Note: Descriptions are shown in the official language in which they were submitted.
WO 94/085~7 2 I 4 7 ~ 7 4 ~ PCr/US93/09937
HAIR CARE COMPOSITIONS PROVID~NG CONDITIONING
AND ENHANCED S~NE
TECHNICAL FIELD
This invention relates to hair care compositions that provide
conditioning and shine to the hair. More particularly, this invention relates tO hair
5 care compositions that provide conditioning and enh~nced levels of shine tO the
hair.
BACKGROUND OF THE ~NVENTION
The shampooing of hair conventionally is pclroll,,ed ~Itili7ing any
20 of numerous detersive surfactant-co..~ .;..g compositions known in the art.
Whereas it is well known how to formulate shampoos that can effi~iently clean
the hair, merely providing clean hair is not, in and of itself, satisfying to
substantial se~...e~l c of consumers who also want their hair to be manageable, and
to also feel and look ple~cing and healthy.
One common method of providing a more pleasin_ and
manageable hair is through the use of hair conditioning agents, such as cationic~
quaternary ammonium surf~ct~nts and polymers, silicone fluids, and hydrocarbon
or other organic oils.
A conullon way to improve the a~)pe~nce of hair is through the
use of hair shine actives, such as shellac, riimpthicone~ oils and waxes, and
quaternary ~..",onium surf~ct~ntc Some hair care in~s.cdie..~s, such as the oilsand waxes, iimethicone, and cationic surf~ ntc provide conditioning as well as
hair shine benefits. However, they can only be used at limited levels without
causing adverse effects on hair appearance or feel. Too much oil, for example,
3 ~ can cause the hair to appear and feel greasy. High levels of dimethicone . cationic
surf~t~nts~ and waxes can cause the hair to develop a dirty, coated feel and to
become limp and without body, especially upon repeated usage. Shellac. on the
other hand, causes the hair to feel stiff or tacky.
WO 94/08~57 2 1 ~ 7 4 7 4 PCI/US93/09937
~ . . 2
The purpose of hair shine actives is to increase the amount of light
reflecting offthe hair surface. The definition of hair shine is generally accepted to
be the contrast between the specular and diffuse light reflected offthe hair fibers.
This contrast creates a perception of "sheen" or "highlight.~" strongly associated
by the consumer with "healthy hair".
Whereas a wide variety of hair shine actives are known in the art
such as those tli~c~lssed above, it remains highly desirable to provide hair care
compositions that can provide enhanced levels of shine to the hair without
incurring the cost, forrnulation tlifficlllties7 or hair aesthetic disadvantages that
would be associated with merely increasing the level of hair shine active in
prior-known compositions. It is an object of this invention to provide such haircare compositions.
It would further be desirable to provide hair care compositions that
could provide ~nh~nced shine, as described above, which could also provide
conditioning the hair, especially improved combing and hair feel. It therefore is
also an object of this invention to provide hair care compositions that can provide
both conditioning and enhance shine to the hair.
These and other benefits as mav be ~ cllssed or apparenl to one of
ordinary skill in the art can be provided according to the invention which is
described below.
All percentages herein are by weight of the compositi~n unless
otherwise inrlir.~ted. All ratios are weight ratios unless otherwise indicated.
Unless otherwise in~icatetl, all percentages, ratios, and levels of ingredients
referred to herein are based on the actual amount of the ingredient, and do not
2~ include solvents, fillers, or other materials with which the ingredient may be
combined as commercially available products.
The invention hereof can comprise, consist of, or consist
ess~nti~lly of the ess~nti~l elements described herein as well as any of the
pl~"~d or other optional ingredients described hererin.
SUMMARY OF THE INVENTION
It has now been found that hair care compositions providing
conditioning and ~nh~nced shine to the hair are provided through the combinationof a high refractive index nonvolatile polysiloxane fluid, a nonvolatile spreading
agent which is colllpa~ible with the polysiloxane fluid, and a carrier suitable for
3~ application to the hair. It is ess~.nti~l that the compositions contain the spreadin~
agent because even though the polysiloxane fluids hereof have high refractive
index. they do not provide the high levels of shine obtainable with the present
invention without the presence of the spreading agent.
WO 94/08557 2 1 4 7 ~ 7 4 PCr/US93/09937
More specifically, the present invention provides a hair care
composition that comprises:
(a) a nonvolatile polysiloxane fluid having a refractive index of
at least about 1.46,
(b) a nonvolatile spreading agent for said silicone fluid
intermixed with said polysiloxane fluid; and
(c) a carrier suitable for application to the hair,
wherein said composition contains a sufficient amount of said spreading agent toreduce the Surface Tension of the polysiloxane fluid. Preferably, the Surface
0 Tension is reduced by at least about 5%, more preferably by at least about 10%,
and the total of the mixture of said polysiloxane fiuid and said spreading agent is
at least about 0.1%, by weight, of the composition. Alternately, the present
invention can be described in terms of cont~ining a sufficient amount of said
spreading agent to increase the Glossmeter Specular Reflectance for said mixturerelative to said polysiloxane fluid, by at least about ~1.0%.
In pler~lled embo~iments, the polysiloxane fluid is a highly
arylated silicone, especially a highly phenylated silicone such as pentaphenyl
trimethyl trisiloxane or diphenyl methylphenyl siloxane copolymer. or diphenyl
dimethyl siloxane copolymer.
Suitable spreading agents include, but are not necessarily limited
to, silicone resins (especially MQ silicone resins), surfactants such as polyether
siloxane copolymers and non-silicone-cc,~ -g organic surf~r,t~ntc.
The present invention also relates to a method for providing
conditioning and enh~nced shine by applying the compositions hereof to the hair.The compositions and methods of the present invention are
advantageous for utilization in connection with a wide variety of hair care
products inclll.iin~ leave-on compositions, such as hair lotions, tonics, gels,
mousses, sprays, etc., and rinse-off compositions, such as shampoos and hair
rinses.
The present invention inr.~ g various optional and preferred
embo-liment~ thereof, is described in more detai; below.
DETAILED DESCRIPTION OF T~ INVENTION
The essçnti~l components and aspects of the invention, as well as
various optional and plerell~d ingredients and embodiments of the invention, are3s described below.
Hi h Refractive Index Nonvolatile Polysiloxane Fluid
The compositions of the present invention contain as an essential
ingredient a nonvolatile polysiloxane fluid ("silicone fluid") having a refractive
W094/085~7 214747~ PCI/US93/09937
index of at least about 1.46, preferably at least about 1.48, more preferably atleast about 1.52, most preferably at least about 1.55. Although not intended to
necessarily limit the invention, the refractive index of the polysiloxane fluid will
generally be less than about 1.70, typically less than about 1.60. Polysiloxane
"fluid" includes fluids as well as gums.
As is well known in the art, refractive index refers to the change in
direction (i.e. appa,~.,l bending) of a light ray passing from one medium to
another. Refractive index shall herein refer to the light ray passing from air to the
polysiloxane fluid or polysiloxane fluid/spreading agent mixture. Refractive index
o of the silicone fluid can be determined using standard equipment common~y
available and know in the art, such as an Abbe refractometer. Techniques for
measuring refractive index are described in the Handbook of Chemical
Microscopy, Volume I - Chemical Methods and Inorganic Qualitative Analysis,
Chemot and Mason, ed., John Wiley & Sons, Inc., New York 1958, pp 311 -334.
The term "nonvolatile" as used herein means the material referred
to exhibits very low or no significant vapor pressure at ambient conditions, as
well-known and understood in the art. Nonvolatile materials will generally exhibit
no more than 0.2mm Hg at 25C and one atmosphere. Nonvolatile materials will
also generally have a boiling point at one atmosphere of at least 275C, preferably
at least 300C.
The polysiloxane fluid for use herein will generally have viscosity
of at least about 10 centistokes at 25C, preferably from about 20 to about
2,000,000 centistokes more preferably from about 30 to about 500.000
centistokes. Other viscosity nonvolatile silicone fluids can also be used in thepresent invention as long as the other requirements described herein are met. Ingeneral, if conditioning as well as hair shine is desired from the silicone fluid,
higher viscosity materials such as those above about 50,000, preferably above
about 100,000, are preferably used. The viscosity can be measured by means of a
glass capilla~y viscometer as set forth in Dow Corning Corporate Test Method
CTMOOG4, July 20, 1970.
The polysiloxane fluid suitable for purposes hereof includes those
represented by general Formula (I~:
R R R
( I ) R- Si - O - Si - O - Si - R
R R n R
WO 94/08557 **' 2 I 4 7 4 7q - PCI/US93/09937
wherein each R independently is substituted or unsubstituted aliphatic (e.~. alkyl
or alkenyl), aryl, aryloxy, alkaryl, alkoxy, alkamino (e.g. alkyl or alken~l amino
groups)~ hydroxy, or hydrogen, or combinations thereof: and n is an integer of at
least about 1, typically from about 1 to about 1,000. The R substituents can also
s include combinations of ether groups, hydroxy groups. and amine groups. as well
as other functional groups, such as halogens and halogen-substituted
functionalities, e.g. halogen-substituted aliphatic and aryl groups.
The polysiloxane fluid can be cyclic or linear. Linear polysiloxanes
are exemplified above by Formula I. Branched chain can also be used. Cyclic
0 polysiloxanes include those le,~"esel-~ed by Formula (II):
(II) - Si ~ -n
R
wherein R is as defined above, n is from about 3 to about 7, preferably from three
to five.
The substituç~t.~ on the si!oxane chain (R) may have any structure
20 as long as the resl-lting polysiloxanes remain fluid at room temperature, arehydrophobic, are neither i~ ing, toxic nor otherwise harmful when applied to
the hair, are compa~ible with the other components of the composition, are
chemically stable under normal use and storage conditions, are capable of being
deposited on the hair, and the resl.lting polysiloxane fluid has a refractive index as
2s set forth above.
Preferred alk,vl and alkenyl substitutes are C I -C5 alkvls and
alkenyls, more prefe~ably from C 1 -C4, most preferably from C 1 -C2. The
aliphatic portions of other alkyl-, alkenyl-, or alkynyl- con~ g groups (such asalkoxy, alkaryl, and ~lk~rnino) can be straight or branched chains and preferably
~o have from one to five carbon atoms, more preferably from one to four carbon
atoms, even more preferably from one to three carbon atoms, most preferably
from one to two carbon atoms. As tii~cussed above, the R substituents hereof canalso, contaln amino functionalities, e.g., ~lk~mino groups, which can be primary~
secondary or tertiary amines or quaternary ammonium. These include mono-, di-,
35 and tri- alkylamino and alkoxyamino groups wherein the aliphatic portion chain
length is preferably as described above. The R substituents can also be
substituted with other groups, such as halogens (e.g. chloride, fluoride, and
bromide), halogenated aliphatic or aryl groups, and hvdroxy (e.g. hvdroxy
WO94/08557 21~7474 ` ` 6 PCI/US93/09937
substituted aliphatic groups). Suitable halogenated R groups could include, for
example, tri-halog~n~ted (preferably fluoro) alkyl groups such as -Rl-C(F)3,
wherein R is Cl-C3 alkyl. Examples of such polysiloxanes include polvmethyl
-3,3,3 trifluoloprol,ylsiloxane.
The high refractive index polysiloxane fluids hereof contain a
sufficient amount of aryl-co,.l~;,.;ng R substituents to increase the refractive index
to the desired level, which is described above.
Aryl-co"l~;..;ng substit~lPnt.c contain alicyclic and heterocyclic five
and six membered aryl rings, and substituçnts co,-l~;"il-g fused five or six
membered rings. The aryl rings themselves can be substituted or unsubstituted.
Substituents include aliphatic substituerltc, and can also include alkoxy
substituents, acyl substituentc, ketones, halogens (e.g., Cl and Br), amines, etc.
Exemplary aryl-con~inin~ groups include substituted and unsubstituted arenes~
such as phenyl, and phenyl derivatives such as phenyls with Cl-C5 alkyl or
alkenyl substit~l~nts, e.g., allylphenyl, methyl phenyl and ethyl phenyl. vinyl
phenyls such as styrenyl, and phenyl alkynes (e.g. phenyl C2-C4 alkynes).
Heterocyclic aryl groups include substitlç~t~ derived from furan, irnidazole,
pyrrole, pyridine, etc. Fused aryl ring substituents include, for example,
napthalene, coumarin, and purine.
In general, the polysiloxane fluids hereof will have a degree of
aryl-cont~ining substit lçntc of at least about 15%, prefel~bly at least about 20%,
more preferably at least about 25%, even more preferably at least about 35%,
most preferably at least about 50%. Typically, although it is not intended to
necess~rily limit the invention, the degree of aryl substitution will be less than
2~ about 90%, more generally less than about 85%, preferably from about 5~% to
about 80%.
The po~ysiloxane fluids hereof are also characterized by relatively
high surface tensions as a result of their aryl substitution. In general, the
polysiloxane fluids hereof will have a Surface Tension of at least about 24
dynes/cm2, typically at least about 27 dynes/cm2. Surface Tension, for purposes
hereof? is measured by a de Nouy ring tensiometer according to Dow Corning
Corporate Test Method CTM 0461, November 23, 1971. Changes in Surface
Tension can be measured acco-ding to the above test method or according to
ASTM Method D 1331.
3s The pl~rel-ed polysiloxane fluids hereofwill have a combination of
phenyl or phenyl derivative substitu~rlts (preferably phenyl), with alkvl
substituents, preferably Cl-C4 alkyl (most preferably methyl) hydroxy, alkylamino
W O 94/08557 21 4 7~ 7~ PC~r/US93/09937
(es?ecially -RlN~IR2NH2 where each R] and R2 independently is a Cl-C alkyl.
alkenyl, and/or alkoxy.
High refractive index polysiloxane are available commercially from
Dow Corning Corporation (Midland, Michigan U.S.A.) Huls America
(Piscataway, New Jersey, U.S.A.), General Electric Silicones (Waterford, New
York, U.S.A.).
Spreadin~ A~ent
The compositions of the present invention will also comprise a
nonvolatile spreading agent for the polysiloxane fluid. The spreading agent hereof
o must be co~ )a~ible with the polysiloxane fluid.
The term "nonvolatile" is as defined previously herein. By
"compatible" what is meant is that the spreading agent is soluble in, dispersible in,
or miscible with the polysiloxane fluid, such that these two components can
remain intermixed in the same phase of the composition. In other words. the
1~ spreading agent and the polysiloxane fluid are intermixed in the composition to
form a mixture wherein the spreading agent reduces the Surface Tension of the
polysiloxane fluid. Surface Tension reductions can be determined according to
the procedure described previously herein. The spreading agent and polysiloxane
fluid phase hereof can be a continuos or discontinuous phase in the present
compositions.
In one aspect of the invention, the compositions hereof can be
defined as co"~ g contain a sufficient amount of the spreading agent to reduce
the Surface Tension of the polysiloxane fluid by at least about 5%, preferably at
least about 10%, more preferably at least about 15%, even more preferably at
least about 20%, most preferably at least about 25%. Reductions in Surface
Tension of the polysiloxane fluid/spreading agent mixture can provide improved
shine enhancement of the hair. Although it is not int~nded to necessarily limit the
maximum degree of Surface Tension reduction to any particular amount, in the
plt;r~led compositions hereof Surface Tension will generally be reduced by from
about 20% to about 35%, more generally from about 25% to about 30%.
In general? the spreading agent should reduce the Surface Tension
by at least about 2 dynes/cm2, preferably at least about 3 dynes/cm2, even more
preferably at least about 4 dynes/cm2, most preferably at least about 5 dynes/cm .
The Surface Tension of the mixture of the polysiloxane fluid and
the spreading agent, at the proportions present in the final p.oduct, is preferably
30 dynes/cm or less, more preferably about 28 dyr.es/cm or less most preferably
about 25 dynes/cm2 or less. Typically the Surface Tension will be in the range of
WO 94/08~57 2 1 4 7 4 7 4 ` PCr/US93/09937
from about 15 to about 30, more typically from about 18 to about 28. and most
generally from about 20 to about 25 dynes/cm .
Gloss is a physical attribute that contributes to the shine or
lustrous appearance of an object. Gloss can be measured in terms of specular
s reflectance. Specular reflectance refers to the fraction, or percentage. of incident
light reflected from a surface in the mirror direction (i.e. Iight reflected in the
direction that is 180 from the light flowing from the light source toward the
reflective surface) within a specified angular toierance. Specular reflectance is a
useful means for measuring shineness of hair. Further background in specular
o reflectance and its use in ev~ tin~ shininess of hair can be found in R. F. Stamm,
M. L. Garcia, and J. J. Fuchs, "The Optical Properties of Human Hair-I.
Fun~m~nt~l Considerations and Goniophotometer Curves, and II. The Lustre of
Human Hair Fibers," J. Soc Cosmet. Chem. 28, 571-599 and 601-609
(September 1977) all incorporated herein by referce.
Specular reflectance measured from a coating of the compositions
hereof on a collagen-coated black ceramic plate correlates with shininess on hair
and is less suspect to e~ ;J~ental variations due to inconsistency between hair
samples and deposition the hair shine agent. Specular reflectance on such
collagen-coated black ceramic plates as measured in the present invention is
20 determined accordingly that the procedure below in the Experimental and is
referred to herein as Glossmeter Specular Reflectance.
W 0 94/085~7 2147~74 ~ PC~r/US93/09937
The present invention can alternately be described in terms of
compositions co~ g a mixture of the spreading agent and the polysiloxane
fluid wherein the composition contains a sufficient amount of the spreading agent
to increase the Glossmeter Specular Reflectance for the mixture. relative to thepolysiloxane fluid, by at least about "delta 1.0%" (hereinafter "~ 1.0%", wherein
delta relers to a change in percentage specular reflectance based upon 100% of
the original light intensity). Preferably, the increase in Glossmeter Specular
Reflectance is at least about ~2.0%, more preferably at least about ~5.0%, even
more preferably at least about ~7.5%, most preferably at least about ~10.0%.
o Glossmeter Specular Reflectance is measured according to the
procedure described below in the Experimental. In general, a 1.0% solution of
the polysiloxane fluid in the same solvent, if any, used in the same phase as the
polysiloxane fluid in the composition is used. If the polysiloxane fluid is not
diluted with a separate solvent in the composition, cyclomethicone should be used
to prepare the 1.0 % solution. If the necessary cyclomethicone/ethanol solutionscan be used to form the 1.0% of polysiloxane for purposes of the test. For the
control, no spreading agent is incorporated. Otherwise, spreading agent is
incorporated into the solution at the same weight ratio of polysiloxane fluid tospreading agent as present in the composition. The test solution is deposited on a
collægen-coated, black ceramic tile and allowed to dry. Specular reflectance is
measured with a glossmeter, a spectrophotometer suitable for measuring specular
reflectance from flat surfaces. Suitable glossmeters are commercially available
and known in the art, e.g. the "micro-gloss" glossmeter available from BYK-
Gardner, Ind., Silver spring, MD, USA.
The weight ratio of the polysiloxane fluid to the spreading agent
will, in general, be between about 1000:1 and about 1:10, preferably between
about 100:1 and about 1 1, more preferably between about 50:1 and about 2:1,
most preferably from about 25:1 to about 2:1. For hair rinse compositions it is
particularly pl ~rt ,I ed for the ratio to be between about 1 0:1 and about 2:1. When
fluorinated surf~S~ntc are used, particularly high polysiloxane: spreading agentratios may be effective due to the efficiency of these surf~ct~nSc. Thus, it is
contemplated that ratios significantly above 1000:1 may be used.
Ple~lled spreading agents for use herein include silicone resins,
and surf~ct~nts, which include both polye.ther siloxane copolymers an~
3~ non-silicone-cor.lAil.;g organic surf~r,t~nts. Especially prertlled spreading agents
are the silicone resins.
WO 94/08~57 2 1 ~ 7 4 ~ 4 ! PCI /US93/09937
Silicone Resin
Silicone resins are highly crosslinked polymeric siloxane svstems.
The cros.slinking is introduced through the incorporation of trifunctional and
tetrafunctional silanes with monofunctional or difunctional monomer units, or
both, during m~nllf~r,hlre of the silicone resin. As is well understood in the art.
the degree of croc.~linking that is required in order to result in a silicone resin will
vary according to the specific silane units inco",o~led into the silicone resin. In
general. silicone materials which have a sufficient level of trifunctional and
tetrafunctional siloxane monomer units (and hence, a sufficient level of
cros.~linking) such that they dry down to a rigid, or hard, film are considered to be
silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of thelevel of cro.c~linking in a particular silicone material. Silicone resins will generally
have at least about 1.1 oxygen atoms per silicon atom. Preferably, the ratio of
oxygen silicon atoms is at least about 1.2:1Ø Typical silanes used in the
m~nl~f~ctllre of silicone resins are monomethyl-, dimethyl-, monophenyl-,
diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and
tetrachlorosilane. Pl~;Çt;~Jed resins are the methyl substituted silicone resins. such
as those offered by General Electric as GE SS4230 and SS4267. Commercially
available silicone resins will generally be supplied in an unhardened form in a low
viscosity volatile or, preferably, nonvolatile silicone fluid. The silicone resins for
use herein will be present in the compositions hereof in non-hardened form rather
than as a hardened resin, as will be readily appal en~ to those skilled in the art.
Background material on silicones inrlutling sections di.cc~ls~ing
silicone fluids, gums, and resins, as well as m~nl-f~r,tllre of silicones, can be found
in Encyclopedia of Polymer Science and Fngineering, Volume 15, Second
Edition, pp 204-308, John Wiley & Sons, Inc., 1989, and Chemistry and
Technology of Silicones, Walter Noll, Academic Press, Inc. (Harcourt Bruce
Javanovich, Publishers, New York), 1968, pp 282-287 and 409-426, both
incorporated herein by ~r~le.,ce.
Silicone materials and silicone resins in particular, can conveniently
be identified according to a shorthand nomenrl~tllre system well known to those
skilled in the art as "MDTQ" nomrnrl~hlre Under this system, the silicone is
described according to presence of various siloxane monomer units which make
up the silicone. Briefly, the symbol M denotes the monofunctional unit
(CH3)3SiO) 5, D denotes the difunctional unit (CH3)2SiO; T denotes the
trifunctional unit (CH3)Sil 5; and Q denotes the quadri- or tetra-functional unit
SiO2. Primes of the unit symbols, e.g., M', D', T', and Q' denote substituents
other than methyL and must be specifically defined for each occurrence. Typical
WO 94/08557 2 1 ~ 7 4 7~ .1 PCr/US93/09937
alternate substituents include groups such as vinyl, phenyls, amines, hvdroxyls~etc. The molar ratios of the various units, either in terms of subscripts to thesymbols indicating the total number of each type of unit in the silicone (or an
average thereof) or as specifically indicated ratios in combination with molecular
weight complete the description of the silicone material under the MDTQ svstem
Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or or M' in a
silicone resin is indicative of higher levels of croc~linking As discussed before,
however, the overall level of crosslinking can also be indicated by the oxygen to
. . .
slhcon ratlo.
lo The silicone resins for use herein which are pler~-,ed are MQ, MT,
MTQ, and MDTQ resins. Thus, the plerelled silicone substituent is methyl.
Especially plt:~--ed are MQ resins particularly those wherein the M:Q molar ratio
is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the
resin is from about 500 to about 10,000, generally from about l.000 to about
1~ 10,000.
Depending upon the particular choice of spreading agent
(particularly the silicone resins) and polysiloxane fluid, it may be necessary or
desirable to incorporate an additional solvent to ensure that the resin and
polysiloxane fluid are compatible with one another. Thus, if the silicone resin isn't
20 corl,palible with the polysiloxane fluid at the desired polysiloxane fluid: silicone
resin weight ratio, it will be useful to incorporate into the polysiloxane/spreading
agent phase a solvent to facilate ~nh~nced solubility or dispersibility of thesecomponents. If the solvent has a refractive index below about 1.46, or is
otherwise below the refractive index of the polysiloxane fluid, it may be desirable
25 to use a solvent which is volatile (materials that exhibit greater than 0.2mmHg at
25 C and one atmosphere, generally with a boiling point of less than 275 C), so
that it does not remain on the hair and potentially impair the shine performanceobtained according to the present invention. Suitable solvents include:
cyclomethicone, other cyclic siloxanes such as those described herein as carrier30 fluids, linear polysiloxane polymers such as dimethicone, and other low viscosity
analogues of the polysiloxane materials described in Formulas I and II, preferably
having viscosity at 25C of about 10 centistokes or less, such materials generally
having lower (or zero) degree of aryl-col,l~illh~g substituents than the highly
arylated, high refractive index polysiloxane of the present invention; volatile liquid
3 ~ hydrocarbons, such as straight or branched chain hydrocarbons having from about
4 to about 16 carbon atoms (e.g., hexane, isobutane, decane, dodecane,
tetradecane, tridecane): lower alcohols (e.g. C~-C4 alcohols such as ethanol andisopropanol); hydrocarbon esters, preferably with a total of about 10 carbon
W094/08557 21 ~ 79 7~ 12 PCI'/US93/09937
atoms or less (e.g. ethyl acetate); halogenated hydrocarbons (e.g. freon). volatile
ketones (e.g. acetone); and mixtures thereof Especially preferre~ is
cyclomethicone. The present invention does not, however. exclude the use of
nonvolatile solvents for the resiniphenylated polysiloxane solvent.
When used, solvents as described above will be used typically at a
weight ratio of (solvent) to (highly arylated nonvolatile polysiloxane plus
spreading agent) OI Up to about 100:1, more typically up to about 50:1~ for
rinse-offhair care products, preferably from aobut 2:1 to about 10:1 for hair rinse
products. For leave-on products, high levels of volatile solvents may be used aso carrier ingredients, as described later.
Surfactants
Surfactants that are compatible with the polvsiloxane fluid hereof
and which is suitable for application to the hair can also be used as a spreadin~
agent. The surfactants can be anionic, cationic, nonionic. amphoteric. or a
s zwitterionic.
Polyether Siloxane Copolymer
Polyether siloxane copolymers, or silicone "copolyols'! as they are
sometimes lef~ d to, are silicone-cont~ining surfactants that can be utilized asspreading agents for the polysiloxane fluid. Silicone copolyols are surfactants
charecterized by a hydrophobic polysiloxane chain and a hydrophilic alkoxy
portion.
Silicone copolyols which may be used include polyalkylene oxide
modified polydimethylsiloxanes ofthe following formulae:
l CH3
(CH3)3SiO-[Si(CH3)20]X- Si - O - Si(CH3)3
I
C3H6
I
0 y
(C2H40) a (C3H60) b-R
and
R~ - Si-- [-0 Si (CH3)2]X- (0C2H4)a - (OC3H6)b -30R
wherein R is hydrogen, an alkyl group having from 1 to about 12 carbon atoms~
an alkoxy group having from I to about 6 carbon atoms or a hydroxyl group. R'
and R" are alkyl groups having from I to about 12 carbon atoms; x is an inteoer
W 0 94/08557 21~7~7 ~ PC~r/US93/09937
of from I to 100, preferably from 20 to 30; y is an integer of I to 20, preferably
from 2 to 10: and a and b are integers offrom 0 to 50, preferably from 20 to 30.Silicone copolyols among those useful herein are also disclosed in
the following patent documents, all incorporated by reference herein: U.S. Patent
4,122,029, Geen, et al., issued October 24, 1978; U.S. Patent 4,265,878. Keil,
issued May 5, 1981; and U.S. Patent 4,421,769, Dixon, et al., issued December
20, 1983. Such silicone copolyol materials are also disclosed, in hair compo-
sitions, in British Patent Application 2,066,659, Abe, published July 15, 1981
(incorporated by reference herein) and Canadian Patent 727,588, Kuehns, issued
February 8, 1966 (incorporated by reference herein). Commercially available
silicone copolyols which can be used herein, include Silwet Surface Active
Copolymers (m~nnfAct~lred by the Union Carbide Corporation); and Dow
Corning Silicone Surf~ct~nt~ (m~nl~f~ctnred by the Dow Corning Corporation).
A variety of suitable non-silicone-con~ g organic surfactants
that can be used are described below.
Anionic Surf~ct~nts
Anionic surf~nt.c useful herein include alkyl and alkyl ether
sulfates. These materials typically have the respective formulae ROSO3M and
RO(C2H4O)XSO3M, wherein R is alkyl or alkenyl of from about 10 to about 20
carbon atoms, x is I to 10, and M is a water-soluble cation such as ammonium,
sodium, potassium and triethanolamine.
Another suitable class of anionic surfactants are the water-soluble
salts of the organic, sulfuric acid reaction products of the general formula:
Rl --SO3--M
2s wherein R1 is chosen from the group consisting of a straight or branched chain,
saturated aliphatic hydrocarbon radical having from about 8 to about 24,
Eeferably about 12 to about 18, carbon atoms; and M is a cation. lmportant
examples are the salts of an organic sulfuric acid reaction product of a
hydrocarbon of the ",~;ll,ane series, inrlll~in~ 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, H2SO4, oleum, obtained according to known
sulfonation methods, inr,lutlin~ bleaching and hydrolysis. P,e~led are alkali
metal and ammonium sulfonated C12 l~i n-paraffins.
Additional examples of anionic surfactants which come within the
3s terms of the present invention are the reaction products of fatty acids esterified
with isethionic acid and neutralized with sodium hydroxide where, for example,
the fatty acids are derived from coconut oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the faity acids, for example, are derived
WO94/08~57 21~7~74 14 PCI/US93/09937
from coconut oil. Other anionic surf~ct~nt~ of this variety are set forth in U.SPatents 2,486,921; 2,486,922; and 2,396,278.
Still other anionic surf~ct~nt~ include the class designated as
s~lccin~m~tes. This class includes such surface active agents as disodium
N-octadecylsulfos~lccin~m~te; tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecylsulfosuc~ e; diamyl ester of sodium
sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of
sodium sulfosuccinic acid.
Other suitable anionic surf~ct~nts utilizable herein are olefin
0 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
sulfonation of a-olefins by means of uncomplexed sulfur trioxide, followed by
neutralization of the acid reaction mixture in conditions such that any sultoneswhich have been formed in the reaction are hydrolyzed to give the corresponding
hydroxy-~lk~nesulfonates. The a-olefins from which the olefin sulfonates are
derived are mono-olefins having about 12 to about 24 carbon atoms, preferably
about 14 to about 16 carbon atoms. Another class of anionic organic surfactants
are the b-alkyloxy alkane sulfonates.
Nonionic Surf~ct~nt.c
Nonionic surf~t~nts can be broadly defined as compounds
produced by the condPnc~tion of alkylene oxide groups (hydrophilic in nature)
with a hydrophobic compound, which may be aliphatic or alkyl aromatic in
nature. Examples of pleîelled classes of nonionic surfactants are:
1. The polyethylene oxide con~n.c~tes of alkyl phenols, e.g
the con-lçnc~tion products of alkyl phenols having an alkyl group collLainillg from
about 6 to about 20 carbon atoms in either a straight chain or branched chain
configuration, with ethylene oxide, the said ethylene oxide being present in
amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of
alkyl phenol.
2. Those derived from the cond~nc~tion of ethylene oxide with
the product res -ltin~ from the reaction of propylene oxide and ethylene diamineproducts.
3. The condçnc~ion product of aliphatic alcohols having from
about 8 to about 18 carbon atoms, in either straight chain or branched chain
3s configuration, with ethylene oxide e.g., a coconut alcohol ethylene oxide
con~tonc~te having from about 10 to about 30 moles of ethylene oxide per mole ofcoconut alcohol, the coconut alconol fraction having from about 10 to about 14
carbon atoms.
W094/0855721 ~ 7~ 7~ 15 PCI/US93/09937
4. Long chain tertiary amine oxides such as those
corresponding to the following general formula:
RIR2R3N > O
wherein R1 contains an alkyl alkenyl or monohydroxy alkyl radical of from about
5 8 to about 18 carbon atoms? from O to about 10 ethylene oxide moieties, and from
O to about 1 glyceryl moiety, and R2 and R3 contain from about I to about 3
carbon atoms and from O to about 1 hydroxy group, e.g., methyl. ethyl, propyl,
hydroxyethyl, or hydroxypropyl radicals (the arrow in the formula represents a
semipolar bond).
lo5. Long chain tertiary phosphine oxides corresponding to the
following general formula:
RR~"P > O
wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from
about 8 to about 18 carbon atoms in chain length, from O to about 10 ethvlene
l~ oxide moieties and from O to about 1 glyceryl moiety and R' and R" are each alkyl
or monohydroxyalkyl groups con~ -il-g from about 1 to about 3 carbon atoms.
The arrow in the formula represents a semipolar bond.
6. Long chain dialkyl sulfoxides cont~il-il-g one short chain
alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually
20 methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy
alkyl, or keto alkyl radicals co..~ -il-g from about 8 to about 20 carbon atoms,from O to about 10 ethylene oxide moieties and from O to about I glycervl moiety.
7. Polysorbates, e.g., sucrose esters of fatty acids. Such materials
are described in U.S. Patent 3,480,616, e.g., sucrose cocoate (a mixture of
2~sucrose esters of a coconut acid, consisting primarily of monoesters, and soldunder the tr~dçn~mes GRILLOTEN LSE 87K from RITA, and CRODESTA
SL-40 from Croda).
8. Alkyl polysaccharide nonionic surf~ct~ntc are disclosed in U.S.
Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
30cont~ining from about 6 to about 30 carbon atoms, preferably from about 10 to
about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic
group. The polysaccharide car. contain from about 1.0 to about 10, preferably
from about 1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units. Any re~uring saccharide cont~ining 5 or 6 carbon atoms can be
3~used, e.g., glucose, galactose and galactosyl moieties can be substituted for the
glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-. 3-, 4-
etc. positions thus giving a giucose or galactose as opposed to a glucoside or
galactoside.) The intersaccharide bonds can be, e.g.. between the one position of
W O 94/08~57 2 1 q 7 ~ 7 4 ! PC~/US93/09937
~ 6
the additional saccharide units and the 2-, 3-, 4-, andlor 6-positions on the
preceding saccharide units. Optionally there can be a polvalkyleneoxide chain
joining the hydrophobic moiety and the polysaccharide moiety. The alkyl group
preferably contains up to about 3 hydroxy groups andlor the polyalkyleneoxide
chain can contain up to about 10, preferably less than 5, alkylene moieties.
Suitable alkyl polysaccharides are octyl, nonyldecyl. undecyldodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-. tetra-,penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides,
fructoses and/or galactoses.
0 9. Polyethylene glycol (PEG) glyceryl fatty esters. as depicted by
the formula RC(O)OCH2CH(OH)CH2(OCH2CH2)nOH wherein n is from about
5 to about 200, preferably from about 20 to about 100, more preferably from
about 30 to about 85, and RC(O)- is an ester wherein R comprises an aliphatic
radical having from about 7 to l9 carbon atom~, preferably from about 9 to 17
carbon atoms, more preferably from about 11 to 17 carbon atoms most
preferably from about 11 to 14 carbon atoms. The combinations of n from about
th C12-C18, preferably C]2-C15 fatty esters, for "~;"i",;~ed
adverse effect on fo~ming, is preiel~ed.
Cationic Surf~ct~nt~
Cationic surf~ct~nts useful in compositions of the present
invention, particularly the conditioner compositions, contain amino or quaternary
ammonium hydrophilic moieties which are positively charged when dissolved in
the aqueous composition of the present invention. Cationic surfactants among
those useful herein are disclosed in the following documents, all incorporated by
2s reference herein: M.C. Publishing Co., McCutcheon's. Deter .ents & Emulsifiers,
(North American edition 1979); Schwartz, et al., Surface Active A~ents, Their
Chemistry and Technology, New York: Interscience Publishers, 1949; U.S.
Patent 3,155,591, Hilfer, issued November 3, 1964; U.S Patent 3,929,678,
hlin, et al., issued December 30, 1975; U.S. Patent 3,959,461, Bailey, et al.,
issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983.
Among the quaternary ammonium-containing cationic surfactant
materials useful herein are those of the general formula:
1~ R -- +
N X
R2~ \ R4
wherein R1-R4 are independently an aliphatic group of from about 1 to about 22
carbon atoms, or an aromatic. alkoxy, polyoxyalkylene. alkylamido, hydroxyalkyl.aryl or alkylaryl group having from about 12 to about ''2 carbon atoms; and X is
W O 94/08~57 2 1 4 7 ~ 74 17 PC~r/US93/09937
an anion selected from halogen, acetate, phosphate, nitrate and alkvlsulfate
radicals. The aliphatic groups may contain, in addition to carbon and hydrogen
atoms, ether linkages, and other groups such as amino groups. The lon_er chain
aliphatic groups, eg., those of about 12 carbons. or higher, can be saturated or5 unsaturated.
Salts of primary, secondary and tertiary fatty amines are also
suitable cationic surfactant materials. The alkyl groups of such amines preferably
have from about 12 to about 22 carbon atoms, and may be substituted or
. unsubstituted. Such amines, useful herein, include stearamido propyl dimethyl
o arnine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyaminesoyarnine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane
minç, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine,
and arachidylbehenylamine. Suitable amine salts include the halogen acetate,
phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts includestearylamine hydrochloride, soyamine chloride, stearylamine formate,
N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate.
Cationic amine surf~r,t~nts insl~ded among those useful in the present inventionare disclosed in U.S. Patent 4,275,055, N~çhti~l et al., issued June 23, 1981,
incorporated by reference herein.
21, Zwitterionic and Amphoteric Surf~ct~nts
Zwitterionic surf~çt~nts, useful in shampoos as ~ well as
conditioners, are eYçmrlified by those which can be broadly described as
derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium
compounds, in which the aliphatic radicals can be straight or branched chain, and
2s wherein one of the aliphatic substitl1~nt~ contains from about 8 to about 18
carbon atoms and one collLains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate, phosphate, or phosphonate. A general formula for these
compounds is:
(R3 ) x
R2- - - -Y(+) - - - -CH2- - - -R4- - - -z (
wherein R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to
about 18 carbon atoms, fiom 0 to about 10 ethylene oxide moieties and from 0 to
about I glyceryl moiety; Y is selected from the group consisting of nitrogen,
35 phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl grou~
CO~ g 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
of from about 1 to about 4 carbon atoms and Z is a radical selected from the
2147~74 ` :-
WO 94/08~57 PCI /US93/09937
18
group consisting of carboxylate sulfonate, sulfate, phosphonate. and phosphate
groups.
Other zwitterionics such as betaines are also useful in the present
invention. Examples of betaines useful herein include the high alkyl betaines. such
as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine,
lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine,lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, and lauryl
bis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines may be
0 represented by coco dimethyl sul~op,upyl betaine, stearyl dimethyl sulfopropyl
betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl
betaine and the like; amidobetaines and amidosulfobetaines, wherein the
RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine are also
useful in this invention.
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 aliphatic 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, sulfate, phosphate, or
phosphonate. Examples of compounds falling within this definition are sodium
3-dodecyl-aminopropionate, sodium 3-dodecylaminop~ opane sulfonate,
N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium
isethionate according to the te~ching of U.S. Patent 2,658,072, N-higher alkyl
2~ aspartic acids such as those produced according to the te~c.hing of U.S. Patent
2,438,091, znd the products sold under the trade name "Miranol" and described inU.S. Patent 2,528,3,78, both of which patents are incorporated herein by
reference.
Other surf~ct~nts that can be used include fluorosurfactants, or
other halogenated surfactants, which can be anionic, nonionic, cationic,
amphoteric, or z~itterionic.
Fluorosurf~c.t~ntc include perfluorinated compounds such as those
represented by the forrnula
CF3- (CF2)x~ (CH2)y
where Z is a water solubilizing group of either organic or inorganic character. x is
an integer which is generally from 2 to 17, particularly from 7 to 11, and y is an
integer from 0 to 4, and said compounds may be cationic, anionic~ amphoteric or
zwitterionic, depending upon the nature of the grouping or groupings
W094/08~57 21~7~7~ PCr/US93/09937
19
encomp~csed by Z. The Z groups may be or may comprise sulfate. sulfonate~
carboxylate, amine salt, quaternary ammonium, phosphate, phosphonate, and
combinations thereof. The perfluorinated compounds are known in the art.
These compounds are described in U.S. Patent 4,176,176, Cella et al.. issued
November 27, 1979; U.S. Patent 3,993,74~, Cella et al. issued November 23.
1976, and U.S. Patent 3,993,744, Cella et al.. .~ ed November 23, 1976. each
being incorporated herein by reference.
Fluorosurf~ct~nt~7 when used, will typically be used at lower levels
than most other spreading agents. They will be used generally at weight ratios of
o polysiloxane fluid to spreading agent of from about 10,000:1 to about 1:1,
preferably about 1,000:1 to about 10:1.
In general, the compositions hereof will contain from about 0.01%
to 100% by weight of the spreading agent in admixture with the polysiloxane
fluid, more generally from about 0.05% to about 5G%, preferably from about
0.1% to about 15%, more preferably from about 0.2% to about 5~0. any amount
can be used as long as the compositions is effective for enhancing hair shine.
Carrier
The compositions of the present invention will comprise a carrier
for the polysiloxane fluid and spreading agent suitable for application to the hair.
2() The carrier is present at from 0% to about 94.99%, more generally from about
50% to about 99.95%, preferably from about 85% to about 99.9%, most
preferably from about 95% to about 99.8%, of the composition. As used herein,
the phrase "suitable for application to hair" means that the carrier does not
damage or negatively affect the aesthetics of hair or cause irritation to skin.
Choice of approp.iate carrier will also depend on the particular polysiloxane fluid
to be used, and whether the product form~ ted is meant to be left on the surfaceto which it is applied (e.g., hair spray, mousse, tonic) or rinsed off (e.g., shampoo,
conditioner) after use.
The carriers used herein include solvents, as well as other carrier
or vehicle components conventionally used in hair care compositions.
Suitable carrier fluids for use in the present invention include, but
are not limited to, water, lower alcohols (e.g. C1-C6) monohydric alcohols. suchas ethanol and isopropanol), hydroalcoholic mixtures, hydrocarbons (such as
isobutane, hexane, decene, acetone), halogenated hydrocarbons (such as Freon),
linalool, hydrocarbon esters (such as ethyl acetate, dibutyl phth~l~te), volatile
silicon derivatives, especially siloxanes (such as phenyl pentamethvl disiloxane,
methoxypropyl heptamethyl cyclotetrasiloxane. chloropropyl pentamethyl
disiloxane, hydroxypropyl pem~methyl disiloxane. octamethyl cyclotetrasiloxane.
WO 94/08557 PCr/US93/09937
21~747~ ` 20
dec~methyl cyclopentasiloxane, cyclomethicone, and dimet'nicone (having for
example, viscosity at 25C of about 15 centipoise or less) and rnixtures thereofPlere--ed carrier fluids include water, ethanol volatile silicone derivatives. and
mixtures thereof. The fiuids used in such mixtures may be miscible or imrniscible
with each other.
The carrier may also include gel vehicle materials. The gel vehicle
comprises two essential components: a lipid vehicle material and a cationic
surfactant vehicle material. Catiorlic surfactant materials are described in detail
above. Gel vehicles are generally described in the following documents, all
incorporated by reference herein: Barry, "The Self Bodying Action- of the Mixed
Fm~ ifier Sodium Dodecyl Sulfate/Cetyl Alcohol", 28 J. of Colloid and Interface
Science 82-91 (1968); Barry, et al., "The Self-Bodying Action of Alkyltrimethyl-ammonium Bromides/Cetostearyl Alcohol Mixed Fmlllcifiers; Influence of
Quaternary Chain Length"? 35 J. of Colloid and Interface Science 689-708
(1971); and Barry, et al., "Rheology of Systems Cont~ining Cetomacrogol 1000 -
Cetostearyl Alcohol, I. Self Bodying Action", 38 J. of Colloid and Interface
Science 616-625 (1972). Gel vehicles are particularly useful for hair rinse
compositions, as well as leave-on hair care compositions such as gel conditioners
and shine enh~ncers.
The carrier may also incorporate one or more lipid vehicle
materials which are essçnti~lly water-insoluble, and contain hydrophobic and
hydrophilic moieties. Lipid vehicle materials include naturally or
synthetically-derived acids, acid derivatives, alcohols, esters~ ethers, ketones. and
amides with carbon chains of from about 12 to about 22, preferably from about
16 to about 18, carbon atoms in length. Fatty alcohols and fatty esters are
eÇel,ed; fatty alcohols are particularly pl~rel~ed.
Lipid vehicle materials among those useful herein are disclosed in
Bailey's Industrial Oil and Fat Products. (3rd edition, D. Swern, ed., 1979),
incorporated by reference herein. Fatty alcohols included among those useful
3() herein are disclosed in the following doc~-m~nt.s all incorporated by reference
herein: U.S. Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent
4,165,369, Watanabe, et al., issued August 21, 1979; U.S. Patent 4,269,824,
Villamarin, et al., issued May 26, 1981; British Specification 1,532,585, published
November 15, 1978; and Fukuchim~ et al., "The Effect of Cetostearyl Alcohol in
Cosmetic Emulsions", 98 Cosmetics & Toiletries 89-112 (1983). Fatty esters
included among those useful herein are disclosed in U.S. Patent 3,341,46j.
n, et al.. issued September 12, 1976 (incorporated bv reference herein). If
included in the compositions of the present invention, the lipid vehicle material is
WO 94/08557 4 7~ 7~ PCr/US93/09937
preferably present at from about 0.1% to about 10.0% of the composition; the
cationic surfactant vehicle material is preferable present at from about 0.05% to
about 5.0% ofthe composition.
P, ~Çel, ed lipids are esters, such as cetyl palmitate and
glycerylmonostearate. Cetyl alcohol and stearyl alcohol are plef~lled alcohols. A
particularly p~ere"ed lipid vehicle material is comprised of a mixture of cetyl
alcohol and stearyl alcohol cont~ining from about 55% to about 65% (by weight
of mixture) of cetyl alcohol.
Preferred carriers for use in the compositions of the present
o invention, especially for hair rinses, include co"~b,nations of
hydrophobically-modified hydroxyethyl cellulose materials with thickeners (such
as locust bean gum), particular surf~ct~nts7 quaternary ammonium compounds
(such as ditallowdimethyl ammonium chloride). and/or ç~ tinç~; agents (such as
EDTA). These vehicles are described in detail in the following patents: U.s.
Patent 5,106,609, issued April 21, 1992 to Bolich et al., U.S. Patent 5,100,658,issued March 31, 1992 to Bolich et al., U.S. Patent 5,104,646, issued April 14,
1992 tc Bolich et al, and U.S. Patent 5,100,657, issued March 31, 1992 to
Ansher-Jackson et al., each incorporated herein by reference.
Suspending agents may also be utilized as carrier components for
suspending the polysiloxane fluid/spreading agent ha~r shine agent and/or other
immic~ble or particulate ingredients (e.g. anti-static cationic surf~ct~nt~ which are
insoluble in the composition, anti-dandruff actives (e.g. zinc pyridinethione), etc.
A suspending agent can be particularly important in pourable liquid formulations,
such as shampoos.
2s Exemplary suspending agents useful in the present compositions
include any of several long chain acyl derivative materials or mixtures of such
materials, such as lo_g chain acyl derivatives, long chain amine oxides. and
mixtures thereof, wherein such suspending agents are present in the composition
in crystalline form. These suspending agents are described in U. S . Patent
4,741,855, Grote and Russell, issued May 3, 1988, incorporated herein by
reference. In~ ded are ethylene glycol esters of fatty acids having from about 16
to about 22 carbon atoms. Plert:lled are the ethylene glycol stearates, both mono
and distearate, but particularly the distearate co~ g less than about 70/D oFthemono stearate. Other suspending agents found useful are alkanol amides of fatty
acids, having from about 16 to about 22 carbon atoms, preferably about 16 to 18
carbon atoms. P~ere"ed alkanol amides are stearic monoethanolamide. stearic
diethanolamide, stearic monoisopropanolamlde and stearic monoethanolamide
stearate. Other long chain acyl derivatives include long chain esters of lon_ chain
WO 94/08557 2 1 4 7 4 7 ~ ~ PCI/US93/09937
fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.), glyceryl esters (e.g.,
glyceryl distearate) and long chain esters of long chain alkanol amides (e.g,
stearamide DEA distearate, stearamide MEA stearate).
Still other suitable suspending agents are alkyl (C 16-c22) dimethyl
amine oxides such as stearyl dimethyl amine oxide. If the compositions contain an
amine oxide or a long chain acyl derivative as a surfactant the suspending function
could also be provided by such surfactant and additional suspending agent may
not be needed if the level of those materials are at least the minimllm level given
below.
0 Other long chain acyl derivatives that can be used include
N~N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K
salts), particularly N,N-di(hydrogenated) C16. C 18 and tallow amido benzoic acid
species of this family, which are commercially available from Stepan Company
(Northfield, Illinois, USA).
The long chain acyl derivative materials, when utilized as the
suspending agent, are typically present in pourable, liquid formulations at a level
offrom about 0.1% to about 5.0%, preferably from about 0.5% to about 3.0%.
The suspending agent serves to assist in suspending the silicone material and may
give pearlescence to the product. Mixtures of suspending agents are also suitable
for use in the compositions of this invention.
Another type of sus~end;ng agent that can be used is xan~}lall gum.
Compositions uti~ ing ~ h~n gum as a suspending agent for a silicone hair
conditioning component are described in U.S. Patent 4,788,006, Bolich and
Williams, issued November 29, 1988, incorporated herein by reference. Xanthan
2~ gum is biosynthetic gum material that is commercially available. It is a
heteropolysaccharide with a molecular weight of greater than 1 million. It is
believed to contain D-glucose, D-mannose and D-glucuronate in the molar ratio
of 2.8:2.0:2Ø the polysaccharide is partially acetylated with 4.7% acetyl. This
h~lllla~ion and other is found in Whistler, Roy L. Editor Industrial Gums -
Polysaccharides and Their Derivatives New York: ~ç~emic Press, 1973. Kelco,
a Division of Merck & Co., Inc. offers ~r~nth~n gum as KeltrolR. The gum, when
used as the silicone hair conditioning component suspending agent, will typically
be present in pourable, liquid formulations at a level of from about 0.3% to about
3%, preferably from about 0.4% to about 1.2% in the compositions of the present
3~ invention.
Colllbhlalions of long chain acyl derivatives and xanthan gum are
disclosed as a suspending agent for silicone hair conditioners in U.S Patent
4,704,272, Oh et al.. issued November 3, 1987. incorporated herein by reference,
WO 94/08~57 2 1 ~ 7~ 74 ~ ` ; s PCr/US93/09937
23
and may also be used in the present compositions. Gel formulations have high
levels of suspending agent relative to pourable, liquid formulations when used as
the primary means of h~lpal ~ing the gel-like viscosity to the composition. In such
compositions, the suspending agent will typically be present at levels of from
s about .1 to about 5%. Alternately, other materials can be used to impart a
gel-like viscosity to the composition, such as gelling agents (e.g., hydroxyethyl
cellulose), thickeners, viscosity modifiers, etc. Mixtures of these materials can
also be used.
Hair care compositions for which the present invention can be
o useful for also inrl~ldP, for example, tonics, mousses, gels and hair sprays.
Tonics, gels and non-aerosol hair sprays utilize a solvent such as water or alcohol
while mousses and aerosol hair sprays additionally utilize a propellant such as
trichlorofluoromethane, dichlorodifluoromethane, difluoroethane. dimethylether~
propane, n-butane or isobutane. A tonic or hair spray product having a low
viscosity may also utilize an emulsifying agent. Examples of suitable emulsifying
agents include nonionic, cationic, anionic surfactants, or mixtures thereof. If such
an emulsifying agent is used, it is p.e~,~bly present at a level of from about
0.01% to about 7.5% of the composition. The level of propellant can be adjusted
as desired but is generally from about 3% to about 30% of mousse compositions
and from about 15% to about 50% of the aerosol hair spray compositions.
Suitable spray containers are well known in the art and include
conventional, non-aerosol pump sprays i.e., "atomizers," aerosol containers or can
having propellantj as described above, and also pump aerosol containers utilizing
col,.plc:ssed air as the propellent. Pump aerosol containers are disclosed, for
2s example, in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July
25, 1989, TerStege, both incorporated by r~rerence herein, and also in U.S. Serial
No. 07/839,648, Gosselin, Lund, Sojka, and Lefebvre, filed February 21, 1992,
"Consumer Product Package Incorporating A Spray Device Utilizing Large
Diameter Bubbles. Pump aerosols hair sprays using colllpressed air are also
currently marketed by The Procter & Gamble Company under their tradename
VIDAL SASSOON AIRSPRAYR hair sprays.
Optional In~redients
The compositions of the present invention may be form~ ted in a
wide variety of product types, inr.l~l~1ing mousses, gels, lotions, tonics, sprays,
shampoos and conditioners. The additional components, in addition to the
carrier, required or desirable to formulate such products vary with product typeand can be routinely chosen by one skilled in the hair care product art. For
example, shampoos, will also contain cle~ncing surfact~nts, a wide variety of
WO 94/08~7 2 I ~ 7 4 7 4 PCr/US93/09937
which are well known. Exemplary surfactants that can be used as cleansing
surf~ctn~t.c are desicribed above. these include anionic. nonionic, amphoteric. and
zwitterionic non-silocone-cont~ining surfactants. Hair conditioners may contain.in addition to the high refractive index polysiloxane fluids, other hair conditioningJ
agents such as lower refractive index silicone fluids, such as those described
herein but with lower degrees of aryl-substitution, e.g., dimethicone, catioric
surf~ct~nt~ and cationic polymers, organic oils and waxes such as hydrocarbon
oils, and fatty acid esters, and alcohols.
A particular category of low refractive index (i.e. refractive index
0 below 1.46, generally below about 1.44, preferably from about 1.38 to about1.42) polysiloxane fluids that can be used are polysiloxane gums. "Polysiloxane
gum" refers to silicone fluids having a viscosity at 25C of 1,000,000 cp or
higher. Preferably, the viscosity will be from 1,000,000 to about 100,000,000 cpat 25C. Expecially ple~l-ed is polydimethylsiloxane gum. Low refractive inde~;
polysiloxane conditioners are generally used at levels of from about 0.01% to
about 1 0%, by weight, of the compositions, preferably from about 0.1 % to about5%, more preferably from about 0.5% to about 5%, most preferably from about
1% to about 4%.
In addition to providing hair conditioring benefits to compositions
20 CO~ g the high refractive index and spreading agent hereof, it has been foundthat the colllbinalion of low refractive index polysiloxane gum and high refractive
index polysiloxane fluids hereof, even in the absence of spreading agent, can
provide excellent hair conditioning with surprising improvements in shine. The
low refractive index polysiloxane gum and high refractive index polysiloxane fluid
2s are used at the previously disclosed levels. The weight ratio for the low refractive
index gum to the high refractive index fluid in this aspect of the invention is from
about 1:100 to about 1001, preferably from about 1:10 to about 10:1, more
preferably from about 1:5 to about 5:1.
Suitable cationic polymers include, for example, copolymers of
vinyl monomers having cationic amine or quaternary ammonium functionalities
with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl
and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkvl
methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl
substituted monomers preferble have Cl-C7 alkyl groups, more preferably Cl-C3
alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcoho}(made by nydrolysis of polyvinyl acetate), maleic anhydride. propylene glycol and
ethylene glycol. Other cationic polymers include cationic-modified
polysaccharides. such as cationic ammonium modified cellulose. Suitable cationic
W- ~4/085~7 2147~71 i PCI/US93/09937
2s
surfactants are generally described above, especeially prt:fe-.ed are di(Cl ~-CIg,
especially C 1 6-C 18) alkyl and alkenyl, dimethyl ammonium salts (especially
chloride salts).
Hair setting compositions, e.g. sprays, mousses, gels, and hair
~ 5 rinses, can contain film forming polymers, i.e. adhesive polymers~ as are well
known in the art.
Exemplary adhesive polymers include polyvinylpyrrolidone (PVP),
particularly poly N-vinyl pyrrolidone, copolymers of PVP and methylmetharylate,
copolymers of PVP and vinyl acetate (VA), and polyvinyl alcohol (PVA).
0 Exemplary adhesive polymers also include copolymers of VA and
crotonic acid, copolymers of methylvinylether and maleic hemiesters (e.g. maleicethyl ester and maleic butyl ester), hydroxypropyl cellulose, hydroxypropyl guargum, polystyrene sulfonate salts, polyacrylic polymers such as polymers and
copolymers of acrylic acid and methacrylic acid, co- and ter- polymers of acrylic
acid and/or methacylic acid with acrylamide and/or vinyl pyrrolidone such as
terpolymers of vinyl pyrrolidone/methyl methacrylate/methacrylic, terpolymers ofvinyl pyrrolidone/ethylmetha~ vlate/methacrylic acid, terpolymers of t-butyl
acrylamide/ethyl acrylate/acryllc acid, and terpolymers of VA/crotonic acid/vinyl
neodecanoate.
Other examples of anionic hair hold polymers are crotonic acid and
a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as
vinyl neodec~no~te; and copolymers of methyl vinyl ether and maleic anhydride
(e.g. molar ratio about 1:1) wherein such copolymers are ~0% esterfied with a
saturated aliphatic alcohol co,.~ from 1 to 4 carbon atoms such as ethanol or
butanol, and acrylic copolymers and terpolymers cor,l~il,;"g acrylic acid or
meth~crylic acid as the anionic radical-co"l~ ing moiety such as copolymers
with, butyl acrylate, ethyl methacrylate, etc.
Polymeric hair hold polymers also include amphoteric polymers.
One class of amphoteric polymers that can be used are acrylic resins with both
cationic and carboxylic groups. Examples include terpolymers of octyl and
acrylamide/acrylic acid/ butylaminoethyl methacrylate, copolymers of acrylic
acid/betaine methacrylate, and copolymers of octylacrylamide/acrylates.
Also silicone grafted adhesive copolymers can be used, such as
those described in which are polysiloxane-co~ ;l-;ng monomers with
non-polysiloxane-co"~ ;ng monomers such that said adhesive agent has a
weight average molecular weight of at least about 20,000, and comprises from
about 1% to about ~0%, by weight, ofthe polysiloxane-containing monomers.
The most pr~..ed polymers comprise an organic backbone.
W094/08~57 2147~7~ ` PCr/US93/09937
26
especially a carbon backbone such as a vinyl polymeric backbone, and also
preferably, a polydimethylsiloxane macromer having a weight average molecular
weight of at least about 500, preferably from about I ,000 to about 100,000, more
preferably from about 2,000 to about 50,000, most preferably about 5,000 to
about 20,000, is grafted to the backbone. Organic backbones contemplated
include those that are derived from polymerizable, ethylenically unsaturated
monomers. These include vinyl monomers, and other condensation monomers
(eg., those that polymerize to form polyamides and polyesters) and ring-opening
monomers (eg., ethyl oxazoline and caprolactone).
o The prefelled polymerizable polysiloxane-co-lLai~ g monomer (C
monomer) can be exemplified by the general formula;
x(Y)nSi(R)3 -mZm
wherein X is a vinyl group copolymerizable with the A and B monomers; Y is a
divalent linking group; R is a hydrogen, hydroxyl lower alkyl (e.g. Cl-C4) aryl,alkaryl, alkoxy, or alkylamino; Z is a monovalent siloxane polymeric moiety
having a number average molecular weight of at least about 500, is essentially
unreactive under copolymenzation conditions, and is pendant from the vinyl
polymeric backbone described above; n is 0 or 1; and m is an integer from I to 3.
Examples of useful polymers and how they are made are described
in detail in U.S. Patent 4,693,935, Mazurek, issued September 15, 1987, U.S.
Patent 4,728,571, Clemens et al., issued March 1, 1988, both of which are
incol ~,o, ~ed herein by reference.
Suitable polymers are also disclosed in EPO Application
90307528.1, published as EPO Application 0 408 311 A2 on January 11. 1991,
2s Hayama, et al., U.S. Patent 5,061,481, issued October 29, 1991, Suzuki et al.,
U.S. Patent 5,106,609, Bolich et al., issued April 21, 1992, U.S. Patent
5,100,658, Bolich et al.l issued March 31, 1992, U.S. Patent 5,100~657,
Ansher-Jackson, et al., issued March 31, 1992, U.S. Patent 5,104,646, Bolich et
al., issued April 14, 1992, and U.S. Serial No. 08/104,232, Bolich et al, filed
August 10, 1993 all of which are incorporated by reference herein. P,efe~l ~d ofthese polymers are copolymers CGnl~ ing t-butyl acrylate and/or t-butyl
methacrylate with vinyl monomers having polydimethylsiloxane macromers
covalently attached thereto.
The compositions herein can contain a variety of other optional
components suitable for rendering such compositions more cosmetically or
aesthetically acceptable or to provide them with additional usage benefits. Suchconventional optional ingredients are well-known to those skilled in the art. e.g
pearlescent aids, such as ethylene glycol distearate; preservatives, such as benzyl
.
-
WO 94/08557 2 ~ 4 7 4 7 4 27 PCI /US93/09937
alcohol. methyl paraben, propyl paraben and imidazolidinyl urea; thickeners and
viscosity modifiers, such as a diethanolamide of a long chain fatty acid (e.g.. PEG
3 lauric diethanolamide), cocomonoethanol amide, guar gum, methyl cellulose
starches and starch derivatives, fatty alcohols, such as cetearyl alcohol sodiumchloride; sodium sulfate; polyvinyl alcohol; ethyl alcohol; pH adjusting agents
such as citric acid, sodium citrate, succinic acid, phosphoric acid~ sodium
hydroxide, sodium carbonate; salts, in general, such as potassium acetate and
sodium chloride; coloring agents, such as any of the FD&C or D&C dyes; hair
oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate
0 salts, hair red~lçing agents, such as the thioglycolates; perfumes; sequestering
agents, such as disodium ethylçne~ mine tetra-acetate; and polymer plasticizing
agents, such as glycerin, disobutyl adipate, butyl stearate, and propylene ~Ivcol.
Such optional ingredients generally are used individually at levels of from about
0.01% to about 10.0%, preferably from about 0.05% to about 5.0/o. of the
composition.
The pH of the present compositions generally will be between
about 3 and about 9, preferably between about 4 and about 8.
As with all compositions, the present invention should not contain
components which unduly interfere with the pe~ ru, ~ance of the compositions.
The hair care compositions of the present invention can be made
using conventional formulation and mixing techniques. Exemplary rhethods of
making various types of cosmetic compositions are also described more
specifically in the Examples below.
Method of Use
2s The hair care compositions of the present invention are used in
conventional ways to provide the conditioning and shine benefits of the present
invention. Such method of use depends upon the type of composition employed
but generally involves application of an effective amount of the product to the
hair, which may then be rinsed from the hair or skin (as in the case of shampoosand some conditioning products) or allowed to remain on the hair (as in the caseof spray, mousse, gel, lotion, and tonic products). By "effective amount" is meant
an amount sufficient to provide a hair shine benefit. Preferably, hair rinse,
mousse, and gel products are applied to wet or damp hair prior to drying of the
hair. After such compositions are applied to the hair, the hair is dried and styled
3s in the usual ways of the user. Hair sprays are typically applied to dry hair after it
has already been dried and styled. Mousses, tonics and lotions are typically
applied to hair in either dry or wet conditioning, depending upon the particular
WO 94/08~57 2 1 ~ 7 9 7 4 - 28 PCI`/US93/09937
intent of the formulation face, skin, or eye area in the conventional manners ofusage for those types of products.
Experimental
The following procedure is used to determine Glossmeter Specular Reflectance.
A collagen solution is prepaled by dissolving I O.Og of gelatin (17
bloom) in 83.0g DRO (double reverse osmosis) water at 155C, with stirring.
Next, 0.05g propylparaben is dissolved in the gelatin solution. Next, 4.5g lM
NaOH is added, followed by 3.0g of Ceraphyl GA-D (a mixture of 10-15% soy
bean oil and 85-90% maleated soy bean oil available from VanDyk lnc.,
o Belleville, NJ, USA) to form a stable, white emulsion. Next, 1.2g of lactic acid is
stired into the emulsion, rt:r~lled hereinafter as Solution A.
A 3.0%, by weight, formaldehyde in water solution, Solution B. is
prepared and contained separately from Solution A.
Ceramic tiles, approximately 7.3cm x 7.3cm in size having a black
s glazed top and an average peak height ("ro~ghness") of 5.0 -7.0 microns (can be
measured with a Rodenstock RM600-2D/3-D Measuring Station (Rodenstock
Meterology, Munich, W. Germany)) are prepared and coated with the collagen on
their top surfaces. Glossmeter Specular Reflectance of the collagen-coated tile
should be from 8.0 - 12.0%.
Specular reflectance of the collagen-coated tile is measured
ili7ing a glossmeter, such as a BYK-Gardner "micro-gloss" glossmeter.
Specular reflection measu, ~IIlt;llLS are made as described in ASTM Method D 523at an angle of incidence of 60. Specular reflectance as measured this way is
referred to herein as "Glossmeter Specular Reflectance." The tiles can be
2~ prepared as follows. Syringe A is filled with 3.0cc of Solution A. Syringe B is
filled with 0.2cc of Solution B. Syringe B contents are emptied onto the top
surface of a tile. Syringe A contents are emptied onto the top of Solution B, onthe top surface of the tile. The solutions are mixed for five seconds and spreaduniformly on the top surface of the tile with a spatula. At 30 seconds after
mixing, a 1.0 inch inside (li~met~r metal ring is placed on the top surface ofthe
tile. The collagen film is allowed to dry for eight hours. The metal ring is
removed. The roughness of the collagen coated surface of the tile should be from3.0 to 5.0 microns.
Polysiloxane and spreading agent mixtures are prepared as
3~ described above, at a 1.00% concentration in a compatible diluent at a weight
ratio of said polysiloxane fluid to said spreading agent corresponding to that
found in the composition. A syringe is used to deposit 0.05cc of the mixture at
the center of the area encompassed by the ring on the surface of the collagen-
W094/08~57 2I~7~74 PCI/US93/09937
coated tile. The mixture is allowed to drv. Glossmeter Specular Reflectance is
measured.
Examples
The following examples further illustrate preferred embodiments
within the scope of the present invention. The examples are given soleh~ for thepurposes of illustration and are not to be construed as limitations of the present
invention as many variations of the invention are possible without departing from
its spirit and scope.
PREMIX EXAMPLES 1-6
0 The following are a variety of exemplary polysiloxane
fluidlspreading agent mixtures useful in the present invention. The mixtures canbe used directly for tre~tment of the hair or. more preferably, can be used as
components in a variety hair care compositions containing other cosmetically or
pharm~ce~-tically active inF~redients, carrier ingredients. or other inF~redients.
lj
Component (Wei ~ht%) Ex. 1 Ex. 2 Ex. 3
Pentaphenyl Trimethyl Trisiloxane (1) 57.00 0.00 50.00
Methylphenyl Diphenyl Siloxane Copolymer (2) 38.00 0.00 0.00
Diphenyl Dimethyl Siloxane Copolymer (3) 0.00 45.00 0.00
Dimethicone (4) 0.00 50 00
MQ Silicone Resin/~'olatile Cyclomethicone (5) 5.00 5.00 0.00
Dimethicone Copolyol (6) 0.00 0.00 50.00
Fluorosurfactant (7) 0.00 1.00 0.00
Cyclomethicone (8) 0.00 0.00 0.00
Component (Wei~ht%) Ex. 4 Ex. 5 Ex. 6
Pentaphenyl Trimethyl Trisiloxane (1) 99.00 15.00 27.00
MethylphenylDiphenylSiloxaneCopolymer(2) 0.00 0.00 12.00
Diphenyl Dimethyl Siloxane Copolymer (3) 0.00 0.00 0.00
Dimethicone (4) 0.00 0.00 0.00
MQ Silicone Resin/V'olatile Cyclomethicone (5) 0.00 5.00 5.00
Dimethicone Copolyol (6) 0.00 0.00 0.00
- Fluorosurfactant (7) 1.00 0.00 1.00
Cyclomethicone (8) 0.00 80.00 55.00
1. Dow Corning 705, Dow Corning
2. PS 1 62. Huls
3 . SFl 265. General Electric
WO 94/085~7 21 ~ 7q 71 PCr~US93/09937
4. SE76 General Electric
5. SS4320, General Electric (50%150% of polytrimethyl
hvdrosilylsilicateldecamethylcyclopentasiloxane)
6. Dow Corning 190, Dow Corning
7. FC- 171 Fluorad, 3M
8. Dow Corning 344, Dow Corning
The premix is prepared by blending all the ingredients with
agitation for about 112 hour at room temperature.
o The following exemplary hair care compositions can be made
utili7inP any of the polysiloxane fluid/spreading agent premix Examples 1-6,
above (hereafter referred to as "Silicone Premix Examples).
EXAMPLES I-III
The following are hair spray compositions representative of the
present invention.
Component Example 3 (Wei~ht %)
II III
Silicone Premix 4.5 4.5 4.5
Ethanol 79.0 79.0 86.4
21~ Diisobutyl adipate 0.7 -- --
Potassium Hydroxide Solution (45% conc) 1.0 1.0 1.0
Perfume 0.2 0.2 0.2
Water --------q.s. to 100%
This product is prepared by dissolving the silicone premix to the ethanol
and mixing for several hours until all of the premix is dissolved. Plasticizer is then
added, if applicable. Potassium hydroxide is then added. Water or
water/surfactant, as applicable, is added. Fragrance is added last. All inEredients
are added under mixing conditions. The product can be packaged in conventional
30 nonaerosol pump spray containers and conlpl essed air pump spray aerosol
containers.
EXAMPLE IV
The following is a hair grooming tonic composition repre-
sentative of the present invention.
3~ Component Wei~ht %
Silicone Premix 0 70
Perfume . 10
Ethanol q.s.
W0 94/08557 1 ~( 7~ 7~ 3~1 PCI`/US93/09937
The composition is made by mixing the above componentstogether in a conventional manner.
EXAMPLE V
The following is a shampoo composition representative of the
present invention.
Component Wei~ht %
Amrnonium Lauryl Sulfate 4.00
Ammonium Laureth Sulfate 12.00
Ammonium Xylene Sulfonate 1.50
Ethylene Glycol Distearate 2.00
Cocomonoethanol Amide 2.00
Tricetyl Methyl Ammonium Chloride 0.50
Cetyl Alcohol 0.42
Stearyl Alcohol 0.18
Silicone Premix (see examples) 1.50
Preservative 0.03
Fragrance 1.20
Distilled Water q.s.
Ammonium lauryl sulfate and citric acid are added to the
2() distilled water at about 15C. The mixture is heated to from 70C. to 80C. The
cocamide MEA and glycol distearate are added at this point. The ammonium
laureth-3 sulfate, cetyl alcohol, stearyl alcohol and silicone premix are blended at
from 70C. to 90C. This mixture is added to the batch following the glycol
distearate. The preservative is then added. The batch is mixed for 5 minutes then
2~ cooled to room temperature (15C. to 25C.). The fragrance is added. then thebatch is milled under high shear for at least 5 minutes using conventional milling
appal ~us.
EXAMPLE VI
The following is a styling gel composition representative of the
3() present invention.
Component Wei~ht %
Silicone Premix 2.00
Carbopol 9401 0.75
Triethanolamine 1.00
Dye solution 0.05
Perfume 0. 10
Laureth-23 0. 10
DRO H~,O q.s.
W O 94/08557 21 ~ 7~ 7~ 32 PC~r/US93/09937
I cross-linked polyacrylic acid. commerciallv available from
B. F. Goodrich
This batch is made bv mixing the listed components together in
a conventional manner.
EXAMPLE VII
The following is a hair mousse composition representative of
the present invention.
Component Wei~ht %
Silicone Premix 3.00
o Ethanol 15.00
Cocamine oxide 0.60
Cocamide DEA 0.30
Perfume 0.10
Isobutane 7.00
DRO H2O q.s.
I dimethicone copolyol, cornmercially available from Dow Corning
The composition is made by blending all of the in_redients
except isobutane at ambient temperature until well mixed. Aluminllm aerosol
cans are then filled with 95 parts of this batch, affixed with a valve which is
20 crimped into position, and lastly pressure filled with 5 parts isobutane.
Examples VIII-X
The following are conditioning rinse compositions
representative of the present invention.
Component Ex. VII Ex. IX Ex. X
Hydroxethyl Cellulose 0.400 0.200 0.000
Cetyl Hydroxyethylcellulose 0.000 0.400 0.500
Crotein Q 1.000 1.000 1.000
Stearylamidopropyl Dimethyl Amine 1.000 1.000 1.000
Ditallowdimethylammonium Chloride 0.750 0.750 0.750
Glyceryl Monostearate 0.250 0.000 0.000
Dipropylene Glycol Isoceteth-20 Acetate 0.000 0.250 0.250
Cetyl Alcohol 0.900 1.700 1.700
Stearyl Alcohol 0.600 0.000 0.000
Emulsifying Wax 0.500 0.000 0.000
Octyl Methoxy Ci~ e 0.000 1.000 1.000
Silicone Premix (see examples) 2.600 2.200 2.200
Trimethyl silvl amodimethicone (1) 0.000 0.000 0.200
~v~)g4/08~57 2~74 7~ ~ ` PCI/US93/09937
Fragrance 0.300 0.300 0.300
CitricAcid 0.220 0.220 0.220
Preservative 0.030 0.030 0.030
Distilled Water q.s. q.s. q.s.
1. Dow Corning Q2-8820 Dow Corning
Hydrox~vethyl cellulose is added to the distilled water at a
temperature of 15C. to 40C. This mixture is well dispersed then heated to a
temperature of from 60C. to 90C. Materials 2 through 10 are added to the
0 batch while the te"~pe~LLIre is ~ ed in this range. The mixture is stirred for
applo~ ately 10min~1tec thencooledtoapp,o~"ldlely50C. Thele,..~ g
materials are added at this temperature. The mixture is milled under high shear
for applo~",a~ely 2 min~ltes using a conventional milling appar~L-Is then cooledto room temperature and collected. Alternatively the Silicone Premix
5 components can be added at the same stage above without ple~ g in advance.
EXAMPLE XI
An aerosol hair spray composition of the present invention is
prepared as follows:
Component Wei~ht %
Silicone Premix 4.00
Water 10.60
Ethanol 63.50
KOH (45% solution) 0.90
Isobutane 1 5.00
Difluoroethane 6.00
All of the ingredients except for the propellants are mixed
~gether at ambient temperature until the polymer is dissolved. The mixture is
placed in an aerosol can which is then equipped with a conventional aerosol spray
can valve which is vacc~ m cl".,ped in place. The propellants are then filled
30 through the valve and the can is equipped with a conventional aerosol spray can
activator.
EXAMPLES X~
Hair rinse compositions of the present invention are prepared as
follows:
35 Component (Wt.%) Ex. XII Ex. X~II Ex. XIV Ex. XV
Oleyl Alcohol 1.0 1.0 1.0 0.2
SalcareR SC951 2.2 0.8 0.8 0.8
Trioctyldodecyl Citrate 1.0 - - -
W094/08~7 21~ 7~ 7~ 34 PCI/US93/09937
Polydimethylsiloxane2 3 5 4.2 4.2 4.2
Silicone Resin3 0.2 0.2 0.2 0.2
Pentaphenyl Trimethyl Trisiloxane4 0 4 0.4 0.4 0.4
DL P~nth~nol 0 04 0 04 0 04 0 04
Panthenyl Ethyl Ether 0.3 0.3 0.3 0 3
Fragrance 0.3 0.3 0.3 0.3
KathonTM CG5 0.03 0.03 0.03 0.03
Hydroxypropyl Guar Gum 0.5 - - -
Hydroxyethyl Cellulose - - 0.2 0.2
0 Cetyl Alcohol - 1.2 1.8 1.8
Stearyl Alcohol - 0.8 1.2 1.2
Ditallow Dimethyl Ammonium
Chloride 1.0 0.8 0.8 0.8
Stearamidopropyl Dimethylamine - 1.0 0.8 0.8
Glycerol Monostearate - 0.2 0.8 0.8
Citric Acid - 0.2 0.2 0.2
Water q.s q.s q.s q.s
Polyquaternium 37 (and) ~Gneral Oil (and) PPG-I Trideceth 6, commercially
available from Allied Colloids Ltd., (Norfolk, VA, USA).
2 An 85%/15% (wt. basis) mixture of D5 Cyclomethicone and dimethicone gum
(weight average molecular weight of about 400,000 to about 600,000).
3 PolyL,i."etl,yl hydrosilyl~ilic~tç7 added as a 50 wt.% solution in
dec~methylcyclopentasiloxane, General Electric Silicone Products, SS 4320.
4 Dow Corning 705~ Dow Corning Corp. (Midland, MI, USA).
5 Methylchloroisothiazoline (and) methylisothiazoline, a preservative from
Rohm & Haas Co., (Philadelphia, PA, USA).
For each-of the exapmles, a silicone premix is prepared by
mixing: the polydimethylsiloxane, MQ resin, and l)e~ ph~nyl trimethylsiloxane ina tank. For Example X~I, the water is heated to about 80C: The hydroxypropyl
guar gum and quaternary ammonium are sequentially added and mixed into the
water. The batch is cooled to about 28C. The following ingredients are then
sequentially well mixed into the batch in the order given, with agitation between
each addition: 1.0% (total wt. basis) SalcareTM SC95, trioctyldodecyl citrate, oleyl
alcohol, p~nth~nol, panthenyl ethyl ether, silicone premix, perfume, KathonTM CG,
and the rem~in-ler ofthe SalcareTM SC95.
For Examples xrv and XV, the water is heated to about 25C
and the hydroxyethyl cellulose is added, with agitation. The water is heated to
about 80C and the following ingredients are sequentially added, with agitation
~''`94/08557 2147~7~ PCI/US93/09937
between each addition: quaternary ammonium salt. cetyl alcohol~ stearyl alcohol,stearamidopropyl dimethylamine, and glyceryl monostearate. Cool the batch to
about 49C. Sequentially add the following ingredients with agitation between
each addition: Silicone premix, citric acid, panthenol, panthenyl ethyl ether,
-- ~ perfume, KathonTM CG, SalcareTM SC 95, and oleyl alcohol. Cool to 25C.
For Example XIII, heat the water to about 80C and mix into it
the quaternary ammonium salt, with agitation. Next add the following ingredientssequentially with agitation between each addition: cetyl alcohol, stearyl alcohol,
oleyl alcohol, stearamidopropyl dimethylamine, and glyceryl monostearate. Cool
o the batch to about 49C. Next add the following ingredients with agitation
between each addition: silicone premix, citric acid, panthenol, panthenyl ethyl
ether, perfume, KathonTM CG, and SalcareTM SC 95. Cool to 25C.
