbetaine,
`
`lauryl-bis—(2-hydroxyethyl)carboxymethyl-
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`betaine,
`
`stearyl-bis—(2-hydroxypropyl)carboxymethylbetaine,
`
`oleyl-
`
`dimethyl-gamma-carboxypropylbetaine,
`aipha-carboxyethylbetaine,
`etc.
`
`lauryl-bis-(2-hydroxypropyl)-
`suitable
`sulfobetaines
`include
`
`cocodimethylsulfopropyl-
`
`betaine,
`
`stearyldimethylsulfopropylbetaine,
`
`and
`
`lauryl-bis-(Z—hydroxyethyl)sulfopropylbetaine.
`
`Suitable amido betaines and amidosulfo betaines for use in the shampoo
`
`compositions
`
`include
`
`the
`
`amidocarboxybetaines,
`
`such
`
`as
`
`cocoamidodimethylcarboxymethylbetaine,
`
`laurylamidodi-
`
`methylcarboxymethylbetaine,
`
`cetylarnidodimethylcarboxymethylbetaine,
`
`laurylantido-bis-(2-hydroxyethyl)-carboxymethylbetaine,
`
`cocoamido-bis-(Z-hydroxyethyl)-carboxymethylbetaine, etc. Amido sulfobetaines
`
`include
`
`cocoamidodimethylsulfopropylbetaine,
`
`stearylamidodimethylsulfopropylbetaine,
`
`and
`
`lauryl-
`
`amido—bis-(2~hydroxyethyl)-sulfopropylbetaine.
`
`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 of the 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:
`
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`PCTfUS9‘7l00081
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`
`0
`R2
`1
`ll
`l
`R —C—N—ER3]~COOMn
`
`wherein RI
`
`is a alkyl or alkenyl radical having from about 8 to about 24 carbOn
`
`atoms, preferably from about 12 to about 13 carbons atoms; R2 is hydrogen, alkyl
`
`having from about
`
`I
`
`to about 4 carbon atoms, phenyl, or CH2COOM, preferably
`
`to about 4 carbon atoms, more preferably alkyl having
`I
`alkyl having from about
`from about
`i
`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 I to about 6 carbon atoms or alkylester thereof; n is an integer from I to
`
`4, preferably 1 or 2‘, and M a hydrogen, alkali metal
`
`(e.g.,
`
`lithium, sodium,
`
`potassium), alkali earth metal (cg, 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 that
`
`the highly solubilizing surfactants described
`
`hereinabove, when used in combination with the guar cationic polymers described
`
`hereinafier, 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 of from about 0.9mequ to about 4mequ, preferably between
`
`about 1.0 and 3meqlg.
`
`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
`
`shampoo compositions.
`
`Effective concentrations of such antimicrobial agents
`
`generally range fi'om 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, oct0pirox, 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
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`WO 97496854
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`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 it + y = 8. Average
`particle diameters for the selenium sulfide (selenium disulftde) are less than lSum,
`
`preferably less than 10 um, as measured by forward laser light scattering device. e.g.,
`
`Malvern 3600 instrument.
`
`Selenium sulfide compounds are well known in the
`
`shampoo art, and are described, for example in US. Patent 2,694,668; US. Patent
`
`3,152,046; US. Patent 4,089,945; and US. Patent 4,885,107, which descriptions are
`
`incorporated herein by reference.
`
`Pyridinethione antimicrobial agents, especially l—hydroxy-2—pyridinethione
`
`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-
`
`hydroxy-Z-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 art, and
`
`are described, for example,
`
`in US. Patent 2,809,971; US Patent 3,236,733; US.
`
`Patent 3,753,196; US. Patent 3,76l,418; US. Patent 4,345,080; US. Patent
`
`4,323,683; US. Patent 4,379,753; and US. Patent 4,470,982, which descriptions are
`
`incorporated herein by reference.
`
`Sulfiir may also be used as the particulate antimicrobial agent in the shampoo
`
`compositions herein. Effective concentrations of the particulate SUlfiJl‘ are generally
`
`from about 1% to about 5%, more preferably from about 2% to about 5%, by weight
`
`of the compositions.
`
`OctOpirox and related salts and derivatives may also be used as
`
`the
`
`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.
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`Suspending or Thickening Agent
`
`The shampoo compositions of the present invention comprise a su5pending 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 10%, 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 acyl derivatives, especially those which can be solubilized