Note: Descriptions are shown in the official language in which they were submitted.
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SHAMPOO COMPOSITIONS WITH IMPROVED
DEPOSITION OF ANTIMICROBL~L AGENTS
FIELD OF T~IE INVENTION
The present invention relates to shampoo compositions containing
antimicrobial agents which provide antidandruff activity. In particular, the present
invention relates to shampoo compositions containing antimicrobial agents,
preferably particulate antimicrobial agents, in combination with a cationic guarpolymer as an antimicrobial agent deposition aid.
BACKGROUND OF T~IE I~VENTION
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, seleniumsulfide and heavy metal salts of pyridinethione During the shampooing process,
these antimicrobial agents deposit on the scalp to provide anti-dandruffactivity.
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
the.erore provide little or no anti-dandruff activity. In addition, the detersive
surf. ~t~nt.c in these shampoo compositions which are designed to remove oil, grease,
dirt, and particulate matter will also carry away particulate antimicrobial agents
during nnsing, thus further decreasing deposition and anti-dandmff activity.
Depos;liQn of particulate antimicrobial agents is especi~lly difficult in anti-
dandn~ff sharnpoo compositions co.~ g crystalline suspendin~ agents. These
sl:~çncl;~g agents help dis,~-~e and suspend particulate antimiGrobial agents in the
shampoo composition. These suspending agents, however, adversely affect lathering
p~.rGl--,ance. It has thcr~,fore bccol,-e conventional practice to enh~nce the lathering
pe. ro"~ance of these sLIIIpoos by increasing detersive surfactant concentrations or
by adding foam boosters, both of which further decrease deposition of particulate
antimicrobial agents from the shampoo compositions.
~ t 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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are cationic derivatives of guar gum which have been found to be most effective
when used in combination with c~stalline 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-dandn~ff
shampoo composition with improved deposition of antimicrobial agents, especiallyparticulate 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-dandru~
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 wei~ht 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 ~ntin~jcrobial agent; (c) from about 0.5% to about 10% by weight of
a suspending agent; (d) from about O.Ol~/o to about 1.0% by weight of a cationicguar 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 watcr, wherein at least about 50% by
weight of the cationic ~uar polymer is in coacervate forrn, said coacervate comprising
detersive surfactant and cationic guar polymer.
.
DETAILED DESCRIPTION OF THE INVENTION
The sl,~,.~)oo compositions of the present invention can comprise, consist of,
or consist e~se~ y of thc ess~n~ ek .,~ and limitations of the invention
des~,~ibcd hcrein, as well any of the additional or optional ing~l;enls, cornponents, or
limitations described herein.
All pcrc~ g~s, parts and ratios are based upon the total weight of the
shampoo compositions of the present invention, unless otherwise s~,eciLcd. 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
co,..me.c;ally available materials.
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Detersive Surfactant
The shampoo compositions of the present invention comprise a detersive
surfactant selected from the group consisting of anionic surfactants, amphotericsurfactants, zwitterionic surfactants, and combinations thereof. The shampoo
compositions preferably comprise an anionic surfactant. The detersive surfactantprovides the shampoo compositions with cleaning performance
Anionic 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 compositions include alkyl and
alkyl ether sulfates. These materials have the respective formulae ROS03M and
RO(C2H40)xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30
carbon atoms, x is an integer from I to 10. and M is a hydrogen, alkali metal (e.g.,
lithium, sodium. potassiun~), alkali earth mctal (e.g., beryllium, magnesium, calcium,
strontium, barium) amrnonium or substituted arnr-loni~
Plefc.~bly, 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. Lauryl alcohol and straight chain alcohols derived from coconut oil
are p-~f~ d. Such alcohols are reacted with between about O and about 10, and
es,~ -'ly about 3, molar proportions of ethylene oxide and the resulting mixture of
I o'ecl~lar species having, for e~ nl-le, an average of 3 moles of ethylene oxide per
molc of alcohol, is sulf7t~d and neutralized.
Specific e~ p'~~ of alkyl ether sulfates which msy be used in the shampoo
cGmpos;lions of the present invention are sodium and am",or Im salts of coconut
alkyl triethylene glycol ether sulfate; tallow alkyl tricthylene glycol ether sulfate, and
tallow alkyl hexaoxyethylene sulfate. Highly prefe.~cd alkyl ether sulfates are those
co,np.-s,ng 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 surf;lct~ntc are the water-soluble salts of organic,
sulfuric acid reaction products of the general forrnula [ Rl-S03-M ] where Rl is
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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,
inciuding 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,H~SO4, obtained according to known sulfonation methods, including bleaching and
hydrolysis. Preferred are alkali meeal and ammonium sulfonated C10 18 n-paraffins.
Still other suitable anionic surf~ct~ntc. are the reaction products of fatty acids
esterified with isethionic acid and neutralized with sodium hydroxide where, forexample, 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. Patent2,486,921, U.S. Patent 2~486,922; and U.S. Patent 2,396,278, which descriptions
are incorporated herein by reference.
Other anionic surf~ct~lts suitable for use in the shampoo compositions are
the succinnates, examples of which include disodium N-octadecylsulfosuccinn~te;
cliso~ m lauryl sulfoslucc~ e; ~ "~o~ ~ lauryl sulfosuccin~te; tetrasodium
N-( 1,2-dicarbox,vethyl)-N-octadecyisl~lfosuc~-innste; diamyl ester of sodium
sulfosl~ccinic acid; dihexyl ester of sodium su1fosuccinic acid; and dioctyl esters of
sodium sulfosuccinic acid.
Other suitable anionic surfa~nts include olefin sulfonates having about 10 to
about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean
co~l~po~Jn~s which can be produced by the sulfonation of alpha-olefins by means of
unc~mr~lexed sulfur trioxide, followed by neutrali7~ion of the acid reaction mixture
in conAi~ionc such that any sulfones which have becn formed in the reaction are
hydrolyzed to give the co,l.,tl)on~lin~ hydroxy-alkanesulfonates. The sulfur trioxide
can be liquit or gwous, and is usually, but not necessarily, diluted by inert dilnents7
for example by liquid S02, chlolindl¢d hydr~ca.l,ons, etc., when used in the liquid
form, or by air, nitrogen, gaQCOUS S02, etc., when used in the g~C~ous form.
The alpha-olefins from which the olcfin sulfonates are derived from
mono-olefins having from about 12 to about 24 carbon atoms, plef~lably from about
14 to about 16 carbon atoms. Straight chain olefins are p,ef~ ,d.
In addition to the tnJe alkene sulfonates and a proportion of
hydroxy-alk~n~su~fonates, the olefin sulron~i~es can contain m~nor amounts of other
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-
materials, such as alkene disulf~nates dependin~ 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.
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:
o~2 H
R'--C--C--SO3M
where Rl is a straight chain alkyl group having from about 6 to about ~0 carbon
atoms, R2 is a lower alkyl group having from about I (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. Frnulsifiers and Dctergents. 1989 Annual, published
by M. C. Publishing Co., and in U.S. Patent 3,929,678, which descriptions are
incol ~GI ated herein by reference.
Pl~fe.le~ anionic surfactants for use in the shampoo compositions include
ammonium lauryl sulfate, ~mmoni--m Iaureth sulfate, triethylamine lauryl sulfate, tri-
ethylamine laureth sulfate, triethanolam;ne lauryl sulfate, triethanolamine laureth
sulfate, ~I~onoe~banola~-l;ne lauryl sulfate, monoethanolamine laureth sulfate,
diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride
sodium sul&te, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,
potassium laureth sulfate, sodium lauryl sarcGsn)ate, sodium lauroyl sarcosinate,
lauryl sar~,~~:lle, cocoyl jal c03ine, ammonium cocoyl sulfate, a~nrno~ium 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 be..7ene sulfonate and
co..lb; ~~ions thereof.
Amphoteric and zwitterionic surf~ct~ntc
The detersive surfactant co"lpon~nl of the shampoo compositions may
comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such
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surfactams can range from about 0 5% to about 20~~o~ pref'erably from about 1~/otO
about 1 0~~o~ by weight of the shampoo compositions.
Arnphoteric 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 1~ 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 ~ 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 forrnula:
(R3~
R --Y --CH2--R4--Z
where R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to
about 18 carbon atoms, from 0 to about }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 1 to about 3 carbon 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 offrom about 1 to about 4 carbon atoms and Z is a radical selected from the group
consisting of carboxylate, sulfonate, sulfate, phosphon~te, and phosphate groups.
Ex~nples of amphoteric and zwitterionic surfactants also include sultaines
and ~idos~ltaines. Sultaines and ~idos~lt~ ec can be used as foam enhancing
surfactants that are mild to the eye in partial replacement of anionic surf~ct~nts.
Sultaincs, including arnidosultaines, include for eY~Inrle7
cocod;~ I hylpr~)yls,Jltaine, stearyldimethylpropylsultaine,
lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the arnidosultainessuch as coco~midod..,.elhylpropylsultaine, stearylarnidododimethylpropylsultaine,
laurylarnidobis42-hydroxyethyl) propylsultaine, and the like. Preferred are
amidohydroxysultaines such as the C12-C18 hydrocarbyl amidopropyl hydroxy-
sultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g.,
laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other
sultaines are des_-ibed in U.S. Patent 3,950,417, which dcsc-;ptions are incor-
porated herein by l.,fe.cnce.
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?
Other suitable amphoteric surfactants are the aminoalkanoates of the
formula R-NH(CH2)nCOO~f~ the imlnodialkanoates of the formula
R-N[(CH2)mCOoM]2
and mixtures thereof; wherein n and m are integers from I to 4, R is C8 - C~2
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-dipropionicacid or salts thereof, and mixtures thereof
Other suitable amphoteric surfactants include those represented by the
t'ormula:
R3
R'CON- (CH2)n ~--CH2Z
R4 R2
where Rl 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
CH2CO2M; R3 is CH2CH20H or CH2CH20CH2CH2COOM; R4 is hydrogen,
CH2CH20H, or CH2CH20CH2CH2COOM, Z is CO2M or CH2CO2M; 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".,agl~es;um, calcium, strontium,barium) arnmonium or substituted ammonium.
This type of surfactant is so.~ .,es çl~csified as an imidazoline-type amphoteric
surfactant, although it does not nece,~ -- ily have to be derived, directly or
indirectly, through an imi~ e intermediate.
S~ le materials of this type are marketed under the trade name
MIRANOL and are understood to co-"pli~e a col rl~ mixture of species, and
can exist in protonated and non-protQn~d species dep~ndi~lg upon pH with
respect to species that can have a hydrogen at R2. All such variations and species
are meant to be e--co l.pqcsed by the above formula.
Examples of surf~~t~ntc of thc above formula are monocarboxylates and
dicarboxylates. Exa.~.ples of these materials include
cocoamphocarboxypropionate, cocoamphocarboxypropionic acid,
cocoamphocarboxyglycinate (alternately l~f~ d to as cocoampho~i~cetA~e), and
cocoampho~cet~te.
Commercial amphoteric surf~çt~ntc include those sold under the trade
names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P.,
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.~fIRANOL C2M SF~ MIRANOL CM SPECIAL ~Miranol, ~nc ); AlKATERIC
2CIB (Allcaril Chemicals), AMPHOTERGE W-2 (Lonza, Inc.), MONATERIC
CDX-38, MOI~iATERIC CSH-32 (Mona Industries), REWOTERIC AM-2C
(Rewo Chemical Group), and SCHERCOTERIC MS-2 (Scher Chemicals)
Betaine surfactants (zwitterionic) suitable f~r use in the shampoo
compositions are those represented by the formula:
O R4 R2
Il l I
Rs--C--N-(CH2)~ N--Y--R'
~3
n
where Rl is COOM or CH(OH)CH2SO3M
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 from 2 to 7, pref~. ably from 2 to 3,
n is the integer I or 0; and
M is a hydrogen, alkali metal, alkali earth metal, ammonium or substituted
ammonlum.
As used in this context, the terrn ''lower alkyl" or "hydroxyalkyl" means straight
or branch ch~ined saturated, aliphatic hydrocarbon radicals and substituted
hydrocarbon radicals ha~ing from one to about three carbon atoms such as, for
eAa~ le, mcthyl, ethyl, propyl, isopr~pyl, 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
hytrocarbon raticals having from about eight to about 20 carbon atoms such as,
for exarnple, lauryl, cetyl, stearyl, oleyl, and the like. lt should be understood that
the term "higher alkyl or alkenyl" includes mixtures of radicals which may contain
one or more inte....eA;~te lin~s such as ether or polyether linkages or
non-functional substit~terlts such as hydroxyl or halogen radicals wherein the
radical remains of hydrophobic character.
Examples of suitable surfactant betaines of the above fonmula wherein n i
zero include the alkylbetaines such as cocodimethylcarboxymethylbetaine,
lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbet~ine.
cetyldimethylcarboxymethylbet~in~, lauryl-bis-(2-hydroxyethyl)carboxymethyl-
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bet~ine, stearyi-bis-(2-hydroxypropyl)carboxymethyibetaine, oleyl-
dimethyl-gamma-carboxypropylbetaine, lauryl-bis-(2-hydroxypropyl)-
alpha-carboxyethylbetaine, etc. Suitable sulfobetaines include
cocodimethylsulfopropyl-
betaine, stearyldimethylsulfopropylbetaine, and
lauryl-bis-(2-hydro~cyethyl)sulfopropylbetaine.
Suitable amido betaines and amidosulfo betaines for use in the shampoo
compositions includ~ the arnidocarboxybetaines, such as
cocoamidodimethy}carboxymethylbetaine, laurylamidodi-
methylcarboxymethylbetaine~ cetylamidodimethylcarboxymethylbetaine,
laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine,
cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. ~nido sulfobetaines
include cocoamidodimethylsulfopropylbetaine,
stearylamidodimethylsulfo~ropylbetaine, and lauryl-
amido-bis-(2-hydroxyethyl)-sulfopropylbetaine.
Highly solubilizin~ surfactants
The shampoo compositions of the present invention are preferably ~ee of
highly solubilizing surf~ct~nt~ such as N-acyl amino acid surf~ct~ntc As used in this
context, "substantially free" means that the shampoo con"~os;lions 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 eSsent~ y zero percent, of
highly solubilizing surfactants by weight of the shampoo compositions
Less preferably, the shampoo compositions may co~ ..se N-acyl amino acid
surfactants as a secondary optional surfactant or as the detersive surfactant
co~ orP .~ ofthe shampoo compositions.
N-acyl amino acid surfactants are well known surfnct~nts for use in a variety
of products. A desc,;ylion of these surf~ct~ntc and their synthesis can be found, for
example, in Anionic Suractants. Part II. Surfactant Science Scries. Vol. III. edited by
Warner M. I.i-.fi~ld7 Marcel DekJcer, Inc. (New York and Basel), pp ~81-617 (1976),
which description is il~co.yol~ted herein by ,~,f. rence.
Suitable N-acyl amino acid surfact~nts for use in the shampoo compositions
herein inctude N-acyl hydrocarbyl acids and salts thereof, which can be ,epresenled
by the formula:
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1()
O R2
Rl--C N [ R3~COOM
wherein Rl is a alkyl or alkenyl radical having from about 8 to about 24 car~on
atoms, preferably from about 12 to about 18 carbons atoms; R2 is hydrogen, alkylhaving from about I to about 4 carbon atoms, phenyl, or CH2COOMl preferably
alkyl having from about I to about 4 carbon atoms~ more preferably alkyl having
from about I to about 2 carbon atoms; R3 is (CR4)2 or alkoxy having from about Ior 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 I or 2; and M a hydrogen, alkali metal (e.g., lithium, sodium,
potassium), alkali earth metal (e.g., berylliuml magnesium, calcium, strontium,
barium) ammonium or substituted ammonium. Especially prefe~, ed are N-acyl
sarcosinates and acids thereofl examples of which include lauroyl sarcosinatel
myristoyl sarcosinatel cocoyl sarcosinate, and oleoyl sarcosinate, preferably assodium or potassium salts.
It has been found that the highly solubilizing surfactants described
hereinabove, when used in combination with the guar cationic poiymers described
hereinafterl 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. Il.c.er~re, the cationic guar polyrner should have a
cationic charge density of from about O.9meq/g to about 4meqJg, p,~f~. ably between
about 1.0 and 3meq/g.
Antin~icrobial ~Pent
The shampoo compositions of the present invention comprise a safe and
effective amount of an antimicrobial agent. The antimicrobial aBent provides theshampoo compositions with antimicrobial activity. The antimicrobial agent is
preferably a crystalline particulate that is insoluble in, and d;sp.,.~ed throughout, the
shampoo. compositions. Effective concentrations of such ~ntimicrobial agents
generally range from about 0.1% to about 5%, more pr~ bly from about 0.3% to
about 5%, by weight of the shampoo compositions. Suitable ~ robial agents
include sulfur, octopirox, selenium sulfide, and pyridinethione salts.
Selenium sulfide is a pref~;lred particulate antimicrobial agent for use in the
shampoo compositions, effective concentrations of which range from about 0.1% to
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Il
about 5 0~O, pret'erably t'rom about 0.3% to about 2 ~~O, more preferably from about
0 5% to about 1.5~/0~ by weight of the shampoo compositions Selenium sulfide is
generally regarded as a compound having one mole of selenium and two moles of
sulfilr, although it may also be a cyclic structure, SexSy, wherein x + y = 8. A~erage
particle diameters for the selenium sulfide (selenium disulfide) are less than 15um~
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 U.S. Patent 2,694,66X; U.S. Patent
3,15~,046; U.S. Patent 4,089,945, and U.S. 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 forrned from heavy metals such as zinc, tin,
cadmium, magnesium, aluminum and zirconium. Zinc salts are most ~refc, - ed,
especially the zinc salt of l-hydroxy-2-pyridinethione (zinc pyridinethione, ZPT).
Other cations such as sodium may also be suitable. Particularly preferred are 1-hydroxy-2-pyridinethione salts in platelet particle form, wherein the particles have an
average size of up to about 20 microns, pr~felably 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 des~,-iplions are
incorporated herein by reference
Sulfur may also be used as the particulate antimicrobial aBent in the shampoo
compositions herein. Effective concenll~tions of the particulate sulfur are generally
from about 1% to about 5%, more pr-,ft:~ably 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, lherefofe, do not d.spcr~e throughout the
composition as crystalline par~icul~tçc as do the other antimicrobial agents described
he. eh~berore.
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12
Suspendin~ or Thickenin~ A~ent
The shampoo compositions of the present invention comprise a suspending or
thickening agent to help maintain dispersion of particulate antimicrobial agentsthroughout 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 par~iculate
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 tell.pe.~tures. In general, effective concentrations of
the crystalline suspending agent range from about 0.5% to about 10%, preferably
from about 0.~% to about 5%, more p.efe.~bly 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 p,ope~ Iy.
~ lefe~,ed crystalline suspending agents are acyl derivatives and amine oxides,
especially acyl derivatives, especially those which can be solubilized in a premix
solution and then be recryst~ 7ed upon cooling. These materials comprise long
chain (e.g., Cg-C22 plef~,.ably C14-C22, more preferably C16-C22) aliphatic
groups, i.e., long chain acy1 derivative materials and long chain amine oxides, as well
as mixtures of such materials. In~ ded are ethylene glycol long chain esters, alkanol
amides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl
long chain esters, long chain esters of long chain allt~nol~nlides, and long chain alkyl
~L".~Ih~l amine oxides, and co",binations thereof.
Crystalline s~ el-cling agents are described, for example, in U.S. Patent
4,741,855, which description is incorporated herein by .efe.ence.
Suitable suspending agents for use in the shampoo compositions herein
include ethylene glycol esters of fatty acids pr~f~.ably having from about 14 to about
22 carbon atoms, more preferably 16-22 carbon atoms. More prtfel-ed are the
ethylene glycol stearates, both mono and distearate, but particularly the distearate
containing less than about 7% of the mono stearate. Other suspending agents include
alkanol amides of fatty acids, pre~erably having from about 16 to about 22 carbon
atoms, more preferably about 16 to 18 carbon atoms. Preferred alkanol amides are
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13
stearic monoethanolamid~ stearic diethanolamide, stea~ic monoisopropanolamide and
stearic monoethanoiamide stearate Other long chain acyl derivatives include longchain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate), glyceryl
esters (e g, glyceryl distearate) and long chain esters of long chain alkanol amides
(e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate)
Ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and
alkanol amides of long chain carboxylic acids, in addition to the preferred materials
listed above, may be used as suspending agents.
Suspending agents also include long chain amine oxides such as alkyl
(C16-C2~) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide.
Other long chain acyl derivatives that can be used include N,N-dihydrocarbyl
(C12-C22, preferably C16-CIg) amido benzoic acid and soluble salts thereof (e.g.,
Na and K salts), particularly N,~-di(C I 6-C 18~ and hydrogenated tallow) amido
benzoic acid species of this family, which are commercially available from Stepan
Company (Northfield, Illinois, USA).
The crystalline suspending agent can be incorporated into the shampoo
compositions herein by solubilizing it into a solution containing water and the anionic
sulfate surfactant at a temperature above the meiting point of the suspending agent.
The suspending agent is then recryst~l~i7~. typically by cooling the solution to a
te"lpc.~lure sufficient to induce cryst~lli7~tion.
Other suitable suspending agents for use in the shampoo compositions include
that can be used include polymeric thickeners, such as carboxyvinyl polymers,
examples of which are described in U.S. Patent 2,79B,053, and U.S. Patent
4,686,254, which descriptions are incorporated herein by ~eference. Examples of
suitable carboxyvinyl polymers include Carbopol(~) 934, -940, -941, -956, -980, -981,
-1342, and -1382, all cor.u"e.,,;ally available from B. F. Goodrich Company
Other suitable sus~end.,~g agents include those which impart a gel-like
viscosity to the composition, such as water soluble or colloidally water solublepolymers like cellulose ethers (e.g., hydroxyethyl cellulose), guar gum, polyvinyl
alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch
derivatives, and other thickeners, viscosity modifiers, gelling agents, xanehan gum and
combinations thereof
Other suitable suspending agents are described in U.S Patent 4,788,006,
which dcs.;-iption is incorporated herein by refelence
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I ~
Cationic Guar PolYmer
The shampoo compositions of the present invention comprise a cationic guar
polymer having a select charge density. The cationic guar polymer~ in combination
with the essential components of the compositions, provides improved deposition of
the antimicrobial agent onto the scalp and other areas of the skin. Concentrations of
the cationic deposition polymer range from about 0 01% to about 1.0~/0, preferably
from about 0.01% to about 0.5%, more preferably from about û.02% to about
0.25%, by weight of the shampoo compositions.
The cationic guar polymer for use in the shampoo composition is fi~rther
defined as having a cationic charge density of from about O.O~meq/g to about
3meq/g, preferably from about O.lmeq/g to about 2meq/g, more preferably from
about 0.8 to about 1.8meq/g, wherein at least about 50%, preferably about 100%, by
weight of the cationic guar polymer forms coacervates with detersive surfactant in the
shampoo compositions. The formed coacervates are in the forrn of hydrated,
dispersed colloids that are insoiuble in the sharnpoo compositions.
The cationic guar polymers for use in the shampoo compositions are
cationically substituted galactomannan (guar) gum derivatives. The molecular weight
of such derivatives ranges generally from about 2,000 to about 3,000,000. Guar gum
for use in preparing these guar gum derivatives is typically obtained as a naturally
occurring material from the seeds of the guar plant. The guar molecule itself is a
straight chain mqnnq~ ched at regular intervals with single mcn,~e,ed galactose
units on alternative mannose units. The mannose units are linked to each other by
means of beta ( 1-4) glycosidic linkages. The galactose bran~hing arises by way of an
alpha ( 1-6) linkage. Cationic derivatives of the guar gums are obtained by reaction
between the hydroxyl groups of the polygalactomannan and reactive quaternary
ammonium compounds. The degree of su~ tion of the cationic groups onto the
guu structure must be suffiei~nt to provide the requisite cationic charge density
des~,.il.ed k_.~,;nb~,~re.
Suitablc quaternary an,l,.onium compounds for use in forming the guar
cationic polymers include
R'
R~ N R2 z
R3
wherein where R~, R2 and R3 are methyl or ethyl groups and R4 is an epoxyalkyl
group of the formula
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H~C - CH-Rs-
o
or R4 is a halohvdrin group of the formula
X--CH2-fH--R5--
OH
where R5 is C l-C3 alkylene and X is chlorine or bromine, and Z is an anion such as
Cl~, Br~, I- or HSO4-.
Cationic guar polymers (cationic derivatives of guar gum) formed from the
reagents described hereinbefore are represented by the formula
Rl
R--O--CH2-CH--R5--~--R2 Z
OH R3
wherein R is guar gum. Preferably, the cationic guar polymer is guar
hydroxypropyltrimethylammonium chloride, which can be more specifically
represented by the formula
R--O--CH2-fH-CH2N~(CH~) ~CI-
OH
~ specific examples of which include Jaguar(~) C- ! 3-S (cationic charge density
0.8meq/g) and Jaguar C-17 (cationic charge density 1.6meq/g) commercially
available from Rhone-Poulenc Surf~ct~n~s and Specialties, Cranbury N..J. U.S.A.
Other suitable cationic guar polymers include hydroxypropylated cationic
guar derivatives.
Water
The shampoo compositions of the prescnt invention are nqueous systems
which comprise from about 40% to about 92%, p,~feldbly from about 50% to about
85%, more preferably from about 60% to about 80%, water by weight of the
composltlons.
The pH of the shampoo compositions ranges, in general, from about 2 to
about 10~ preferably from about 3 to about 9, more preferably from about 4 to about
X, most preferably from about 5.5 to about 7.5. For zwitterionic or amphoteric
surfactant systems, the pH should be adjusted according to the isoelectric point of the
selected surfactant to maintain an anionic species on the selected surfactant prior to
forming a coacervate with the cationic guar polymer described herein.
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16
Optional ComPonents
The shampoo compositions of the present invention may further comprise one
or more optional components known for use in shampoo compositions, provided thatthe optional components are physically and chemically compatible with the essential
components described herein, or do not otherwise unduly impair product stability,
aesthetics or performance. Concentrations of such optional components typically
range from about 0.00~% to about 10% by weight ofthe shampoo compositions.
Optional components include preservatives, conditioning agents, styling
polymers, organic solvents, pearlescent aids, foam boosters, nonionic surfactants, pH
adjusting agents, perfumes, proteins, dyes, skin active agents, sunscreens, vitamins,
and viscosity adjusting agents. This list of optional components is not meant to be
exclusive, and other optional components can be used
METHOD OF USE
The shampoo compositions of the present invention are used in a
conventional manner for cleaning hair and controlling dandruff on the scalp. Theshampoo compositions herein are also useful for cleansing the skin and other areas of
the body such as underarm and groin areas. An effective amount of the composition,
typically from about I g to about 20 g of the composition, for cleaning hair, skin or
other area of the body, is applied to the hair, skin or other area that has pre~lably
been wetted, generally with water, and then rinsed off. Application to the hair
typical!y includes working the shampoo composition through the hair such that most
or all of the hair is contacted with the shampoo composition.
E~AMPLES
The compositions illustrated in Exa~,lples l-XX illustrate specific
embod~ ents of the shampoo c~.l,po~ilions of the present invention, but are not
intended to be limiting thereof: Other modifications can be undertaken by the skilled
artisan without depa~ting from the spirit and scope of this invention. These
exemplified embodiments of the shampoo compositions of the present invention
provide excellent cle~n.~in~ of hair and dandruffcontrol.
All exemplified compositions can be prepaled by conventional formulation
and mixing techniques. Component amounts are listed as weight percents and
exclude minor materials such as diluents, filler, and so forth. The listed formulations,
therefore, comprise the listed components and any minor materials associated with
such components.
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I _
Examples I - XVI
Component Exampl Exampl Example Example Exampl
e e III IV e
Il V
Arnmonium Laureth Sulfate 15.00 15 00 15 00 15 00 7 50
Ammonium Lauryl Sulfate 5 00 5 00 5 00 5 00 2 50
Sodium Lauroyl Sarcosinate 1 50 1 50 1 50 1 50 0 75
Ethylene Glycol Distearate 1.50 1.50 l 50 1 50 1 50
Zinc Pyrithione 1 00 1 00 1 00 --- 1 00
Selenium Disulfide --- - 1 00
Jaguar C17S 0 10 0 05 0 50 0 10 0 10
Fragrance q s q s q s q s q s
Color q.s qs qs qs qs
pH adjustment (Mono/Di sodium q.s q s q s q s q s
Phosphate)
viscosityadjustment (Sodium q.s q s q s q.s q s.
Chloride,
preservative (D~)M Hydantoin);q.s q.s. q.s q.s q s
Water
Component Esample Example Example Exampl Exampl
Vl V~l VIIl e e
~C X
AmmonumLaurethSulfate 750 1500 1500 10.00 1000
Ammonum Lauryl Sulfate 2.50 5 00 5 00 2 50 2 50
Co.~ idopropyl Betaine --- --- --- 2.50 2.50
Sodium Lauroyl Sarcosinate 0 75 --- --- --- ---
Ethylene Glycol Distearate 1.50 1 50 1 50 1.50 1 50
zinc P~ 1.00 1.00 1.00 1.00 1.00
Ja~uar C13'' --- 0 10
JaRuarcl7~ 0.05 --- 0 10 --- 0.10
Fragrance q.s q.s q.s. q.s. q s
Color qs qs qs. q.s. q.s.
pHadjustment (MonolDi sodium q.s q.s q s q.s. q s.
Phosphate)
Sodium Sulfate, PEG-600, q s q s q.s q s. q s
Ammonium Xylene Sulfonate)
preservative (DMDM Hydantoin)q s q s q s q.s q s.
Water
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18
Component Exampl Exampl Exampl Exampl Examp Exampl
e e e e le e
Xl XII XIII XIV XV XVI
.~nmonium Laureth Sulfate15 00 15 00 15 00 15 00 15 00 15 00
Ammonium Lauryl Sulfate 5 00 5 00 5 00 5 00 5 00 5 00
Cocamidopropyl Betaine 2 . 00 --- --- --- --- ---
Sodium Lauroyl Sarcosinate --- 1 50 1 50 --- --- ---
Sodium Cocoyl Glutamate --- --- --- --- 1 50
Ethylene Glycol Distearate 1 50 1 50 1 50 1 50 1 50 1 50
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19
Stearyl Alcohol --- --- --- --- --- --- ~
Zinc Pyrithione 1.00 0 30 0.30 0.30 0.30 1.00
Jaguar C13S 0.20 --- --- 010 0.0~ ---
JaeuarC17S --- 0.10 0.05 --- --- 0.10
Fragrance ~.s. q.s. q.s q.s. q.s. q.s
Color q.s. q.s. q.s. q s. q.s. q s.
pH adjustment (Mono/Di sodium q.s. q.s. q.s. 4.s. q.s. q.s
Phosphate)
viscosity adjustment (Sodium q s q.s. q.s. q.s. q.s. q.s
Chloride,)
preservative (DMDM q.s. q.s. q.s. q.s. q.s q.s.
Hydantoin)
Water q.s. q.s. q.s. q.s q.s. q.s
In preparing each of the compositions described in Examples I to XVI,
about one-third of the ammonium laureth sulfate (added as 25wt% solution) is
added to a jacketed mix tank and heated to about 74~C with slow agitation to
form a surfactant solution. Salts (sodium chloride) and pH modifiers (disodium
phosphate, monosodium phosphate) are added to the tank and allowed to
disperse. Ethylene glycol distearate (EGDS) is added to the rnixing vessel and
allowed to melt. After the EGDS is melted and dispersed (e.g., after about 5-20
minutes), preservative and additional viscosity modifier are added to the
surfactant solution. The resulting mixture is passed through a heat .oYc}l~n~eerwhere it is cooled to about 3~~C and collected in a finishing tank. As a result of
this cooling step, the EGDS cryst~ 7es to form a crystalline network in the
product. The remainder of the ammonium laureth sulfate and other components
are added to ~he finishing tank with agitation to ensure a homogeneous mixture.
Cationic gu r polymer is dispersed in water as a 0.5-2.5% ~queous solution
before addition to the final mix. Once all components have bcen added, viscosityand pH modifiers are added to the mixture to adjust product viscosity and pH to
the extcnt desired.
Each exe.."~lified composition provides excellent hair cle~n~ing lathering,
antimicrobial agent deposition on the scalp and dandruffcontrol.
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Component Example ExampleExample
X VII xvm xrx
Ammonium Laureth Sulfate 14.00 14 00 14.00
Cocamidopropyl Betaine --- 2.50 2 50
Cocoamphodiacetate 2.50
Cocamide MEA 1.00 I 00 I 00
Ethylene Glycol Distearate 1.50 1.50 1.50
Cetyl Alcohol 042 0.42 0.42
Stearyl Alcohol 0.18 0.18 0.18
Zinc Pyrithione 1.00 1.00 1.00
JaguarC13S 0.15 0.15
Jaguar C 1 7S --- 0 1 5
Fragrance q.s. q.s q.s.
Color q.s. q.s. q.s.
pH adjustment (Mono/Di sodium q.s. q.s. q.s.
Phosphate)
viscosity adjustment (Sodium q.s. q.s. q.s.
Chloride,
preservative (DMDM Hydantoin); q.s. q.s. q.s.
Water
In plepc~ lg each of the compositions described in Examples XVII to
XIX, from 50% to 100% by weight of the detersive surfAct~nts are added to a
jacketed mix tank and heated to about 74~C with slow agitation to form a
surfactant solution. If used, pH modifiers (monosodium phosphate, disodium
phosphate) are added to the tank and allowed to disperse. Ethylene glycol
dislealate (EGDS) and fatty alcohols (cetyl alcohol, stearyl alcohol) are then
added to the n~ixing vessel and allowed to melt. After the EGDS is melted and
dispe,rsed (usually about 5-10 minutes), preservative (if used) is added and mixed
into the surfactant solution. Additional viscosity modifier are added to the
surfactant solution if ne~esss.~r. The rçsl~lting nuxture is passed through a heat
exc~l~nger where it is cooled to aboue 35~C and collected in a finishing tank. As a
result of this cooling step, the EGDS cryst~lli7~s to form a crystalline network in
the product. Any lc,ma;ning surfactant and other con.poncl1~s are added to the
fini~hing tank with agitation to ensure a homogeneous mixture. Cationic guar
polyrner is dispersed in water as a 0.5-2.5% aqueous solution before addition tothe final mix. Once all components have been added, viscosity and pH modifiers
are added to the mixture to adjust product viscosity and pH to the extent desired.
Each exempiified composition provides excellent hair cle~ns;ng lathering,
antimicrobial agent deposition on the scalp, and dandruffcontrol.
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Example X,Y
ComponentExample
Ammonium Laureth Sulfate 15 00
Ammonium Lauryl Sulfate 5 oo
Cocamide MEA 1 00
Ethylene G ycol Distearate 1.50
Zinc Pyrith one 1.00
Jaguar C13S 0.20
Color 4.s.
pH adjustment (Mono/Di sodium Phosphate) q.s.
viscosity adjustment (sodium Chloridc, q.s.
preservative (DMDM Hydantoin). Water q.s.
In preparing the composition described in Examples XX, about one-third
to all of the total surfactant are added to a jacketed mix tank and heated to about
74~C with slow agitation to form a surfactant solution. Salts are added to the
tank and allowed to disperse. Ethylene glycol distearate (EGDS) is then added tothe mixing vessel and allowed to melt. A~er the EGDS is melted and dispersed
(usually a~er about 5-20 minutes), preservative (DMDM hydantoin) if used is
added to the surfactant solution. The res..hing mixture is passed through a heatexchanger where it is cooled to about 35~C and collected in a finishing tank. As a
result of this cooling step, the EGDS cryst~lli7es to form a crystalline network in
the product. The remainder of the detersive surfactant and other components are
added to the finishing tank with agitation to ensure a homogeneous mixture.
Cationic guar polymer is dispersed in water as a 0.5-2.5% aqueous solution
before ~ditiQn to the final mix. Once ail components have been added, viscosity
and pH modifiers are added to the mixture to adjust product viscosity and pH to
the extent desired.
The resulting composition provides excellent hair cleansing, lathering,
antimicrobial agent deposition on the scalp and dandruff control.
