Note: Descriptions are shown in the official language in which they were submitted.
w o 93/18737 2 1 31 6 2 6 PCT/US93/0212X
~ild shampoo co~pos~tions
TECHNICAL FIELD
The present invention is related to shampoo premix composi-
tions as well as f~nished shampoo compositions. The present
invention also relates to methods of making said mild shampoo and
shampoo premix compositions.
RACKG~OUND QFJ~ XllQ~
Mild shampoo compositions which provide low irritation to the
skin are highly desirable. Conventiona1 shampoos contain high
leve1s of harsh anionic surfactants. These sur~actants can
provide excellent latherin~ and cle~ning characteristics. How-
ever, they can also penetrate the~skin and destroy its integrit~.
This results, at the very least, in rough and/or dry skin, and can
ultimately lead to red, irritated skin. Ideal shampoo composi-
tions should provide suff kient lathering and cleaning benefits to
cleanse the hair wh~le at the same time causing l~ttle or no
irr~tation to the skin. This is particularly essential for
shampoo compositions used on babies, small children, or adults
with dry or sensitive sk~n~ ~ ~
Mild shampQo compositions, in general, are well known in the
art having been taught inf for example, European Patent Applica-
tion 0250181, p~blished December 23, 1987; U.S. Patent 4,578,216,
Fujii et al., issued March 25, 1986; U.S. Patent 4,726,915,
Verdicchio, issued February 23, 1988; U.K. Patent Specification
1,5~8,929, published April 26, 1978; European Patent Application
016026g!, published N!ovember 6, 1985; U.S. Patent 4,435,300, IGuth
;o et al., issued March 6, 1984; ~.S. Patent 4,426,310, Vernunica,
issued January 17, 1984; U.S.~Patent 3,950,417, Verdicchio et al.,
issued April 13, 1976; U.S. Patent 4,443,362, Guth et al., issued
Aprîl 17. 1984; U.S. Patent 4,654,207, Preston, issued March 31,
~ 1987; U.S~ Patent 4,851,1S4,~ Grollier et al., issued July 25,
; 35 1989; U.S. Patent 4,292,212~, Melby, issued September 29, 1981; and
~ U.5. Patent ~,329~334, ~Su et al., issued May 11, 1982. These
: `
:
WO 93/18737 PCl/~S93/0212X
3~6~6
. ~
references teach the use of a wide variety of surfactant combina
tions to achieve mildness. These surfactants include mild anionic
surfactants, such as ethoxylated alkyl sulfates, amphoterio
surfactants, nonionic surfactants, and various combinations
thereof.
One well-known mild shampoo is Johnson's Baby Shampoo (John-
son ~ Johnson). This product contains relatively high levels of
nonionic surfactant (PEG~80 Sorbitan Laurate) and other mild
surfactants ~o boost its cleaning performance (betaine, ethoxy~
lated alkyl sulfate, an imidazoline~derived amphoteric, and an
ethoxylated alkyl carboxy1ate).
The formulation of such mild shampoo compositions, however,
generally is an exercise in efficacy and mildness trade-offs, with
the resulting composition pro~iding either good cleaning and
lathering benefits, or good mildnes~ or skin irritation benefits,
but not good cleaning and lathering in combination with mildness
and low skin ir~itation.
Hence, it is an object of the present invention to provide a
mild shampoo~composition whtch provides good in-use character-
istics such as lathering, both in terms of stability, creaminess,
and abundance of: lather,~ while at the same time providing good
cleaning and skin mildness bene~its. It is also preferable that
the shampoo have~a ~pleasing aesthetic appearance which is also
referred to as~pearlescence, in addition to providing the above
`25 characteristics ~
Also desirable in ~state of the art shampoo compositions are
conditioning benefits i~nherent in the sham~oo compositions. Such
products are sometimes termed two-in-one shampoos, meaning the
compositions include bothicleaning and conditioning ingredients in
the same product. Such compositions are difficult to formulate
because the cleaning ingredients, ln general, tend to be incompat-
ible with the conditioning~ingredients. One highly successful
solution to this~ di!emma~ has been to use dispersed insoluble
~ non-volatile silicone materials~ together with certain suspending
;~ 3s agents for the sil~icone~s in shampoo compositions. Such technology
is taught in U.S. Patent 4,704,272, Oh et al., issued November 3,
~'rIT~ IT~ ~E~
PCl /US93/021 28
WO 93/18737 21316 2 6
- 3 -
1987; V.S. Patent 4,741,~55, Grote et al., issued May 3, l98B; and
U.S. P~tent 4,788,006, Bolich et al., issued June 5, l984. This
technology can also be used, usually at relatlvely lower silicone
levels, to provide some conditioning benefit in shampoos not
exp~icitly marketed as 2-in-l shampoos. Another benefit of
certain of the suspending agents referred to in these patents ts
their abil;ty to improve the aesthetic appearance of shampoos by
adding pearlescence. However, one problem with the use o~ sili-
cone materials to deliver hair conditioning from shampoo composi~
I0 tions is that such materials, in general, tend to suppress lath-
ering of the composition. If silicones are used with robust
high-lathering surfactants, such as most anionic surfactants,
lathering may not be unduly affected. However, if such materials
are used with mi1der, less robust lathering surfactants, lathering
may well be suppressed to an unacceptab~e level from a consumer
standpoint.
Hence, it is a further object of the present invention to
provide a shampoo composit~on which pro~ides excellent 1athering
and cleaning benefits while at the same time be~n~ mild to the
skin and provid~ng hair conditioning benefits through the use of
dispersed insoluble non-volatile sil~cone conditioning agents.
Alkyl sulfate surfactants can provide excellent lather an~
cleaning but tend to be harsh to the skin and are therefore not
conducive to formulating mild shampoos. Unfortunately, in the
absence of such alkyl sulfates it is difficult ta get the sus-
pending agent into the shampoo in crystalline form. It is when
the suspending agent is present ;n the shampoo in the form of a
c~ystallinè network that it is effective in suspending the sili-
cone composition. P~ovidjing the suspending agent in crystalline
form is also critical for obtaining good lathering shampoo
formulations.
It is also desirable to provide antidandruff shampoos that
are mild to the skin but retain good cleaning and lathering
characteristics. Preferably, the shampoo will contain particulate
antidandruff agents, such as zinc pyridinethione or se~enium
disulfide. These particulate antidandruff agents must be sus-
pended in the shampoo to provide a stable composition. The same
WO 93/18737 PCr/US93/02128
~,3JlL62l6 ~ '
types of suspending agents that can be used to suspend silicone
have also been found to be preferred for suspending the anti-
dandruf~ agent. Thus, the same difficulties with respect to pre-
paring high lathering, mild shampoos with the suspending agent
free of harsh alkyl sulfate surfactants are again experienced.
These and~other objects will become readtly apparent from the
detailed description which follows.
Unless otherwise indicated, all percentages are calculated by
weight of the total composition and all ratios are ca k ulated on a
weight basis.
The compositions and processes herein can comprise, consist
essentially of, or consist of any of the critical and optional
etements and steps described in this application.
SUMMARY ~F THE INVENTION
lS Mild, good lathering and cleaning shampoo c~mpositions are
provided herein comprising:
(a) from about 5% to about 20%, by weight, a1kyl ethoxytated
sulfate anionic surfactant ;
(b) from abo~t l% to aboùt l0% of a betaine surfactant of
the formula
R5 ¦ C - n - (CH2)~ - N~ - Y - R
. n R3
` 2S wherein Rl is a member selected from the group consisting o~
C N M and CH-CH250~M
OH
R~ is lower alkyl or hydroxyalkyl;
R3 is lower alkyl`or hydroxgalkyl;
R, is a member selected from the group consisting of hydrogen and
lower alkyl;
Rs is higher alkyl or alkenyl;
Y is lower alkyl,~ preferably methyl;
is an integer from 2 to 7;
n is the inteqer l~or 0; ~
is hydrogen or a cation:
:
~3lJE~E~rlT U T E ~i~UEESr
~?~-Y~ ?,~ ~Sg;~y , ~"~
WO 93/18737 PCI/VS93/02128
2131626
(c) about 2X to about 10%, by weightt of an amphoteric
surfactant having the formu1a
R~
RIcoN(cH2)n-l+ cH2Z
R~ R2
wherein R1 ls C0-C22 alkyl or alkenyl, Q2 is hydrogen or
CH2CO~M, R3 is CH2CH20H or CH2~HOCH2CH2COOM, R~ is
hydro~en, CH2CH20H, or CH2CH20CH2CH2COOM, Z ls C02M or
CH~C02M, n ~s Z or 3, and M is hydrogen or a cation;
(d) fro~ about 0.5% to about 5%, by weight, of a crystal-
lized suspending agent; ~nd
(e) from about 60% to about 85% water
wherein said composition is substant~ally free of alkyl su7fate
anionic surfactant, and the co~posit~on has a weight ratio of
~a):(b)~(c) of about 1:1 to about 4:1, preferably about 4:3 to
about 3:1, more preferably about 8:5 to about 7:3, and a weight
ratio of (d):total surfactant of about 1:4 about 1:25, prefcrably
about 1:6 to about 1:18, more preferably about 1:8 to about 1:13.
Alss preferably, the shampoo compssitions contain at least
about 15%, by weight, of total surfactants, preferably at least
about 16%, even more preferab1y at least about 17%, most
preferably at least about 18%.
In general, the preferred shampoo co~positions of the present
invention will be made from a shampoo premix compos1tion that
comprise alkyl ethoxylated anianic surfactant, specific imidazo-
linium-type amphoteric surfactant, suspending agent that has been
solubilized in the: premix at an e1evated temperature and then
crystallized to form a crystalline network by cooling the solution
(hereinafter, ~rqcrystallized suspending agent~), and about 30% to
about 70Y, water. The shampoo premix composition is also substan-
tially free of alkyl sulfates. These premixes can be used to make
,
the shampoo formulations above,: as well as other formulations as
may be desired by the formulator.:
~ More particularly, the preferred shampoo premix compositions
: 35 comprlse:
231JE3l5TIT U T E ~ #F~
w o 93/18737 P~r/~lS93/02128
2 ~ 3 ~ 6 ~ 6 - 6 -
(a) at least about 10%, by weight, of alkyl ethoxylated
sulfate anionic surfastant;
(b~ at least about 6%, by weight, of an amphoteric surfac-
tant of the formula:
R3
R~CON~CI12Jn-N~CH22
R4 R2
wherein R~ is C~-C22 alkyl or alkenyl, preferably
Cl2-C~6, R2 is hydrogen or CH2C02M, R3 is CH?CH20H or
CH2CH20CH2CH2CCOM, R4 is hydrogen, CH2CH20H, or
CH2CH20CH2CH2COOM, Z is CO~M or CH2C02M~ n is 2 or 3,
preferably 2, and M is hydrogen or a cation;
(c) from about 2% to about lSYo~ b~ weightt o~ a suspending
agent recrystallized ~n s~id premix composit~n; and
(d) from about 3~% to about 70% water;
wherein said premix has a ~eight ratio of (a):(b) of about 2:3 to
~bout 3:1, a weight ratio of (c) to total surfa~tant present of
from about 1~1 to about 1:6, and a weight ratio of (c):(d) of
about 1:2 to about 1:15, and said premix composition is substan-
tially free of alkyl sulfate anionic surfactant.
The present inYention also proYides shampoo compositions
comprisi ng shampoo premixes, as described above, further com-
prising: additional levels of the r~quired surfactants or op-
2S tionally other surfactants, though preferably the shampoo remains
substantially free of alkyl sulfate or other ingredients that are
harsh to the skin; condit~oning agents, such as the preferred
insoluble, nonvolatile silicone; antidandruff a~ents, including
particulate and soluble ant jidandruff agents; foam boosters,
prefera~ly polyquaternium 10 or other mild-to-the-skin, non amide
foam boosters; color solutions; perfumes; preservatives; or other
ingredients useful in shampoo composition; or mixtures thereof.
The present invention also provides a method for making
shampoo premix compositions comprising the steps af ( i ) preparing
a solution comprisin~: -
~VEI~T~TUTE 8HI~T
w o 93/18737 21316 2 6 PCT/US93/0212X
(a) at least about IOX, by weight, o~ alkyl ethoxylated
sulfate anionic surfactant;
(b) at least about 6X, by weight, of ~mphoteric surfac-
tant of the formula;
R3
RlCON(CH2)n~ 1+"C1-12Z
R~ R2
wherein R1 is C~-C22 alkyl or alkenyl, R2 is hydrogen or
CH2C02M, R3 is CH2CH20H or CH2CHOCW2CH2COOM, R~ is
hydrogen, CH2CH20H, or CH2CH2aCH2CH2COOM~ Z is C02M or
CH2CO~M, n is 2 or 3, and M is hydrogen or a cation; and
(c) from about 30% to about 7~%, by weight, water;
(ii) adding to the solution ~rom about 2% to about 15%, by
}5 weight of the premix, of a suspending agent wheirein said
solution is heated and said suspending agent is provided in
solubilized form; and (iii) cooliny said composition to
provide the solubilized suspending agent 1n crystalline form;
wherein said premix has a weight ratio of (a):~b) of about 2:3 to
about 3:1, a weight ratio of suspending agent to total surfactant
present of from about l:l to about 1:6, and a weight ratio of
s~spending agent:water of abs~t 1:2 to about 1:15, and said premix
composition is prepared substantially free of alkyl sulfate
anionic surfactant.
In another aspect of the invention hereof, the pH of the
premix is reduced pri~r to providing the solubilized suspending
agent in crystalline form to within about 2.0 pH, more preferably
wit~in about 1.5 pH, most preferably within about l.0 pH, of the
average PKa of the carboxylate(s) of said amphoteric surfactant.
In addition to meeting the objects of the invénti~n described
above, the shampoo and shampoo premixes hereof can also be charac-
terized by having excellent pearlescence.
The invention. ineluding preferred embodîments thereof, is
described in ~ore detail in: the Detailed Des~ription of the
3s Invention, which fol~ows.
~aBTlTUTE
WO 93/18737 PCr/US93/02128
~3~6~6 . ...
DETAILED DESCRIPTION Of THE INVEH~IOH
The essential as well as certain preferred and optimal
components of the compositions of the present invention are
described below.
A!ky~_~thoxYlated Sulfate
The shampoo composition hereof comprises at least about 5%,
~y weight, genera11y from about 5% to about 20%, preferably from
about 6% to about 17%, more preferably from about 7% to about 15%,
of alkyl ethoxylated sulfate anionic surfactant. The preferred
IO shampoo premixes for making such shampoo will comprise from about
lOX to about 25%, preferably about I~X to about 23%t more prefer-
ably from about 1~% to about 20% of said surfactant. These types
of surfactants are well known in the art. They typically have the
formula RO~C2H4O)XSO3M, wherein R is alkyl or alkenyl of from
about 8 to about 24 carbon atoms, x is I to 12, preferably, and M
is a water-soluble ~cation such as ammonium, sodium, potassium and
triethanolamine. Useful alkyl ethoxylated sulfates are conden-
sation products of ethylene oxide and monohydric alcohols having
from about 8 to about 2~ carbon atoms. Preferably, R has from
20 a~out 10 to about 18 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 hereln.~ Such~alcohols are typically reacted
` with from about'l to about 12, preferably about 2 to about 6, more
preferably about about 3, mo1ar proportions of ethylene oxide and
the resulting m1xture~of molecu1ar spectes having, for example, an
average moles of ethyléne oxide per mole of alcohol also within
the 'above limits, is sulfated and neutralized.
Specific examples of a1kyl~ethoxylated sulfates which may!be
0 used in !the present invention are sodium and/or ammonium salts of
coconut alkyl tr1ethy1ene~g1ycol ethoxylated sulfate, tallow alkyl
triethylene glycol ethoxy1ated sulfate, and tallow alkyl hexaoxy-
ethylene s~ulfate.~;Typically the alkyl ether sulfates will com-
prise a mixture of indivi;dual compounds, said mixture preferably
having an average alkyl chain length of from about IO to about 16
: : :
~VelSTlTUTE SH~
W O ~3/18737 2131 6 2 6 PCT/~S93/021 2X
carbon atoms and an average degree of ethoxylation of from about 2
to about 6 moles of`ethylene oxide, especially about 3. Espe-
cially preferred are narrow range alkyl ethoxylate sulfates such
as those having ethoxylation levels primarily in the range of l to
about 6, especially about 3.
AmDhoteric Surfactant
The amphoteric surfactant will be present in the shampoo
ccmpositions hereof at levels of from aboùt 2% to about IOZ, by
weight of the composition, preferably from about 2% to about ~%,
19 more preferably about 2.5% to about 6%. The amphoteric surfactant
will ~e used in the preferred shampoo premix compositions at a
level of at least about 6%, by weight, of the premix, preferably
about 8% to abo~t 18%, more preferably about gY. to about 15X. The
essential amphoteric surfactant hereof is depicted by Formula I:
R~
RICO;l~(cH2 )n7+-CH2Z ( I )
~ R~ R2
wherein R1 is C~ - C22 alkyl or alkenyl, preferably Cl2-C~6, R2 is
hydrogen or CH2CO2M, R~ is C~2CH20H or CH2CH20CHzÇH2COO~ R' is
hydrogen, CH2CH20H, or CH2~H20CH2CH2COOM, Z is CO2M or CH2CO2M, n
is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali
metal, alkaline earth metal, or ammonium. Examples of ~alkali
metal~ include ~ thium, sodium, and potassium. Examples of
~alkaline earth~;metal~ inc~1ude berylltum, magnesium, caicium,
strontium, and ~barium. This type of surfactant is sometimes
classified as an i~midazoline-type amphoteric surfactant, although
it should be recognized that it does not necessarily have to be
.. .
derived, directl!y olr indirectly, through an imidazoline
intermediate.
Suitable materials of thls type are marketed under the
tradename MIRANOL and are understood to comprise a complex mixture
of species, and can ex1st in protonated an~ non-protonated species
depending upon pH~with r;espect~to species that can have a hydrogen
3s at R2~ All such variations and species are meant to be encom-
passed by Formula 1. ~ ~
~ ~lJE3lSTIT U T E ~iH~EEFr
W 2 ~ 3~ 6 PCI~/ USg3/02128
- 10 ~
Preferred amphoteric surfactants of Formula I are monocar-
boxylates and Jicarboxylates. Examples of these materials include
cooamphocarboxypropionate cocoamphocarboxypropionic acid
cocoamphocarboxyglycinate ~alternately referred to as cocoampho-
diacetate) and cocoamphoacetate.
Specific commercta1 products prov~ding the amphotertc surfac-
tant component of the present compositions ~nc1ude those sold
under the trade names MIRAHOL C2M CONC. N.P. MIRANO~ C2M COHC.
O.P. MI M NOL C2M Sf MI M HOL CM SPECIAL (Miranol Inc.); ALKA-
TERIC 2CIB (Alkaril Chemicals); AMPHOTERGE ~-2 (Lonza Inc.);
MONA~ERIC CDX~38 MOHATERIC CSH-32 (Mona Industries); REWOTERIC
AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemi-
cals).
Betaine Surfactant
li The shampoo compositions will generally comprise from about
1% to about 10% preferably bout 2% to abou~ 8% more preferably
about 2.5% to about 6% of a betaine surfactant.
The betaine surfactant hereof is depicted by compounds hav~ng
the formula:
~ _ ~ R~
Rs - C-N-~CH2)m - N~-Y-R~ ( I I )
. n
~herein:
Rl is a member selected from the group consisting of
COOM and CH-CH250~M
I
OH
R2 i s l ower al ky'l or: hydrffxyal kyl;
R~ is lower al;kyl or hydroxyalkyl;
R~ is a member~selected from the group consisting of hydrogen and
lower alkyl;
R5 is higher alkyl~or al~keng~
Y is lower alkyl preferably methyl;
m is an integer from 2 to 7 preferably from 2 to 3;
~; ~U~STlTUTE ~;H~ET
w o 93/18737 2 I 31 6 2 6 P~/US~3/02128
n is the ~nteger 1 or 0;
M is hydrogen or a cation, as previously described, such as an
alkali metal, alkaline earth metal, or ammonium.
~he term ~lower alkyl~ or ~hydroxyalkyl~ means straight or
branch chained, saturated, aliphatic hydrocarban radicats and
substituted hydrocarbon radic~ls having from one to about three
carbon atoms such as, for example, methyl, ethyl, propyl, iso-
propyl, hydroxypropyl, hydroxyethyl, and the 1ike~ The term
~higher alkyl or a1kenyl~ means straight or branch chained satù-
rated (i.e., ~higher alkyl~) and unsaturated (~.e., ~hlgher
alkenyl~) aliphatic hydrocarbon radicals having ~rom about eight
to about 20 carbon atoms such as, for example, lauryl, cetyl,
stearyl, oleyl, and the like. tt should be understood that the
term ~higher alkyl or alkenyl~ inc1udes mixtures of radica1s which
may contain one or more intenmediate linkages such as ether or
polyether linkages or non-functional substitutents such as
hydroxy1 or halogen radica1s wherein the radical remains of
hydrophobic character.
Examples of surfactant bet~ines o~ fonmula ~ wherein n is
~ero which are useful herein include the alkylbetaines such as
cocodimethy1carboxymethylbetaine,~ lauryldimethyicarboxymethyl-
betaine, lauryl ;dimethyl-alpha-carboxyethylbetaine, cetyldimethyl-
carboxymethylbetaine, lauryl-bis-(2-hydroxyethyl)carboxymethyl-
bet~ine, stearyl-bis-(2-hydroxypropy1)carboxymethylbetaine, oleyl-
dimethyl-gamma-carboxypropylbetaine, lauryl-bix-(2-hydroxypropy1J-
alpha-carboxyethylbetaine, etc.~ The sulfobetaines may be repre-
sented by cocodimethylsulfopropylbetaine, stearytdimethylsulfo-
pro wlbetaine, laur~yl-bis-(2-hydroxyethyl)s~lfopropylbetaine, and
the like
Surfactant amido betaines and amidosulfo betaines useful in
; ~ the present inventlon are exemp1ified~ by compounds of formula II
wherein n is one ~but otherwise corresponding to the above ex-
amples. Examples of surfactant betalnes of formula II wherein n
is one which are useful herein include the amidocarboxybetaines,
such as cocoamidodimethylcarboxymethylbetaine, laurylamidodi-
:
: ~
f3lJEUE~rlT U T E ~i~UEE~r
w o 93/~8737 PCT/~'S93/0212
3 ~ 6 ~ 6 - 12 -
methylcarboxymethylbetaine, cetylamidodimethylcarboxymethyl-
betaine, laury1amido-bis-(2-hydroxyethyl)-car~oxymethylbetaine,
cocoamido-bis (2-hydroxrethyl)-carboxymethYlbetaine~ etc. The
amido sulfobetaines may be represented by cocoamidodimethylsulfo-
propylbetaine, stearylamidodimethylsulfopropylb2taine, laury1-
a~ido-bis-(2-hydroxyethyl)~sulfopropylbeta~ne, and the like.
The preferred betaine in the present invention is a me~ber
selected from the group consist~ng of surfactant amidocarboxy-
betaines and amidosulfobetaines. More preferred betaines are the
surfactant amidocarboxybetaines, particularly cocoamidodimethyl-
carboxymethylbetaines, sold by Goldschmidt Co. under the trade
name Tegobetaine F, and by Hoechst~Celanese under the trade name
Genagen CAB. These most preferred betaines have the formula:
O CH~
R ,-I-NH-(CH2 j,-N-CH2-COOM
CH3
wherein R'~ is selected from C8 to C18 alkyl radicals and M ts as
defined above. In general, the preferred betaines hereof will
have low levels of resid~al amide~and sodium monochloroacetate.
; Suspendin~ Aqent
Suspending~agents useful in the present compositions include
those which can exist in the~ comp~ositions hereof in crystalline
form. Other suspending agents useful for suspending nonyolatile,
insoluble silicone ~fluids and/or particulate matter (such as
particulate antidandruff agents) can also be used. Preferred
crystalline suspending agents are acyl derivatives and amine
oxides especially acyl derivatives, which can be solublized in the
shampoo premix solution and then be recrystallized upon cooling.
These materials~ wil~l clomprise long chain (e.g., C~-C22 preferably
Cl6.C22) aliph~atic~ groups,~ i.e., long chain acyl derivative
. materials and 1ong cha;in~amine ox~ides, as we!l as mixtures of such
materials. This suspending agent is present in the shampoo
I ~ compositions hereof at a level of about 0.5% to about 5%, prefer-
ably about 1% to about 4%, most preferably about 1% to about 3X~
;: :
` ~V E31STIT U T E ~i~llEe~r
WO g3/18737 2 1 ~ 1 6 2 6 PCI/US93/02128
- 13 -
and in the shampoo premixes hereof at a level of from about 2% to
about 15%, by weight, preferably from about 4% to about I2%, more
preferably ~rom about 5% to about 9X.
In addition to providing a network to support insoluble
materials, the suspending agents hereo~ can also impart
pearlescence to the compositions. ~hereas it is preferred to
include insoluble materia1s, such as stlicone conditioning agents
and particulate matter (e.g., antidandruff agents) into the
composit~ons, it is also contemplated that th~s in~ent~on to
compositions containing the suspending a9ents hereof without also
containing insolubte materials that need suspending. Such
compositinns can st111 beneflt by combintng mi1dness and good
cleaning and lathering in combination with improved aesthetic
appearance~ i.e., pearlescence.
I5 Examples of suitable suspending agents are described in U.S.
Patent 4,741,855, Grote and Russell, issued May 3, 1988, incorpo-
rated herein by reference. Suitable suspending agents for ~se
herein include ethylene gl~col esters of fatty acids preferably
having from about l4 to about 22 carbon atoms, more preferably
I6-22 carbon atoms. More preferred are the ethylene glycol
stearates, both mono and dlstearate, but particularly the di-
stearate containing less than about 7X of the ~ono stearate.
Other suspending agents found ~seful inc1ude alkanol amides of
fatty acids, preferably having from about 16 to about ~2 carbon
atoms, more preferably about 16 to 18 carbon atoms. Preferred
alkanol amides are stearic monoethanolamide, stearic diethanol-
amide, stearic mon~oisopropanolamide and stearic monoethanolamide
stea-rate. Other long chain acyl derivatives include long chain
esters of long chain fatty acl,ds (e.g., stearyl stearate, cetyl
palmitate); glycery~ esters (e.g., glyceryl distearate) and long
chain esters o~ long cha~in 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.`
'
~UU EIE~rIT U T E ~itUEE~r
.. .. .. . . .. . . . . ... ... . .. .. ... . .. . .. . .
WO 93/18737 PCT/US93~0212~
3~6~6
- 14 -
Suspending agents a1so include lon~ chain amine oxides such
as alkyl (Cl~-C22) dimethyl amine oxides, e.g., stearyl dimethyl
amine oxide. If the compositions contain an amine oxide or a long
chain acyl derivative which is a surfactant, the suspending
function could also be provided SbY such amine oxide or acyl
derivative, provided at least a p~rt~on of ~hem are present in
crystalline form, and add~tiona1 suspend~ng ag~nt may not be
needed.
Other lcng chain acyl derivatlYes that can be used include
N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof
(e.g., Na and K salts), particularly H,N-di(hydrogenated) C16, Cl~
and tallow amido benzoic acid species of this family, which are
commercially available from Step~n Company (Northf~eld, Illinois,
USA).
~he suspending agent serves to assist in suspending the
silicone material, particulate antldandruff agent, or other
particulate matter in shampao compositions hereof, and may give
pearlescence to the product.
The suspending a~ent can be incorporated ~nto the shampoo
premixes hereof by solubilizing it into a solution containing the
above described ingredients at a temperature above the melt~ng
point of the suspending agent in the surfactant premix. The.
suspending agent is then recrystallized, typically by cooling the
solution to a temperature sufficient to induce crystallizatton.
In order to facilitate this, it ~s preferred that the pH of the
solution be below about 7. In a particularly preferred aspect of
the invention hereof, the pH is reduced prior to providing the
suspending agent in crystalline form to with;n about 2.0 pH, more
preferably within about l.5 pH, most preferably within about 1 0
pH of the average PKa of the carboxylate(s) of said amphoteric
surfactant. In general, the pH is adjusted in the preferred
embodiments, such as for cocoamphoacetate and cocoamphodiacetate,
to levels of from below 7.0 to about 4.0, more preferably from
about 4.5 to about 6.5. The pH of the solutton, unadjusted, will
3S normally be h~gher than that, and can be reduced by addition of
.
:
~3U13BTITUTE ~;HEE'r
WO 93/18737 PCI/US~3/02128
2131 626
- 15 -
acids according to known techntques for pH adjustment. Suitable
pH ad,~us~rs inc1ude hydrochloric acid, citric actd, sulfuric
acid, etc., preferably hydrochloric acid and citric ac1d.
Wate~
S The shampoo ~ompos1tton hereof will also comprise water.
Generally, the compos~t1On w~11 contain ~rom about 50X to about
90% water, preferably about 60% to about 85% water, more prefer-
ably from about 65% to about 80%.
The shampoo premtxes p~eferably used herein ln making the
shampoo composition wi~l contain water at a level of from about
30% to about 70%, by weight, of the premix, preferably from about
45% to about 65%.
The shampoo premix compositions hereof are further charac-
terized by a weight ratio of alkyl ethoxylate sulfate to the
amphoteric surfactant of formula (I) of about 2:3 to a~out 3:1,
preferably about 1:1 to about 5:2, by a weight rat~o of suspending
agent to total surfactant of about 1:1 to about 1:6, preferably
about 2:3 to ~bout 1:5, and b~ a weight rat10 of suspendtng agent
to water of about 1:2 to about:l:l5, preferably about 1:4 to about
1:1~, more preferably about 1:6 to about 1:12.
The shampoo and premixes hereof are substantially free of
alkyl sulfate surfactants. It is recognized that there will
generally be some alkyl sulfate pr~sent as a result of it being
pr~sent in commercially availabl~ alkyl ethoxylated su~fate raw
mater~als. For example, commercially available alkyl (3} ethoxy-
lated sulfate typically contains ~about 20% by weight alkyl sul-
fate; commercially available alkyl (2J ethoxylated sulfate, about
: 25% to about 40% alkyl sulfate. For purposes hereof~ to be
substantially free of alkyl su1`fate the compositions hereof should
have an alkyl sulfate:alkyl ethoxylated sulfate weight ratio of no
more than about 0-.35 (preferably no more than about 0.30, more
preferably no more than about 0.25 for average ethoxylate levels
of 2.5 and highcr. :For alkyl ethoxylated sulfate with an average
ethoxylate level of less than 2.5, the ratio should be no more
than about 0.40, preferably no more than about 0.35, more prefer-
~JE3~iTIT U TE~ E~r
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2~3~626
- 16 -
ably no more than about 0.30, most preferably no mare than about
O.Z5. It ~s preferred that no additional amount of alkyl sulfate
be added other than that which occurs inherently ~ith the alkyl
ethoxylated sulfate. It is also preferred that shampoo composi-
S tions made fro~ the premixes hereof also be substant1ally free of
alkyl sulfate, as defined above. The use of narrow range ethoxy-
lates to lower the alky1 su1fate: alkyl ethoxylated sulfate weight
ratio is preferred. ~Narrow range ethoxylate~ refers to alkyl
ethoxylated sulfate surfactants that have been processed to reduce
alkyl sulfates and optionally alkyl ethoxylated sulfates outside
o~ the desired range of ethoxylation. The use of narrow range
ethoxylates can be used to lower the alkyl sulfate:alkyl ethoxy-
lated sulfate weight ratio to the preferred levels hereof, in-
cluding to levels as low as abaut 0.2 or even about 0.1, and less.
lS It is also preferred that no other ingredients that are harsh
to the skin or cause undue eye irritation, such as amide foam
boosters (e.g., cocomonoethanolamide, CMEA), be added to the
premix or shampoo compositions hereof.
Method of Makinq ShamDoo Prem~
The preferred shampoo premixes can be made according to a
process comprising the steps o~f:
(i) preparing a solution comprising:
~a) at least about lOZ, by weight, of alkyl ethoxylated
sulfate anion~c surfactant;
~b) at~;1east about 6% by weight, of amphoteric surfac-
tant of the formula;
~ R~
R~CON~CH2)n~l+ C~2Z
~ ; R' ! R2
wherein R1 is t~-C22 alkyl or alkenyl, RZ is hydrogen or
CH2C02M, R3 is CH2CH20H or CH2CHOCH2CH2COOM, R' is
hydrogen;, CHzCH20H, or CH2CH20CH2CH2COOM, Z is C02M or
CH2C02M, n is 2 or 3, and M is hydrogen or a cation as
~; 35 defined ~above;~and
1JEa~STIT U TE~ t~Ee~r
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- 17 -
(c) from abo~t 30% to about 70%, by weight, water;
(ii) adding to the solution from about 2Z to about 15%, by
weight of the premix, o~ a suspending aqent wherein said
solution is heated and said suspending agent is provided in
solubilized form; and cool1ng said compositton to proYide the
solubilized suspending agent iln crysta1t~n~ form;
wherein said premix has a weight rat~o 9f (a):(b) of about 2:3 to
about 3:1, a weight ratio of suspend1ng agent to total surf~ct~nt
present of from about 1:1 to about 1:6, and a weight rat~o of
10suspending agent to water of about 1:2 to about 1:15, and s3id
premix compositiion is prepared substant~ally free of alky1 su~f~te
anionic surfact~nt. Preferred rat~os are the same as those listed
above ~or the premix composit~on.
Typically, the solution will be heated to from about 6~C to
15about ~5-C, preferably about 65'C to about 80-C, to solubillze
suspending agent which has been add2d in crystalline foro.
Alternately, the solution can be first heated to a suffic~ent
tewperature for the suspending agent to remaiin or become sol~
lized, and then the suspend~n~ agent can be added to it in eitber
solubilized or crystalline form. As used herein ~solubilized~
suspending agent, suspending agent in ~solub1l~zed fon~, and
~solubilizing~ the suspending agent shall include solubilization,
emulsification, and/or melting of the suspending agent. Th,e
temperature required will vary accordin~ to the particul~r surf~c-
tants and levels chosen, as well as the level of and selection ofparticular suspending agent.~ These factors will also affect the
temperature to which the premix must be cooled to induce cryst~-
lization. fo~ example,~higher levels of alkyl ethoxylated sulfa~e
and lower leYels of imidazolinium will generally require low2r
crystallization temperaturè. Typically, the composition wil~ ~e
cooled to between about 15-C and about 60-C, preferably between
about 20-C and about 55-C`, more preferably between about 2~^C to
about 45-C. ~ ~
-The pH of the solution ~(prior to recrystallizing the sus-
pending agent~ in preferred embodiments is below about ?, prefer-
; ably from about 4 to about 7. The pH of the solution, unadjusted~
will normally~ be higher than that, and can be reduced by addition
~3~EaErrIT U ~r~ r
WO g3/18737 pcr/lJs93/o2128
6~6
- 18 -
of acids according to know techniques for pH adjustment. Suitable
pH adjustors include hydrochloric acid, citric acid, sulfuric
acid, etc., preferably hydrochloric acid and citric acid. In a
particularly preferred aspect of the invention hereof, the p~ is
reduced prior to providing the suspending agent in crystalline
form to within about 2.0 pH, more preferably with1n about 1.5 pH,
most preferably within about I.0 pH of the average pKa of the
carboxylatets) of said amphoteric surfactant. In general, the pH
is adjusted in the pre~erred embodiments, such as for cocoampho-
acetate and cocoamphodiacetate to levels of from below 7.0 to
about 4,0, more preferably from about 4,5 to about 6.5.
The shampoo premix compositions hereof can be utilized
directly for cleaning purposes. Preferably it is formulated into
shampoo compositions, as described herein, said shampoos optional-
ly containing additional surfactants of the type included in the
premix, other surfactants, and other ingredients useful in the
formulation of shampoos. The premixes hereof can also be used to
make other shampoo fonmulations. Preferably, the ingredients
added do not cause signiflcant harshness to the sktn. Preferred
shampoo compositions have low or essentia11y zero levels ~prefer-
ably less than about 5%, more prefer-bly less than about 3%, eYen
more preferably less than 2%) of alkyl sulfates. The compositions
hereof also preferably have low or essentially zero levels of
other harsh-to-the-skin surfactants. Preferably sa~d harsh
ingredients present come from the natural distribution produced in
the ethoxylation process) and are not added separately, although
they may be so~long as they are present within the above-defined
limits. further, the shampoo compositions hereof and shampoo
premixes preferably have jlow or essentially zero level of am!ide
foam boosters (preferably less than about 0.5%, more preferably
0%) .
Additional Inqredients
In preferred formulat~ions,~ the present invention provides a
shampoo comprising shampoo premix and insoluble, nonionic silicor.e
conditioning agent, a; mild-to~-the-skin foam booster, an anti-
,
:: :
8U~TITUTE ;H~ET
WO 93/18737 21 31 6 2 6 pcr/us93/o212x
19
dandruff agent, or a combination thereof. Exemplary additional
composition in~redtents are described below.
Additional ingredients that can be ùsed ~nclude other an-
ionic, nonionic, and amphateric surfactants, as well as zwitter-
ionic and cationic surfactants and additional amounts of the
surfactants described above.
Anionic S_rI~actants
A suitable class of antonic surfactants are the water-
soluble, organic salts of the general formula:
Rl-S03-M
wherein Rl is chosen from the 9roup conststin9 of a straight or
branched chain, saturated aliphatic hydrocarbon rad~cal ha~ing
from about 8 to about 24, preferably about 12 to about 18, carbon
atoms; and M is a catton. Important examples are the salts of an
lS 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, H2SO~, oleum,
obtained according to known sulfonation methods, including bleach-
20 ing and hydrolysis. Preferred are alkali metal ~and ammonium
sulfonated Cl2.1g paraffins.
M ditional examples of anionic surfactants whtch come within
the terms of the~present inventton are the reaction products of
fatty acids esterified with 1sethionic actd and neutral~ied with
25 sodium hydroxtde~where, for example, the fatty acids are derived
from coconut oil; sodium or potassium salts of fatty acfd amides
of methgl tauride in ~ which~ the ~fatty acids, for example, are
derived from coconut oil. Other anionic synthettc surfactants of
this variety~ are~set forth in!U!.S. Patents 2,486,g2I; 2,486,922;
3~ and 2,396,278.
Still other anlonic~ surfactants include the class designated
as succinamates. This cl-ss ;~ncludes such surface active agents
as disodium N-octadecylsulfosuccinamate; tetrasodium N-(1,2-
dicarboxyethyl)-N-cctadecyl~sulfosuccinamate; diamyl ester of
sodium sul hsucclnic~ acid;~dihexyl~ ester of sodium sulfosuccinic
acid; dioctyl esters~of sodium sulfosuccinic acid.
~ U Et~3T1T U T E StUEEFr
WO 93/18737 PC~/US93/02128
3~L6C~6 - 20-
Other suitable anionic surfactants utilizable herein are
olefin sulfonates having about 12 to about 24 carbon atoms. The
term ~olefin sulfonates~ is used herein to mean compounds which
can be produced by the sul~onation of ~-olefins by means of
uncomplexed sulfur trioxite, followed by neutral k atton of the
acid reaction mixture in conditions such that any sulfones ~h~ch
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, ch10rinatet hydro-
carbons, etc., when used ~n the liquid form, or by air, nitrogenS
gaseous S02, etc., when uset in the gaseous form.
The ~-olefins from which the olefin sulfonates are derived
are mono-olefins having about I2 to about 24 carbon atoms, pre-
ferably about 14 to abo~t 16 carbon atoms. Preferably, they are
straight chain olefins. Examples of suitable l-olefins include
}-dodecene; l-tetradecene; I-hexadecene; l-octadecene; l-eicosene
and l-tetracosene. ;
In addition to the true alkene sulfonates and a proportion of
hydroxy-alkanesulfonates. the olefin sulfonates can contain m~nor
amounts of other 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~dùring the sulfonation process.
A specific ~-olefin sulfonate mixture of the above type is
described more fully~in the U.S. Patent 3,332,880, Pflaumer and
Kessler, issued Juty 25, l967, incorporated herein by reference.
Another class~of anionic sur~actants are the B-alkYloxY
alkane sulfonates. These compounds have the following formula:
! OR2 H I I
Rl - C - ~C -;S03M
:
~; ~ H
~:; ~: :
~3 U i3~iTIT U T E ~; HlE~r
WO ~3/18737 2 1 3 1 6 2 6 PCl`/US93/0212X
- 21 -
where Rl is a straight chain alkyl group havtng 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 is a water-soluble
cation as hereinbefore described.
Specific examples of ~-alkyloxy~alkane-l-sulfonates, or
alternatively 2-alkyloxy-alkane l-sulfonates, having low hardness
~calcium ~on) sensit~vity useful hereln include: potassium-~-
methoxydecanesulfonate, sod~um 2-methoxy-tridecanesulfonate,
potassium 2-ethoxytetradecylsulfonate, sodium 2-isopropoxyhexa-
decylsulfonate, lithium 2-t-butoxytetradecy1-sulfonate, sodium
~-methoxyoctadecylsulfonate, and ammonium ~-n~propoxydodecyl-
sulfonate.
Many addit~onal synthet~c anionic surfactants are described
in McCutcheon's. Emulsifiers and Deterqents. 1989 Ann~al, pub-
lished by M. C. Publishing Co., which is incorporated herein by
reference. Also U.S. Patent 3,929,678, Laughlin et al., issued
December 30, t975, discloses many other anionic as well as other
surfactant types and is incorporated herein by reference. Soaps,
of course, also fall within the scope of anionic detersive
surfactants that can be used.
Nonionic Surfactants~
Nonionic surfactants in addition to the PEG glyceryl fatty
esters can be used as detersive surfactants. They are preferably
used in combination with an anionic, amphoteric, or zwi-tterionic
surfactant, or mixtures thereof. Nonionic surfactants include
those broadly defined as compounds produced by the condensation of
alkylene oxide groups (hydroph~lic in nature) with an organic
hydrophobic compound, which may be aliphatic or alkyl aromatic in
nature. Examples of classesIofjnonionic surfactants are: -
1. The polyethylene oxide condensates of alkyl phenols,
e~., the condensation products of alkyl phenols having an alkyl
group containing from~about 6 to about 20 carbon atoms, preferably
from about 6 to about l2, in either a straight chain or branched
chain configurat10n,~ with~ethylene oxide, the said ethylene oxide
being present in amounts equal to from about lO to about 60 moles
~IJE3~1rIT U T E ~ EEFr
WO ~3/18737 . PCI~/US93/02128
~,~3~6C~6 - 22 -
of ethylene oxide per mole of alkyl phenol. The alkyl substituent
in such compounds may be derived from polymerized propylene,
d;isobutylene, octane, or nonane, for example.
2. Those derived from the condensation of ethylene oxide
with the product result1ng from the reactton of propylene axide
and ~thylene diamtne products wh1ch may be var~ed 1n co~pos;tion
depending upon the balance between the hydrophob~c and hydrophilic
elements which is desired. For examp1e, compounds containing from
about 40% to about 80% polyoxyethylene by weight and having a
10~olecular weight of from about 5,000 to about 11,000 resulting
from the reaction of ethylene oxide groups with a hydrophobic base
constituted of the reaction product of ethylene diamine and excess
propylene oxide, said base having a molecular weight of the order
of about 2,500 to about 3,000, are sat~sfactory.
153. ~he condensation product of aliphat~c alcohols having
~rom about 8 to about 18 carbon atomst in either straight chain or
branched chain configuration, with ethylene oxide, e.g., a coconut
alcoho1 ethylene oxide condensate having from about 10 to about 30
mo1es of ethylene oxide per mole of coconut alcohol, the coconut
alcohol fraction having from abo~t lO to about 14~carbon atoms.
4. Long chain tertiary amine oxides correspond;ng to the
following general formula:
RlR2R3N ~ > O
wherein Rl contains an alkyl, alkenyl or monohydroxy alkyl radical
2S of from about 8 to about I8 carbon atoms, from 0 to about 10
ethylene oxide moieties, and~ from 0 to about 1 glyceryl moiety,
and R2 and ~3 contain from about l to about 3 carbon atoms and
from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl,
~ hydroxyethyl, or hydroxypropyl~ radicals. The arrow in the formula
is a conventional representation of a semipolar bond. Examples of
amine oxides su;table for use in this invention include dimethyl-
dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyl-
octylamine oxide, dimethyl-decylamine oxide, d;methyl-tetradecyl-
amine oxidei 3,6,9-trioxaheptadecyldiethylamine oxide, dit2-
hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine
:
~3~J~3SiTIT U T E S H ~Fr
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- 23 -
oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropYl) amine oxide,
dimethylhexadecylamine oxide.
5. Long chain tert1ary phosphine oxides corresponding to
the following general formula:
RR'R~P -~ 0
wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical
ranging from about 8 to about 18 carbon atoms ~n chain length,
from 0 to about lO ethy1ene oxide moieties and fram 0 to about l
glyceryl moiety and R' and R~ are each alkyl or monohydraxyalkyl
groups containing from about 1 to about 3 carbon atoms. The arrow
in the formula is a conventional representation of a semipolar
bond. Examples of suitable phosphine oxides are:
dodecyldimethylphosphine oxide, tetradecyldimethy1phosphin2 oxide,
tetradecylmethylethylphosphine oxide. 3,6,9,-trioxaoctadecyldl-
lS methylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-
hydroxypropyldi(2-hydroxyethyl) phosphine oxide, stearyldlmethyt-
phosphine oxide, cetylethylpropylphosphine oxide, oleyldiethyl-
phosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethyl-
phosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hy-
droxymethyl)phosphine oxide, dodecyld~(2-hydroxyethyl)phosphine
oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydi-
methylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.
6. Long chain dialkyl sulfoxides contatning one short chain
alkyl or hydroxy alkyl radical of from about l to about- 3 carbon
2S atoms (usually: methyl) and one long hydrophobic chain which
include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals
containing from about 8 to about 20 carbon atoms, from 0 to about
: ~0 ethylene oxide moieties and fro~ 0 to about l glyceryl moiety.
Examples include: octadecy! j methyl sulfoxide, 2-ketotridecyl
methyl sulfoxide, 3,6,9,-trixaoctadecyl 2-hydroxyethyl sulfoxide,
dodecyl methyl sulfoxide, oleyl 3-hy~roxypropyl sulfoxide, tetra-
decyl methyl sul foxide, 3-methoxytridecyl methyl sulfoxide,
3-hydroxytridecvl methyl sulfoxide, 3-hydruxy-4-dodecoxybutyl
; methyl sulfoxide.
~ 35
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6?J~ - 24 -
7. Other nonionic surfactants can also be used in the
compositions hereof. Polysorbates, e.g.~ sucrose esters of fatty
acids. Such materials are described in V.S. Patent 3,480,616,
e.g., sucrose cocoate (a mixture of sucrose esters of a coconut
acid, consist1ng primarily of monoesters, and sold under the
tradenames GRILLOTEH LSE 87K from RITA, and CRODESTA SL-40 from
Croda).
Alkyl polysaccharide nonionic surfactants are disclased in
U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a
hydrophobic group containing from about 6 to about 30 carbon
atoms, preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g., a polyglycos~de, hydroph~t~c group. The
polysaccharide can contain from ab~ùt 1.0 to about 10, preferably
from abcut 1.3 to about 3, most preferably from about 1.3 to about
2.7 saccharide units. Any reducing sacchar1de containing 5 or 6
carbon atoms can be used, e.g., gl~cose, galactose and galactosyl
moieties can be substituted for the glucosy1 mo~eties. (Op-
~onally the hydrophobic group is attached at the 2-, 3-, 4-, etc
pos~ttons thus giving a glucose or galactose as opposed to a
glucoside or galactoside.) The intersaccharide~ bonds can be,
e.g., between the one position of the additional saccharide units
and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide
units.
Optionally~, and less desirabty, there can be a polyalkytene-
oxide cha~n joining the hydrophobic moiety and the polysaccharide
moiety. The preferred alkyleneoxide is ethylene oxide. Typical
hydrophobic groups ~include alky1 groups, elther saturated or
unsiturated, branched or unbranched containing from about 8 to
about 18, preferablyl from about 10 to about 16~ carbon atoms.
Preferably, the alkyl group is a straight chain saturated alkyl
gro~p. The alkyl group can contain up to about 3 hydroxy groups
and/or the polyalkyleneoxide cha~in can contain up to about 10,
preferably less than 5, alkylene moieties. Suitable alkyl poly-
saccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl,
~etradecyl~ pentadetyl, hexadecyl, heptadecyl, and oc~adecyl, di-,
~31JE~E~rlT U T E ~; H~Sr
WO 93/18737 2 1 3 1 6 2 6 PCI/~S93/0212X
- 25 -
tri-, tetra-, penta~, and hexaglucosides, galactosides, lacto-
sides, glucoses, fructosides, fructoses and/or galactoses.
Suitable mixtures inelude coconut alkyl, di-, tr~-, tetra-, and
pentagluscosides and tallow a1kyl, tetra-, penta-, and hexagluco-
sides.
Th~ preferred alkyl polysaccharides are alkylpolyglycosides
of the formula
R~o(cnHtno)(glycosyl)x
wherein R2 is selected from the group cons~stlng of alkyl, alkyl-
phenylt hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in
which alkyl groups contain from about lO to about 18, preferably
from about 12 to about 14, carbon atoms; n is 2 or 3, preferably
2; t is from 0 to about 10, preferab1y 0; and x is from 1.3 to
about lO, preferably from 1.3 to about 3, most preferably from
lS about 1.3 to about 2.7. The glycosyl is preferably derived from
glucose. To prepare these compounds, the a1cohol or alkylpo1y-
ethoxy alcohol is formed first and then reacted with glucose, or a
source of glucose, to form~ the glucoside (attachment at the
l-positiont. The additional glycosYl units can then be attached
;~ 20 b~tween their I posit10n and;the preceding glycosyl units 2-, 3-,
-4- and/or 6-position, preferably predominantly the 2-position.
Zwitterionic and Amphoteric ~urfactants
Zwitterionic surfactants~ re exemplified by those which can
` be broadly~ described as ~derivattves of aliphatic quaternary
ammonium, phosphonium,;~ and~ sul *nium compounds, in which the
aliphatic radicals can be~stnight or branched chain, 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,; pqosphate, or phosphonate. A general formula
for these compounds is:
(R3)x~
; R2~- Y(+)~ CH2~- R4Z(-)
wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of
from about 8 to about~I8 carbon atoms, from 0 to about 10 ethylene
IEa~STIT U T E ~iH~EE~r
WO 93/18737 PCI/US93/02128
2~3~ 626
- 26 -
oxide moiet~es and from 0 to about I glyceryl moiety; Y is se-
lected 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 ~s 1 when Y ~s a sulfur atom,
S and 2 when Y ~s a nitrogen or phosphorus atom; R4 ~s an alkylene
or hydroxyalky1ene of from about I to about ~ carbon atoms and Z
is a ratical selected from the group consist~ng of carboxy1ate,
sulfonate, su1fate, phosphonate, and phosphate groups.
Examples of such surfactants tnclude:
4-~N,N-di(2-hydroxyethyl)-N-octadecylammonio~-butane-l-carboxy-
late;
5-~S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-l-
sulfate;
3-~P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxy-
propane-l-phosphate;
3-~N,N-dipropyl-H-3-dodecoxy-2-hydroxypropylammonio]-propane-1-
phosphonate;
3-(N,N-dimethyl-N-hexadecylammonio)propane-l-su1fonate;
3-(N,N-dimethyl-N-hexadecylammo:nio)-2-hydroxypropane-1-sulfonate;
~-[H,N-di(2-hydroxyethyl)-H-(2-hydroxydodecyl)ammoni,o~-butane-1-
: carboxylate; : :
3-lS-ethyl-S-(3~-dodecoxy-Z-hydroxypropgl)sulfoniol-propane-l-
phosphate; :
3-[P,P-dimethyl-P-dodecylphosphoniol-propane-l-phosphonate, and
: 2S 5-lH,N-di(3-hydroxypropyl?-N-hexadecy!ammonio]^2-hydroxy-pentane-
l-sulfate. ::
Examples of:amphoteric surfactants which can be used in the
~: compositions of the present invention are those which are broadly
described as derivatives~ of.~ aliphatic secondary :and tertiary
amines in which the al;iphatic radical can be straight or branched
chain and wherein one of the aliphatic substituents contains from
~ :: about 8 to:about :18 carbon atoms and one contains an anionic water
-~ solubilizing group:, e.g.,~carboxy, sulfonate, su!fate~ phosphate,
: or phosphonate. Examples of compounds falling within this defini-
tion are sodium 3-dodecyl-am~nopropionate, sodium 3 dodecylamino-
~ : ,
~ 8~JBBTITUTE ~iHEE~
w o 93/18737 21316 2 6 P ~ /uss3/o2128
- 27 -
propane sulfonate, sodium lauryl sarcostnate, N-alkyltaurines such
as the ~ne prepared by reacting dodecylamtne with sodium ise-
thionate according to the teaching of U.S. Patent 2,658,072,
N-higher alkyl aspartic acids such as those produced according to
the teaching of U,S. Patent 2,438,091, and the products sold under
the trade name ~Mlranol~ and described ln U,S. Patent 2,52~,378.
Other amphoteric surfactants lnclude sultaines and amidosul-
taines. Sultaines and amidosultaines can advantageously be
utilized as foam enhancing surfactants that are mild to the eye in
part~al replacement of anionic surfactants. Sultaines, includtng
amidosultaines, include for example, cocodimethylpropylsultatne,
stearyldimethylpropylsultaine, lauryl-bis-(2-h~droxyeth~l) pro-
pylsultaine and the 11ke; and the am~dosulta~nes such as coco-
amidodimethytpropylsultaine, stearylamidodadimethylpropylsultaine,
laurylamidobis-~2-hydroxyethyl) propylsultaine, and the l~ke.
Pre~erred are amidohydroxysultaines such as the Ct2~C~ h~dro-
carbyl amidopropyl hydroxysultaines, especia11y Cl2-C~ hydro-
carbyl amito propyl hydroxysultaines, e.g., laurylamidopropyl
hydroxysultaine and cocamidopropyl hydroxysuIta1ne. Other sul-
taines are disclosed in U.5. Patent 3,950,417, issued April 13,
1976, incorporated herein by reference.
Another specific class~ of amphoteric surfactants is defined
by the aminoalkanoates of the~formula:
R-NH~CH2)nCOOM ; and
~:
the iminodialkanoates of the~formula:
' ~
R-N[(CH2)mcOoM] 2
and mixtures thereof; wherein n and m are numbers from 1 to 4, R
is C~ - C22 alkyl or alkenyl, and M is hydrogen, alkali metal,
alkaline earth metal, ammonium or alkanolammonium.
Examples of amphoteric surfactants falling within the
aminoalkanoate form:ula include n-alkylamino-propionates and
:: ~
:
~U EUE~rIT U T E ~i~UEE~r
w o 93/1X737 PCT/~S93/02tZ8
2 ~ 3 ~ 6 ~ 6 - 28 -
~ n-alkyliminodipropionates. Such materials are sold under thetradename DERIPHAT by Henkel and MIRATAINE by Miranol, lnc;
Specific examples include N-lauryl-beta-amino propionic acid or
salts thereof, and N-lauryl-beta-imino-dipropionic acid (DERIPHAT
160C) or salts thereof, and mixtures thereof.
Conditionina Aqent
A preferred optional component hereof is a conditioning agent
suitable for conditioning hair or çkin. Especially preferred are
si1iccne cond~t~oning agents, parttcularly nonvolat~le, insoluble
silicone conditioning agents. The shampoo compos1tlons, in partl-
cular, will preferably comprise from about 0.01% to about lOX, by
weight, of such siticone conditioning a~ent, more preferably from
about 0.0l% to about 5%, even more preferably from about 0.05% to
about 3%, and most preferably from about O.lX to about 2.5%. The
silicone conditioning agent comprises a nonvolat~le, insoluble
silicone fluid. The silicone conditioning agent for use herein in
shampoo compositions will preferably hav:e aver-ge viscosity of
~rom about 1,000 to about 2,000,000 centistokes at 25-C, more
preferabl~ from about I0,000 to about 1,800,000 centistokes, even
more preferably from about lO0,000 to about 1,500,000 centistokes.
Lower viscosity nonvolatile silicone conditioning agents, however,
can also be used. Viscosity can be measured by ~eans of a glass
capillary viscometer as set forth in Oow Corning Corporate Test
Method CTM0004, July 20, 1970.
~ 25 As used hereinafter, the term ~insolub1e~ in reference to the; silicone cond~tioning agent shall mean that the si1 k one material
is not solubl- ~in water. The term ~nonvolatile~ in reference to
the silicone conditioning agent as used herein sha11 be inter-
preted according to the meaning well understood to those skilled
in the i~art, i.e., the silicone fluid exhibits very low or no
significant ~apor~ pressure~ at ambient conditions. The term
; ~silicone fluid~sha11 mean ~lowab1e silicone materials having aviscosity of 1ess than~l,000,000 centistokes at 25-C. Generally,
the viscosity of the fluid wil1 be between about 5 and 1,000,000
centistokes at~25-C,~preferably between about lO and about 100,000
~: -
~3~lf3lgnrlT U T E ~ EEFr
WO 93/18737 2 1 3 1 6 2 6 PCr/US93/02t2X
,....
- 29 -
centtstokes. The sil kone condittoning agent hereof can also
comprise silicone gums~ which are also nonvolatile and insoluble,
Silicone gums are later described. The term ~silicone~, as used
herein, shall be synonomous with the term ~polysiloxane~.
Suitable nonvolatile silicone fluids for use in hair condi-
tioning agents include polyalkyl siloxanes, polyaryl siloxanes,
polyalkylaryl stloxanes, po1yether s110xane copolymer and mixtures
thereof. However, other sil~cone fluids having ha~r condit~oning
propert~es may be used. ~he nonvolat~le polyalkyl siloxane fluids
that may be used include, for example, polydimethylsiloxanes.
These siloxanes are availabl e, for example, from the General
Electric Company as a Viscasil series and from Oow Corning as the
Oow Corning 200 series. Preferably, the viscosity ranges from
about 10 centistokes to about lOO,OOO centistokes at 25'C.
The polyalkylaryl siloxane fluids that may be used, also
include, for e~amp1e, polymethylphenylsiloxanes. These siloxanes
are available, for example, from the General Electric Company as
Sf 1075 methyl phenyl fluid or from Oow Corning as 556 Cosmetic
Grade Fluid.
~he polyether siloxane copolymer that ~ay be used includes,
for ex~mple, a polypropylene oxide modified dimethylpolysiloxane
~e.g., Dow Corning OC-1248) although ethylene oxide or mixtures o~
ethylene oxide and propylene oxide~may also be used. The ethylene
oxide and polypropylene oxide level must be sufficiently low to
prevent solubility in water and the composition hereof.
Silicone fluids hereof~also include polyalkyl or polyaryl
~ siloxanes with the fo;llowing~structure:
;~ R R R
~; 30 A - Si - O Si - O - Si - A
R~ R x R
:: ~
wherein R is alkyl or aryl, and x is an integer from about 7 to
about 8,000 may :~be used~ A" represents groups which block the
ends of the silicone;chains.
~ .
~ ~3 UI3I3TIT U T E ~i~UEEFr
WO 93/18737 PCr/US93/02t2X
3~6~ 30-
The alkyl or aryl groups substituted on the slloxane chain
~R) or at the ends of the siloxane chains (A) may have any
; structure as long as the result1ng silicones remain fluld at room
temperature, are hydrophobic, are neither irritatlng, toxic nor
S otherwise harmful when applied to the hair, are compatib1e with
the other components of the composition, are chemically stable
under normal use and storage condittons, and are capable of being
deposited on and af conditianing hair.
Suitable A groups include methyl, methoxy, ethoxy, propoxy,
IO and aryloxy. The two R groups on the silicone atom may represent
the same group or different groups. Preferabl~, the two R groups
represent the same group. Suitable R groups include methyl,
ethyl, propy1, phenyl, methy1phenyl and phenylmethyl. The pre-
ferred silicones are polydimethy1 siloxane, polydiethylsi10xane,
and polymethylphenylsiloxane. Polydimethylsiloxane is especially
preferred.
References disc10sing suitable si1icone fluids include U.S.
Patent 2,826,551, Geen; U.S. Patent 3,964,500, Orakoff, issued
June 22, 1976; U.S. Patent 4,36~,837, Pader; and British Patent
8~9,~33, ~oolston. All of these patents are incorporated herein
by reference. Also ircorporated herein by referqnce is Siticon
~; Compounds distributed by Petrarch Systems, Inc., 1984. This~
reference provides an extensive (though not exclusi~e) listing of
` suitable silicone~f~luids.
` 25 Another silicone material that can be especially useful in
the silicone conditioning agents is insoluble silicone gum. The
term ~silicone gum~,~as used herein, means polyorganosiloxane
~aterials having a viscosity~at 25-C of greater than or equal to
I,OOO,OOO centist~okes. Silicane gums are descri,bed by Petrarch
and others including U.S. Patent 4,1S2,416, Spitzer et al., issued
May I, 19~9, and~Noll, Walter,~ Chem~'str~ and ~echno70gy of Si7i-
cones, New York: Academic Press 1968. Also describing silicone
gums are General Electric Silicone Rubber Product Oata Sheets SE
30, SE 33, SE 54~and SE 76. All of these described references are
incorporated herein ~by reference. ~he ~silicone gums~ will
~ ~3lJE3tiTIT U T E ~ EE~r
WO 93/18737 2131 6 2 6 PCr/US93/02128
- 31
typically have a mass molecular welght ln excess of about 200,000,
generally between about 200,000 and about l,OOO,OOO. Specific
examples include polydimethylsiloxane, (polydimethylsiloxane)
(methylvinylsiloxane) copolymer, poly(dimethylslloxane) (dlphenyl
siloxane)~methylvinylsiloxane) copolymer and mixtures thereof.
Preferably the sil k one hair condit10ning agent comprises a
mixture of a polydimeth~lsiloxane gum, having a viscosity, at
25-C, greater than about l,OOO,OOO centtstokes and polydimethyl-
siloxane fluid having a viscosity, at 25'C, of from about lO
centipoise to about 100,000 centistokes, wherein the ratin of gum
to fluid is from about 30:70 to about 70:30, preferably from about
~0:60 to about 60:40.
Cationic sil icone fluids and gums may be used, although
nonionic silicone f1uids and gums are preferred.
Antidandruff Aqent
The shampoo compositions also contain one or msre
antidandruff agents. 501uble antidandruff agents as well as
particulate ant1dandruff agents can be ~sed. Especlally preferred
are particulate antidandru~f agents, particularly pyr1dinethione
sa~ts and selenium sulfide.
Selenium sulfide is a staple item of commerce. Selenium
sulfide is genera~lly regarded as a compound having one mole of
selenium and two moles of sul~ur. However, it may take the form
of a cyclic structure, SexSy~ wherein x ~ y ~ 8.
U.S. Patent 2,694,668, Baldwin et al., issued November 16~,
.
l95~; U.5. Patent 3,15Z~,046, Kapra~l, issued October 6, 1984; U.S.
Patent 4,089,945,~Brinkman, issued~May l6, l978; and U.S. Patent
4,885,10~, ~etzel, issued ~ecember 12, 1989, all incorporated
herein by reference, disclose selenium disulfide as an activ~
` ingredient in antidandruff shim~oo compositions.
Selenium sulfide as provided bg suppliers can be used in the
present compositions~ provided the~ particle size of the selenium
sulfide particles, on an average, is tess than about lS~,
preferably less than about lO~. These measurements are made using
` 35 a forward laser li~ght scattering device (e.g., a Malvern 3600
instrument). ~;
:
; ~3 U E3R3TIT U T E S ~E~Fr
WO 93/18737 PCr/US93/02128
~,~3~6~6 - 32 -
If used, selenium sulftde ls typictlly present ln the shampoo
compositions of this inventlon at a lever of from about O.lX to
about 5.0%, preferably from about .6% to about 2.5X.
Preferred pyridinethione ant1dandruf~ agents are
l-hydroxy-~-pyridinethione salts. These types of antidandruff
agents are well known in the art. Particularly preferred are
those 1-hydroxy~2-pyridînethlone salts in platelet particle form,
wherein the particles have an average size af from about 1 micron
to about 29 microns, preferably fro~ about 2 microns to about 8
microns. The act1ve is generally used at a level of from about
0.1% to about 4%~ preferably about 0.5% to about 2X, o~ the
shampoo composition. l-hydroxy-2~pyrid~nethione salts are dis-
closed for use in antidandruff shampoos in U.S. Patent 2,809,971,
Bernstein, issued October 15, I957; U.S. Patent 3,236,733, Karsten
et al., issued February 22, 1966; U.S. Patent 3,753,196, Parran,
issued August 2I, 1973; US. Patent 3,i61,418, Parran, issued
September 25, 1973; U.S~ Patent 4,345,080, 80lich, issued August
17, 1982; U.S. Patent 4,323,683, Bcl~ch et al., issued April 6,
1982i U.S. Patent 4,379,753, Bolich, issued Apri1 12, 1983; and
U.S. Patent 4,470,982, ~nkl~r~ is ~ed September 11, 1984; all
incorporated herein by reference. The pyridinethione salts
preferred herein can generally be defined as water-insoluble salts
of l-hydroxy-2-pyridinethione.
Preferred sa1ts are formed from metals such as zinc, tin~
2~ cadmium,:magnesium, aluminium and zirconium. The most pre~erred
metal herein is zinc which forms 2-zinc pyrithione or ZPT. Other
cations such as sodium are also suitable.
. In addition the shampoo composition disclosed herein may
inctude sther known antidandruff actives. Such antidandruff
aetives can include, for e~ample, pyridone salts, coal tar, etc.
: Hydroxypyridone salts are disclosed in Cosmettcs and Drug
Preservation, Princip7es:and Pract jce, p 742 (edited by J. Kabura,
1984), incorporated herein by reference. Hydroxypyridone salts
used herein include those generally described as l-hydroxy-4-
3~ methyl-(lH)-pyridones havlng an aliphatic or aromatic moiety (R)
.
~B~TITUTE ~iHE~
W o 93/18737 2 1 3 1 6 2 6 PCT/USg3/0212X
at the 6 position thereof, wherein R has a factor of at least
1:3, preferably from 2 to 6, more preferably from 3 to 5.5. The
factor is a measure of the lipophilicity/ hydrophilicity of the
substituent and is defined in deta~l in the paper by ~ Dittmar,
S E. Druckrey and H. Urbach, J. Med. Chem. 17(7), 753-6 (I974) and
references cited therein; all of which are incorpar~ted herein by
reference.
~n structural terms, preferred R substituents are selected
from l~near and branched C~-CIl, preferably C6~ct 1~ atkyl and
IO alkenyl groups, Cs~~ cycloalkyl groups, and C~-C~ aryl groups.
The cyclic moieties, discussed above, can also be subst~tuted with
one or more alkyl or alkenyl groups up to C~. ~he R groups can
further be substituted with halogen atoms. Of the above, pre-
ferred R moieties are cyclohexyl and 2,4,~-trimethyl pentyl, the
I5 latter being highly preferred.
The above mentioned compounds can be used both in the free
form and as salts, for example, salts with organic bases or
inorganic cations. Low molecular weight alkanolam1nes are espe-
: ciallr preferred organic bases. The preferred hydroxypyridone
salt for use herein is monoethanolamine salt known as piroctone
olamine or Octopirox; see Cosmet ~'c and Orug Preser~at ion, supra.
; Piroctone olamine is described for use in deodorant composi-
tions in Japanese Patent Applicàtion Sho 57-104,3I3, published
Oecembr 23, I983; Japanese Patent Application Sho 5~-I27,893,
published Febru-ry S, 1985 (both to Lion) and U.S. Patent Appli-
;~ cation Serial No. 314,627, Melanson and Sturm, filed February 23,
1989. Japanese Patent Application Sho 5~-080,644 (Lion), pub-
lished November 18, 198~3, ~discloses the use of a broad group of
~ hydroxypyridone compounds~ for dandruff control. All above cited
; 30 referènces are incorparated heréin by rèference.
ODtional ComDonents
The compositions herein can`ccntain a variety of non-essen-
; tial optional components. Such optional ingredients include, for
example, preservatives such as benzyl alcohol, methyl paraben,
3s propyl paraben and imidazolidinyl urea; cationic conditioning
3 U~3~3TIT U T E S H~EE~r
.. , ., . . . .. ", .. ,.. ~, .... . .
wo 93/18737 PCI~/US93/02t2
3~,6cl6 3~,
agents, including both cationic conditioning surfactant and
cationic conditionfng polymers; fatty aloohols; block polymers of
ethylene oxide and propylene oxide such as Pluronic F88 offered by
BASF ~yandotte; sodium chloride; sodium sulfate; ammonium xylene
sulfonate; propylene glycol; polyvinyl alcohol; ethyl a1cohol;
foam boosters such as Polyquaternium-10 (an industry term desig-
nated by The Cosmetic. ToiIetry and fragrance A5sociat1On ~CTfA)
for the potymeric qu3ternary ammonium salt of hydroxyethyl cellu-
lose reacted with trimethyl ammonium substituted epoxide), commer~
cially available from Un~on Carbide Corp. (Danbury, Connecticut,
USA) under their UCARE POLYMER JR series of materials, e.g., UCARE
POLYMER JR-30M, JR-125 and JR-~00, such foam boosters being a
preferred ingredient for use in the shampoos herein; additional pH
ad~usting agents for the final shampoo composition such as citric
acid, succinic acid, phosphoric acid, sodium hydroxide, sodium
carDonate, etc.; perfumes; dyes; and sequestertng agents such as
disodium ethylenediamine tetraacetate. These opt1Onal ingredients
are typically used at levels of from about 0.01% to about lOX of
the composition. ~his list of; opt~onal ingred~ents is not meant
to be inclusive, and other opttonal components can be utilized.
Pedicu~icides can also be included in the compositions hereof
to provide control of lice infestations. Suitable pediculicides
are well known in the art and~ in~clude, for examplet pyrethrins
such as those disclosed in U.5. Patent 4,668,666, Allan,-incorpo-
~25 rated herein by ~reference.
ODtional Thickeners and SusDendinq Aqents
Another type of suspending agent that can be used is
carboxyv1nyl polymer. ; Preferred polymers are copolymers of
acrylic acid crosslinked with polyallylsucrose as described in
U.S. Patent 2,798,053, Brown, issued July 2, 1957, incorporated
herein by reference. ~ These polymers are provided by B. f.
Goodrich Company as, for exampIe,~Carbopol 93-, 940, 941, and 956.
A carboxyvinyl polymer is an interpolymer of a monomeric
mixture comprising a~monomeric olefinicallY unsaturated carboxylic
5~ acid, and from about 0.1% to about 10% by weight of the total
: . ~
::
~ ~V EIE~rIT U T E ~itt~EEFr
WO 93/18737 21 31 6 2 6 PCr/US93/0212~
- 35 -
monomers of a polyether of a polyhydr k alcohol, which polyhydr1c
alcohol contatns ~t least four carbon atoms to which are attached
at least three hydroxyt groups, the polyether containing mor~ than
one alkeny1 group per molecule. Other monoo1ef1nie monomeric
S materials may be present in the monomer k mixture if desired, even
in predom~nant proport~on. Carboxyvinyl polymers are substan-
tially insoluble in liquid, volat~le organic hydrocarbons and are
dimensional~y stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvin~1
polymers include polyols selected from the class consisting of
oligosaccharides, reduced dertvatives thereof ~n wh~ch the car-
bonyl group is converted to an alcohol groùp, and pentaerythritol;
more preferred are oligosaccharides, most preferred is sucrose.
It is preferred that the hydroxyl groups of the po1yol wh~ch are
lS modified be etherified with allyl groups, the polyol having at
least two a11yl ether groups per polyol molecule. When the Dolyol
is sucrose, it js preferred that the sucrose have at least about
five allyl ether groups per sucrose molecule. It ~s preferred
that the polyether of the polyol comprisé ~rom about 0.1% to about
4X of the total monomers, more preferably from about 0.2X to about
2.5X. ~ ~
Preferred monomeric olefinically unsaturated carboxylic acids
for use in producing carboxyvinyl polymers used herein include
monomeric, polymerlzable, alpha-beta monoolefinicall~ unsaturated
lower aliphatic carboxylic acids; more preferred are monomeric
monoolefinic acrylic acids of the structure
R
CH2 . I - COOH
where R is a substituent selected from the group consisSing of
hydrogen and lower alkyl groups; most preferred is acrylic acid.
Preferred carboxyvinyl polymers used in formulations of the
present invention have ~a molecular we)~ht of at least about
750,000; more preferred are carboxyvinyl po1ymers having a mole-
lS cular weight of at least about 1,2SO,OOO; most preferred are
carboxyvinyl polymers having a molecular weight of at least about
3,000,000.
;~Vi~TITUTE 8~ET
WO ~3/18737 PCI/llS93/0212X
,~.~
~6 ) 5 - 36 -
Other materials can also be used as suspenslon agents,
including those that can impart a gel-like viscosity to ~he
composition, such as water so1uble or colloidally water soluble
polymers like cellulose ethers (e.g., hydroxyethyl cellulose),
guar gum, polyvinyl alcohol, polyvinyl pyrrolldone, hydroxypropyl
guar gum, starch and starch derivatlves, and other thickeners,
viscosity modifiers. gelling agents, etc. Mixtures of these
materials can a1so be used.
Such optional suspending agent thickeners, and viscosity
modifiers, etc., in genera1, are used at a level of from about
0~1% to about lOX, most commonly from about 0.3% to about 5.~% by
weight of the total compositton.
Another type of suspendlng agent that can be used is xanthan
gum. Shampoo compositions utilizing xanthan gum as a suspending
lS agent for the silicone hair conditloning component are described
in U.S. Patent 4,788,006, Bolich and Williams, issued November 29,
1988, incorporated herein by reference~ Xanthan gum is ~io-
synthetlc gu~ material th~t is commercially available. It is a
heteropolysaccharide with a molecul-r weight of greater than 1
million. It is believed to contain O-glucose, D-mannose and
D-glucuronate in the molar ratio; of 2.8:2.0:2Ø ~ The polysac-
charide is parti-lly~acetylated with 4.7% acetyl. ~his informa-
tion and other is found in ~histler, RQY L. Editor ndustria~ Gums
- Po7~saccharJdes and Their Doriv~tives New York: Academi~ Press,
1973. Kelco " 01v~sion of Merck ~: Co., Inc. offers xanth~n gum
as Keltrol. The gum, when used as the silicone hair conditioning
component suspending~agent, will typically be present in pourable,
liquid formulations~at a !evel of from about 0.3% to about 3%,
preferably from about 0.4X to about 1.2%, in the compositions of
the present inYention. ~ ! ' ' !
The pH of the compositions~ for direct use for cleaning
applications is~not generally critical and may be in the range of
from 2 to abo~t lOt preferably from about 3 to about 9, more
preferably from about 4 to about 8, most prefera~ly from about 6
3S to about 8.
~ ~3 UEIEfrlT UlrE ~ EE~r
WO 93/1X737 2131 6 2 6 PC~/US93/0212X
- 37 -
~Q~E~
The present compositions are used in a conventional manner
for cleaning hair. An effective amount of the composition for
cleaning hair typically from about l g to about 20 g of the
composition is applied to ha~r that has preferably been wetted
generally with water and then rinsed out Applicatton to the
hair typ1ca11y inc1udes working the composition through the ha1r
such that most or all o~ the hair is contacted with the
composition.
EXAMP~E$
The following Examples further describe and demonstrate the
preferred embodiments within the scope o~ th~ present invention.
The Examples are given solely for the purpose of il1ustration and
are not to be construed as limitat~ons of the present invention as
many variations thereof are possible without departing from its
spirit and scope.
EXAMPLES I-XX
The following examples exempllfy shampoo compositions of the
present invention.
~g~_l
CO~DOnent ~ V V
(ppm or % by weight
of compositionj
Sodium Laureth-3~5ulfate (X)~ 1~.00 14.00 13.60 13.60 13.00Cocoamphodiacetate (%)' 3.50 3.50 3.40 3.40 3.50
CAPB5~ ~ 2.00 2~00 3.40 3.40 3.50
LIDP' ~ 3.50 3.50 - - -
Poly~uaternium l0 (%)1 ~ O.OS 0.05 O.OS 0.05 0 OS
Ethy~ene Glycol Distear-te~(X) 2.00 2.00 2.00 2.00 2.00
Dimethicone t%)2 ; ~ -oo 1.00 l.00 l.40 1.00
~; Perfume Sol~tion (%) 0.70 0.70 0.70 0.70 0.70
DMDM Hydantoin (%) ~ 0.20 0.20 0.20 0.20 0.20
Citric~Acid t%); ~ 0 34
Cetyl Alcohol (%) ~ 0.12 0.06 0.06 O.lO 0.06
:
~: :: : :
~3~E3eSTIT U T E ~;H EeFr
WO 93/1~737 PCI/US93/0212X
~6~ Stearyl Alcohol (X) 0.06 0.}2 0.12 0.18 0.12
Tr~cetylmethylammonium
ch~oride~ (X) - 0.57 0.57 0.57
Zinc Pyridinethione (%) - - - - 1.00
Color Solution (ppm) 4 4 4 4 4
~ater - - - - - q. s. to 100X - - - - -
Table LI
ComDonen~ V~ _ YII X~ X
(ppm or %, by weight,
of composition)
Sodium Laureth-3 Sulfate (X)~ 10.00 13.00 14.00 13.00 13.00
Cocoamphodiacetate (%)~ 3.50 4.50 4.50 3.00 3.00
CAPBs 3.50 3.00 2.00 5.D0 5.00
LIDP6
Polyquaternium 10 (%)1 0.10 - 0.09 0.03
Ethylene Glycol Distearate (%) 1.00 3.00 1.00 3.00 1.50
Dimethicone ~%)2 0.50 2.00 0.50 1.00
Perfume Solution (%) 0.60 0.60 0.60 0.60 0.50
DMDM Hydantoin (%) 0.20 0.~0 0.20 0.20 0.20
Citric Acid (%J 0.30 0.45 0.45~ 0.28 0.28
Cetyl Alcohol (%) 0.03 0.12 - 0.16
Stearyl Alcohol (%) 0.06 0.24 - 0.12
~ Tricetylmethylammonium
: ~ 25 chlori~de~ (X) - 0.50 0.57
Zinc Pyridinethione t%) - - 1.00 2.00
Color Solution ~ppm) 20 20 20 20 2D
~ater ~ q. s. to 10C% - - - - -
~able I I l
ComDonent i ~ ` XI XI~XIII XIV XV
~ppm or %, by weight,
: of composition)
: Sodium Laureth-3 Sulfate (%)~' 10.00 14.0013.60 13.60 13.00
: Cocoamphoacetate t~)' 3.~0 3.503.40 3.40 3.503$ CAPB5 : : 2.00 2.00 3.40 3.40 3.50
::
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~3~E3~TIT U T E SJ~E~r
W o 93/18737 2 I 31 6 2 6 PCT/US93/02128
LIDP6 3.50 3.50 - - -
Polyquaternium 10 (%)1 0.05 0.05 0.05 0.05 0.05
Ethylene Glycol Distearate (%) 2.00 2.00 2.00 2.00 2.00
Dimethicone (%)2 1.OO 1.00 1.00 1.~0 1.00
Perfume Solution (%) 0.70 0.70 0.70 0.70 0.70
OMDM Hydantoin (%) 0.20 0.20 0.20 0.20 0.20
Citric Ac~d (%) - 0.25 0.25 0.25 0.25
Cetyl Alcohol ~%) 0.12 0.06 0.06 0.l0 0.06
Stearyl Alcohol (%) 0.06 0.12 O.IZ 0.18 0.12
Tricetylmethytammonium
chloride~ (%) - O.S7 0.57 0.57
I Zinc Pyridinethione (X)
Color Sotution (ppm) 4 4 4 4 4
~ater ~ q. s. to lOOX - - - - -
Table IY
Component X~I XVII XVIII XIX XX _
(ppm or X, by weight,
of composi tion)
Sodium Laureth-3 Sulfate (X)~ 10.00 13.00 14.00 13.00 13.00
Cocoamphodiacetate (X)~ 3.50 4.50 4.50~ 3.00 3.00
CAPBS ` : 3.50 3.00 2.00 5.00 5.00
LIDP~
Polyquaternium lO (X)l ~ ~ 0.l0 - 0.09 0.03
Ethrlene 61ycol D:istearate (X) 1.00 3.00 1.00 3.00 l.50
Dimethicone t%)2 : ~ : : 0.50 2.00 O.S0 l.ûO
Perfume Sol~ution (%)~ 0.60 0.60 0.60 0.60 0.S0
: DMOM Hydantoin: (%) 0.20 0.20 0.20 0.20 0.20
,
Citric Acid (%) ; :0.20 0.30 0.30 0.20 0.20
~; 30 Cetyl Alcohol (%) i~ 0.03 0.12 ! 0.16
~ - Stearyl Alcohol t%)~ ~ 0.06 0.24 - 0.12
`~ Tricetylmethylammonium
chloride~tX) ; ~ - 0.50 0.57
Zinc Pyridin:ethiane ~%) - - 1.00 2.00
~ 35
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`~ 3~1EIE~rIT U T E ~ Ee~r
~VO 93/18737 PCI/US93/0212X
~ ~ 3 ~ 6 ~ 6 - 40 -
- Color Solution (ppm) 20 20 20 20 20
~ater - - - - - q. s. to lOOX - ~
UCARE Polymer JR-30M commercially available from Union
Carbide Corporation.
2 A 50/50 blend of SE-76 sil~cone gum available from GE Sili-
cones and a silicone flu~d having a viscosity of about 350
centistokes.
3 Availab1e under the traden-me MIRAHOL C~2M from Miranol Inc.
in a 38% active solut10n.
~ Available under the tradename MIRANOL CM CONC from Miranol
Inc. in a 37% active sol~tion.
S Available under the tradename GENAGN CAB from Hoechst
Celanese as a'30%`act~ve solut10n.
6 Available under the tradename DERIPHAT from Henkel Corp. as a
30% active solution.
'' Available~commercially as a 28.5% act~ve solution.
~TCMA~ Avai1ab1e comm~rcially from Akzo-Chemie as ARQUAD-316
as a 90X~suspension~ ~
The compositions ~re prepared as follows. A silicone premix
is first prep-r-d by add~ng a small portion (e.g. about 0.2% by
weight of the~`finished product~ of the sod1um laureth-3 sulfate to
the premix `tank and heat~ng to 71-C. ~ The cetyl and stearyl
alcohols as~app1icable ~are added. The dimethicone is then added
and mixed until in emulsion ~s formed.
~ For ~Examp~les 1-}V;~and XI-X1V about one-third of the sodium
` laureth-3 sulf-te the~cocoamphodiacetate and/or cocoamphoacetate
the CAPB and TCMAC as applicab1e are placed in a tank. The
mixture (the ~main Fremix;~) is agitated and heated to 71-C. The
.,
ethylene glycol distearate is then added and 'allowed to melt. The
citric acid'~in ~tHe ;fonm '^of' a 50X active solution is added to
- adjust pH~. The main~ mix~is passed through a heat exchanger where
it~is~ cooled~to 32-C and collected in a finishing tank. As a
'~ result of this; cooling step ~the ethylene glycol distearate
M~ crystallizes~ to ~form ~a~crystal~1ine network in the product. The
~ 35~ Polyquaternium ~10 ~ if app11cable is then added as a solid or
``' ~ 3 U E313nrIT U T E ~ IEEFr
2131626
WO 93/18737 PCI`/US93/0212X
predissolved ln water to the main prem1x. For Examples V-X and
XV-XX, the CAPB ts mixed into the ma1n premix after the ethylene
glycol distearate has been crystallized instead of being added at
the above-indicated earl~er stage. The sil~cone premtx is col-
S lected in the same finishing tank after being cooled to about
30-C, where the main premix and the silicone premix are mixed
until homogeneous. Finally, the remainder of the ingredients are
added and mixed into the shampoo composit10n. ~he final pH ~s
adjusted as des~red by the addition of citrtc acid and/or NaOH.
The final viscosity is adjusted as desired by the addition of
ammonium xylene sulfonate and/or HaCl.
The compositions of the Examples can provide excellent ~n-use
hair cleaning, lather, mildhess, conditioning and dandruff control
(where applicable), and pearlescence.
15
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~3 U Ea~TIT U T E ~;~t~EEFr
