Note: Descriptions are shown in the official language in which they were submitted.
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HAIR CONDITIONING COMPOSITION COMPRISING
HYDROPHOBICALLY MODIFIED CELLULOSE ETHER
10
TECHNICAL FIELD
The present invention relates to hair conditioning composition comprising
a hydrophobically modified cellulose ether.
BACKGROUND
Human hair becomes soiled due to its contact with fhe surrounding
environment and from the sebum secreted by the scalp. The soiling of hair
causes it to have a dirty feel and an unattractive appearance. The soiling of
the
hair necessitates shampooing with frequent regularity.
Shampooing cleans the hair by removing excess soil and sebum.
However, shampooing can leave the hair in a wet, tangled, and generally
unmanageable state. Once the hair dries, it is often left in a dry, rough,
lusterless, or frizzy condition due to removal of the hair's natural oils and
other
natural conditioning and moisturizing components. The hair can further be left
with increased levels of static upon drying, which can interfere with combing
and
result in a condition commonly referred to as "fly-away hair", or contribute
to an
undesirable phenomena of "split ends", particularly for long hair.
A variety of approaches have been developed to alleviate these after
shampoo problems. These approaches range from post-shampoo application of
hair conditioners such as leave-on and rinse-off products, to hair
conditioning
shampoos which attempt to both clean and condition the hair from a single
product.
Although some consumers prefer the ease and convenience of a
shampoo which includes conditioners, a substantial proportion of consumers
prefer the more conventional conditioner formulations which are applied to the
hair as a separate step from shampooing, usually subsequent to shampooing.
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Conditioning formulations can be in the form of rinse-off products or leave-on
products, and can be in the form of an emulsion, cream, gel, spray, and
mousse.
Such consumers who prefer the conventional conditioner formulations value the
relatively higher conditioning effect, or convenience of changing the amount
of
conditioning depending on the condition of hair or amount of hair.
Some consumers with fine hair have a desire to volume-up their hair. The
term "hair volume-up" as used herein is not equal to fly-away hair. Fly-away
hair
is due to the increased level of static, and represents volume increase of
only
very minor amount of the hair as a whole, and is not desirable. On the other
1o hand, hair volume-up as used herein relates to increase of the bulk of the
hair
volume. Consumers having fine hair have the desire to achieve hair volume-up
while controlling undesirable fly-away of the hair. Generally, hair
conditioner
products targeted for such consumers provided the volume-up or less volume-
down benefit by decreasing the level of conditioning actives included in the
composition. This is thought to be emerging from the concept that conditioning
actives weigh down the hair. Consequently, hair conditioner products targeted
for consumers which desire volume-up generally had only compromised
conditioning benefits.
Based on the foregoing, there remains a desire to provide hair
conditioning compositions which provide hair volume-up while not compromising
basic conditioning benefits such as soft, smooth, easy to comb, clean, draggy
feel to the hair.
United States Patents 5,100,658, 5,106,609, and 5,855,878 disclose the
use of hydrophobically modified nonionic water-soluble polymers in hair
conditioning compositions. It is disclosed in each reference that such
composition provides effective delivery of an active cosmetic component to the
hair or skin. European Patent Application EP-0,875,557-A discloses aqueous
compositions of surfactant mixtures with hydrophobically-modified polymers; in
particular, hydrophobically-modified polymeric rheology modifiers (thickeners)
to
provide enhanced thickening efficiency. European Patent Application EP-
0,786,249-A discloses a topical composition containing active cosmetic and/or
dermatological agent including cetyl hydroxyethyl cellulose as gelling agent.
Hair conditioning compositions containing hydrophobically modified
cellulose polymers can become very viscous and provide negative performance
to the feel of hair or manufacturing of the composition. Thus, there is also a
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desire to provide such hair conditioning compositions while maintaining
acceptable rheology profiles to provide satisfactory spreadability on the
hair, and
so as to be made by a convenient manufacturing method.
None of the existing art provides all of the advantages and benefits of the
present invention.
SUMMARY
The present invention is directed to a hair conditioning composition
comprising by weight:
(a) from about 0.001 % to about 2% of a hydrophobically modified cellulose
ether comprising a hydrophilic cellulose backbone and a hydrophobic
substitution group; the hydrophilic cellulose backbone being water soluble
and selected from the group consisting of methyl cellulose, hydroxymethyl
cellulose, hydroxyethyl cellulose, hydroxyethyl ethylcellulose,
hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxybutyl
cellulose, and mixtures thereof; and having grafted thereto the
hydrophobic substitution group to render the hydrophobically modified
cellulose ether to have less than 1 % water solubility, the hydrophobic
substitution group selected from a straight or branched chain alkyl group
of from about 10 to about 22 carbons; wherein the ratio of the hydrophilic
groups in the hydrophilic cellulose backbone to the hydrophobic
substitution group being from about 2:1 to about 1000:1;
(b) from about 0.1 % to about 15% of a high melting point fatty compound
having a melting point of 25°C or higher;
(c) from about 0.1 % to about 10% of a cationic conditioning agent having
saturated alkyl groups; and
(d) an aqueous carrier.
These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
3o present disclosure.
DETAILED DESCRIPTION
While the specification concludes with claims which particularly point out
and distinctly claim the invention, it is believed the present invention will
be better
understood from the following description.
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All cited references are incorporated herein by reference in their entireties.
Citation of any reference is not an admission regarding any determination as
to
its availability as prior art to the claimed invention.
Herein, "comprising" means that other steps and other ingredients which
do not affect the end result can be added. This term encompasses the terms
°'consisting of and "consisting essentially of'.
All percentages, parts and ratios are based upon the total weight of the
compositions of the present invention, unless otherwise specified. All such
weights as they pertain to listed ingredients are based on the active level
and,
therefore, do not include carriers or by-products that may be included in
commercially available materials.
HYDROPHOBICALLY MODIFIED CELLULOSE ETHER
The composition of the present invention comprises by weight from about
0.001 % to about 2%, preferably from about 0.01 % to about 0.5%, more
preferably from about 0.05% to about 0.5%, of a hydrophobically modified
cellulose ether.
The hydrophobically modified cellulose ethers useful herein have been
known in the art as hydrophilic thickeners to aqueous compositions. It has
been
surprisingly found that, when included in a gel matrix vehicle system at
certain
levels, the hydrophobically modified cellulose ethers provide increase in bulk
hair
volume. It has further been surprisingly found that cellulose ethers with no
hydrophobic modifications, such as hydroxyethyl cellulose, do not provide such
increase in bulk hair volume. Without being bound by theory, it is believed
this is
due to the significant substantivity and controlled water solubility of the
hydrophobically modified cellulose ethers herein. The hydrophobically modified
cellulose ethers would deposit on the hair as discrete particles, thus enhance
the
inter fiber interactions and change its spatial orientation, and consequently
provide more volume to the hair.
The controlled level of hydrophobically modified cellulose ether also
provides acceptable rheology profiles in the conditioning composition of this
invention, so this composition provides satisfactory spreadability on the
hair, and
can be made by a convenient manufacturing method.
The hydrophobically modified cellulose ethers useful herein comprise a
hydrophilic cellulose backbone and a hydrophobic substitution group. The
hydrophilic cellulose backbone has a sufficient degree of nonionic
substitution to
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cellulose to be water soluble. Such hydrophilic cellulose backbone is selected
from the group consisting of methyl cellulose, hydroxymethyl cellulose,
hydroxyethyl cellulose, hydroxyethyl ethylcellulose, hydroxypropyl cellulose,
hydroxypropyl methylcellulose, hydroxybutyl cellulose, and mixtures thereof.
The
amount of nonionic substitution is not critical, so long as there is an amount
sufficient to assure that the hydrophilic cellulose backbone is water soluble.
The
hydrophilic cellulose backbone has a molecular weight of about less than
800,000, preferably from about 20,000 to about 700,000, or from about 75 D. P.
to about 2500 D. P. Further, where a high viscosity building effect is not
desirable, a lower molecular weight cellulose backbone is preferred. One of
the
preferred hydrophilic cellulose backbone is hydroxyethyl cellulose having a
molecular weight of from about 50,000 to about 700,000. Hydroxyethyl cellulose
of this molecular weight is known to be one of the most hydrophilic of the
materials contemplated. Thus, hydroxyethyl cellulose can be modified to a
greater extent than other hydrophilic cellulose backbones.
The hydrophilic cellulose backbone is further substituted with a
hydrophobic substitution group via an ether linkage to render the
hydrophobically
modified cellulose ether to have less than 1 % water solubility, preferably
less
than 0.2% water solubility. The hydrophobic substitution group is selected
from a
straight or branched chain alkyl group of from about 10 to about 22 carbons;
wherein the ratio of the hydrophilic groups in the hydrophilic cellulose
backbone
to the hydrophobic substitution group being from about 2:1 to about 1000:1,
preferably from about 10:1 to about 100:1.
Commercially available hydrophobically modified cellulose ethers useful
herein include: cetyl hydroxyethylcellulose having tradenames NATROSOL
PLUS 330CS and POLYSURF 67, both available from Aqualon Company, Del,
USA, having cetyl group substitution of about 0.4% to about 0.65% by weight of
the entire polymer.
HIGH MELTING POINT FATTY COMPOUND
The composition of the present invention comprises a high melting point
fatty compound. The high melting point fatty compound useful herein have a
melting point of 25°C or higher, and is selected from the group
consisting of fatty
alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and
mixtures
thereof. It is understood by the artisan that the compounds disclosed in this
section of the specification cari in some instances fall into more than one
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classification, e.g., some fatty alcohol derivatives can also be classified as
fatty
acid derivatives. However, a given classification is not intended to be a
limitation
on that particular compound, but is done so for convenience of classification
and
nomenclature. Further, it is understood by the artisan that, depending on the
number and position of double bonds, and length and position of the branches,
certain compounds having certain required carbon atoms may have a melting
point of less than 25°C. Such compounds of low melting point are not
intended
to be included in this section. Nonlimiting examples of the high melting point
compounds are found in International Cosmetic Ingredient Dictionary, Fifth
1o Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.
These high melting point fatty compounds, together with the cationic
conditioning agent, provide a gel network suitable for providing various
conditioning benefits such as slippery and slick feel on wet hair, and
softness,
moisturized feel, and fly-away control on dry hair.
The high melting point fatty compound is included in the composition at a
level by weight of from about 0.1 % to about 15%, preferably from about 0.5%
to
about 10%, more preferably from about 1 % to about 7%.
The fatty alcohols useful herein are those having from about 14 to about
30 carbon atoms, preferably from about 16 to about 22 carbon atoms. These
fatty alcohols are saturated and can be straight or branched chain alcohols.
Nonlimiting examples of fatty alcohols include, cetyl alcohol, stearyl
alcohol,
behenyl alcohol, and mixtures thereof.
The fatty acids useful herein are those having from about 10 to about 30
carbon atoms, preferably from about 12 to about 22 carbon atoms, and more
preferably from about 16 to about 22 carbon atoms. These fatty acids are
saturated and can be straight or branched chain acids. Also included are
diacids, triacids, and other multiple acids which meet the requirements
herein.
Also included herein are salts of these fatty acids. Nonlimiting examples of
fatty
acids include lauric acid, palmitic acid, stearic acid, behenic acid, sebacic
acid,
and mixtures thereof.
The fatty alcohol derivatives and fatty acid derivatives useful herein
include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl
ethers of
alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of
compounds
having esterifiable hydroxy groups, hydroxy-substituted fatty acids, and
mixtures
thereof. Nonlimiting examples of fatty alcohol derivatives and fatty acid
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derivatives include materials such as methyl stearyl ether; the ceteth series
of
compounds such as ceteth-1 through ceteth-45, which are ethylene glycol ethers
of cetyl alcohol, wherein the numeric designation indicates the number of
ethylene glycol moieties present; the steareth series of compounds such as
steareth-1 through 10, which are ethylene glycol ethers of steareth alcohol,
wherein the numeric designation indicates the number of ethylene glycol
moieties present; ceteareth 1 through ceteareth-10, which are the ethylene
glycol ethers of ceteareth alcohol, i.e. ~a mixture of fatty alcohols
containing
predominantly cetyl and stearyl alcohol, wherein the numeric designation
1o indicates the number of ethylene glycol moieties present; C,-C3o alkyl
ethers of
the ceteth, steareth, and ceteareth compounds just described; polyoxyethylene
ethers of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate,
stearyl
stearate, myristyl myristate, polyoxyethylene cetyl ether stearate,
polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate,
ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene
distearate, propyleneglycol monostearate, propyleneglycol distearate,
trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate,
glyceryl
monostearate, glyceryl distearate, glyceryl tristearate, and mixtures thereof.
High melting point fatty compounds of a single compound of high purity
are preferred. Single compounds of pure fatty alcohols selected from the group
of pure cetyl alcohol, stearyl alcohol, and behenyl alcohol are highly
preferred.
By "pure" herein, what is meant is that the compound has a purity of at least
about 90%, preferably at least about 95%. These single compounds of high
purity provide good rinsability from the hair when the consumer rinses off the
composition.
Commercially available high melting point fatty compounds useful herein
include: cetyl alcohol, stearyl alcohol, and behenyl alcohol having tradenames
KONOL series available from Shin Nihon Rika (Osaka, Japan), and NAA series
available from NOF (Tokyo, Japan); pure behenyl alcohol having tradename 1-
3o DOCOSANOL available from WAKO (Osaka, Japan), various fatty acids having
tradenames NEO-FAT available from Akzo (Chicago Illinois, USA), HYSTRENE
available from Witco Corp. (Dublin Ohio, USA), and DERMA available from Vevy
(Genova, Italy).
CATIONIC CONDITIONING AGENT
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The composition of the present invention comprises a cationic
conditioning agent. This cationic conditioning agent, together with the high
melting point fatty compounds, provide a gel network suitable for providing
various conditioning benefits such as slippery and slick feel on wet hair, and
such as softness, moisturized feel, and fly-away control on dry hair.
The cationic conditioning agent is included in the composition at a level by
weight of from about 0.1 % to about 10%, preferably from about 0.25% to about
8%, more preferably from about 0.5% to about 3%.
The cationic conditioning agent herein is selected from cationic surfactants
1o having saturated alkyl groups. Cationic surfactants having unsaturated
alkyl
groups provide a suitable gel network and provides good hair feel.
The cationic surfactants useful herein include those corresponding to the
general formula (I):
~ _
R R X
I (I)
a
wherein at least one of R1, R2, R3, and R4 is selected from an aliphatic
group of from 8 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene,
alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon
atoms, the remainder of R1, R2, R3, and R4 are independently selected from an
aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy,
polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up
to
about 22 carbon atoms; and X is a salt-forming anion such as those selected
from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate,
phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkyl sulfonate
radicals.
The aliphatic groups can contain, in addition to carbon and hydrogen atoms,
ether linkages, and other groups such as amino groups. The longer chain
aliphatic groups, e.g., those of about 12 carbons, or higher, are saturated.
Preferred is when R1, R2, R3, and R4 are independently selected from C1 to
about C22 alkyl. Nonlimiting examples of cationic surfactants useful in the
present invention include the materials having the following CTFA
designations:
quaternium-8, quaternium-14, quaternium-18, quaternium-18 methosulfate,
quaternium-24, and mixtures thereof.
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Among the cationic surfactants of general formula (I), preferred are those
containing in the molecule at least one alkyl chain having at least 16
carbons.
Nonlimiting examples of such preferred cationic surfactants include: behenyl
trimethyl ammonium chloride available, for example, with tradename
INCROQUAT TMC-80 from Croda and ECONOL TM22 from Sanyo Kasei; cetyl
trimethyl ammonium chloride available, for example, with tradename CA-2350
from Nikko Chemicals, hydrogenated tallow alkyl trimethyl ammonium chloride,
dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium
chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl
1o dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride,
di(behenyl/arachidyl) dimethyl ammonium chloride, dibehenyl dimethyl
ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl
propyleneglycol phosphate dimethyl ammonium chloride, stearoyl amidopropyl
dimethyl benzyl ammonium chloride, stearoyl amidopropyl dimethyl
(myristylacetate) ammonium chloride, and N-(stearoyl colamino formyl methy)
pyridinium chloride.
Also preferred are hydrophilically substituted cationic surfactants in which
at least one of the substituents contain one or more aromatic, ether, ester,
amido, or amino moieties present as substituents or as linkages in the radical
2o chain, wherein at least one of the R1 - R4 radicals contain one or more
hydrophilic moieties selected from alkoxy (preferably C1 - C3 alkoxy),
polyoxyalkylene (preferably C1 - C3 polyoxyalkylene), alkylamido,
hydroxyalkyl,
alkylester, and combinations thereof. Preferably, the hydrophilically
substituted
cationic conditioning surfactant contains from 2 to about 10 nonionic
hydrophile
moieties located within the above stated ranges. Preferred hydrophilically
substituted cationic surfactants include those of the formula (II) through
(VIII)
below:
CH3(CH2)n-CH2 N~ (CH2CH20)xI-I X II
(CH2CH20)yH ( )
3o wherein n is from 8 to about 28, x+y is from 2 to about 40, Z1 is a short
chain alkyl, preferably a C1 - C3 alkyl, more preferably methyl, or
(CH2CH20)zH
wherein x+y+z is up to 60, and X is a salt forming anion as defined above;
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6
R-~+ CH2 m-~+ R 2X-
( ) Rlo W
wherein m is 1 to 5, one or more of R5, R6, and R7 are independently an
C1 - C3p alkyl, the remainder are CH2CH20H, one or two of R8, R9, and R10
are independently an C1 - C3p alkyl, and remainder are CH2CH20H, and X is a
salt forming anion as mentioned above;
2
R I ~~- CH2 - ~~ CH
2)q
Z
2
R ~ ~-O- CH2 - ~~ CH -O-~-R12 X_
)P I3 ( 2)q
Z
wherein, independently for formulae (IV) and (V), Z2 is an alkyl, preferably
a C1 - C3 alkyl, more preferably methyl, and Z3 is a short chain hydroxyalkyl,
preferably hydroxymethyl or hydroxyethyl, p and q independently are integers
from 2 to 4, inclusive, preferably from 2 to 3, inclusive, more preferably 2,
R11
and R12 , independently, are substituted or unsubstituted hydrocarbyls,
preferably C12 - C20 alkyl, and X is a salt forming anion as defined above;
4
13
R-N5 (CH2~H0)aH X
Z CH3
25
wherein R13 is a hydrocarbyl, preferably a C1 - C3 alkyl, more preferably
methyl, Z4 and Z5 are, independently, short chain hydrocarbyls, preferably C2 -
C4 alkyl, more preferably ethyl, a is from 2 to about 40, preferably from
about 7
to about 30, and X is a salt forming anion as defined above;
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14
6-~~
Z I1.T CHz~HCH2 A X (V I I )
IS
R OH
wherein R14 and R15, independently, are C1 - C3 alkyl, preferably methyl,
Z6 is a C12 - C22 hydrocarbyl, alkyl carboxy or alkylamido, and A is a
protein,
preferably a collagen, keratin, milk protein, silk, soy protein, wheat
protein, or
hydrolyzed forms thereof; and X is a salt forming anion as defined above;
16
~+
HOCH2 (CHOH)4 CNH(CH2)b-N 7 CH2CHzOH X (
R
wherein b is 2 or 3, R16 and R17, independently are C1 - C3 hydrocarbyls
preferably methyl, and X is a salt forming anion as defined above. Nonlimiting
examples of hydrophilically substituted cationic surfactants useful in the
present
invention include the materials having the following CTFA designations:
quaternium-16, quaternium-27, quaternium-30, quaternium-33, quaternium-43,
quaternium-52, quaternium-53, quaternium-56, quaternium-60, quaternium-61,
quaternium-62, quaternium-70, quaternium-71, quaternium-75, quaternium-76
hydrolyzed collagen, quaternium-77, quaternium-78, quaternium-80, quaternium-
83, and mixtures thereof.
Highly preferred hydrophilically substituted cationic surfactants include
2o dialkylamido ethyl hydroxyethylmonium salt, dialkylamidoethyl dimonium
salt,
dialkyloyl ethyl hydroxyethylmonium salt, dialkyloyl ethyldimonium salt, and
mixtures thereof; for example, commerically available under the following
tradenames; VARISOFT 110, VARIQUAT K1215 and 638 from Witco Chemical,
MACKPRO KLP, MACKPRO WLW, MACKPRO MLP, MACKPRO NSP,
MACKPRO NLW, MACKPRO WWP, MACKPRO NLP, MACKPRO SLP from
Mclntyre, ETHOQUAD 18/25, ETHOQUAD O/12PG, ETHOQUAD C/25,
ETHOQUAD S/25, and ETHODUOQUAD from Akzo, DEHYQUAT SP from
Henkel, and ATLAS 6265 from ICI Americas.
Salts of primary, secondary, and tertiary fatty amines are also suitable
cationic surfactants. The alkyl groups of such amines preferably have from
about
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12 to about 22 carbon atoms, and can be substituted or unsubstituted.
Particularly useful are amidoamines of the following general formula:
R1 CONH (CH2)m N (R2)2
wherein R1 is a residue of C11 to C24 fatty acids, R2 is a C1 to C4 alkyl,
and m is an integer from 1 to 4.
Preferred amidoamine useful in the present invention includes
stearamidopropyldimethylamine, stearamidopropyldiethylamine,
stearamidoethyldiethylamine, stearamidoethyldimethylamine,
palmitamidopropyldimethylamine, palmitamidopropyldiethylamine,
1o palmitamidoethyldiethylamine, palmitamidoethyldimethylamine,
behenamidopropyldimethylamine, behenamidopropyldiethylamine,
behenamidoethyldiethylamine, behenamidoethyldimethylamine,
arachidamidopropyldimethylamine, arachidamidopropyldiethylamine,
arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, and mixtures
thereof; more preferably stearamidopropyldimethylamine,
stearamidoethyldiethylamine, and mixtures thereof.
The amidoamines herein are preferably partially quaternized with the
acids selected from the group consisting of L-glutamic acid, lactic acid,
hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, L-
glutamic
2o acid hydrochloride, tartaric acid, and mixtures thereof; preferably L-
glutamic acid,
lactic acid, hydrochloric acid, and mixtures thereof.
Preferably, the mole ratio of amidoamine to acid is from about 1:0.3 to
about 1:1, more preferably from about 1:0.5 to about 1:0.9.
AQUEOUS CARRIER
The composition of the present invention comprises an aqueous carrier.
The level and species of the carrier are selected according to the
compatibility
with other components, and other desired characteristic of the product.
The carrier useful in the present invention include water and water
solutions of lower alkyl alcohols and polyhydric alcohols. The lower alkyl
alcohol
useful herein are monohydric alcohols having 1 to 6 carbons, more preferably
ethanol and isopropanol. The polyhydric alcohols useful herein include
propylene glycol, hexylene glycol, glycerin, and propane diol.
Preferably, the aqueous carrier is substantially water. Deionized water is
preferably used. Water from natural sources including mineral cations can also
be used, depending on the desired characteristic of the product. Generally,
the
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compositions of the present invention comprise from about 20% to about 95%,
preferably from about 30% to about 92%, and more preferably from about 50% to
about 90% water.
CATIONIC POLYMER
The hair conditioning composition of the present invention may further
comprise a cationic polymer selected from the group consisting of
hydrophobically modified cationic cellulose, a copolymer of hydrophilic-
cellulose
and diallyldimethyl ammonium chloride, and mixtures thereof.
The cationic polymers herein provide increase in bulk hair volume while
not deteriorating conditioning benefits such as fly-away control. The cationic
polymers herein are typically included in the hair styling compositions as an
antistatic agent, a film former, or a -hair fixative. It has been surprisingly
found
that, when the cationic polymers are included in hair conditioning
compositions in
combination with the hydrophobically modified cellulose ether, increase in
bulk
hair volume is improved, and increased draggy and clean feel to the hair is
provided.
The hair conditioning composition of the present invention may comprise
by weight from about 0.001 % to about 5%, preferably from about 0.05% to about
2.0%, more preferably from about 0.1 % to about 1.0% of a cationic polymer.
The hydrophobically modified cationic celluloses useful in the present
invention are those having the following formula:
20H H H
H OH \~~~n OH
2 ~-
~2~20~~ - Rl
Y
~3
wherein R1 is an alkyl having from about 8 to about 22 carbons, preferably
from about 10 to about 18 carbons; n is an integer from 1 to about 10,000,
preferably from about 100 to about 4,000; x is 0 or an integer from 1 to about
6,
preferably from about 1 to about 3; and y is the level of cationic
substitution from
0.1 to 1Ø
Commercially available hydrophobically modified cationic celluloses
include, for example, the polymeric quaternary ammonium salts of hydroxyethyl
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cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred
to
in the industry (CTFA) as Polyquaternium 24, available from Amerchol Corp.
(Edison, NJ, USA) under the tradenames Polymer LM-200~ and BioCare
Polymer HA-24.
The copolymers of hydrophilic-cellulose and diallyldimethyl ammonium
chloride useful herein are those having hydrophilic-cellulose units and
diallyldimethyl ammonium chloride units, the hydrophilic cellulose units
selected
from the group consisting of methyl cellulose, hydroxymethyl cellulose,
hydroxyethyl cellulose, hydroxyethyl ethylcellulose, hydroxypropyl cellulose,
hydroxypropyl methylcellulose, hydroxybutyl cellulose, and mixtures thereof,
preferably hydroxyethylcellulose. The ratio of the number of the hydrophilic-
cellulose units to the diallyldimethyl ammonium chloride units comprised in
the
copolymer is from about 1:100 to about 10:1, preferably from about 1:10 to
about
10:1, more preferably from about 1:3 to about 5:1, still preferably from about
1:1
to about 3:1, and wherein the molecular weight of the copolymer is from about
10,000 to about 250,000, preferably from about 15,000 to about 200,000. To
provide preferred copolymers, the hydrophilic-cellulose units are contained at
a
range of from about 40 to about 350, and the diallyldimethyl ammonium chloride
units are contained at a range of from about 40 to about 120.
Highly suitable copolymers are hydroxyethylcellulose diallyldimethyl
ammonium chloride copolymers known in the industry as Polyquaternium-4
(CTFA Dictionary). Commercially available hydroxyethylcellulose
diallyldimethyl
ammonium chloride copolymers are those with tradenames CELQUAT L-200 and
CELQUAT H-100 available from National Starch Corp.
POLYPROPYLENE GLYCOL
The hair conditioning composition of the present invention may further
comprise a polypropylene glycol. The polypropylene glycol useful herein is
selected from single-polypropylene glycol-chain segment polymers, multi-
polypropylene glycol-chain segment polymers, and mixtures thereof, having a
weight average molecular weight of from about 200 g/mol to about 100,000
g/mol, preferably from about 1,000 g/mol to about 60,000 g/mol. When included
in the composition of the present invention in combination with the
hydrophobically modified cellulose ether, polypropylene glycol may deliver
flyaway hair control benefits without affecting the bulk hair volume.
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Accordingly, a highly preferred single-polypropylene glycol-chain segment
polymer has the following formula:
HO-(C3H60)aH ,
wherein a is a value from about 4 to about 400, preferably from about 20
to about 100, and more preferably from about 20 to about 40.
The single-polypropylene glycol-chain segment polymer useful herein is
typically inexpensive, and is readily available from, for example, Sanyo Kasei
(Osaka, Japan), Dow Chemicals (Midland, Michigan, USA), Calgon Chemical,
Inc. (Skokie, Illinois, USA), Arco Chemical Co. (Newton Square Pennsylvania,
USA), Witco Chemicals Corp. (Greenwich, Connecticut, USA), and PPG
Specialty Chemicals (Gurnee, Illinois, USA).
A highly preferred multi-polypropylene ,glycol-chain segment polymer has
the following formula:
(C H2 )c-O-(C3Hs0)y-H
R-C--E(CH2)b-O-(C3Hs0)
a
n
(CH2)d-O-(C3Hs0)z-H
(Formula II)
wherein n is a value from about 0 to about 10, preferably from about 0 to
about 7, and more preferably from about 1 to about 4. In Formula II, each R is
independently selected from the group consisting of H, and C,-C3o alkyl, and
preferably each R is independently selected from the group consisting of H,
and
C,-C4 alkyl. In Formula II, each b is independently a value from about 0 to
about
2, preferably from about 0 to about 1, and more preferably b = 0. Similarly, c
and
d are independently a value from about 0 to about 2, preferably from about 0
to
about 1. However, the total of b + c + d is at least about 2, preferably the
total of
b + c + d is from about 2 to about 3. Each a is independently a value of 0 or
1, if
n is from about 1 to about 4, then a is preferably equal to 1. Also in Formula
II, x,
y, and z are independently a value of from about 1 to about 120, preferably
from
about 7 to about 100, and more preferably from about 7 to about 100, where x +
y + z is greater than about 20.
Examples of the multi-polypropylene glycol-chain segment polymer of
Formula II which is especially useful herein includes polyoxypropylene
glyceryl
ether (n = 1, R = H, b = 0, c and d = 1, a = 1, and x, y, and z independently
indicate the degree of polymerization of their respective polypropylene glycol-
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chain segments; available as New Pol GP-4000, from Sanyo Kasei of Osaka,
Japan), polypropylene trimethylol propane (n = 1, R = CZHS, b = 1, c and d =
1, a
= 1, and x, y, and z independently indicate the degree of polymerization of
their
respective polypropylene glycol-chain segments), polyoxypropylene sorbitol (n
=
4, each R = H, b = 0, c and d = 1, each a = 1, and y, z, and each x
independently
indicate the degree of polymerization of their respective polypropylene glycol-
chain segments; available as New Pol SP-4000, from Sanyo Kasei, Osaka,
Japan), and PPG-10 butanediol (n = 0, c and d = 2, and y + z = 10; available
as
Probutyl DB-10, from Croda, Inc., of Parsippany, New Jersey, U.S.A.).
RHEOLOGY MODIFIER
The hair conditioning composition of the present invention may further
comprise a rheology modifier. The rheology modifier may be any polymer which
increases the rheology of the composition, and which are compatible with the
other polymers included in the composition, and do not negatively affect the
benefits provided by the composition. Rheology modifiers particularly suitable
in
the present invention are those selected from the group consisting of methyl
cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl
ethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose,
hydroxybutyl cellulose, and mixtures thereof. Without being bound by theory,
it is
believed that, by the rheology being increased, the composition provides
better
spreadability to the hair and increases deposition of components such as the
hydrophobically modified cellulose ether and the cationic polymer to the hair.
Commercially available hydroxyethyl ethylcellulose are those available from
Akzo
Nobel with tradename Elfacos CD481.
LOW MELTING POINT OIL
The hair conditioning composition of the present invention may further
comprise a low melting point oil, which has a melting point of less than
25°C, and
is preferably included in the composition at a level by weight of from about
0.1
to about 10%, more preferably from about 0.25% to about 6%.
Low melting point oils useful herein include unsaturated fatty alcohols
having from about 10 to about 30 carbon atoms, unsaturated fatty acids having
from about 10 to about 30 carbon atoms, fatty acid derivatives, fatty alcohol
derivatives, ester oils, and mixtures thereof. Fatty alcohols useful herein
include
those having from about 10 to about 30 carbon atoms, preferably from about 12
to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon
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atoms. These fatty alcohols are unsaturated and can be straight or branched
chain alcohols. Suitable fatty alcohols include, for example, oleyl alcohol,
isostearyl alcohol, tridecylalcohol, decyl tetradecyl alcohol, and octyl
dodecyl
alcohol. These alcohols are available, for example, from Shinnihon Rika.
Low melting point oils useful herein include pentaerythritol ester oils,
trimethylol ester oils, poly a-olefin oils, citrate ester oils, glyceryl ester
oils, and
mixtures thereof, and the ester oil useful herein is water-insoluble. As used
herein, the term "water-insoluble" means the compound is substantially not
soluble in water at 25°C; when the compound is mixed with water at a
1o concentration by weight of above 1.0%, preferably at above 0.5%, the
compound
is temporarily dispersed to form an unstable colloid in water, then is quickly
separated from water into two phases.
Pentaerythritol ester oils useful herein are those having the following
formula:
O
C H20-C-R2
O O
R~ C-OCHZ- ~ -CH20-C-R3
O
H O-C-R 4
wherein R', R2, R3, and R4, independently, are branched, straight,
saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to
about
30 carbons. Preferably, R', Rz, R3, and R4, independently, are branched,
straight, saturated, or unsaturated alkyl groups having from about 8 to about
22
carbons. More preferably, R', R2, R3 and R4 are defined so that the molecular
weight of the compound is from about 800 to about 1200.
Trimethylol ester oils useful herein are those having the following
formula:
O
C H20-C-R12
O
R1 ~ ~ Hz-CH20-C-R13
O
H20-C-R 14
wherein R" is an alkyl group having from 1 to about 30 carbons, and R'2,
R'3, and R'4, independently, are branched, straight, saturated, or unsaturated
alkyl, aryl, and alkylaryl groups having from 1 to about 30 carbons.
Preferably,
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R" is ethyl and R'2, R'3, and R'4, independently, are branched, straight,
saturated, or unsaturated alkyl groups having from 8 to about 22 carbons. More
preferably, R", R'2, R'3 and R'4 are defined so that the molecular weight of
the
compound is from about 800 to about 1200.
Particularly useful pentaerythritol ester oils and trimethylol ester oils
herein
include pentaerythritol tetraisostearate, pentaerythritol tetraoleate,
trimethylolpropane triisostearate, trimethylolpropane trioleate, and mixtures
thereof. Such compounds are available from Kokyo Alcohol with tradenames
KAKPTI, KAKTTI, and Shin-nihon Rika with tradenames PTO, ENUJERUBU
TP3S0.
Poly a-olefin oils useful herein are those derived from 1-alkene monomers
having from about 6 to about 16 carbons, preferably from about 6 to about 12
carbons atoms. Nonlimiting examples of 1-alkene monomers useful for
preparing the poly a-olefin oils include 1-hexene, 1-octene, 1-decene, 1-
dodecene, 1-tetradecene, 1-hexadecene, branched isomers such as 4-methyl-1-
pentene, and mixtures thereof. Preferred 1-alkene monomers useful for
preparing the poly a-olefin oils are 1-octene, 1-decene, 1-dodecene, 1-
tetradecene, 1-hexadecene, and mixtures thereof. Poly a-olefin oils useful
herein further have a viscosity of from about 1 to about 35,000 cst, a
molecular
2o weight of from about 200 to about 60,000, and a polydispersity of no more
than
about 3.
Poly a-olefin oils having a molecular weight of at least about 800 are
useful herein. Such high molecular weight poly a-olefin oils are believed to
provide long lasting moisturized feel to the hair. Poly a-olefin oils having a
molecular weight of less than about 800 are useful herein. Such low molecular
weight poly a-olefin oils are believed to provide a smooth, light, clean feel
to the
hair.
Particularly useful poly a-olefin oils herein include polydecenes with
tradenames PURESYN 6 having a number average molecular weight of about
500 and PURESYN 100 having a number average molecular weight of about
3000 and PURESYN 300 having a number average molecular weight of about
6000 available from Mobil Chemical Co.
Citrate ester oils useful herein are those having a molecular weight of at
least about 500 having the following formula:
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O
C H2-C-O-R22
O
R21 ~ -C-O-R 23
O
H2-C-O-R24
wherein R2' is OH or CH3C00, and R22, Rz3, and R24, independently, are
branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl
groups
having from 1 to about 30 carbons. Preferably, RZ' is OH, and R22, R2s, and
Rz4,
independently, are branched, straight, saturated, or unsaturated alkyl, aryl,
and
alkylaryl groups having from 8 to about 22 carbons. More preferably, RZ', R2z,
RZs
and R24 are defined so that the molecular weight of the compound is at least
about 800.
Particularly useful citrate ester oils herein include triisocetyl citrate with
tradename CITMOL 316 available from Bernel, triisostearyl citrate with
tradename PELEMOL TISC available from Phoenix, and trioctyldodecyl citrate
with tradename CITMOL 320 available from Bernel.
Glyceryl ester oils useful herein are those having a molecular weight of at
least about 500 and having the following formula:
O
C H20-C-R41
O
H ~ -O-C-R 42
O
H20-C-R43
wherein R4', R42, and R43, independently, are branched, straight,
saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to
about
30 carbons. Preferably, R4', R4z, and R43, independently, are branched,
straight,
saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 8 to
about
22 carbons. More preferably, R4', R4z, and R43 are defined so that the
molecular
weight of the compound is at least about 800.
Particularly useful glyceryl ester oils herein include triisostearin with
tradename SUN ESPOL G-318 available from Taiyo Kagaku, triolein with
tradename CITHROL GTO available from Croda Surfactants Ltd., trilinolein with
tradename EFADERMA-F available from Vevy, or tradename EFA-
GLYCERIDES from Brooks.
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POLYETHYLENE GLYCOL
The composition of present invention may further comprise a polyethylene
glycol having the formula:
H(OCH2CH2)n -OH
wherein n has an average value of from about 2,000 to about 14,000,
preferably from about 5,000 to about 9,000, more preferably from about 6,000
to
about 8,000.
The polyethylene glycol is preferably included in the composition at a level
by weight of from about 0.1 % to about 10%, more preferably from about 0.25%
1o to about 6%.
The polyethylene glycol described above is also known as a polyethylene
oxide, or polyoxyethylene. Polyethylene glycols useful herein that are
especially
preferred are PEG-2M wherein n has an average value of about 2,000 (PEG-2M
is also known as Polyox WSR~ N-10 from Union Carbide and as PEG-2,000);
PEG-5M wherein n has an average value of about 5,000 (PEG-5M is also known
as Polyox WSR~ N-35 and as Polyox WSR~ N-80, both from Union Carbide and
as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein n has an
average value of about 7,000 (PEG-7M is also known as Polyox WSR~ N-750
from Union Carbide); PEG-9M wherein n has an average value of about 9,000
(PEG-9M is also known as Polyox WSR~ N-3333 from Union Carbide); and
PEG-14M wherein n has an average value of about 14,000 (PEG-14M is also
known as Polyox WSR~ N-3000 from Union Carbide).
SILICONE COMPOUND
The present composition may further contain a silicone compound. The
amount of silicone compound to the entire composition is preferably from about
0.1 % to about 10% by weight. The silicone compounds hereof can include
volatile soluble or insoluble, or nonvolatile soluble or insoluble silicone
conditioning agents. By soluble what is meant is that the silicone compound is
miscible with the carrier of the composition so as to form part of the same
phase.
3o By insoluble what is meant is that the silicone forms a separate,
discontinuous
phase from the carrier, such as in the form of an emulsion or a suspension of
droplets of the silicone. The silicone compounds herein may be made by
conventional polymerization, or emulsion polymerization.
The silicone compounds for use herein will preferably have a viscosity of
from about 1,000 to about 2,000,000 centistokes at 25oC, more preferably from
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about 10,000 to about 1,800,000, and even more preferably from about 25,000 to
about 1,500,000. The viscosity can be measured by means of a glass capillary
viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July
20, 1970, which is incorporated by reference herein in its entirety. Silicone
compound of high molecular weight may be made by emulsion polymerization.
Silicone compounds useful herein include polyalkyl polyaryl siloxanes,
polyalkyleneoxide-modified siloxanes, silicone resins, amino-substituted
siloxanes, and mixtures thereof. The silicone compound is preferably selected
from the group consisting of polyalkyl polyaryl siloxanes, polyalkyleneoxide-
1o modified siloxanes, silicone resins, and mixtures thereof, and more
preferably
from one or more polyalkyl polyaryl siloxanes.
Polyalkyl polyaryl siloxanes useful here in include those with the following
structure (I)
A ~ -O- f ~ -O-lx ~ -A (I )
R R R
wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000.
"A" represents groups which block the ends of the silicone chains. The alkyl
or
aryl groups substituted on the siloxane chain (R) or at the ends of the
siloxane
2o chains (A) can have any structure as long as the resulting silicone remains
fluid
at room temperature, is dispersible, is neither irritating, toxic nor
otherwise
harmful when applied to the hair, is compatible with the other components of
the
composition, is chemically stable under normal use and storage conditions, and
is capable of being deposited on and conditions the hair. Suitable A groups
include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R
groups on the silicon atom may represent the same group or different groups.
Preferably, the two R groups represent the same group. Suitable R groups
include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The
preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane,
and
polymethylphenylsiloxane. Polydimethylsiloxane, which is also known as
dimethicone, is especially preferred. The polyalkylsiloxanes that can be used
include, for example, polydimethylsiloxanes. These silicone compounds are
available, for example, from the General Electric Company in their ViscasilR
and
SF 96 series, and from Dow Corning in their Dow Corning 200 series.
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Polymethylphenylsiloxanes, for example, from the General Electric Company as
SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid,
are useful herein.
Also preferred, for enhancing the shine characteristics of hair, are highly
arylated silicone compounds, such as highly phenylated polyethyl silicone
having
refractive index of about 1.46 or higher, especially about 1.52 or higher.
When
these high refractive index silicone compounds are used, they should be mixed
with a spreading agent, such as a surfactant or a silicone resin, as described
below to decrease the surface tension and enhance the film forming ability of
the
material.
Another polyalkyl polyaryl siloxane that can be especially useful is a
silicone gum. The term "silicone gum", as used herein, means a
polyorganosiloxane material having a viscosity at 25°C of greater than
or equal to
1,000,000 centistokes. It is recognized that the silicone gums described
herein
can also have some overlap with the above-disclosed silicone compounds. This
overlap is not intended as a limitation on any of these materials. Silicone
gums
are described by Petrarch, and others including U.S. Patent No. 4,152,416, to
Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Technology
of
Silicones, New York: Academic Press 1968. Also describing silicone gums are
2o General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54
and
SE 76. All of these described references are incorporated herein by reference
in
their entirety. The "silicone gums" will typically have a mass molecular
weight in
excess of about 200,000, generally between about 200,000 and about
1,000,000. Specific examples include polydimethylsiloxane,
poly(dimethylsiloxane methylvinylsiloxane) copolymer, poly(dimethylsiloxane
diphenylsiloxane methylvinylsiloxane) copolymer and mixtures thereof.
Polyalkyleneoxide-modified siloxanes useful herein include, for example,
polypropylene oxide modified and polyethylene oxide modified
polydimethylsiloxane. The ethylene oxide and polypropylene oxide level should
be sufficiently low so as not to interfere with the dispersibility
characteristics of
the silicone. These material are also known as dimethicone copolyols.
Silicone resins, which are highly crosslinked polymeric siloxane systems,
are useful herein. The crosslinking is introduced through the incorporation of
tri-
functional and tetra-functional silanes with mono-functional or di-functional,
or
both, silanes during manufacture of the silicone resin. As is well understood
in
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the art, the degree of crosslinking that is required in order to result in a
silicone
resin will vary according to the specific silane units incorporated 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
crosslinking, 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
the
level of crosslinking in a particular silicone material. Silicone materials
which
have at least about 1.1 oxygen atoms per silicon atom will generally be
silicone
resins herein. Preferably, the ratio of oxygen:silicon atoms is at least about
1.2:1Ø Silanes used in the manufacture of silicone resins include monomethyl-
,
dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-., monovinyl-, and
methylvinylchlorosilanes, and tetrachlorosilane, with the methyl substituted
silanes being most commonly utilized. Preferred resins are offered by General
Electric as GE SS4230 and SS4267. Commercially available silicone resins will
generally be supplied in a dissolved form in a low viscosity volatile or
nonvolatile
silicone fluid. The silicone resins for use herein should be supplied and
incorporated into the present compositions in such dissolved form, as will be
readily apparent to those skilled in the art. Without being bound by theory,
it is
believed that the silicone resins can enhance deposition of other silicone
compounds on the hair and can enhance the glossiness of hair with high
refractive index volumes.
Other useful silicone resins are silicone resin powders such as the
material given the CTFA designation polymethylsilsequioxane, which is
commercially available as TospearITM from Toshiba Silicones.
Silicone resins can conveniently be identified according to a shorthand
nomenclature system well known to those skilled in the art as the "MDTQ"
nomenclature. Under this system, the silicone is described according to the
presence of various siloxane monomer units which make up the silicone.
Briefly,
the symbol M denotes the mono-functional unit (CH3)3Si0).5; D denotes the
difunctional unit (CH3)2Si0; T denotes the trifunctional unit (CH3)Si01.5; and
Q
denotes the quadri- or tetra-functional unit Si02. 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 alternate substituents
include
groups such as vinyl, phenyl, amino, hydroxyl, etc. The molar ratios of the
various units, either in terms of subscripts to the symbols indicating the
total
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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 system. 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 crosslinking. As discussed before, however, the
overall level of crosslinking can also be indicated by the oxygen to silicon
ratio.
The silicone resins for use herein which are preferred are MQ, MT, MTQ,
MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl.
Especially preferred are MQ resins wherein the M:Q 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 1000
to about 10,000.
Amino-substituted siloxanes useful herein include those represented by
the following structure (II)
I H3
HO-[-$i-O]x-[-$i-O-]y-H
ICH3 ( I~H2)a ( II )
NH
(~H~b
INH2
wherein R is CH3 or OH, x and y are integers which depend on the
molecular weight, the average molecular weight being approximately between
5,000 and 10,000. This polymer is also known as "amodimethicone".
2o Suitable amino-substituted siloxane fluids include those represented by
the formula (III)
(R1 )aG3-a-Si-(-OSiG2)n-(-OSiGb(R1 )2-b)m-O-SiG3-a(R1 )a
(III)
in which G is chosen from the group consisting of hydrogen, phenyl, OH,
C1-Cg alkyl and preferably methyl; a denotes 0 or an integer from 1 to 3, and
preferably equals 0; b denotes 0 or 1 and preferably equals 1; the sum n+m is
a
number from 1 to 2,000 and preferably from 50 to 150, n being able to denote a
number from 0 to 1,999 and preferably from 49 to 149 and m being able to
denote an integer from 1 to 2,000 and preferably from 1 to 10; R1 is a
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monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and
L
is chosen from the groups
-N(R2)CH2-CH2-N(R2)2
-N(R2)2
-N(R2)3A
-N(R2)CH2-CH2-NR2H2A-
in which R2 is chosen from the group consisting of hydrogen, phenyl,
benzyl, a saturated hydrocarbon radical, preferably an alkyl radical
containing
from 1 to 20 carbon atoms, and A- denotes a halide ion.
1o An especially preferred amino-substituted siloxane corresponding to
formula (III) is the polymer known as "trimethylsilylamodimethicone", of
formula
(IV):
_~H3 r H3
(CH3)3Si-Of ~i O-~n-~-~i O-lm- Si 1CH3)3 (IV 1
CH3 (~H2)a
INH
(~H2)b
NH2
In this formula n and m are selected depending on the molecular weight of
the compound desired.
Other amino-substituted siloxane which can be used are represented by
the formula (V):
R CHZ CHOH-CH2 N+(R)3Q
3
R
~, 3
(R J3S1-O-L-~i-O-~r-W~i-O-~S-Si(R )3 ( V )
3
R3 R
where R3 denotes a monovalent hydrocarbon radical having from 1 to 18
carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R4
denotes a
hydrocarbon radical, preferably a C1 - C1g alkylene radical or a C1 - Clg, and
more preferably C1 - Cg, alkyleneoxy radical; Q is a halide ion, preferably
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chloride; r denotes an average statistical value from 2 to 20, preferably from
2 to
8; s denotes an average statistical value from 20 to 200, and preferably from
20
to 50. A preferred polymer of this class is available from Union Carbide under
the name "UCAR SILICONE ALE 56."
In one preferred embodiment of the present invention, the silicone
compound is contained in the hair conditioning composition in the form of a
cationic silicone emulsion. The cationic silicone emulsion herein is a pre-
dispersed stable emulsion comprising at least a cationic surfactant, a
silicone
compound, and water. The cationic surfactant useful herein is any known to the
artisan, such as those selected from the species disclosed above under the
title
"Cationic Conditioning Agent".
The cationic silicone emulsion herein is also believed to minimize hair
volume reduction, while not deteriorating conditioning benefits such as fly-
away
control. It is of particular significance that, in this preferred embodiment,
the
cationic surfactant is present in the silicone emulsion, and not just in the
bulk of
the composition. The cationic silicone emulsion herein also provides
acceptable
rheology profiles in conditioning compositions.
The cationic silicone emulsion typically contains, by weight of the cationic
silicone emulsion, from about 1 % to about 20%, preferably from about 2% to
about 8%, of a cationic surfactant; and an emulsifiable amount of silicone
compound. The silicone compound is preferably contained from about 0.1 % to
about 70%, more preferably from about 5% to about 60% by weight of the
cationic silicone emulsion. The amount of silicone compound to the entire
composition is preferably from about 0.1 % to about 10% by weight.
The cationic silicone emulsion is included in the composition at a level by
weight from about 0.1 % to about 20%, more preferably from about 0.5% to about
5%.
The cationic silicone emulsion can be made by any convenient method
known in the art.
For example, the cationic silicone emulsion may be made by mechanical
emulsification by taking a polysiloxane polymer and emulsifying it in water in
the
presence of at least one emulsifying agent using mechanical means such as
agitation, shaking and homogenization. The emulsifying agent can be the
cationic surfactant comprised in the cationic silicone emulsion, or other
suitable
surfactant. Mechanical emulsification may require use of two or more
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surfactants, and two or more mixing processes using different surfactants. Two
or more types of silicone compounds, such as a highly viscous silicone
compound and a low viscosity silicone compound, may be used. One particularly
preferred process for obtaining the cationic silicone emulsion of the present
invention via mechanical emulsification is through the process disclosed in EP
Publication 460,683A, which is incorporated herein by reference in its
entirety. In
this reference, it is disclosed that the emulsion is prepared by combining the
polysiloxane, water, and a primary nonionic surfactant having an HLB value of
15-19 to form a first mixture, adding to the first mixture a co-surfactant
selected
1o from the group consisting of nonionic, cationic and anionic surfactants
having an
HLB value of 1.8-15 to form a second mixture and mixing the second mixture at
a
temperature of about 40°C, until the particle size of the polysiloxane
in the
emulsion is less than about three hundred nanometers.
The cationic silicone emulsion herein may be made by emulsion
polymerization. An emulsion polymerization process includes taking a
polysiloxane monomer and/or oligomer and emulsifying it in water in the
presence of a catalyst to form the polysiloxane polymer. It is understood that
unreacted monomers and oligomers may remain in an emulsion polymerized
silicone emulsion. One particularly preferred process for obtaining the
cationic
silicone emulsion of the present invention via emulsion polymerization is
through
the process disclosed in GB application 2,303,857, which is incorporated
herein
by reference in its entirety. This reference discloses a process for making
stable
cationic silicone oil-in-water emulsion comprising: 1 ) blending a mixture of
silicones selected from the group consisting of cyclic silicone oligomers,
mixed
silicone hydrolyzates, silanol stopped oligomers, high molecular weight
silicone
polymers, and functionalized silicones with 2) water, and 3) an anionic
surfactant;
4) heating the blend to a temperature ranging from about 75 to about
98°C for a
period of time ranging from about 1 hours to about 5 hours; 5) cooling the
heated
blend to a temperature ranging from 0 to about 25°C for a period of
time ranging
from about 3 hours to about 24 hours; 6) adding a compatibilizing surfactant
selected from the group consisting of nonionic surfactant having an HLB ratio
greater than 9; and 7) adding a cationic surfactant.
The silicone compound in the cationic silicone emulsion has a particle size
of less than about 50 microns, preferably from about 0.2 to about 2.5 microns,
more preferably from about 0.2 to about 0.5 microns. The particle size of the
27
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silicone compound is believed to affect the deposition of the silicone
compound
on the hair. The particle size of the silicone compound is determined based on
the desired deposition and uniformity of distribution of the silicone
compound.
COMPOSITIONS
In one preferred embodiment of the present invention, the composition
comprises:
(a) from about 0.01 % to about 2% of a hydrophobically modified cellulose
ether;
(b) from about 0.1 % to about 10%, preferably from about 1 % to about 7% of a
high melting point fatty compound;
(c) from about 0.1 % to about 10%, preferably from about 0.25% to about 8%,
more preferably from about 0.5% to about 3% of a cationic conditioning
agent;
(d) an aqueous carrier.
This composition can provide increase in bulk hair volume, softness,
moisturized feel, and fly-away control. It can also provide satisfactory
spreadability on the hair, and can be made by a convenient manufacturing
method.
In another preferred embodiment of the present invention, the composition
2o comprises:
(a) from about 0.01 % to about 2% of a hydrophobically modified cellulose
ether;
(b) from about 0.1 % to about 10% of a high melting point fatty compound;
(c) from about 0.55% to about 7%, preferably from about 1.2% to about 4.5%
of a cationic conditioning agent, the cationic conditioning agent comprising
an amidoamine and an acid; and
(d) the aqueous carrier.
This composition may further contain a low melting point oil selected from
the group consisting of pentaerythritol ester oils, trimethylol ester oils,
poly a
olefin oils, citrate ester oils, glyceryl ester oils, and mixtures thereof,
which is
preferably included in the composition at a level by weight of from about 0.1
% to
about 10%, more preferably from about 0.25% to about 6%.
This composition can provide provide the same benefits as those of the
first embodiment, and further can provide the benefits such as slippery and
slick
feel on wet hair.
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In 'another preferred embodiment of the present invention, the
composition comprises:
A hair conditioning composition comprising:
(a) from about 0.01 % to about 2% of a hydrophobically modified cellulose
ether;
(b) from about 0.1 % to about 5%, preferably from about 0.25% to about 2% of
a high melting point fatty compound;
(c) from about 0.1 % to about 10%, preferably from about 0.25% to about 5%
of a cationic conditioning agent;
(d) an aqueous carrier;
(e) from about 0.1 % to about 10%, preferably from about 0..25% to about 6%
of a low melting point oil, the low melting point oil being an unsaturated
fatty alcohol; and
(f) from about 0.1 % to about 10%, preferably from about 0.25% to about 6%
of a polyethylene glycol.
This composition can provides the same benefits as those of the first
embodiment, and further can provide the benefits such as increase in bulk hair
volume, softness, moisturized feel, and fly-away control on dry hair.
ADDITIONAL COMPONENTS
2o The composition of the present invention may include other additional
components, which may be selected by the artisan according to the desired
characteristics of the final product and which are suitable for rendering the
composition more cosmetically or aesthetically acceptable or to provide them
with additional usage benefits. Such other additional components generally are
used individually at levels of from about 0.001 % to about 10%, preferably up
to
about 5% by weight of the composition.
A wide variety of other additional components can be formulated into the
present compositions. These include: other conditioning agents such as
hydrolysed collagen with tradename Peptein 2000 available from Hormel, vitamin
E with tradename Emix-d available from Eisai, panthenol available from Roche,
panthenyl ethyl ether available from Roche, a mixture of Polysorbate 60 and
Cetearyl Alcohol with tradename Polawax NF available from Croda Chemicals,
glycerylmonostearate available from Stepan Chemicals, hydroxyethyl cellulose
available from Aqualon, hydrolysed keratin, proteins, plant extracts, and
nutrients; hair-fixative polymers such as amphoteric fixative polymers,
cationic
29
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WO 01/08644 PCT/US00/20662
fixative polymers, anionic fixative polymers, nonionic fixative polymers, and
silicone grafted copolymers; preservatives such as benzyl alcohol, methyl
paraben, propyl paraben and imidazolidinyl urea; 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 salts;
hair reducing agents such as the thioglycolates; perfumes; and sequestering
agents, such as disodium ethylenediamine tetra-acetate; ultraviolet and
infrared
screening and absorbing agents such as octyl salicylate, antidandruff agents
such as zinc pyridinethione; and optical brighteners, for example
polystyrylstilbenes, triazinstilbenes, hydroxycoumarins, aminocoumarins,
triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles, and
mixtures
thereof.
METHOD OF PREPARING COMPOSITION
The hair conditioning composition of the present invention may be made
by any method of preparation known in the art.
In one embodiment, the hydrophobically modified cellulose ether is
dispersed in water at room temperature to make a polymer solution, and is
either
heated up to above 70°C, or added to a water base preheated to above
70°C.
Alternatively, the hydrophobically modified cellulose ether, which is
typically
obtained in the form of a powder, is directly added to the preheated water
base.
The cationic conditioning agent and the high melting point fatty compound are
also added in the heated solution to form a gel matrix together with the
hydrophobically modified cellulose ether. The mixture thus obtained is cooled
down to below 60°C, and the remaining components are added with
agitation,
and further cooled down to about 30°C.
In a particularly preferred embodiment, the hair conditioning composition
of the present invention is prepared by the following steps;
(a) mixing the high melting point fatty compound, the cationic conditioning
agent, and the aqueous carrier at a temperature of at least about 70°C;
(b) cooling the mixture obtained in step (a) to below about 60°C;
(c) adding the hydrophobically modified cellulose ether to the cooled mixture
obtained in step (b); and
(d) mixing until a homogeneous composition is obtained.
CA 02379651 2002-O1-21
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In step (a), the gel matrix is formed. The hydrophobically modified
cellulose ether is added to this gel matrix, preferably after the gel matrix
is cooled
to a temperature of below about 60°C, still preferably about
40°C to 60°C in step
(b). The hydrophobically modified cellulose ether can be added in the form of
a
powder, as typically obtained, or in the form of a partially or completely
dissolved
water solution in step (c). The obtained mixture is thoroughly mixed, as
necessary using a triblender and/or mill, until homogeneous in step (d). When
cationic polymers, polypropylene glycols or rheology modifers are included in
the
composition, such components are added in either step (a) or (c). Any
1o remaining components of the compositions are added in step (d). Heat
sensitive
components may be added after the mixture is cooled to room temperature.
Without being bound by theory, it is believed that, when the preferred
embodiment method is used for preparing the present composition, the
hydrophobically modified cellulose ether is mixed in the composition in a
fully
solubilized manner, thereby providing a stable composition in terms of
rheology.
Surprisingly, this stable composition may further provide an improved increase
to
bulk hair volume of the hair when applied to the hair.
EXAMPLES
2o The following examples further describe and demonstrate embodiments
within the scope of the present invention. The examples are given solely for
the
purpose of illustration and are not to be construed as limitations of the
present
invention, as many variations thereof are possible without departing from the
spirit and scope of the invention. Ingredients are identified by chemical or
CTFA
name, or otherwise defined below.
The compositions of the present invention are suitable for rinse-off
products and leave-on products, and are particularly useful for making
products
in the form of emulsion, cream, gel, spray or, mousse.
Examples 1 through 20 are hair conditioning compositions of the present
invention which are particularly useful for rinse-off use.
C'.nmnncitinn~ of FxamnIPS 1 throUC7h 5
Com onents Ex. Ex. Ex. Ex Ex.
1 2 3 4 5
Cet I h drox eth /cellulose-10.2 0.25 0.25 0.1
*1
Cet I h drox eth /cellulose-1 0.25
*2
Cet I Alcohol *3 4.5 1.5 1.5 1.5 4.5
Stea I Alcohol *4 2.5 2.7 2.7 2.7 1.5
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Behen I Alcohol *5 1.0
Stearamido ro I Dimeth lamine2.0 1.2 1.2 1.2 2.0
*6
2-Glutamic Acid *7 0.64 0.384 0.384 0.384 0.64
Pentae hritol Tetraisostearate1.0 1.0
*8
Cationic Silicone Emulsion-11.05
*9
Cationic Silicone Emulsion-2 0.69
*10
Silicone Blend *11 2.52 2.52 4.20
Preservatives 0.033 0.033 0.033 0.033 0.033
Benz I alcohol 0.4 0.4 0.4 0.4 0.4
Perfume 0.6 0.6 0.6 0.6 0.6
H drol zed colla en *12 0.01 0.01 0.01 0.01 0.01
Vitamin E *13 0.01 0.01 0.01 0.01 0.01
Panthenol *14 0.05 0.05 0.05 0.05 0.05
Panthen I Eth I Ether *15 0.05 0.05 0.05 0.05 0.05
Citric Acid *16 amount
necessa
to
ad'ust
H
3-7
Deionized Water .s.
to
100%
Compositions of Examples 6 through 10
Com onents Ex. Ex. Ex. Ex Ex.
6 7 8 9 10
Cet I h drox eth (cellulose-10.25 0.25 0.1 0.25 0.25
*1
Cet I h drox eth (cellulose-1 0.25
*2
Cet I Alcohol *3 0.96 0.96 1.2 0.96 0.7
Stea I Alcohol *4 0.64 0.64 0.8 0.64 0.5
Behen I Alcohol *5 0.20
Polawax NF *17 0.25 0.25 0.125 0.25 0.125
Stearamido ro I Dimeth lamine1.0 1.0 1.0 1.0 0.75
*6
Ditallow dimethyl ammonium 0.75 0.75 0.75 0.75 0.5
chloride *18
Pentae hritol Tetraisostearate 0.5
*8
Pentae hritol Tetraoleate 0.5
*19
Ole I alcohol *20 0.25 0.25 0.10 0.25 0.25
PEG 2M *21 0.5 0.5 0.25 0.5 0.5
Cationic Silicone Emulsion-1 0.8
*9
Cationic Silicone Emulsion-2 1.05 3.0
*10
Silicone Blend *11 4.2 4.2
GI ce Imonostearate *22 0.25 0.25 0.25 0.25 0.25
Preservatives 0.04 0.04 0.04 0.04 0.04
Benz I alcohol 0.4 0.4 0.4 0.4 0.4
Perfume 0.6 0.6 0.6 0.6 0.6
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Acid EDTA 0.1 0.01 0.02 0.1 0.01
H drol zed colla en *12 0.01 0.01 0.01 0.01 0.01
Vitamin E *13 0.01 0.025 0.01 0.01 0.01
Panthenol *14 0.05 0.2 0.1 0.05 0.05
Panthen I Eth I Ether *15 0.05 0.05 0.01 0.05 0.05
Citric Acid *16 amount
necessa
to
ad'ust
H
3-7
Deionized Water .s.
to
100%
Compositions of Examples 11 through 15
Com onents Ex.11 Ex. Ex. Ex. Ex.15
12 13 14
Cet I h drox eth (cellulose-10.25 0.25 0.1 0.25
*1
Cet I h drox eth (cellulose-1 0.05
*2
Cet I Alcohol *3 1.5 1.5 1.5 0.9 1.5
Stea I Alcohol *4 2.7 2.7 2.7 0.64 2.7
Polawax NF *17 0.5
Stearamido ro I Dimeth lamine1.2 1.2 1.2 1.0 1.2
*6
.2-Glutamic Acid *7 0.384 0.3840.384 0.384
Ditallow dimethyl ammonium 0.75
chloride *18
Ole I alcohol *20 0.25
PEG 2M *21 0.5 0.25
Silicone Blend *11 2.52 2.52 2.52 4.2 2.52
GI ce Imonostearate *22 0.25
Preservatives 0.033 0.0330.033 0.033 0.033
Benz I alcohol 0.4 0.4 0.4 0.4 0.4
Perfume 0.6 0.6 0.6 0.6 0.6
Acid EDTA 0.1 0.1 0.1 0.1 0.1
Pol uaternium-24 *23 0.25
Pol uaternium-24 *24 1.0
Pol ro lene GI col *25 0.25 0.25
Pol uaternium-4 *26 0.25 0.25
Pol uaternium-4 *27 0.25
H drox eth I Eth (cellulose 0.5
*28
Pol onum extract *29 0.1
Biotin *30 0.1
Citric Acid *16 amount
necessa
to
ad'ust
H
3-7
Deionized Water .s.
to
100%
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WO 01/08644 PCT/US00/20662
Compositions of Examples 16 through 20
Com onents Ex.16 Ex. Ex. Ex. Ex.20
17 18 19
Cet I h drox eth (cellulose-12.0 0.25 0.10 0.25 0.25
*1
~Cet I h drox eth (cellulose-1 0.25
*2
Cet I Alcohol *3 0.5 0.96 1.2 0.96 1.500
Stea I Alcohol *4 0.9 0.64 0.8 0.64 2.70
Polawax NF *17 0.25 0.125 0.25
Stearamido ro I Dimeth lamine0.4 1.0 1.0 1.0 1.20
*6
2-Glutamic Acid *7 0.13
Ditallow dimethyl ammonium 0.75 0.75 0.75
chloride *18
Ole I alcohol *20 0.25 0.1 0.25
PEG 2M *21 0.5 0.25 0.50
Silicone Blend *11 0.8 1.05 0.8 4.2 2.52
GI ce Imonostearate *22 0.25 0.25
Preservatives 0.033 0.033 0.033 0.033 0.033
Benz I alcohol 0.4 0.4 0.4 0.4 0.4
Perfume 0.6 0.6 0.6 0.6 0.6
Acid EDTA 0.1 0.1 0.1 0.1 0.1
Pol uaternium-24 *23 0.25
Pol uaternium-24 *24 0.1 1.0
Pol ro lene GI col *25 0.1 0.2 0.1 0.25
Pol uaternium-4 *26 0.25
Pol uaternium-4 *27 0.5
H drox eth I Eth (cellulose0.1 0.1 0.5 1.0
*28
Pol onum extract *29 0.1 0.1
Biotin *30 0.1 0.1
Citric Acid *16 amount
necessa
to
ad'ust
H
3-7
Deionized Water .s.
to
100%
Definitions of Components
*1 Cetyl hydroxyethylcellulose-1: Polysurf 67 available from Aqualon.
*2 Cetyl hydroxyethylcellulose-2: NATROSOL PLUS 330CS available from
Aqualon
*3 Cetyl Alcohol: Konol series available from Shin Nihon Rika.
*4 Stearyl Alcohol: Konol series available from Shin Nihon Rika.
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*5 Behenyl Alcohol: 1-Docosanol (97%) available from Wako.
*6 Stearamidopropyl Dimethylamine: Amidoamine MPS available from Nikko.
*7 ~-Glutamic Acid: ~-Glutamic acid (cosmetic grade) available from Ajinomoto.
*8 Pentaerythritol Tetraisostearate: KAK PTI available from Kokyu alcohol.
*9 Cationic Silicone Emulsion-1: PE2006 available from Dow Corning;
mechanically emulsified emulsion containing 60% silicone compound and
3.0% cationic surfactant, wherein the silicone compound has a particle size
of about 280 nm, and is made by using polydimethylsiloxane having about
900 repeating units and polydimethylsiloxane having about 100 repeating
units, in a ratio of 27:73.
*10 Cationic Silicone Emulsion-2: PE2016 available from Dow Corning; is
mechanically emulsified emulsion containing 55% silicone compound and
3.0% cationic surfactant, wherein the silicone compound has a particle size
of about 280 nm, and is made by using polydimethylsiloxane having about
900 repeating units and polydimethylsiloxane having about 100 repeating
units, in a ratio of 27:73.
*11 Silicone Blend: SE76 available from G.E.
*12 Hydrolyzed collagen: Peptein 2000 available from Hormel.
*13 Vitamin E: Emix-d available from Eisai.
*14 Panthenol: available from Roche.
*15 Panthenyl Ethyl Ether: available from Roche.
*16 Citric Acid: Anhydrous Citric acid available from Haarman & Reimer.
*17 Polawax NF: Mixture of Polysorbate 60 and Cetearyl Alcohol available from
Croda Chemicals.
*18 Ditallow dimethyl ammonium chloride: available from Witco Chemicals.
*19 Pentaerythritol Tetraoleate: available from Shin NihonRika.
*20 Oleyl alcohol: available from New Japan Chemical.
*21 PEG-2M: Polyox available from Union Carbide.
*22 Glycerylmonostearate: available from Stepan Chemicals.
*23 Polyquaternium-24: Quaterisoft Polymer LM-200 available from Amerchol
*24 Polyquaternium-24: BioCare Polymer HA-24 available from Amerchol
*25 Polypropylene Glycol: New Pol PP-2000 available from Sanyo Kasei
*26 Polyquaternium-4: Celquat L-200 available from National Starch Corp.
*27 Polyquaternium-4: Celquat H-100 available from National Starch Corp.
*28 Hydroxyethyl Ethylcellulose: Elfacos CD 481 available from Akzo Nobel
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*29 Polygonum Extract: Polygonum multiflorum extract available from Lipo
*30 Biotin: d-Biotin available from Roche
Method of Preparation
The compositions of Examples 1 through 20 as shown above can be
prepared by any conventional method as follows: Cetyl hydroxyethylcellulose
and, if present, polyethylene glycol are dispersed in water at room
temperature to
make a polymer solution, and heated up to above 70°C. Amidoamine and
acid,
or other cationic conditioning agents, and if present, ester oils are added in
the
1o solution with agitation. Then, the high melting point fatty compound, and
if
present, other low melting point oils and benzyl alcohol are also added in the
solution with agitation. The mixture thus obtained is cooled down to below
60°C,
and the remaining components such as silicone blend or cationic silicone
emulsion are added with agitation, and further cooled down to about
30°C.
A triblender and/or mill can be used in each step, if necessary to disperse
the materials.
In a particularly preferred embodiment, Examples 1 through 20 as shown
above are prepared as follows: Amidoamine and acid, or other cationic
conditioning agents, and if present, ester oils are added in the solution with
2o agitation, and added to water base which was preheated to above
70°C. Then,
the high melting point fatty compound, and if present, other low melting point
oils
and benzyl alcohol are also added in the solution with agitation. The
Polyquaternium-24, Polyquaternium-4, Polypropylene glycol and hydroxyethyl
ethylcellulose, if present, can be included at this point, or after the
mixture is
cooled. The mixture thus obtained is cooled down to between 40°C to
60°C, and
the cetyl hydroxyethylcellulose and remaining components such as silicone
blend
or cationic silicone emulsion are added with agitation. The Polyquaternium-24,
Polyquaternium-4, Polypropylene glycol and hydroxyethyl ethylcellulose can
optionally be added at this stage. The finally obtained mixture is further
cooled
3o down to about 30°C.
A triblender and/or mill can be used in each step, if necessary to disperse
the materials.
The embodiments disclosed and represented by the previous examples
have many advantages. For example, they can provide increase in bulk hair
volume, softness, moisturized feel, and fly-away control. They can also
provide
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WO 01/08644 PCT/US00/20662
satisfactory spreadability on the hair, and can be made by a convenient
manufacturing method.
It is understood that the examples and embodiments described herein are
for illustrative purposes only and that various modifications or changes in
light
thereof will be suggested to one skilled in the art without departing from its
spirit
and scope.
37
