Note: Descriptions are shown in the official language in which they were submitted.
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1
A HAIR CARE COMPOSITION COMPRISING A POLYPROPYLENE GLYCOL
AND AN ESTER OIL
FIELD OF THE INVENTION
The present invention relates to a hair care composition. More
specifically, the present invention relates to a hair care composition which
provides a conditioning benefit.
~5 BACKGROUND OF THE INVENTION
Human hair becomes soiled due to its contact with the surrounding
environment and from sebum secreted by the scalp. The soiling of the hair
causes it to have a dirty or greasy feel, and an unattractive appearance. The
soiling of the hair necessitates shampooing with regularity.
2o Shampooing cleans the hair by removing excess soil and sebum.
However, shampooing can leave hair in a wet, tangled, and generally
unmanageable state. After shampooing, hair is often left in a dry, rough,
lusterless, or frizzy condition due to removal of the hair's natural oils and
other
natural conditioning components. Furthermore, such hair may also suffer from a
25 perceived loss of softness. In addition, hair may possess increased levels
of
static after drying, which can interfere with combing and reduce hair
manageability. This results in a condition commonly referred to as "flyaway
hair."
Certain consumers consider such flyaway hair and the corresponding increase in
total hair volume undesirable. Thus, it is desirable to provide smooth, soft,
silky-
3o feeling, and healthy-looking hair, while decreasing flyaway hair volume and
total
hair volume. In addition, it is typically desirable to increase the
biodegradability
of a hair care composition.
A variety of approaches have been developed to address these issues.
Such approaches typically seek to increase smoothness, softness, and luster by
35 including hair conditioning compounds, typically cationic compounds, such
as
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2
cationic surfactants, into a hair care composition. Such hair conditioning
compounds may also reduce static. In theory, these cationic compounds,
including quaternary ammonium compounds, seek to neutralize the static charge
on the hair, and thus reduce flyaway hair volume. However, these hair
s conditioning compounds do not sufficiently reduce total hair volume, and may
be
harsh on the hair, skin, or scalp.
Alternatively, oily compounds, such as a silicone, an ester oil, and/or a
hydrocarbon oil have been included in hair care compositions to reduce flyaway
hair. However, while these oily compounds may make hair feel smoother, more
~o silky, and/or appear more lustrous, they are not sufficient to satisfy
certain
consumers.
Accordingly, the need remains for a hair care composition which
noticeably reduces total hair volume and is easily biodegradable. The need
also
remains for a hair care composition which provides smoother, softer, more
silky,
~ s and more lustrous hair. The need also remains for a hair care composition
possessing these benefits, which is effectively deposited onto hair.
SUMMARY OF THE INVENTION
The present invention relates to a hair care composition which includes a
2o polypropylene glycol, an ester oil, and a gel matrix. The polypropylene
glycol has
a weight average molecular weight of from about 200 g/mol to about 100,000
g/mol. The ester oil has the formula R'COOR', wherein each R' is independently
a C,-C22 alkyl, and the HLB value of the ester oil is less than about 4. The
gel
matrix includes a cationic surfactant, a solid fatty compound, and water.
2s In another aspect, the present invention relates to a hair care composition
which includes a polypropylene glycol, an ester oil, and a suitable carrier.
The
polypropylene glycol has a weight average molecular weight of from about 200
g/mol to about 100,000 g/mol. The ester oil is selected from the group of
pentaerythritol ester oils, trimethylol ester oils, and mixtures thereof,
wherein the
3o ester oil has an HLB value of less than about 4.
It has now been found that total hair volume is actually the sum of the
"flyaway hair volume" and the "bulk hair volume." It has also been found that
a
measurable reduction of bulk hair area, flyaway hair area, and total hair
area, by
the Image Analysis Protocol described herein, corresponds to a noticeable
3s decrease in the bulk hair volume, flyaway hair volume, and the total hair
volume,
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respectively. Accordingly, it has been found that reducing the bulk hair area
can
therefore play a significant role in reducing the total hair volume. While
certain
compounds and compositions are known to reduce fly-away hair volume, for
example, by reducing the static charge of hair, these compositions do not
noticeably reduce bulk hair volume. It has now been found that a hair care
composition which moisturizes the hair may noticeably reduce bulk hair volume,
and may also noticeably reduce flyaway hair volume. This, in turn, provides a
significant, noticeable reduction in total hair volume.
It has now been found that a hair care composition, preferably a hair
conditioning composition, and/or a styling composition, containing a
polypropylene glycol, an ester oil, and a suitable carrier may also more
effectively
deposit onto hair, and provide significant consumer-desirable benefits, such
as
an improved look and feel for hair, reduced bulk hair volume, reduced flyaway
hair volume, and reduced total hair volume. Furthermore, the hair care
~s composition is inexpensive to formulate, easily biodegradable, and
possesses a
non-oily feel.
These and other features, aspects, advantages, and variations of the
present invention, and the embodiments described herein, will become evident
to
those skilled in the art from a reading of the present disclosure with the
2o appended claims, and are covered within the scope of these claims.
BRIEF DESCRIPTION OF THE FIGURE
While the specification concludes with claims particularly pointing out and
distinctly claiming the invention, it is believed that the invention will be
better
2s understood from the following description of the accompanying figure in
which:
Fig. 1 is a top view of a preferred embodiment of the Image Analysis
System.
DETAILED DESCRIPTION OF THE INVENTION
3o All percentages, ratios and proportions herein are by weight of the final
hair care composition, unless otherwise specified. All molecular weights
herein
are weight average molecular weights, unless otherwise specified. All
temperatures are in degrees Celsius (°C) unless otherwise specified.
All
documents cited are incorporated herein by reference in their entireties.
Citation
35 Of any reference is not an admission regarding any determination as to its
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4
availability as prior art to the claimed invention. The drawing herein is not
necessarily drawn to scale.
As used herein, the term "alkyl" means a hydrocarbyl moiety which is
straight, branched, or cyclic, saturated or unsaturated. Unless otherwise
s specified, alkyl moieties are preferably saturated or unsaturated with
double
bonds, preferably with one or two double bonds. Included in the term "alkyl"
is
the alkyl portion of acyl groups.
As used herein, the term "hair conditioning benefit" indicates a
conditioning, softening, bulk hair volume reduction, flyaway hair volume
reduction, total hair volume reduction, moisturizing, improved wet-hair or dry-
hair
feel, lubricating, smoothening, softening, and/or other effect when applied to
hair.
All reductions in bulk hair volume, flyaway hair volume, and/or total hair
volume
are according to the Image Analysis Protocol, as described herein.
As used herein, the term "water-insoluble" means the compound is
~5 substantially not soluble in water at 25 °C, when the compound is
mixed with
water at a 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.
2o POLYPROPYLENE GLYCOL
The hair care composition of the present invention contains a
polypropylene glycol 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. Without intending to be limited by theory, it is believed that
the
25 polypropylene glycol herein deposits onto, or is absorbed into hair to act
as a
humectant/moisturizer, and/or provides one or more other desirable hair
conditioning benefits. As used herein, the term "polypropylene glycol"
includes
single-polypropylene glycol-chain segment polymers, and multi-polypropylene
glycol-chain segment polymers. The general structure of branched polymers
3o such as the multi-polypropylene glycol-chain segment polymers herein are
described, for example, in "Principles of Polymerization," pp. 17-19, G.
Odian,
(John Wiley & Sons, Inc., 3~d ed., 1991 ).
The polypropylene glycol herein are typically polydisperse polymers. The
polypropylene glycols useful herein have a polydispersity of from about 1 to
3s about 2.5, preferably from about 1 to about 2, and more preferably from
about 1
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to about 1.5. As used herein, the term "polydispersity" indicates the degree
of
the molecular weight distribution of the polymer sample. Specifically, the
polydispersity is a ratio, greater than 1, equal to the weight average
molecular
weight divided by the number average molecular weight. For a further
discussion
s about polydispersity, see "Principles of Polymerization," pp. 20-24, G.
Odian,
(John Wiley & Sons, Inc., 3~d ed., 1991 ).
The polypropylene glycol useful herein may be either water-soluble, water-
insoluble, or may have a limited solubility in water, depending upon the
degree of
polymerization and whether other moieties are attached thereto. The desired
solubility of the polypropylene glycol in water will depend in large part upon
the
form (e.g., leave-on, or rinse-off form) of the hair care composition. The
solubility
in water of the polypropylene glycol herein may be chosen by the artisan
according to a variety of factors. A water-soluble polypropylene glycol is
especially useful in, for example, a leave-on product. Without intending to be
limited by theory, it is believed that such a water-soluble polypropylene
glycol
may possess many advantages in such a product. For example, such a
polypropylene glycol may be easy to formulate, inexpensive, highly
biodegradable, and easily obtainable. Accordingly, for a leave-on hair care
composition, it is preferred that the polypropylene glycol herein be a water-
2o soluble polypropylene glycol. Solubility information is readily available
from
polypropylene glycol suppliers, such as Sanyo Kasei (Osaka, Japan).
However, the present invention may also take the form of a rinse-off hair
care composition. Without intending to be limited by theory, it is believed
that in
such a composition, a water-soluble polypropylene glycol may be too easily
2s washed away before it effectively deposits on hair and provides the desired
benefit(s). For such a composition, a less soluble, or even a water-insoluble
polypropylene glycol is therefore preferred. Accordingly, for a rinse-off hair
care
composition, it is preferred that the polypropylene glycol herein has a
solubility in
water at 25 °C of less than about 1 g/100 g water, more preferably a
solubility in
3o water of less than about 0.5 g/100 g water, and even more preferably a
solubility
in water of less than about 0.1 g/100 g water.
The polypropylene glycol is typically present at a level of from about 0.5%
to about 10%, and preferably from about 2% to about 6%, by weight of the hair
care composition.
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Preferably the polypropylene glycol is selected from the group consisting
of a single-polypropylene glycol-chain segment polymer, a multi-polypropylene
glycol-chain segment polymer, and mixtures thereof, more preferably selected
from the group consisting of a single-polypropylene glycol-chain segment
s polymer of Formula I, below, a multi-polypropylene glycol-chain segment
polymer
of Formula II, below, and mixtures thereof. Without intending to be limited by
theory, it is believed that these polypropylene glycols provide a good balance
between performance, availability, biodegradability, and cost.
~o Sinqle-Polypropylene Glycol-Chain Seament Polymer
Accordingly, a highly preferred single-polypropylene glycol-chain segment
polymer has the formula:
HO-(C3H60)aH (Formula I),
wherein a is a value from about 4 to about 400, preferably from about 20 to
about
~5 100, 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,
2o USA), Witco Chemicals Corp. (Greenwich, Connecticut, USA), and PPG
Specialty Chemicals (Gurnee, Illinois, USA).
Without intending to be limited by theory, it is believed that once it has
deposited onto a strand of hair, the shape and relatively small size of the
single-
polypropylene glycol-chain segment polymer herein allows it to easily
penetrate
2s the hair. While useful for both a leave-on and a rinse-off form, a single-
polypropylene glycol-chain segment polymer is especially preferred if the hair
care composition is to take a leave-on form. Furthermore, the multiple
propylene
oxide groups attract and maintain a significant amount of water to the hair so
as
to impart significant moisturization properties. This increased moisturization
so results in reduced flyaway hair volume, reduced bulk hair volume, and/or
increases the manageability of the hair.
Multi-Polypropylene Glycol-Chain Segment Polymer
A highly preferred multi-polypropylene glycol-chain segment polymer has
35 the formula:
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(CH2)c O-(CsHsO)y-H
R-C-~(CH2)b-O-(CsHsO)x~"-H
I I a In
(CH2)d-O-(C3H60)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
1 o 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 is 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.
15 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-
chain segments; available as New Pol GP-4000, from Sanyo Kasei, Osaka,
2o Japan), polypropylene trimethylol propane (n = 1, R = C2H5, 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-
2s 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.).
In a preferred embodiment, one or more of the propylene repeating groups
in the polypropylene glycol is an isopropyl oxide repeating group. More
so preferably one or more of the propylene oxide repeating groups of the
polypropylene glycol of Formula I and/or the polypropylene glycol of Formula
II is
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an isopropyl oxide repeating group. Even more preferably, substantially all of
the
propylene oxide repeating groups of the polypropylene glycol of Formula I
and/or
the polypropylene glycol of Formula II are isopropyl oxide repeating groups.
Accordingly, a highly preferred single-polypropylene glycol-chain segment
s polymer has the formula:
HO-(C H-C H2-O)a-H
CH3 (Formula III),
wherein a is defined as described above for Formula I. Similarly, a highly
preferred multi-polypropylene glycol-chain segment polymer has the formula:
CH3
(CH2)~ O-(CH-CH2-O)y-H
CH3
R-C~(CH2)b-O-(CH-CH2-O)x~H
~ a In
(C H2 )d-O-(C H -C H2-O)z- H
CH3 (Formula IV),
wherein n, R, b, c, d, e, x, y, and z are defined as above, for Formula II. It
is
recognized that the isopropyl oxide repeating groups may also correspond to:
-(C H2-C H-O)-
C H3
either alone, or in combination with the isomer depicted in Formula IV.
~5 ESTER OIL
The hair care composition of the present invention also contains an ester
oil therein. The ester oil useful herein is of the formula:
R'COOR' (Formula V),
wherein each R' is independently a C,-C22 alkyl, and preferably at least one
R' is
2o a C8 C22 alkyl. Each R' may be either a straight or branched alkyl chain.
If R' is
branched, it is preferred that R' have from 2 to 4 branches. The HLB value of
the
ester oil is less than about 4, preferably from about 0 to about 3. The ester
oil
useful herein should be easy to formulate, and process. Accordingly, the ester
oil typically has a melting point of less than about 40 °C, and is
preferably water
25 insoluble, and in a liquid form at 25 °C.
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The HLB value is a theoretical index value which describes the
hydrophilicity-hydrophobicity balance of a specific compound. Generally, it is
recognized that the HLB index ranges from 0 (very hydrophobic) to 40 (very
hydrophilic). The HLB value of the alkyl alkoxylate may be found in tables and
charts known in the art, or may be calculated with the following general
equation:
HLB = 7 + (hydrophobic group values) + (hydrophilic group values). The HLB
and methods for calculating the HLB of a compound are explained in detail in
"Surfactant Science Series, Vol. 1: Nonionic Surfactants", pp. 606-13, M. J.
Schick (Marcel Dekker, Inc., New York, 1966).
Unless otherwise noted herein, the ester oils useful herein have a weight
average molecular weight of greater than about 70 g/mol, preferably from about
100 g/mol to about 2,000 g/mol, and more preferably from about 160 g/mol to
about 1,200 g/mol are especially useful herein. The preferred ester oil useful
herein includes pentaerythritol ester oils, trimethylol ester oils, citrate
ester oils,
glyceryl ester oils, and mixtures thereof.
Without intending to be limited by theory, it is believed that ester oils
efficiently deliver the polypropylene glycol to the hair, reduce flyaway hair
volume, and/or provide other hair conditioning benefits. Furthermore, the
ester
oil herein provides moisturized feel, smooth feel, and manageability control
to the
2o hair when the hair is dried, yet does not leave the hair feeling greasy.
Thus, with
the addition of the ester oil, a composition is obtained which may provide
particularly suitable conditioning benefits both when the hair is wet and also
after
it has dried. The ester oil may be included at a level of from about 0.5% to
about
20%, preferably from about 2% to about 10%, and more preferably from about
3% to about 7% by weight of the composition.
Pentaerythritol ester oils useful herein are those of the following formula
having a weight average molecular weight of at least 800 g/mol:
O
C H20-C-R2
O O
R~ C-OCH2- ~ -CH20-C-R3
O
H O-C-R 4
2
wherein R', R2, R3, and R4, independently, are branched, straight, saturated,
or
3o unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30
carbons.
Preferably, R', R2, R3, and R4, independently, are branched, straight,
saturated,
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or unsaturated alkyl groups having from about 8 to about 22 carbons. More
preferably, R', RZ, R3 and R4 are defined so that the weight average molecular
weight of the compound is from about 800 g/mol to about 1,200 g/mol.
Trimethylol ester oils useful herein are those of the following formula
5 having a weight average molecular weight of at least 800 g/mol:
O
C H20-C-R12
O
R1 ~ ~ H -CH O-C-R13
2 2
O
C 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, R"
is
~o 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 weight average molecular weight
of
the compound is from about 800 g/mol to about 1,200 g/mol.
Particularly preferable ester oils are pentaester oils and trimethylol ester
~s oils, and more preferably pentaerythritol tetraisostearate, pentaerythritol
tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate,
and
mixtures thereof. Such compounds are available from Kokyo Alcohol (Japan)
with the tradenames KAK P.T.I., and KAK T.T.I., and Shin-nihon Rika (Tokyo,
Japan) with the tradenames PTO, and ENUJERUBU TP3S0.
2o Citrate ester oils useful herein are those having a weight average
molecular weight of at least about 500 g/mol having the following formula:
O
C H2-C-O-R22
R21 ~ -~-O-R 23
O
H2-C-O-R24
wherein R2' is OH or CH3C00, and R22, R2s, and R24, independently, are
branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl
groups
2s having from 1 to about 30 carbons. Preferably, Rz' is OH, and R2z, R2s, and
Rz4,
independently, are branched, straight, saturated, or unsaturated alkyl, aryl,
and
alkylaryl groups having from 8 to about 22 carbons. More preferably, R2', R22,
R2s
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and Rz4 are defined so that the weight average molecular weight of the
compound is at least about 800 g/mol. 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
s trioctyldodecyl citrate with tradename CITMOL 320 available from Bernel.
Glyceryl ester oils useful herein are those having a weight average
molecular weight of at least about 400 g/mol 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
o unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30
carbons.
Preferably, R4', R42, and R43, independently, are branched, straight,
saturated, or
unsaturated alkyl, aryl, and alkylaryl groups having from 8 to about 22
carbons.
More preferably, R4', R42, and R43 are defined so that the weight average
molecular weight of the compound is at least about 500 g/mol.
~5 Particularly useful glyceryl ester oils herein include caprylic/capric
triglyceride with the tradename Miglyol812, from Degussa-Huls AG (Frankfurt,
Germany), triisostearin with tradename SUN ESPOL G-318 available from Taiyo
Kagaku, triolein with tradename CITHROL GTO available from Croda, Inc.
(Parsippany, New Jersey, USA), trilinolein with tradename EFADERMA-F
2o available from Vevy (Genova, Italy), or tradename EFA-GLYCERIDES from
Brooks (South Plainfield, New Jersey, USA).
SUITABLE CARRIER
In an embodiment of the present invention, a hair care composition
2s contains an ester oil selected from a pentaerythritol ester oil, a
trimethylol ester
oils, and mixtures thereof, a polypropylene glycol, and a suitable carrier.
The
suitable carrier contains a continuous phase, which is typically either water,
or oil.
The continuous phase is preferably water, but even a water continuous phase
may also contain an oil emulsified, or dispersed therein, and visa-versa.
Other
so carrier ingredients and/or other additional components may also be added
into
the suitable carrier. Without intending to be limited by theory, it is
believed that
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pentaerythritol ester oils, trimethylol ester oils, and mixtures thereof
deposit
especially well onto hair when included in a suitable carrier, such as an
aqueous
carrier. It is believed that their combination of bulkiness, branching, and
high
molecular weight contribute significantly to their deposition and
effectiveness,
s even in the absence of a gel matrix. Thus, while a gel matrix is preferred,
these
ester oils provide significant, desirable benefits, even in the absence of a
gel
matrix.
In another embodiment of the present invention, a hair care composition
contains an ester oil according to Formula V, a polypropylene glycol, and a
gel
o matrix. Without intending to be limited by theory, it is believed that for
the ester
oils of Formula V, a gel matrix significantly improves deposition and
effectiveness.
1. Water
~5 The final hair care composition of the present invention typically
comprises
at least about 60%, preferably at least about 70% water, and more preferably
from about 75% to about 95% water. Deionized water is preferably used. Water
from natural sources including mineral cations may also be used, depending on
the desired characteristic of the product. The level and species of the
suitable
2o carrier are selected according to the compatibility with other components,
and
other desired characteristics of the product.
The suitable carrier may also include therein a lower alkyl alcohol, a
polyhydric alcohol, and a mixture thereof. Lower alkyl alcohols useful herein
are
monohydric alcohols having 1 to 6 carbons, more preferably ethanol and
25 isopropanol. The preferred polyhydric alcohols useful herein include
propylene
glycol, hexylene glycol, glycerin, and propane diol.
In a preferred embodiment, the suitable carrier is in the form of a gel
matrix containing a cationic surfactant, a solid fatty alcohol, and water, and
is
typically characterized by a high viscosity of from about 5,000 cps to about
30 40,000 cps, preferably from about 10,000 cps to about 30,000 cps, and more
preferably from about 12,000 cps to about 28,000 cps, as measured at 25
°C, by
means of a Brookfield Viscometer at shear rate of 1.0 rpm. If present, the gel
matrix comprises from about 60% to about 99%, preferably from about 70% to
about 95%, and more preferably from about 80% to about 95%, by weight of the
35 hair care composition.
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In a highly preferred embodiment, the gel matrix is preferably a lamellar
gel matrix, which provides improved deposition, wet hair feel, softness, and
other
substantial benefits. In a lamellar gel matrix, the weight ratio of cationic
surfactant to solid fatty compound is from about 1:1 to about 1:20, preferably
s from about 1:2 to about 1:10, and more preferably form about 1:3 to 1:5.
Generally, the preferred cationic surfactants in the lamellar gel matrix
contain one
or two long chain (e.g., C,2~o) alkyl groups, and a tertiary or quaternary
amine
group. Tertiary amine groups having one or two C,6_z2 alkyl chains are
preferred.
The existence of a lamellar gel matrix may be detected by differential
scanning calorimetry (hereinafter referred to as "DSC") measurement of the
composition. A profile chart obtained by DSC measurement describes chemical
and physical changes of the scanned sample that involve an enthalpy change or
energy gradient when the temperature of the sample is fluctuated. As such, the
phase behavior and interaction among components of hair conditioning
~s compositions of the present invention may be understood by their DSC
profiles.
DSC measurement of compositions of the present invention may be conducted
by any suitable instrument available. For example, DSC measurement may be
suitably conducted by Seiko DSC 6000 instrument available from Seiko
Instruments Inc. In a typical measurement procedure, a sample is prepared by
2o sealing an appropriate amount of the composition into a container made for
DSC
measurement and sealed. The weight of the sample is recorded. A blank
sample i.e.; an unsealed sample of the same container is also prepared. The
sample and blank sample are placed inside the instrument, and run under a
measurement condition of from about -50 °C to about 130 °C at a
heating rate of
25 from about 1 °C/minute to about 10 °C/minute. The area of the
peaks as
identified are calculated and divided by the weight of the sample to obtain
the
enthalpy change in mJ/mg.
In a preferred lamellar gel matrix, the DSC profile shows a formation peak
of larger than about 3 mJ/mg. The position of the peaks are identified by the
3o peak top position. The DSC profile of the preferred lamellar gel matrix
shows a
single peak having a peak top temperature of from about 55 °C to about
75 °C,
and from about 6 mJ/mg to about 10 mJ/mg, and no peaks larger than 3 mJ/mg
from 40 °C to 55 °C. It is believed that a composition formed
predominantly with
such a lamellar gel matrix shows a relatively stable phase behavior during the
35 temperature range of from about 40 °C to about 55 °C. In an
even more
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14
preferred lamellar gel matrix, the DSC profile shows a single peak having a
peak
top temperature of about 69 °C, at about 8 mJ/mg, and no peaks larger
than 3
mJ/mg from 40 °C to about 65 °C.
a. Cationic Surfactant
Among the cationic surfactants useful herein are those corresponding to
the general Formula (I):
101
R
R02 N+ 8103 X_
8104
(I)
wherein at least one of R,°', R'°2, R,o3 and R'°4 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 R'°', R'°2, R,°3 and R'°4
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,
2o ether linkages, and other groups such as amino groups. The longer chain
aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated
or
unsaturated. Preferred is when R'°', R,°z, 8103 and R'°4
are independently
selected from C, 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.
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
3o trimethyl ammonium chloride available, for example, with tradename
INCROQUAT TMC-80 from and ECONOL TM22 from Sanyo Kasei (Osaka,
Japan); cetyl trimethyl ammonium chloride available, for example, with
tradename CA-2350 from Nikko Chemical (Tokyo, Japan), hydrogenated tallow
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alkyl trimethyl ammonium chloride, dialkyl (14-18) dimethyl ammonium chloride,
ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl
dimethyl
ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl
ammonium chloride, di(behenyl/arachidyl) dimethyl ammonium chloride,
s 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
methyl) pyridinium chloride.
Also preferred as cationic surfactants are hvdro~hilicallv 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 chain, wherein at least one of the R'°'-
R'°4 radicals contain
one or more hydrophilic moieties selected from alkoxy (preferably C,-C3
alkoxy),
15 polyoxyalkylene (preferably C,-C3 polyoxyalkylene), alkylamido,
hydroxyalkyl,
alkylester, and combinations thereof. Preferably, the hydrophilically
substituted
cationic surfactant contains from 2 to about 10 nonionic hydrophile moieties
located within the above stated ranges. Preferred hydrophilically substituted
cationic surfactants include those of Formulas (II) through (VIII) below:
Z1
CH3(CH2) ~ CH2-N~CH2CH20~H ~(-
n
~CH2CH20-~H
Zo (II)
wherein n' is from 8 to about 28, m'+m2 is from 2 to about 40, Z' is a short
chain
alkyl, preferably a C,-C3 alkyl, more preferably methyl, or (CH2CH20)m3H
wherein
m'+m2+m3 is up to 60, and X- is a salt-forming anion as defined above;
R1 os R1 os
R o5 N~ C H N~ R o9 2X
( 2) 2
8107 ~ R110
(Ill)
2s wherein n2 is 1 to 5, one or more of R'°5, R,os, and R'°' are
independently an C,-
C3° alkyl, the remainder are CHZCH20H, one or two of R'°$,
R'°9, and R"° are
independently an C,-C3° alkyl, and remainder are CHZCHZOH, and X- is a
salt-
forming anion as mentioned above;
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16
O H Z2 H O
111 II I , ~I~ ~I II 112
R-C-N-~CH2 3 N CH2 N-C-R X
Z
(IV)
O Z2 O
111 I) f ~ i+~ ~ II 112
R-C-O C H2~=~ 3 N C H2 O-C-R X
Z
(V)
wherein, independently for formulas (IV) and (V), Z2 is an alkyl, preferably
C,-C3
alkyl, more preferably methyl, and Z3 is a short chain hydroxyalkyl,
preferably
hydroxymethyl or hydroxyethyl, n3 and n4 independently are integers from 2 to
4,
inclusive, preferably from 2 to 3, inclusive, more preferably 2, R"' and R"2,
independently, are substituted or unsubstituted hydrocarbyls, C12 C2o alkyl or
alkenyl, and X- is a salt-forming anion as defined above;
Z4
R 13 N~CH2CHO~H X
Z CH3
(VI)
~o wherein R"3 is a hydrocarbyl, preferably a C1-C3 alkyl, more preferably
methyl, Z4
and Z5 are, independently, short chain hydrocarbyls, preferably C2 CQ alkyl or
alkenyl, more preferably ethyl, m4 is from 2 to about 40, preferably from
about 7
to about 30, and X- is a salt-forming anion as defined above;
114
s R
Z-N CH2~HCH2-A X
8115 ~H
(VII)
wherein R"4 and R"5, independently, are C,-C3 alkyl, preferably methyl, Z6 is
a
C,2 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;
8116
HOCH2-(CHOH)4-C-NH(CH2)~5 i~ CH2CH20H X
R 117
(VIII)
2o wherein n5 is 2 or 3, R"6 and R"', independently are C,-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
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17
invention include the materials having the following CTFA designations:
quaternium-16, quaternium-26, 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-72,
s quaternium-75, quaternium-76 hydrolyzed collagen, quaternium-77, quaternium
78, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin,
quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk,
quaternium-79 hydrolyzed soy protein, and quaternium-79 hydrolyzed wheat
protein, quaternium-80, quaternium-81, quaternium-82, quaternium-83,
~o quaternium-84, and mixtures thereof.
Highly preferred hydrophilically substituted cationic surfactants include
dialkylamido ethyl hydroxyethylmonium salt, dialkylamidoethyl dimonium salt,
dialkyloyl ethyl hydroxyethylmonium salt, dialkyloyl ethyldimonium salt, and
mixtures thereof; for example, commercially available under the following
~5 tradenames; VARISOFT 110, VARISOFT 222, VARIQUAT K1215 and
VARIQUAT 638 from Witco Chemicals (Greenwich, Connecticut, USA),
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,
2o ETHOQUAD S/25, and ETHODUOQUAD from Akzo, DEHYQUAT SP from
Henkel (Germany), and ATLAS 6265 from ICI Americas (Wilmington, Delaware,
USA).
Salts of primary, secondary, and tertiary fatty amines are also suitable
cationic surfactants. The alkyl groups of such amines preferably have from
about
2s 12 to about 22 carbon atoms, and can be substituted or unsubstituted.
Particularly useful are amido substituted tertiary fatty amines. Such amines,
useful herein, include stearamidopropyldimethylamine,
stearamidopropyldiethylamine, stearamidoethyldiethylamine,
stearamidoethyldimethylamine, palmitamidopropyldimethylamine,
3o palmitamidopropyldiethylamine, palmitamidoethyldiethylamine,
palmitamidoethyldimethylamine, behenamidopropyldimethylamine,
behenamidopropyldiethylamine, behenamidoethyldiethylamine,
behenamidoethyldimethylamine, arachidamidopropyldimethylamine,
arachidamidopropyldiethylamine, arachidamidoethyldiethylamine,
35 arachidamidoethyldimethylamine, diethylaminoethylstearamide. Also useful
are
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18
dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine,
ethylstearylamine, N-tallowpropane diamine, ethoxylated (with 5 moles of
ethylene oxide) stearylamine, dihydroxyethylstearylamine, and
arachidylbehenylamine. These amines are typically used in combination with an
s acid to provide the cationic species. The preferred acid useful herein
includes L
glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid,
acetic acid,
fumaric acid, tartaric acid, citric acid, L-glutamic hydrochloride, and
mixtures
thereof; more preferably L-glutamic acid, lactic acid, citric acid. Cationic
amine
surfactants included among those useful in the present invention are disclosed
in
~o U.S. Patent 4,275,055 to Nachtigal, et al., issued June 23, 1981.
The molar ratio of protonatable amines to H+ from the acid is preferably
from about 1:0.3 to 1:1.2, and more preferably from about 1:0.5 to about
1:1.1.
b. Solid Fatty Compound
~5 The solid fatty compound useful herein has a melting point of 25°C
or
higher, and is selected from the group consisting of fatty alcohols, fatty
acids,
and mixtures thereof. It is understood by the artisan that the compounds
disclosed in this section of the specification can in some instances fall into
more
than one classification, e.g., some fatty alcohol derivatives may also be
classified
2o 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
25 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 Edition, 1993, and CTFA Cosmetic Ingredient Handbook,
Second Edition, 1992.
so The solid fatty compound is included in the composition at a level by
weight of from about 0.1 % to about 20%, preferably from about 1 % to about
15%, more preferably from about 2% to about 10%.
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
35 fatty alcohols are saturated and can be straight or branched chain
alcohols.
Nonlimiting examples of fatty alcohols include, cetyl alcohol, stearyl
alcohol,
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19
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
s 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.
Solid 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 may
15 provide good rinsability from the hair when the consumer rinses off the
composition.
Commercially available solid 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
2o NOF (Tokyo, Japan); pure behenyl alcohol having tradename 1-DOCOSANOL
available from Wako Chemical (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).
25 While poly fatty alcohols may form the gel matrix, mono fatty alcohols are
preferred. Either the cationic surfactant, and/or the solid fatty compound may
be
first mixed with, suspended in, and/or dissolved in water when forming a gel
matrix.
30 2. Oil
In addition to the ester oil described above, an oil, having a melting point
of less than about 25 °C, may also be useful herein. These oils may
provide
conditioning benefits such as softness and flexibility to the hair.
Nonlimiting
examples of the oils useful herein are found in International Cosmetic
Ingredient
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Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook,
Second Edition, 1992.
In a preferred embodiment containing an alkyl alkoxylate (described
below), an oil is also present. It has now been found that when present, an
alkyl
s alkoxylates may undesirably migrate to the aqueous phase, suffer from
stability
issues, and/or possess inadequate deposition efficiency when included by
themselves in an aqueous carrier. Without intending to be limited by theory,
it is
believed that these stability problems arise from solubility differences
between
the typical production temperature and the typical storage temperature,
chemical
1o degradation of the oil-miscible agent, etc. In certain cases, it is
believed that a
phase change in-and-of-itself may affect stability and/or deposition
efficiency.
For example, the alkyl alkoxylates described herein may be more water-soluble
at lower temperatures (e.g., storage temperatures), than at higher
temperatures
(e.g., production temperatures). If such an alkyl alkoxylate enters the
aqueous
~s phase from the oil-phase, its deposition efficiency onto hair may be
significantly
reduced. In such a case, even though it is not degraded or otherwise
chemically
altered, the alkyl alkoxylate may not efficiently deposit on the hair, because
it is
too easily washed away during use. Such a low deposition efficiency is
undesirable.
2o Thus, it has now been found that stability and deposition efficiency of
certain alkyl alkoxylates may decrease as they migrate from one phase to the
other over time (e.g., during storage, transport, etc.). Thus, such a phase
change may result in a significant decrease in the overall performance of the
composition. It is therefore desirable to minimize such undesirable phase
2s changes. Accordingly, in a preferred embodiment, the suitable carrier
comprises
an oil having an HLB value of from about 0 to about 3, preferably from about 0
to
about 2, and more preferably from about 0 to about 1. Without intending to be
limited by theory, it is believed that such oils tend to have an affinity for
hair, and
thus easily deposit thereupon. As noted, the preferred alkyl alkoxylate is
miscible
3o in oil. Thus, when mixed with this alkyl alkoxylate prior to its addition
to the
suitable carrier, the oil may entrap the alkyl alkoxylate therein.
Furthermore, the
low HLB value of these oils provides a highly hydrophobic environment which
reduces the likelihood that the alkyl alkoxylate will undergo a phase change
during storage. This in turn enhances the alkyl alkoxylate's stability during
35 storage, and prevents it from easily washing away during, for example,
rinsing of
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21
the hair. Thus, such an oil is especially preferred in a rinse-off hair
conditioning
composition, or a hair shampoo composition. In addition to entrapping the
alkyl
alkoxylate therein, these oils may also act as a carrier which itself further
enhances actual deposition. Additionally, the oil may itself provide desirable
s benefits, such as improved combability, dry-hair feel, shininess, softness,
smoothness, and/or slipperiness.
The oil useful herein is typically a liquid at room temperature, and
therefore has a melting point below about 25 °C. Preferred examples of
the oil
useful herein include liquid fatty alcohols and their derivatives, fatty acids
and
~o their derivatives, hydrocarbons, silicone compounds, and mixtures thereof
which
possess an HLB value of from about 0 to about 3, preferably from about 0 to
about 2, and more preferably from about 0 to about 1. More preferred examples
of the oil useful herein include fatty acid esters, liquid fatty alcohols,
hydrocarbons, and mixtures thereof which possess the above HLB value. Even
~5 more preferred examples of the oil useful herein include liquid fatty
alcohols such
as oleyl alcohol, isostearyl alcohol, isocetyl alcohol and mixtures thereof
which
fall within the above HLB range.
Unless otherwise specifically noted, the oil may be included at a level of
from about 0.1 % to about 20%, preferably from about 0.5% to about 10%, more
2o preferably from about 1 % to about 5% by weight of the hair care
composition.
a. Liquid Fatty Alcohol and Fattv Acid
The liquid fatty alcohols useful herein include those having from about 10
to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms,
2s and more preferably from about 16 to about 22 carbon atoms. These liquid
fatty
alcohols maybe straight or branched chain alcohols and may be saturated or
unsaturated alcohols, preferably unsaturated alcohols. Solid fatty compounds
are those fatty alcohols which, when in their substantially pure forms, are
solid at
25 °C, while liquid fatty alcohols are those fatty alcohols which are
liquid at 25
so °C. Nonlimiting examples of these compounds include oleyl alcohol,
palmitoleic
alcohol, isostearyl alcohol, isocetyl alcohol and mixtures thereof. While poly
fatty
alcohols are useful herein, mono fatty alcohols are preferred.
The fatty acids useful herein include those having from about 10 to about
30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more
35 preferably from about 16 to about 22 carbon atoms. These fatty acids can be
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22
straight or branched chain acids and can be saturated or unsaturated. Suitable
fatty acids include, for example, oleic acid, linoleic acid, isostearic acid,
linolenic
acid, ethyl linolenic acid, ethyl linolenic acid, arachidonic acid, and
ricinolic acid.
The fatty acid derivatives and fatty alcohol derivatives are defined herein
to include, for example, esters of fatty acids, alkoxylated fatty alcohols,
alkyl
ethers of fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, and
mixtures
thereof. Nonlimiting examples of fatty acid derivatives and fatty alcohol
derivatives, include, for example, methyl linoleate, ethyl linoleate,
isopropyl
linoleate, isodecyl oleate, isopropyl oleate, ethyl oleate, octyldodecyl
oleate, oleyl
~o oleate, decyl oleate, butyl oleate, methyl oleate, octyldodecyl stearate,
octyldodecyl isostearate, octyldodecyl isopalmitate, octyl isopelargonate,
octyl
pelargonate, hexyl isostearate, isopropyl isostearate, isodecyl isononanoate,
isopropyl isostearate, ethyl isostearate, methyl isostearate and oleth-2.
Commercially available liquid fatty alcohols and their derivatives useful
~5 herein include: oleyl alcohol with tradename UNJECOL 90BHR available from
Shin-nihon Rika, various liquid esters with tradenames SCHERCEMOL series
available from Scher, and hexyl isostearate with a tradename HIS and isopropyl
isostearate having a tradename ZPIS available from Kokyu Alcohol.
2o b. Hydrocarbon
The hydrocarbons useful herein include straight chain, cyclic, and
branched chain hydrocarbons which can be either saturated or unsaturated, so
long as they have a melting point of not more than about 25 °C. These
hydrocarbons have from about 12 to about 40 carbon atoms, preferably from
25 about 12 to about 30 carbon atoms, and preferably from about 12 to about 22
carbon atoms. Also encompassed herein are polymeric hydrocarbons of alkenyl
monomers, such as polymers of C2~ alkenyl monomers. These polymers can be
straight or branched chain polymers. The straight chain polymers will
typically
be relatively short in length, having a total number of carbon atoms as
described
3o above. The branched chain polymers can have substantially higher chain
lengths. The number average molecular weight of such materials can vary
widely, but will typically be up to about 500 g/mol, preferably from about 200
g/mol to about 400 g/mol, and more preferably from about 300 g/mol to about
350 g/mol. Also useful herein are the various grades of mineral oils. Mineral
35 oils are liquid mixtures of hydrocarbons that are obtained from petroleum.
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23
Specific examples of suitable hydrocarbon materials include paraffin oil,
mineral
oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene,
isoeicosene, tridecane, tetradecane, polybutene, polyisobutene, and mixtures
thereof. Preferred for use herein are hydrocarbons selected from the group
consisting of mineral oil, poly a-olefin oils such as isododecane,
isohexadecane,
polybutene, polyisobutene, and mixtures thereof.
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 cps, a weight
average molecular weight of from about 200 g/mol to about 60,000 g/mol, and a
polydispersity of no more than about 3.
Poly a-olefin oils having a weight average molecular weight of at least
about 800 g/mol are useful herein, to provide long lasting moisturized feel to
the
2o hair. However, poly a-olefin oils having a weight average molecular weight
of
less than about 800 g/mol are also useful herein, to provide a smooth, light,
clean feel to the hair. Particularly useful poly a-olefin oils herein include
polydecenes with tradename PURESYN 6 having a weight average molecular
weight of about 500 and PURESYN 100 having a weight average molecular
weight of over 3000 g/mol available from Mobil Chemical Co.
Commercially available hydrocarbons useful herein include isododecane,
isohexadecane, and isoeicosene with tradenames PERMETHYL 99A,
PERMETHYL 101A, and PERMETHYL 1082, available from Presperse (South
Plainfield New Jersey, USA), a copolymer of isobutene and normal butene with
so tradenames INDOPOL H-100 available from Amoco Chemicals (Chicago Illinois,
USA), mineral oil with tradename BENOL available from Witco Chemicals,
isoparaffin with tradename ISOPAR from Exxon Chemical Co. (Houston Texas,
USA), and polydecene with tradename PURESYN 6 from Mobil Chemical Co.
The suitable carrier may also include therein solutions of lower alkyl
s5 alcohols and polyhydric alcohols. Lower alkyl alcohols useful herein are
CA 02382391 2002-02-18
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24
monohydric alcohols having 1 to 6 carbons, more preferably ethanol and
isopropanol. The preferred polyhydric alcohols useful herein include propylene
glycol, hexylene glycol, glycerin, and propane diol.
ALKYL ALKOXYLATE
The hair care composition preferably includes an alkyl alkoxylate therein.
The alkyl alkoxylates useful herein may provide, for example, softening,
conditioning, total hair volume reduction, flyaway hair volume reduction, bulk
hair
volume reduction, and/or other benefits. The alkyl alkoxylate useful herein
has
the formula: R3-O-(R2-O)~H,
wherein each R2 is independently a C2 C4 alkyl group, preferably each R2
is independently selected from the group consisting of a saturated CZH4
group, and a saturated C3H6 group, and more preferably each R2 is
independently selected from the group consisting of a saturated and linear
C2H4 group, and a saturated and linear C3H6 group; wherein R3 is an alkyl
group having from about 1 to about 30 carbon atoms, preferably from
about 6 to about 22 carbon atoms, and more preferably from about 8 to
about 18 carbon atoms; R3 may be branched or linear, and saturated or
unsaturated, but is preferably linear and saturated, or unsaturated having
2o about one double bond;
n is a value from about 1 to about 10, preferably from about 2 to about 8,
and more preferably from about 3 to about 6;
the weight average molecular weight of the alkyl alkoxylate is less than
about 500 g/mol, preferably from about 100 to about 500 g/mol, and more
preferably from about 200 to about 500 g/mol; and
the HLB value of the alkyl alkoxylate is from about 5 to about 12,
preferably from about 6 to about 11, and more preferably from about 6 to
about 10.
As may be seen from the HLB values, such alkyl alkoxylates are miscible
3o in both oil and water. Furthermore, such alkyl alkoxylates typically have a
melting point of less than about 30 °C, preferably less than about 25
°C, and
more preferably less than about 20 °C, and have a cloud point (1 %
solution) of
less than about 50 °C, preferably less than about 40 °C, and
more preferably
less than about 35 °C.
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Without intending to be limited by theory, it is believed that the alkyl
alkoxylates useful herein provide a bulk hair volume reduction benefit by the
following mechanism: The hydrophobic alkyl chains attach to hair fibers, even
under rinse-off conditions, while the hydrophilic alkoxylate groups attract
water
5 molecules and bring them to the hair fibers. This moisturizes the hair
fiber, and
helps maintain it in a flexible, soft, and plastic state. This in turn, allows
the hair
fiber to maintain a well-aligned conformation (with respect to other hair
fibers)
and to easily recovery from deformation. This further increases the likelihood
that the hair fibers will remain parallel, and/or hang straight down. This
significantly reduces the space between the individual hair fibers, and
therefore
reduces bulk hair volume.
Without intending to be limited by theory, it is also believed that the alkyl
alkoxylate may reduce flyaway hair volume as well. By moisturizing the hair
fiber, the alkyl alkoxylate may also reduce the hair fiber's static charge and
crookedness. This in turn, reduces the electrostatic repulsion and space
between hair fibers, which leads to a reduction in flyaway volume.
From a cost, availability, and performance standpoint, alkyl ethoxylates
are especially preferred alkyl alkoxylates useful herein, and include, for
example,
by CTFA name: oleth-5, oleth-3, steareth-5, steareth-4, ceteareth-5, ceteareth-
4,
2o and ceteareth-3, as well as mixtures of C9_"E05, mixtures of C9_"E02.5,
mixtures of C,2_,3E03, mixtures of C"_,3E05, and mixtures thereof. These alkyl
ethoxylates are available from, for example, Croda, Inc., of Parsippany, New
Jersey, U.S.A., Shell Chemical of U.S.A., BASF of Germany, Mitsubishi Chemical
of Tokyo, Japan, and Nikko Chemical of Tokyo, Japan. Such alkyl ethoxylates
25 are especially preferred for use in rinse-off hair conditioning
compositions.
If present, the alkyl alkoxylate is provided in the hair care composition at a
level of from about 0.1 % to about 20%, preferably from about 0.2% to about
15%, and more preferably from about 0.5% to about 10%, by weight of the hair
care composition. If the hair care composition is a rinse-off hair
conditioning
so composition, then the alkyl alkoxylate is preferably present at a level of
at least
about 1 %, more preferably from about 2% to about 20%, and even more
preferably from about 3% to about 10%, by weight of the rinse-off hair
conditioning composition.
If the hair care composition is intended for use as a rinse-off hair
conditioning composition, it is highly preferred that the alkyl alkoxylate
have a
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26
cloud point of less than about 40 °C. Without intending to be limited
by theory, it
is believed that this significantly improves the deposition efficiency of the
alkyl
atkoxylate onto hair.
OTHER ADDITIONAL COMPONENTS
Certain other additional components are preferred in the present
invention. These include, compounds which may provide, for example, an
additional hair care, and/or hair conditioning benefit when included herein.
Preferred other additional components include a silicone compound, a
1o hydrophobically modified cellulose ether, a cationic conditioning compound,
an
anti-microbial agent, an herbal extract, and mixtures thereof. Unless
otherwise
noted, such other additional components generally are typically used
individually
at levels from about 0.001 % to about 10.0%, preferably from about 0.01 % to
about 5.0% by weight of the composition.
1. Silicone Compound
The compositions of the present invention preferably contain a silicone
compound. The silicone compounds useful herein include volatile soluble or
insoluble, or nonvolatile soluble or insoluble silicone conditioning agents.
By
2o 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. 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 any suitable method known in
the art, including emulsion polymerization. The silicone compounds may further
be incorporated in the present composition in the form of an emulsion, wherein
the emulsion is made my mechanical mixing, or in the stage of synthesis
through
emulsion polymerization, with or without the aid of a surfactant selected from
anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures
3o thereof.
The silicone compounds for use herein will preferably have a viscosity of
from about 1,000 to about 2,000,000 centistokes at 25 °C, more
preferably from
about 10,000 to about 1,800,000, and even more preferably from about 100,000
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
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27
CTM0004, July 20, 1970. Silicone compounds of high molecular weight may be
made by emulsion polymerization. Suitable silicone fluids include polyalkyl
siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane
copolymers, and mixtures thereof. Other nonvolatile silicone compounds having
s hair conditioning properties can also be used.
The silicone compound is preferably included in the composition at a level
by weight from about 0.01 % to about 20%, more preferably from about 0.05% to
about 10%.
The silicone compounds herein also include polyalkyl or polyaryl siloxanes
~o with the following structure (I)
8123 8123 8123
Z$ Si-O~SI-O~SI-Z$
8123 L 8123 J p R 123
wherein R'23 is alkyl or aryl, and x is an integer from about 7 to about
8,000. Z$
represents groups which block the ends of the silicone chains. The alkyl or
aryl
groups substituted on the siloxane chain (R'23) or at the ends of the siloxane
chains Z8 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 Z8 groups
2o include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two
R'23
groups on the silicon atom may represent the same group or different groups.
Preferably, the two R'23 groups represent the same group. Suitable R'23 groups
include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The
preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane,
and
2~ 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 Viscasil~
and
SF 96 series, and from Dow Corning in their Dow Corning 200 series.
3o Polyalkylaryl siloxane fluids can also be used and include, for example,
polymethylphenylsiloxanes. These siloxanes are available, for example, from
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28
the General Electric Company as SF 1075 methyl phenyl fluid or from Dow
Corning as 556 Cosmetic Grade Fluid.
Especially 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.
The silicone compounds that can be used include, for example, a
polypropylene oxide modified polydimethylsiloxane although ethylene oxide or
mixtures of ethylene oxide and propylene oxide can also be used. The ethylene
oxide and polypropylene oxide level should be sufficiently low so as not to
interfere with the dispensability characteristics of the silicone. These
material
~5 are also known as dimethicone copolyols.
Other silicone compounds include amino substituted materials. Suitable
alkylamino substituted silicone compounds include those represented by the
following structure (II)
CH R~24
I 3 I
HO~Si-O~Si-O~H
L C H3 ~ p' I p2
( C H2 ~q'
NH
(CH2~q2
NH2
2o wherein R'24 is H, CH3 or OH, p', p2, q' and q2 are integers which depend
on the
molecular weight, the weight average molecular weight being approximately
between 5,000 and 10,000. This polymer is also known as "amodimethicone".
Suitable amino substituted silicone fluids include those represented by the
formula (III)
25 (R'25)aG3_a Si-(pSiG2)ps (OSIGb(R125)Z_b)~ ~-SIG3_a(R'25)a (III)
in which G is chosen from the group consisting of hydrogen, phenyl, OH, C,-C$
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 p3+p4 is a number
from 1 to 2,000 and preferably from 50 to 150, p3 being able to denote a
number
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29
from 0 to 1,999 and preferably from 49 to 149 and p4 being able to denote an
integer from 1 to 2,000 and preferably from 1 to 10; R'25 is a monovalent
radical
of formula Cq3H2q3L in which q3 is an integer from 2 to 8 and L is chosen from
the
groups
-N(R,zs)CH2 CH2 N(R'26)z
-N(R,ZS)
z
-N(R,2s)3X~
-N(R'zs)CH2 CH2 NR'ZSH2X'
in which R'26 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 X' denotes a halide ion.
An especially preferred amino substituted silicone corresponding to
formula (III) is the polymer known as "trimethylsilylamodimethicone" wherein
R'24
is CH3.
Other amino substituted silicone polymers useful herein include cationic
amino substituted silicones represented by the formula (V):
R~2s
~Zs
R-C H2-C HOH-C H2-N~ R 2sQ
R~2s
R~2s R~2s R~2s
R 2$ S i-O~S i-O~S i-O~S i-R12s
R~2s R~2s p R~2s p R~2s
(v)
where R'28 denotes a monovalent hydrocarbon radical having from 1 to 18
carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R'29
denotes
2o a hydrocarbon radical, preferably a C,-C,$ alkylene radical or a C,-C,B,
and more
preferably C,-C8, alkyleneoxy radical; Q- is a halide ion, preferably
chloride; p5
denotes an average statistical value from 2 to 20, preferably from 2 to 8; ps
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."
References disclosing suitable nonvolatile dispersed silicone compounds
include U.S. Patent No. 2,826,551 to Geen; U.S. Patent No. 3,964,500 to
Drakoff, issued June 22, 1976; U.S. Patent No. 4,364,837 to Pader, issued
December 21, 1982; and British Patent No. 849,433 to Woolston. "Silicon
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Compounds" distributed by Petrarch Systems, Inc., 1984, provides an extensive,
though not exclusive, listing of suitable silicone compounds.
Another nonvolatile dispersed silicone that can be especially useful is a
silicone gum. The term "silicone gum", as used herein, means a
5 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.
~o 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 General Electric Silicone Rubber Product Data
Sheets SE 30, SE 33, SE 54 and SE 76. The "silicone gums" will typically have
a weight average molecular weight in excess of about 200,000, generally
15 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.
Also useful are silicone resins, which are highly crosslinked polymeric
2o siloxane systems. 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
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
25 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
3o have at least about 1.1 oxygen atoms per silicon atom will generally be
silicone
resins herein. Preferably, the ratio of oxygenailicon 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
s5 silanes being most commonly utilized. Preferred resins are offered by
General
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31
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
s 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
~o material given the CTFA designation polymethylsilsequioxane, which is
commercially available as TospearlT"" from Toshiba Silicones.
The method of manufacturing these silicone compounds, can be found in
Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition,
pp. 204-308, John Wiley & Sons, Inc., 1989.
15 Silicone materials and silicone resins in particular may 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
20 (CH3)3SIOo.S; D denotes the difunctional unit (CH3)2Si0; T denotes the
trifunctional unit (CH3)Si0,.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.
2s The molar ratios of the various units, either in terms of subscripts to the
symbols
indicating the total number of each type of unit in the silicone, or an
average
thereof, or as specifically indicated ratios in combination with the weight
average
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
so 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.
35 Especially preferred are MQ resins wherein the M:Q ratio is from about
0.5:1.0 to
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32
about 1.5:1.0 and the weight average molecular weight of the resin is from
about
1000 to about 10,000.
Commercially available silicone compounds which are useful herein
include Dimethicone with tradename D-130, cetyl Dimethicone with tradename
s DC2502, stearyl Dimethicone with tradename DC2503, emulsified polydimethyl
siloxanes with tradenames DC1664 and DC1784, and alkyl grafted copolymer
silicone emulsion with tradename DC2-2845; all available from Dow Corning
Corporation, and emulsion polymerized Dimethiconol available from Toshiba
Silicone as described in GB application 2,303,857.
2. Hydrophobically Modified Cellulose Ether
It is preferred that the hair care composition contain therein from about
0.01 % to about 2%, preferably from about 0.01 % to about 1 %, and more
preferably from about 0.1 % to about 0.5%, of a hydrophobically modified
1s cellulose ether.
The hydrophobically modified cellulose ethers may provide an increase in
bulk hair volume. When combined with the polypropylene glycol and ester oil of
the present invention, the hydrophobically modified cellulose ethers may
provide
a balance between decreased flyaway hair, and increased bulk hair. The
2o 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. The
hydrophilic
cellulose backbone has a weight average molecular weight of about less than
800,000 g/mol, preferably from about 20,000 g/mol to about 700,000 g/mol, and
25 more preferably form about 50,000 g/mol to about 700,000 g/mol.
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
so 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
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33
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
s PLUS 330CS and POLYSURF 67, both available from Aqualon Company,
Delaware, USA, having a cetyl group substitution of about 0.4% to about 0.65%
by weight of the entire polymer.
3. Cationic Conditionina Compound
A cationic hair conditioning compound is preferred herein, and includes
the cationic surfactants described above, cationic polymers, the cationic
amino
substituted silicones described above, and mixtures thereof. If present, the
cationic hair conditioning compound is typically at a level of preferably from
about
0.5% to about 5%, more preferably from about 1 % to about 3% by weight of the
15 composition.
The hair care compositions of the present invention may comprise one or
more cationic polymers. As used herein, the term "polymer" includes materials
whether made by polymerization of one type of monomer or made by two (i.e.,
copolymers) or more types of monomers. Preferably, the cationic polymer is a
2o water-soluble cationic polymer. As used herein, the term "water-soluble"
cationic polymer, indicates a polymer which is sufficiently soluble in water
to form
a substantially clear solution to the naked eye at a concentration of 0.1 % in
water
(distilled or equivalent) at 25 °C. The preferred cationic polymer will
be
sufficiently soluble to form a substantially clear solution at 0.5%
concentration,
2s more preferably at 1.0% concentration.
The cationic polymers herein will generally have a weight average
molecular weight which is at least about 5,000, preferably from about 10,000
to
about 10 million, more preferably, from about 100,000 to about 2 million. The
cationic polymer will generally have cationic nitrogen-containing moieties
such as
so quaternary ammonium or cationic amino moieties, and mixtures thereof.
The cationic nitrogen-containing moiety will be present generally as a
substituent, on a fraction of the total monomer units of the cationic hair
conditioning polymers. Thus, the cationic polymer may comprise copolymers,
terpolymers, etc. of quaternary ammonium or cationic amine-substituted
3s monomer units and other non-cationic units referred to herein as spacer
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34
monomer units. Such polymers are known in the art, and a variety may be found
in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin,
Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,
Washington, D.C., 1982).
The cationic charge density of the cationic polymer is preferably at least
about 0.1 meq/gram, more preferably at least about 0.5 meq/gram, even more
preferably at least about 1.1 meq/gram, and still more preferably at least
about
1.2 meq/gram. Cationic charge density of the cationic polymer may be
determined according to the Kjeldahl Method. Those skilled in the art will
recognize that the charge density of amino-containing polymers may vary
depending upon pH and the isoelectric point of the amino groups. The charge
density should be within the above limits at the pH of intended use.
Any anionic counterion may be utilized for the cationic polymers so long
as the water solubility criteria is met. Suitable counterions include, for
example,
halides (e.g., CI, Br, I, or F, preferably CI, Br, or I), sulfate, and
methylsulfate.
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, alkyl
2o methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The cationic
amines may
be primary, secondary, or tertiary amines, depending upon the particular
species
and the pH of the composition. In general, secondary and tertiary amines,
especially tertiary amines, are preferred. The alkyl and dialkyl substituted
monomers preferably have C1 - C7 alkyl groups, more preferably C1 - C3 alkyl
2s groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol
(made by hydrolysis of polyvinyl acetate), malefic anhydride, propylene
glycol,
and ethylene glycol.
Amine-substituted vinyl monomers may be polymerized in the amine
form, and then optionally may be converted to ammonium by a quaternization
3o reaction. Amines may also be similarly quaternized subsequent to formation
of
the polymer. For example, tertiary amine functionalities may be quaternized by
reaction with a salt of the formula R'X wherein R' is a short chain alkyl,
preferably
a C1 - C7 alkyl, more preferably a C1 - C3 alkyl, and X- is an anion which
forms a
water-soluble salt with the quaternized ammonium.
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Suitable cationic amino and quaternary ammonium monomers include, for
example, vinyl compounds substituted with dialkylaminoalkyl acrylate,
dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,
monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt,
s trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and
vinyl
quaternary ammonium monomers having cyclic cationic nitrogen-containing rings
such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl
vinyl
imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl
portions
of these monomers are preferably lower alkyls such as the C1 - C3 alkyls, more
preferably C1 and C2 alkyls. Suitable amine-substituted vinyl monomers for use
herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,
dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein
the
alkyl groups are preferably C1 - C7 hydrocarbyls, more preferably C1 - C3,
alkyls.
15 The cationic polymers useful herein may comprise mixtures of monomer
units derived from amine- and/or quaternary ammonium-substituted monomer
and/or compatible spacer monomers.
Suitable cationic hair conditioning polymers include, for example:
copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt
(e.g.,
2o chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and
Fragrance
Association, "CTFA", as Polyquaternium-16), such as those commercially
available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the
LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-
pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry
by
25 CTFA as Polyquaternium-11 ) such as those commercially available from Gaf
Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT
755N); cationic diallyl quaternary ammonium-containing polymers, including,
for
example, dimethyldiallylammonium chloride homopolymer and copolymers of
acrylamide and dimethyldiallylammonium chloride, referred to in the industry
30 (CTFA) as Polyquaterniurfi 6 and Polyquaternium 7, respectively; and
mineral
acid salts of amino-alkyl esters of homo- and co-polymers of unsaturated
carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent
4,009,256 issued to Nowack, et. al., on February 22, 1977.
Other useful cationic polymers include cationic polysaccharide polymers,
ss such as cationic cellulose derivatives and cationic starch derivatives.
Cationic
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36
polysaccharide polymer materials suitable for use herein include those of the
formula:
~
A -O-R- + R x
C J
I2
R
wherein: A is an anhydroglucose residual group, such as a starch or cellulose
s anhydroglucose residual, R is an alkylene oxyalkylene, polyoxyalkylene, or
hydroxyalkylene group, or combination thereof, R1, R2, and R3 independently
are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each
group
containing up to about 18 carbon atoms, and the total number of carbon atoms
for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3)
1o preferably being about 20 or less, and X- is an anionic counterion, as
previously
described.
Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in
their Polymer JR~ and LR~ series of polymers, as salts of hydroxyethyl
cellulose
reacted with trimethyl ammonium substituted epoxide, referred to in the
industry
15 (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes
the
polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with
lauryl dimethyl ammonium-substituted epoxide, referred to in the industry
(CTFA)
as Polyquaternium 24. These materials are available from Amerchol Corp.
(Edison, NJ, USA) under the tradename Polymer LM-200~.
2o Other cationic polymers that may be used include cationic guar gum
derivatives, such as guar hydroxypropyltrimonium chloride (commercially
available from Celanese Corp. in their Jaguar R series). Other materials
include
quaternary nitrogen-containing cellulose ethers (e.g., as described in U.S.
Patent
3,962,418, incorporated herein by reference), and copolymers of etherified
25 cellulose and starch (e.g., as described in U.S. Patent 3,958,581,
incorporated
herein by reference.)
4. Anti-Microbial A_qent
Anti-microbial agents useful as encompassed material include those
3o useful as cosmetic biocides and antidandruff agents including: water-
soluble
components such as piroctone olamine, water insoluble components such as
3,4,4'- trichlorocarbanilide (trichlosan), triclocarban and zinc pyrithione.
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37
5. Herbal Extract
The compositions of the present invention may contain herbal extracts,
including both water-soluble and water-insoluble herbal extracts. Useful
herbal
extracts herein include: Polygonatum multiflori extract, Houttuynia cordate
s extract, Phellodendron Bark extract, melilot extract, white dead nettle
extract,
licorice root extract, herbaceous peony extract, soapwort extract, dishcloth
gourd
extract, cinchona extract, creeping saxifrage extract, Sophora angustifolia
extract, candock extract, common fennel extract, primrose extract, rose
extract,
Rehmannia glutinosa extract, lemon extract, shikon extract, alloe extract,
iris bulb
extract, eucalyptus extract, field horsetail extract, sage extract, thyme
extract, tea
extract, layer extract, cucumber extract, clove extract, raspberry extract,
melissa
extract, ginseng extract, carrot extract, horse chestnut extract, peach
extract,
peach leaf extract, mulberry extract, cornflower extract, hamamelis extract,
placenta extract, thymus extract, silk extract, algae extract, althea extract,
~s angelica dahurica extract, apple extract, apricot kernel extract, arnica
extract,
Artemisia capillaris extract, astragal extract, balm mint extract, perilla
extract,
birch bark extract, bitter orange peel extract, Theasinensis extract, burdock
root
extract, burnet extract, butcherbroom extract, Stephania cepharantha extract,
matricaria extract, chrysanthemum flower extract, citrus unshiu peel extract,
2o cnidium extract, coix seed extract, coltsfoot extract, comfrey leaf
extract,
crataegus extract, evening primrose oil, gambir extract, ganoderma extract,
gardenia extract, gentian extract, geranium extract, ginkgo extract, grape
leaf
extract, crataegus extract, henna extract, honeysuckle extract, honeysuckle
flower extract, hoelen extract, hops extract, horsetail extract, hydrangea
extract,
2s hypericum extract, isodonis extract, ivy extract, Japanese angelica
extract,
Japanese coptis extract, juniper extract, jujube extract, lady's mantle
extract,
lavender extract, lettuce extract, licorice extract, linden extract,
lithospermum
extract, loquat extract, luffa extract, malloti extract, mallow extract,
calendula
extract, moutan bark extract, mistletoe extract, mukurossi extract, mugwort
so extract, mulberry root extract, nettle extract, nutmeg extract, orange
extract,
parsley extract, hydrolyzed conchiorin protein, peony root extract, peppermint
extract, philodendron extract, pine cone extract, platycodon extract,
polygonatum
extract, rehmannia extract, rice bran extract, rhubarb extract, rose fruit
extract,
rosemary extract, royal jelly extract, safflower extract, saffron crocus
extract,
35 sambucus extract, saponaria extract, Sasa albo marginata extract, Saxifraga
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38
stolonifera extract, scutellaria root extract, Cortinellus shiitake extract,
lithospermum extract, sophora extract, laurel extract, calamus root extract,
swertia extract, thyme extract, linden extract, tomato extract, turmeric
extract,
uncaria extract, watercress extract, logwood extract, grape extract, white
lily
extract, rose hips extract, wild thyme extract, witch hazel extract, yarrow
extract,
yeast extract, yucca extract, zanthoxylum extract, and mixtures thereof.
Commercially available herbal extracts useful herein include Polygonatum
multiflori extracts which are water-soluble, and available from Institute of
Occupational Medicine, CAPM, China National Light Industry, and Maruzen, and
~o other herbal extracts listed above available from Maruzen.
The hair care compositions herein may further contain 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
compositions more cosmetically or aesthetically acceptable or to provide them
with additional usage benefits.
Additional examples of preferred other additional components which may
be formulated into the present compositions include: other conditioning agents
such as hydrolysed collagen with tradename Peptein 2000 available from
Hormel, panthenol available from Roche, panthenyl ethyl ether available from
2o Roche, hydrolysed keratin, proteins, plant extracts, and nutrients;
vitamins and/or
amino acids, such as vitamin E with tradename Emix-d available from Eisai;
surfactants such as a cationic surfactant, a nonionic surfactant, an anionic
surfactant, an amphoteric surfactant, and mixtures thereof; hair-fixative
polymers
such as amphoteric fixative polymers, cationic fixative polymers, anionic
fixative
2s 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
3o 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; sequestering agents, such as disodium
ethylenediamine tetra-acetate; ultraviolet and infrared screening and
absorbing
agents, such as optical brighteners and octyl salicylate; and antidandruff
agents,
3s such as zinc pyridinethione.
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39
MANUFACTURING PROCESS
The hair care compositions of the present invention may be formed by
processes known in the art. Typically, the polypropylene glycol, the ester
oil, and
s the gel matrix are combined in a large-scale batch or continuous mixing
apparatus, heated, mixed together and/or homogenized, and then cooled to
room temperature for packaging and storage. Alternatively, the pentaerythritol
ester oil and/or the trimethylol ester oil may be combined with the suitable
carrier
via any suitable mixing apparatus.
To form a highly preferred lamellar gel matrix, water is typically heated to
at least about 70 °C, preferably between about 80 °C and about
90 °C. The
cationic surfactant and the solid fatty compound are combined with the water
to
form a mixture. The temperature of the mixture is preferably maintained at a
temperature higher than both the melting temperature of the cationic
surfactant
~s and the melting temperature of the solid fatty compound, and the entire
mixture is
homogenized. After mixing until no solids are observed, the mixture is
gradually
cooled (e.g., at a rate of about 2 °C/minute) to a temperature below 60
°C,
preferably less than about 55 °C. During this gradual cooling process,
a
significant viscosity increase is observed at between about 55 °C and
about 75
20 °C. This indicates the formation of a lamellar gel matrix. After the
formation of
this gel matrix, the polypropylene glycol is added. This is then cooled to
room
temperature, to form the finished hair care composition. This results in a
hair
care composition containing the alkyl ethoxylate which possesses significantly
improved stability and excellent performance.
2s Alternatively, a polypropylene glycol, an ester oil, and an alkyl
alkoxylate
(if present) are first combined to form a premix, and then added and mixed
into
the already-formed gel matrix. Typically, the weight ratio of the premix to
the gel
matrix is from about 1:1 to about 1:99, preferably from about 1:2 to about
1:80,
and more preferably from about 1:5 to about 1:50. Without intending to be
30 limited by theory, it is believed that by adding the premix at a lower
temperature
which is closer to the storage temperature of the final hair care composition,
phase changes during storage are minimized, viscosity is maintained, and
greater stability is achieved.
35 METHOD OF USE
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The hair care composition of the present invention is suitable for use as,
for example, hair cosmetic compositions, hair styling compositions, and hair
conditioning compositions, preferably as a leave-on and/or rinse-off hair
conditioning composition, and more preferably as a rinse-off hair conditioning
s composition. These hair care compositions are used in conventional ways to
provide the conditioning, styling, and/or other 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 (as in the case of hair rinses) or
allowed
to remain on the hair (as in the case of gels, lotions, and creams).
"Effective
amount" means an amount sufficient enough to provide the desired bulk hair
reduction benefit. In general, from about 1 g to about 50 g is applied to the
hair,
and/or the scalp. The hair care composition may be distributed throughout the
hair, typically by rubbing or massaging the hair and scalp, or the composition
1s may be selectively applied to certain parts of the hair. For a leave-on
form, the
hair care composition is preferably applied to wet or damp hair prior to
drying of
the hair. After such hair care compositions are applied to the hair, the hair
is
dried and styled in accordance with the preference of the user. In the
alternative,
such as for a hair styling composition, it may be applied to dry hair, and the
hair
2o is then combed or styled in accordance with the preference of the user.
IMAGE ANALYSIS PROTOCOL
The Image Analysis Protocol is a system and procedure which is designed
to digitally measure and analyze the components of bulk hair area and flyaway
25 hair area, which in turn form the total hair area. This protocol provides a
quantifiable, repeatable method for accurately distinguishing, measuring, and
comparing total hair area, flyaway hair area, and bulk hair area before and
after
treatment with a hair care composition. This total hair area, flyaway hair
area,
and bulk hair area directly correlate with total hair volume, flyaway hair
volume,
so and bulk hair volume, respectively. The hair care compositions of the
present
invention provide a significant, noticeable reduction in the bulk hair area,
preferably by at least about 10%, more preferably by at least about 15%, and
even more preferably by at least about 25%, as measured by the method
described, below.
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41
It has been found that a reduction in bulk hair area correlates with one or
more noticeable consumer-desirable benefits, such as enhanced manageability,
and/or improved combability. For example, it is believed that reduced bulk
hair
area correlates with moisturized hair which is softer, more plastic, smooth,
and
flexible than hair which is dried out. When hair is moisturized, the bulk hair
area
is reduced, because the hair is better aligned with other hairs and has less
space
in-between the individual hairs. Moisturized hair is also easier to comb and
manage.
Referring to the drawing, Fig. 1 shows a top view of a preferred
embodiment of the Image Analysis System useful herein. The Image Analysis
System, 10, consists of a white screen, 12, lighting equipment, 14, a sample
holder, 16, a high-resolution digital camera, 18, and a personal computer, 20.
The sample holder, 16, is placed between the white screen, 12, and the high-
resolution digital camera, 18. The sample holder, 16, is typically a clip or
clamp
~5 which stably suspends a hair sample, 22, about 40 cm in front of the white
screen, 12. The sample holder, 16, is typically about 80 cm from the high-
resolution digital camera, 18, and positioned above the high-resolution
camera's
field of view, so that it is not visible in the captured images.
The white screen, 12, is a matte-finish (e.g., non-glare) white-colored
2o screen which is illuminated to provide a constant and repeatable background
against which the hair sample, 22, is measured. As the difference between bulk
hair area and flyaway hair area is judged according to the brightness of the
image (see below), it is important that the hair sample be photographed in
front
of a background which has a constant brightness. As seen in Fig. 1, the
25 preferred lighting equipment, 14, consists of twin photography lights
located on
each side of the sample, and pointing towards the white screen. Each of these
lights is preferably a twin florescent tube light contained within a lighting
fixture,
and is typically from about 20 cm to about 60 cm to the side of the sample
holder,
16. This places them far enough away from the hair sample, 22, so that they
are
3o not visible by the high-resolution digital camera, 18. This assures that
the
captured image will only include the image of the hair sample, 22, and will
not
include, for example, the back-side of the lighting equipment, 14. Therefore,
the
lighting equipment, 14, should not interfere with or block the picture to be
taken.
Also, in such a configuration, the hair sample, 22, is not directly
illuminated by
35 the lighting equipment, 14. Instead, light is first reflected from the
white screen,
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42
12, and then passes through the hair sample, 22, in order to reach the high-
resolution digital camera, 18. The high-resolution digital camera, 18, is
focused
on the hair sample, 22, and not the white screen, 12. For ease of use, the
high-
resolution digital camera, 18, is connected to a personal computer, 20, and
s automatically transfers the captured image to the computer's imaging
software.
Such an arrangement provides a precise picture of the profile of the hair
sample,
22, and avoids any glare and/or shadows which could interfere with
measurement and analysis of the hair sample, 22.
Preferably, the Image Analysis System should be located away from air
currents or other forces which would disturb the hair sample, and is in a
controlled temperature and humidity environment, so as to ensure repeatable
results. The high-resolution digital camera (e.g., Model HC-2500 3-CCD from
Fujifilm Co., of Tokyo, Japan) has a resolution of at least 1280 horizontal
pixels,
and 1000 vertical pixels. The high-resolution digital camera is calibrated to
a
15 linear gain, so that the incremental difference between all brightness
values (an
8-bit, 0-255 brightness scale) is equal. Such a calibration may be achieved
via,
for example, utilizing a standard gray-scale calibration cell and/or the high
resolution digital camera's internal look-up-table (LUT). For calibration
purposes,
the white screen (when lit with the lighting equipment) should have a
brightness
2o value of greater than about 245, preferably from about 250 to about 255.
The typical hair sample consists of 15 cm (5 g) straight black Asian hair
switches (available from Kawamuraya Co., Osaka, Japan) or straight brown
Caucasian hair switches (available from International Hair Importers &
products
Inc., Bellerose, New York, U.S.A.). Straight black Asian hair switches are
25 preferred, because their contrast against the white screen is more easily
observable. The measurements using the Image Analysis Protocol are
significantly easier and more reproducible when black hair switches are used.
However, the hair area reduction benefits, and the corresponding hair volume
reduction benefits, of the present invention are applicable to all types of
hair
3o switches. Further, it has been shown that the results achieved with hair
switches
are comparable to the results achieved during actual use on people.
The hair sample is prepared as follows:
1 ) Wet hair sample with warm water (38 °C) for 30 seconds.
2) Apply 1 ml of ammonium lauryl sulfate solution to the hair sample
35 and lather for 30 seconds.
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43
3) Rinse the hair sample for 60 seconds.
4) Soak the hair sample in warm water for 24 hours.
5) Apply 1 ml of ammonium lauryl sulfate solution to
the hair sample
and lather for 30 seconds.
s 6) Rinse the hair sample for 30 seconds.
7) Apply 1 ml of ammonium lauryl sulfate solution to
the hair sample
and lather for 30 seconds.
8) Rinse the hair sample for 60 seconds.
9) For a treated hair sample: apply 1 ml of a hair care
composition to
be tested to the hair sample.
10) For a treated hair sample: rinse off the hair sample
for 10 seconds.
11 ) Comb through the front of the hair sample 5 times.
12) Comb through the back of the hair sample 5 times.
13) Squeeze off excess water from the hair sample and
make the
15 cross-section round.
14) Leave the hair sample in a 21 C / 65% relative humidity
room and
dry for 24 hours.
15) The hair sample is then ready to be measured by the
Image
Analysis System.
2o Steps
9 and 10
are only
performed
for the
treated
hair samples.
To
compare the
effect of
a hair care
composition
on the bulk
hair area,
flyaway
hair
area, and
total hair
area, an
"untreated
picture"
is first
taken of
a hair sample,
and
then a "treated
picture"
is taken.
The untreated
and treated
bulk hair
areas,
flyaway hair
areas, and
total hair
areas shown
in the pictures,
are then
2s compared.Typically, the same hair switch is first used for
the untreated hair
sample, and
then used
for the
treated
hair sample,
according
to the procedure
described above. Using the same hair switch minimizes sample-to-sample
variations.
Once a hair sample (either treated, or untreated), 22, is prepared, it is
3o placed on the sample holder, 16, in front of the white screen, 12. The
distance
from the high-resolution digital camera, 18, and the hair sample, 22, should
be
the same for both the untreated and treated pictures. For both the untreated
and
treated pictures, the hair sample is aligned so that the widest profile
(according to
the bottom end of the hair sample) is captured by the high-resolution digital
ss camera. This alignment approximates the way hair is arranged on the head,
and
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44
therefore provides the most accurate view of the effect on hair area (and
therefore hair volume), after treatment. This also assures an accurate
measurement of the bulk hair area reduction, flyaway hair area reduction,
and/or
total hair area reduction effects.
s Once the hair is essentially motionless, an 8-bit, gray-scale picture is
taken with the high-resolution digital camera, 18. Typically, the high-
resolution
digital camera, 18, assigns each pixel a brightness value of from 0 (pure
black) to
255 (pure white). The picture is then transferred to the personal computer,
20.
Alternatively, but less preferably, the personal computer may assign each
pixel a
~o brightness value from 0 to 255. Such a picture is also referred to as a
"captured
image," and may be saved electronically as, for example, a TIFF (Tagged Image
File Format) file, for future reference. In the captured image, each hair
sample
appears as gray-to-black on a white background. The imaging software (e.g.,
Optimas v. 6.2, available from Media Cybernetics of Silver Springs, Maryland,
15 U.S.A.) then analyzes the captured image, pixel-by-pixel. The imaging
software
uses the brightness value assigned to each pixel by the camera to classify
each
pixel as either black (brightness value = 0 - 120), gray (brightness value =
121 -
235), or white (brightness value = 236 - 255). The imaging software then
defines
"bulk hair" in the captured image as the largest continuous region bounded by
2o black lines. The "flyaway hair" is defined as black, gray, and white
regions
bounded by one or more gray lines, excluding the bulk hair. The term "bounded"
as used herein with respect to the imaging software indicates that the
referred-to-
area is completely surrounded by at least one line of the specified shade.
The imaging software then calculates the area of each region, typically in
25 cm2, to find the bulk hair area and the flyaway hair area. The total hair
area is
the sum of the bulk hair area and the flyaway hair area. Thus, the bulk hair
area
and/or the flyaway hair area may also be calculated as a percentage of the
total
hair area. In a preferred embodiment, the imaging software automatically sets
the untreated total hair area equal to a value of 1.0, and normalizes the
other
3o values, accordingly. The imaging software may also outline and/or color
code
the bulk hair area and/or flyaway hair area for easy reference.
The reduction in hair volume after treatment is based on comparing the
data obtained from analyzing the treated and untreated hair samples. The hair
areas are calculated for the untreated total hair area (UTA), the untreated
bulk
3s hair area (UBA), and the untreated flyaway hair area (UFA). These are then
CA 02382391 2002-02-18
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compared to the calculated hair areas for the treated total hair area (TTA),
the
treated bulk hair area (TBA), and the treated flyaway hair area (TFA). The
reduction in bulk hair area after treatment corresponds to a reduction in the
bulk
hair volume, and is calculated according to the following equation:
s bulk hair area reduction = 100 * [1 - (TBA/UBA)].
Similarly, the percent reduction in flyaway hair area after treatment
corresponds
to a reduction in the flyaway hair volume, and is calculated according to the
following equation:
flyaway hair area reduction = 100 * [1 - (TFA/UFA)].
The percent reduction in total hair area after treatment corresponds to a
reduction in the total hair volume, and calculated according to the following
equation:
total hair area reduction = 100 * [1 - (TTA/UTA)].
A given hair care composition (or control) is typically tested on at least
15 three separate hair samples. The bulk hair area reduction, flyaway hair
area
reduction, and total hair area reduction are then calculated for each hair
sample,
and an average bulk hair area reduction, average flyaway hair area reduction,
and average total hair area reduction are calculated.
In a preferred embodiment of the Image Analysis Protocol, two pictures of
2o each treated and untreated hair sample are taken. The first picture
corresponds
to the widest profile of the hair sample, while the second picture corresponds
to
the most narrow profile of the hair sample, which is typically a 90°
rotation from
the widest profile. Then, average values are calculated for the untreated bulk
hair area, treated bulk hair area, etc. These average values are then employed
2s in the above equations. Such a procedure is especially useful with hair
samples
which are slightly curved, due to their natural contours, or because of
washing.
Examples of the invention are set forth hereinafter by way of illustration
and are not intended to be in any way limiting of the invention, as many
variations thereof are possible without departing from the spirit and scope of
the
so invention. Ingredients are identified by chemical or CTFA name, or
otherwise
defined below.
EXAMPLE 1
A hair conditioning composition is formed by the following process. All
35 percentages are by weight of the final hair care composition.
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46
The suitable carrier is a lamellar gel matrix, which is formed as follows (all
percentages are by weight of the final hair conditioning composition): about
78%
deionized water is heated to 85 °C, and 2%
Stearamidopropyldimethylamine,
available from Nikko Chemical (Tokyo, Japan) is mixed together with 2.5% cetyl
alcohol and 4.5% stearyl alcohol from Shin-nihon Rika (Tokyo, Japan), and
0.64% L-glutamic acid from Ajinomoto (Osaka, Japan). The aqueous carrier is
maintained at a temperature of about 85 °C for about 5 minutes with
continuous
mixing, until the components are homogenized, and no solids are observed. The
aqueous carrier is then gradually cooled to about 55 °C and maintained
at this
1o temperature, until a lamellar gel matrix forms. 5% ester oil
(caprylic/capric
triglyceride under trade name Miglyol812 available from Degussa-Huls AG of
Frankfurt, Germany) and 1 % pentaerythritol tetraisostearate (KAK P.T.I.
available
from Koukyu Alcohol Kogyo Co. of Chiba Prefecture, Japan) are also added to
the lamellar gel matrix.
5% PPG-34 (New Pol PP-2000 available from Sanyo Kasei, Osaka,
Japan; weight average molecular weight = 2,000 g/mol) is mixed with the
lamellar
gel matrix with constant stirring for 15 minutes, to assure homogenization. A
perfume, a preservative, and the remaining ingredients are also added to the
hair
care composition. The lamellar gel matrix is maintained at about 55 °C
during
2o this time. After it is homogenized, it is allowed to cool to room
temperature,
packaged, and stored.
This hair conditioning composition is suitable for use as either a rinse-off,
or leave-on form. When normally applied and used, this hair conditioning
composition also provides a noticeable reduction in bulk hair area and total
hair
area.
EXAMPLE 2
The following example is representative of the benefits of the present
invention. Example 2, a rinse-off hair conditioning composition of the present
3o invention was re ared accordin to the method described in Example 1.
EXAMPLE
2
Cet I Alcohol 2.857
Stea I Alcohol 5.143
Stearamido ro Idimeth lamine2.000
L-Glutamic Acid 0.640
P PG-34 5.000
Mi I 01812 5.000
Pentae thritol tetraisostearate1.000
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47
Water, minors balance
Viscosit c s 23900
Volume data
vs. Untreated
Bulk hair area reduction 29
%
FI awa hair area reduction 32
/
Total hair area reduction~ 30
%
Example 2 provides a significant reduction in bulk hair area, flyaway hair
area, and total hair area.
EXAMPLE 3
The following hair conditioning compositions having a lamellar gel matrix
are formed by the arocess described in Examale 1:
Com onent A B C D E F
PPG-34 *1 5.0 - - - - 2.0
Pol ro lene I col *2 - 3.0 - - - 1.0
Pol ox ro lene I ce I - - 4.0 - - -
ether *3
Pol ox ro lene sorbitol - - - 5.0 - -
*4
PPG-10 butanediol *5 - - - - 2.0 1.0
Ce I h drox eth I cellulose0.25 - - - - 0.25
*6
Ole I alcohol *7 - - - 1.0 - 1.0
Ca lic/ca ric tri I ceride5.0 5.0 3.0 5.0 5.0 -
*8
Pentae thritol tetraisostearate1.0 1.0 1.0 - - 7.5
*9
Mineral oil *10 - - 1.0 - 1.0 -
Stearamido ro Idimeth 2.0 2.0 - - - 1.0
lamine *11
L-Glutamic acid 0.6 - - - - 0.3
Lactic acid - 1.0 - - - -
Behentrimonium chloride - - 2.0 - - -
*12
Stea Itrimonium chloride- - - 2.0 - -
*13
Cetrimonium chloride - - - - - 1.0
*14
Distea Idimonium chloride- - - - 2.0 -
*15
Cet I alcohol *16 2.5 2.4 5.6 1.8 2.0 3.0
Stea I alcohol *17 4.5 3.6 - 2.7 4.0 5.0
C clomethicone & Dimethicone4.0 - 8.0 3.0 4.0 2.0
*18
Dimethicone/Dimethiconol- 1.0 - - - 2.0
*19
C clomethicone/Dimethiconol- - - 2.0 - -
*20
Hexylene Glycol - - - - 2.0 -
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48
Pol eth lene GI col 200 - 1.0 - - - 1.0
*21
2,4-dimethoxy-6-(1'pyrenyl)-1,3,5-- - - - - 0.5
triazine *22
Por h rin *23 - - - - 0.5
Benzo henone-4 *24 - - 0.2 - - -
Oc I Methox cinnamate - 0.1 - 1.0 - -
*25
Vitamin E - - - - 0.05 -
Panthenol *26 0.1 - - - - -
Meth I Paraben 0.2 0.2 0.2 0.2 0.2 0.2
Phenox ethanol 0.3 0.3 0.3 0.3 0.3 0.3
EDTA 0.2 0.1 - - 0.1 0.2
Disodium EDTA - 0.1 0.1 0.2 0.1 -
Benz I alcohol 0.4 0.4 0.5 0.4 0.2 0.40
Perfume 0.2 0.1 0.2 0.2 0.20 0.2
Deionized Water q,s.
to
100%
_
_
Definitions of Components
*1 New Pol PP-2000 available from Sanyo Kasei
*2 New Pol PP-4000 available from Sanyo Kasei, weight average molecular weight
= 4000.
*3 New Pol GP-4000 available from Sanyo Kasei
*4 New Pol SP-4000 available from Sanyo Kasei
*5 Probutyl DB-10 available from Croda, Inc.
*6 NATROSOL PLUS 330CS from Aqualon Co., Delaware, USA.
*7 UNJECOL 90BHR available from Shin-nihon Rika
*8 Miglyol812 available from Degussa-Huls AG
*9 KAK P.T.I. available from Koukyu Alcohol Kogyo Co. of Chiba Prefecture,
Japan
*10 BENOL available from Witco Chemicals, Greenwich, Connecticut, USA
*11 available from Nikko Chemical, Tokyo, Japan
*12 Varisoft BT85 available from Witco Chemicals
*13 Varisoft TSC available from Witco Chemicals
*14 Varisoft CTB40 available from Witco Chemicals
*15 Varisoft TA100 available from Witco Chemicals
*16 KONOL series available from Shin-nihon Rika
*17 KONOL series available from Shin-nihon Rika
*18 85%/15% mixture of D5 cyclomethicone and dimethicone gum (weight molecular
weight of
about 400,000 to about 600,000) from General Electric Co.
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49
*19 DCQ2-1403 available from Dow Corning
*20 DCQ2-1401 available from Dow Corning
*21 Carbowax PEG200 available from Union Carbide
*22 available from Ciba Geigy
*23 available from Wako Chemical, Osaka, Japan
*24 Uvnul MS-40 available from BASF
*25 Parasol MCX available from Roche
*26 available from Roche
1o EXAMPLE 4
A hair care composition is formed by the following process. All
percentages are by weight of the final hair care composition.
About 2% polyoxypropylene glyceryl ether (trade name New Pol GP-4000
available from Sanyo Kasei, Osaka, Japan) is mixed with an aqueous carrier
[95% deionized water, 0.5% acrylic acid/alkyl acrylate copolymer 1 (tradename
PEMULEN TR-1 available from B.F. Goodrich, Cleveland, Ohio, U.S.A.), 0.2%
Laureth-12 (Nikko Chemical, Tokyo, Japan), and 0.5% dimethicone and
Dimethiconol (tradename DCQ2-1403 available from Dow Corning, Midland,
Michigan, U.S.A.)], at a temperature of 35 °C. 1 % trimethylol propane
trioleate
(KAK T.T.I. available from Koukyu Alcohol Kogyo Co. of Chiba Prefecture,
Japan) is added. A perfume, a preservative, and the remaining minor
ingredients
are also added to the hair care composition.
The hair care composition formed possesses significantly improved
stability of the alkyl ethoxylate, and/or improved deposition efficiency, even
though the suitable carrier is not a gel matrix. When applied to hair as a
hair
lotion composition, and the hair is dried, a significant, noticeable reduction
in bulk
hair area and total hair area is observed.
EXAMPLE 5
3o The following hair care compositions are formed by the process described
herein
TABLEI A B C D E F
PPG-34 *1 5.0 - - - - 2.0
Pol ro lene I col *2 - 3.0 - - - 1.0
Polvoxvaropvlene alvcervl - - 4.0 - - -
ether *3 ~
CA 02382391 2002-02-18
WO 01/17491 PCT/US99/20327
Pol ox ro lene sorbitol *4 - - - 5.0 - -
PPG-10 butanediol *5 - - - - 2.0 1.0
Ole I alcohol *6 1.0 - - - - -
Ca lic/ca ric tri I ceride - - 1.0 0.5 - -
*7
Trimeth lol ro ane trioleate - 2.0 - 1.0 - 1.5
*8
Pentae thritol tetraisostearate1.0 - 2.0 - 2.5 -
*9
Mineral oil *10 - - - - - 1.0
Carbomer 1 *11 0.1 - 0.2 - 0.1 -
Carbomer 2 *12 - - - 0.5 - 0.3
Triethanolamine *13 0.5 0.6 0.7 0.6 0.5 0.5
Dimethicone/Dimethiconol *14 1.0 1.0 - - - 2.0
C clomethicone/Dimethiconol - - - 2.0 - -
*15
C clomethicone/Dimethicone - - 2.0 - 2.0 -
*16
C clomethicone *17 - - 1.0 - - -
Pol uaternium-39 *18 0.2 0.1 - - - -
Hex lene GI col - - - - 2.0
Pol eth lene GI col 200 *19 - 2.0 - _ - 1.0
2 4-dimethox -6- 1' ren I -1 - - - - - 1.0
3 5-triazine *20
Por h rin *21 - - - - 1.0 -
Benzo henone-4 *22 0.1 - 0.2 - - -
Oc I Methox cinnamate *23 - 0.1 - 1.0 - -
Vitamin E - - - - 0.05 -
Panthenol *24 0.1 - - - - -
Meth I Paraben 0.2 0.2 0.2 0.2 0.2 0.2
Phenox ethanol 0.3 0.3 0.3 0.3 0.3 0.3
Disodium EDTA 0.1 0.1 0.1 0.1 0.1 0.1
Perfume solution 0.1 0.1 0.1 0.1 0.1 0.1
Deionized Water -. -___________________
p.s.
to
100%
-________-_-_-__
Definitions of Co J~onents
*1 New Pol PP-2000 available from Sanyo Kasei
*2 New Pol PP-4000 available from Sanyo Kasei, weight average molecular weight
= 4000.
*3 New Pol GP-4000 available from Sanyo Kasei
5 *4 New Pol SP-4000 available from Sanyo Kasei
*5 Probutyl DB-10 available from Croda, Inc.
*6 UNJECOL 90BHR available from Shin-nihon Rika
CA 02382391 2002-02-18
WO 01/17491 PCT/US99/20327
51
*7 Miglyol812 available from Degussa-Huls AG
*8 KAK T.T.I. available from Koukyu Alcohol Kogyo Co. of Chiba Prefecture,
Japan
*9 KAK P.T.I. available from Koukyu Alcohol Kogyo Co.
*10 BENOL available from Witco Chemicals
*11 Carbopol 981 available from B.F. Goodrich
*12 Carbopol Ultrez 10 available from B.F. Goodrich
*13 available from Nippon Shokubai
*14 DCQ2-1403 available from Dow Corning
*15 DCQ2-1401 available from Dow Corning
*16 Gum/Cyclomethicone blend available from Shin-Etsu
*17 DC345 available from Dow Corning
*18 Merquat 3330 available from Calgon, Co., Pittsburgh, Pennsylvania, USA.
*19 Carbowax PEG200 available from Union Carbide
*20 available from Ciba Geigy
*21 available from Wako Chemical, Osaka, Japan
*22 Uvnul MS-40 available from BASF
*23 Parasol MCX available from Roche
*24 available from Roche
